A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were...A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were used to characterize the different Ni–P coatings’ morphologies, phase structures, elemental compositions, and corrosion protection. The gradient coating showed good adhesion and high corrosion and wear resistance, enabling the application of aluminum alloy in harsh environments. The results showed that the double zinc immersion was vital in obtaining excellent adhesion (81.2 N). The optimal coating was not peeled and shredded even after bending tests with angles higher than 90°and was not corroded visually after 500 h of neutral salt spray test at 35℃. The high corrosion resistance was attributed to the misaligning of these micro defects in the three different nickel alloy layers and the amorphous structure of the high P content in the outer layer. These findings guide the exploration of functional gradient coatings that meet the high application requirement of aluminum alloy parts in complicated and harsh aviation environments.展开更多
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 proc...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.展开更多
High velocity oxygen fuel(HVOF)spraying process is commonly used to produce superalloy coatings.Inconel 625 coating was prepared on Q235B low carbon steel by HVOF.A series of experiments were conducted to examine the ...High velocity oxygen fuel(HVOF)spraying process is commonly used to produce superalloy coatings.Inconel 625 coating was prepared on Q235B low carbon steel by HVOF.A series of experiments were conducted to examine the surface and corrosion resistance properties of Inconel 625 HVOF coating.In this paper,potentiodynamic polarization tests and electrochemical impedance spectroscopy(EIS)tests were carried out to evaluate the corrosion resistance of Inconel 625 coating under simulated marine environment.The experiment-al results showed that Inconel 625 coating revealed low porosity and desired coating thickness.Shift in the corrosion potential(E_(corr))to-wards the noble direction combined with much low corrosion current density(i_(corr))indicating a significant improvement of HVOF Inconel 625 coating compared with the substrate.展开更多
Rare-earth silicates are promising environmental barrier coatings(EBCs)that can protect SiC_(f)/Si C_(m)substrates in next-genera tion gas turbine blades.Notably,RE_(2)Si_(2)O_(7)(RE=Yb and Ho)shows potential as an EB...Rare-earth silicates are promising environmental barrier coatings(EBCs)that can protect SiC_(f)/Si C_(m)substrates in next-genera tion gas turbine blades.Notably,RE_(2)Si_(2)O_(7)(RE=Yb and Ho)shows potential as an EBC due to its coefficient of thermal expansion(CTE)compatible with substrates and high resistance to water vapor corrosion.The target operating temperature for next-generation tur bine blades is 1400°C.Corrosion is inevitable during adhesion to molten volcanic ash,and thus,understanding the corrosion behavior o the material is crucial to its reliability.This study investigates the high-temperature corrosion behavior of sintered RE_(2)Si_(2)O_(7)(RE=Yb and Ho).Samples were prepared using a solid-state reaction and hot-press method.They were then exposed to volcanic ash at 1400°C for 224,and 48 h.After 48 h of exposure,volcanic ash did not react with Yb_(2)Si_(2)O_(7)but penetrated its interior,causing damage.Meanwhile Ho_(2)Si_(2)O_(7)was partially dissolved in the molten volcanic ash,forming a reaction zone that prevented volcanic ash melts from penetrating the interior.With increasing heat treatment time,the reaction zone expanded,and the thickness of the acicular apatite grains increased The Ca:Si ratios in the residual volcanic ash were mostly unchanged for Yb_(2)Si_(2)O_(7)but decreased considerably over time for Ho_(2)Si_(2)O_(7).Th Ca in volcanic ash was consumed and formed apatite,indicating that RE^(3+)ions with large ionic radii(Ho>Yb)easily precipitated apatit from the volcanic ash.展开更多
The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion res...The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion resistance of Q235 carbon steel.Scanning electron microscopy results indicated that the CeO_(2) grains were rod-like and ellipsoidal in shape,and the distribution pattern of BTA was analyzed by energy dispersive spectroscope.The dynamic potential polarization curve proved the excellent corrosion resistance of the composite epoxy resin with CeO_(2) and BTA co-addition,and electrochemical impedance spectroscopy test analysis indicated the significantly enhanced long-term corrosion protection performance of the composite coating.And the optimal protective performance was provided by the coating containing 0.3%(mass)CeO_(2) and 20%(mass)BTA,which was attributed to the barrier performance of CeO_(2) particles and the chemical barrier effect of BTA.The formation of corrosion products was analyzed using X-ray diffraction.In addition,the corrosion resistance mechanism of the coating was also discussed in detail.展开更多
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 applica...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.展开更多
The double-layer NiCr-Cr_(3)C_(2)/Ni-Zn-Al_(2)O_(3) coatings with sufficient corrosion and wear resistance were prepared on low carbon steel substrates.The intermediate layers Ni-Zn-Al_(2)O_(3) were fabricated by usin...The double-layer NiCr-Cr_(3)C_(2)/Ni-Zn-Al_(2)O_(3) coatings with sufficient corrosion and wear resistance were prepared on low carbon steel substrates.The intermediate layers Ni-Zn-Al_(2)O_(3) were fabricated by using low-pressure cold spray (LPCS) method to improve the salt fog corrosion resistance properties of the supersonic plasma spray (SPS) NiCr-Cr_(3)C_(2) coatings.The friction and wear performance for the double-layer and single-layer NiCr-Cr_(3)C_(2) coatings were carried out by line-contact reciprocating sliding,respectively.Combined with the coating surface analysis techniques,the effect of the salt fog corrosion on the tribological properties of the double-layer coatings was studied.The results showed that the double-layer coatings exhibited better wear resistance than that of the single-layer coatings,due to the better corrosion resistance of the intermediate layer;the wear mass losses of the double-layer coatings was reduced by 70%than that of the single layer coatings and the wear mechanism of coatings after salt fog corrosion conditions is mainly corrosion wear.展开更多
In this article,NiCr coatings with chromium content of 13%,27%and 41%were prepared by arc spraying.They were exposed in molten salts(NaCl-Na_(2)SO_(4))at 800℃for 200 hours.The effect of chromium content on the hot co...In this article,NiCr coatings with chromium content of 13%,27%and 41%were prepared by arc spraying.They were exposed in molten salts(NaCl-Na_(2)SO_(4))at 800℃for 200 hours.The effect of chromium content on the hot corrosion behavior of the coatings was in-vestigated.X-ray diffraction(XRD)and scanning electron microscope with energy dispersion spectrum(SEM-EDS)were used to analyze the phase compositions,morphologies and chemical compositions of the coatings.The results show that NiCr13 coating exhibited the worst hot corrosion resistance due to the low chromium content,which resulted in NiO being the major reaction product.It should be noted that the hot corrosion resistance of NiCr27 coating was better than that of NiCr41 coating.The basic fluxing of Cr_(2)O_(3) lowered its protection during the hot corrosion process and led to the formation of porous Cr_(2)O_(3) on the NiCr41 coating.The molten salts accelerated the oxidation reac-tion resulting in thicker and porous oxide scales formed on the surfaces of coatings.展开更多
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 p...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.展开更多
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-ar...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.展开更多
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 allo...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.展开更多
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 oxidat...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.展开更多
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 ...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.展开更多
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 AZ...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.展开更多
Although magnesium(Mg)and its alloys are proposed as the next generation orthopedics transplanted materials,their clinical applications are limited by the fast degradation.To reduce the degradation rate,a strong adhes...Although magnesium(Mg)and its alloys are proposed as the next generation orthopedics transplanted materials,their clinical applications are limited by the fast degradation.To reduce the degradation rate,a strong adhesion poly-dopamine(PDA)layer was introduced as an intermediate layer for the subsequent alginate(ALG)spin-coating on high-purity Mg.The surface morphology and chemical composition were detected by scanning electron microscope,energy disperse spectroscopy,and Fourier transform infrared spectroscopy.The corrosion resistances of all samples were evaluated by electrochemical and 10-day immersion tests in Hanks’balanced salt solution.Our results suggest that the thickness of the fabricated PDA/ALG composite coating is 8.58±0.65μm,and the intermediate PDA layer evidently enhances the adhesion between the substrate and ALG coating.The corrosion current density of Mg coated with the PDA/ALG composite coating decreases more than 10 times compared to that of the Mg substrate,and the charge transfer resistance is 12 times bigger than that of the bare Mg,which indicates the improved corrosion resistance.Moreover,the mechanism of corrosion protection of the composite coating is also discussed.展开更多
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 properti...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.展开更多
Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategi...Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.展开更多
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 con...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.展开更多
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 the...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.展开更多
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 ...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.展开更多
基金financially supported by the National Natural Science Foundation of China (No.52271073)。
文摘A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were used to characterize the different Ni–P coatings’ morphologies, phase structures, elemental compositions, and corrosion protection. The gradient coating showed good adhesion and high corrosion and wear resistance, enabling the application of aluminum alloy in harsh environments. The results showed that the double zinc immersion was vital in obtaining excellent adhesion (81.2 N). The optimal coating was not peeled and shredded even after bending tests with angles higher than 90°and was not corroded visually after 500 h of neutral salt spray test at 35℃. The high corrosion resistance was attributed to the misaligning of these micro defects in the three different nickel alloy layers and the amorphous structure of the high P content in the outer layer. These findings guide the exploration of functional gradient coatings that meet the high application requirement of aluminum alloy parts in complicated and harsh aviation environments.
基金the National Natural Science Foundation of China(Grant number 51771178)Shaanxi Outstanding Youth Fund project(Grant number 2021JC-45)+2 种基金Key international cooperation projects in Shaanxi Province(Grant number 2020KWZ-007)the Major Program of Science and Technology in Shaanxi Province(Grant number20191102006)Open Fund of State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body(Grant number 32115019)。
文摘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.
基金supported by Zhejiang Provincial Natural Science Foundation of China(No.LTGC23E010001)the Youth Science and Technology Project of Zhejiang Provincial Administration for Market Regulation(No.QN2023427)Science and Techno-logy Project of State Administration for Market Regulation(No.2022MK054).
文摘High velocity oxygen fuel(HVOF)spraying process is commonly used to produce superalloy coatings.Inconel 625 coating was prepared on Q235B low carbon steel by HVOF.A series of experiments were conducted to examine the surface and corrosion resistance properties of Inconel 625 HVOF coating.In this paper,potentiodynamic polarization tests and electrochemical impedance spectroscopy(EIS)tests were carried out to evaluate the corrosion resistance of Inconel 625 coating under simulated marine environment.The experiment-al results showed that Inconel 625 coating revealed low porosity and desired coating thickness.Shift in the corrosion potential(E_(corr))to-wards the noble direction combined with much low corrosion current density(i_(corr))indicating a significant improvement of HVOF Inconel 625 coating compared with the substrate.
基金supported by JSPS KAKENHI(No.23K19087)“Dynamic Alliance for Open Innovation Bridging Human,Environment and Materials”from the Ministry of Education,Culture,Sports,Science and Technology o f Japan(MEXT).
文摘Rare-earth silicates are promising environmental barrier coatings(EBCs)that can protect SiC_(f)/Si C_(m)substrates in next-genera tion gas turbine blades.Notably,RE_(2)Si_(2)O_(7)(RE=Yb and Ho)shows potential as an EBC due to its coefficient of thermal expansion(CTE)compatible with substrates and high resistance to water vapor corrosion.The target operating temperature for next-generation tur bine blades is 1400°C.Corrosion is inevitable during adhesion to molten volcanic ash,and thus,understanding the corrosion behavior o the material is crucial to its reliability.This study investigates the high-temperature corrosion behavior of sintered RE_(2)Si_(2)O_(7)(RE=Yb and Ho).Samples were prepared using a solid-state reaction and hot-press method.They were then exposed to volcanic ash at 1400°C for 224,and 48 h.After 48 h of exposure,volcanic ash did not react with Yb_(2)Si_(2)O_(7)but penetrated its interior,causing damage.Meanwhile Ho_(2)Si_(2)O_(7)was partially dissolved in the molten volcanic ash,forming a reaction zone that prevented volcanic ash melts from penetrating the interior.With increasing heat treatment time,the reaction zone expanded,and the thickness of the acicular apatite grains increased The Ca:Si ratios in the residual volcanic ash were mostly unchanged for Yb_(2)Si_(2)O_(7)but decreased considerably over time for Ho_(2)Si_(2)O_(7).Th Ca in volcanic ash was consumed and formed apatite,indicating that RE^(3+)ions with large ionic radii(Ho>Yb)easily precipitated apatit from the volcanic ash.
基金financially supported by the National Natural Science Foundation of China(22178242)the Shanxi Provincial Key Research and Development Project(202102040201009).
文摘The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion resistance of Q235 carbon steel.Scanning electron microscopy results indicated that the CeO_(2) grains were rod-like and ellipsoidal in shape,and the distribution pattern of BTA was analyzed by energy dispersive spectroscope.The dynamic potential polarization curve proved the excellent corrosion resistance of the composite epoxy resin with CeO_(2) and BTA co-addition,and electrochemical impedance spectroscopy test analysis indicated the significantly enhanced long-term corrosion protection performance of the composite coating.And the optimal protective performance was provided by the coating containing 0.3%(mass)CeO_(2) and 20%(mass)BTA,which was attributed to the barrier performance of CeO_(2) particles and the chemical barrier effect of BTA.The formation of corrosion products was analyzed using X-ray diffraction.In addition,the corrosion resistance mechanism of the coating was also discussed in detail.
文摘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.
基金Fundamental Research Funds for Central Universities Project (No. 1CX05021A)Shandong Provincial Key R&D Plan Project (No. 2GHY15108)Shandong Postdoctoral Innovation Project and Qingdao Postdoctoral Applied Research Project。
文摘The double-layer NiCr-Cr_(3)C_(2)/Ni-Zn-Al_(2)O_(3) coatings with sufficient corrosion and wear resistance were prepared on low carbon steel substrates.The intermediate layers Ni-Zn-Al_(2)O_(3) were fabricated by using low-pressure cold spray (LPCS) method to improve the salt fog corrosion resistance properties of the supersonic plasma spray (SPS) NiCr-Cr_(3)C_(2) coatings.The friction and wear performance for the double-layer and single-layer NiCr-Cr_(3)C_(2) coatings were carried out by line-contact reciprocating sliding,respectively.Combined with the coating surface analysis techniques,the effect of the salt fog corrosion on the tribological properties of the double-layer coatings was studied.The results showed that the double-layer coatings exhibited better wear resistance than that of the single-layer coatings,due to the better corrosion resistance of the intermediate layer;the wear mass losses of the double-layer coatings was reduced by 70%than that of the single layer coatings and the wear mechanism of coatings after salt fog corrosion conditions is mainly corrosion wear.
基金supported by Corporate Talent Fund Program of Zhengzhou Research Institute of Mechanical Engineering Co.,Ltd.(No.201SJ2023013)the Faculty of Materials and Manufacturing,Beijing University of Technology.
文摘In this article,NiCr coatings with chromium content of 13%,27%and 41%were prepared by arc spraying.They were exposed in molten salts(NaCl-Na_(2)SO_(4))at 800℃for 200 hours.The effect of chromium content on the hot corrosion behavior of the coatings was in-vestigated.X-ray diffraction(XRD)and scanning electron microscope with energy dispersion spectrum(SEM-EDS)were used to analyze the phase compositions,morphologies and chemical compositions of the coatings.The results show that NiCr13 coating exhibited the worst hot corrosion resistance due to the low chromium content,which resulted in NiO being the major reaction product.It should be noted that the hot corrosion resistance of NiCr27 coating was better than that of NiCr41 coating.The basic fluxing of Cr_(2)O_(3) lowered its protection during the hot corrosion process and led to the formation of porous Cr_(2)O_(3) on the NiCr41 coating.The molten salts accelerated the oxidation reac-tion resulting in thicker and porous oxide scales formed on the surfaces of coatings.
基金financially supported by the Guangxi Natural Science Foundation,China(No.2020GXNSFAA 159011)the National Natural Science Foundation of China(No.51664011).
文摘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.
基金supported by Guangxi Natural Science Foundation of China(No.2020GXNSFAA159011)National Natural Science Foundation of China(No.51664011)Guangxi Key Laboratory Foundation of China(No.EMFM20211120).
文摘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.
基金support from the Fundamental Research Funds for the Central Universities of Hohai university(B200202122)National Natural Science Foundation of China(51878246 and 51979099)+1 种基金the Natural Science Foundation of Jiangsu Province of China(BK20191303)Key Research and Development Project of Jiangsu Province of China(BE2017148).
文摘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.
基金financially supported by Guangxi Natural Science Foundation of China (No.2020GXNSFAA159011)National Natural Science Foundation of China (No.51664011)。
文摘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.
基金financially supported by the National Key Research and Development Program of China (Nos. 2016YFB0301105 and 2017YFB0702100)。
文摘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.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.51601108 and 52071191)the Natural Science Foundation of Shandong Province(ZR2020ME011).
文摘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.
基金financially supported by National Key Research and Development Project of China(No.2020YFC1107202)Shanxi Provincial Key Research and Development Project(No.2019ZDLSF03–06)+1 种基金Guangdong Basic and Applied Basic Research Foundation(No.2020B1515120078)Science and Technology Planning Project of Guangdong Province(No.2021A0505030042)。
文摘Although magnesium(Mg)and its alloys are proposed as the next generation orthopedics transplanted materials,their clinical applications are limited by the fast degradation.To reduce the degradation rate,a strong adhesion poly-dopamine(PDA)layer was introduced as an intermediate layer for the subsequent alginate(ALG)spin-coating on high-purity Mg.The surface morphology and chemical composition were detected by scanning electron microscope,energy disperse spectroscopy,and Fourier transform infrared spectroscopy.The corrosion resistances of all samples were evaluated by electrochemical and 10-day immersion tests in Hanks’balanced salt solution.Our results suggest that the thickness of the fabricated PDA/ALG composite coating is 8.58±0.65μm,and the intermediate PDA layer evidently enhances the adhesion between the substrate and ALG coating.The corrosion current density of Mg coated with the PDA/ALG composite coating decreases more than 10 times compared to that of the Mg substrate,and the charge transfer resistance is 12 times bigger than that of the bare Mg,which indicates the improved corrosion resistance.Moreover,the mechanism of corrosion protection of the composite coating is also discussed.
基金the financial support from the National Natural Science Foundation of China (Nos.52204389,U19A2084 and 52234009)the National Key Research and Development Program (No.2022YFE0122000)Program for the Central University Youth Innovation Team。
文摘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.
基金appreciate the financial support by the National Natural Science Foundation of China (52071191,52201077)the Natural Science Foundation of Shandong Province (ZR2022QE191)+1 种基金Elite Scheme of Shandong University of Science and Technology (0104060541123)Talent introduction and Research Start-up Fund of Shandong University of Science and Technology (0104060510124)。
文摘Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.
基金the financial support received from the National Science Foundation (NSF-CMMI 2131441) under the direction of Dr.Alexis Lewis。
文摘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.
文摘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.
基金supported by the Key Research and Development Program of Shaanxi Province (2019ZDLSF03-06) and (2020ZDLGY13-05)the National Key Research and Development Program of China (2020YFC1107202)。
文摘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.