Enhancement of Active Anticorrosion via Ce-doped Zn-Al Layered Double Hydroxides Embedded in Sol-Gel Coatings on Aluminum Alloy

Ce-doped Zn-Al layered double hydroxide（LDH） nanocontainer was synthesized by a co-precipitation method. X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM） and transmission electron microscopy（TEM） methods were used for the characterization of the LDH nanocontainer. The anticorrosion activity of the LDH powders embedded in a hybrid sol-gel coating on aluminum alloy 2024 was investigated by electrochemical impendence spectroscopy（EIS）. The results showed that Ce（III） ions were successfully incorporated into LDHs layers. The sol-gel coating modified with Ce-doped Zn-Al LDHs exhibited higher anticorrosion behavior compared with both unmodified and Ce-undoped LDHs containing coatings, which proved the applicability of Ce-doped LDHs in delaying coating degradation and their potential application as nanocontainers of corrosion inhibitors in self-healing coatings.

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.

Combining the 8-hydroxyquinoline intercalated layered double hydroxide film and sol-gel coating for active corrosion protection of the magnesium alloy

8-hydroxyquinoline(8-HQ)intercalated layered double hydroxides(LDH)film as underlayer and sol-gel layer was combined for active corrosion protection of the AM60B magnesium alloy.The LDH,LDH/sol-gel,and LDH@HQ/sol-gel coatings were analyzed using the scanning electron microscopy(SEM),field emission scanning electron microscopy(FESEM),energy dispersive X-ray spectroscopy(EDS),X-ray diffraction(XRD),atomic force microscopy(AFM),and electrochemical impedance spectroscopy(EIS)methods.The SEM images showed that the surface was entirely coated by the LDH film composed of vertically-grown nanosheets.The same morphology was observed for the LDH/sol-gel and LDH@HQ/sol-gel coatings.Also,almost the same topography was observed for both composite coatings except that the LDH@HQ/sol-gel coating had relatively higher surface roughness.Although the LDH film had the same impedance behavior as the alloy sample in 3.5wt%NaCl solution,its corrosion resistance was much higher,which could be due to its barrier properties as well as to the trap-ping of the chloride ions.Similar to the LDH film,the corrosion resistance of the LDH/sol-gel composite diminished with increasing the ex-posure time.However,its values were much higher than that of the LDH film,which was mainly related to the sealing of the solution path-ways.The LDH@HQ/sol-gel composite showed much better anti-corrosion properties than the LDH/sol-gel coating due to the adsorption of the 8-HQ on the damaged areas through the complexation.

Droplet transfer behavior of the stainless steel coated electrode with double-layer coating

In this paper, the droplet transfer behavior of the stainless steel coated electrode with double layer coating is researched by means of those experimental methods, such as high speed camera, collecting droplet in water, surfacing on the steel plate et al. The results show that the droplet transfer indexes of coated electrode are mainly controlled by the size of droplet, which affects the transfer behavior of droplet. The distribution characteristic of the droplet size of the electrode affects the numerical relationship among droplet transfer indexes. The metallurgical process of the coated electrode with double layer coating is carried out continuously in different zones. The main reason for the coated electrode with double layer coating gaining excellent usability quality is that the droplets realize the 'quasi flux wall guided transfer pattern'.

Optical, Mechanical and Laser-induced Damage Threshold Properties of 1064 nm, 532 nm Frequency-doubled Antireflection Coating for LBO

1 064 nm, 532 nm frequency-doubled antireflection （AR） coatings with buffer layer of SiO2 between the coating and the substrate were fabricated by the electron beam evaporation technology on the substrate of lithium triborate （LiB3O5 or LBO） crystals. The residual reflectance of the sample is 0.07% and 0.11% at 1 064 nm and 532 nm, respectively. The adhesion and the laser-induced damage threshold （LIDT） of the sample are greater than 200 mN and 18.6 J/cm2. The strengthening mechanism of adhesion and LIDT of the buffer layer of SiO2 were discussed by considering full plastic indentation and shear theory, and spallation of a plated film induced by thermal shock stress, respectively.

Corrosion resistance of Mg（OH）2/Mg-Al-layered double hydroxide coatings on magnesium alloy AZ31:influence of hydrolysis degree of silane

Mg(OH)2/Mg-Al-layered double hydroxide (LDH) coatings were modified with methyltrimethoxysilane (MTMS) on magnesium alloys. Effect of hydrolysis degree of silane solution on coating formation was investigated. Chemical compositions and surface morphologies of the coatings were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electronic microscopy (FESEM). Results indicated that the composite coatings consisted of polymethyltrimethoxysilane (PMTMS), LDH and Mg(OH)2. Electrochemical and hydrogen evolution measurements revealed that the composite coatings possessed good corrosion resistance, especially the ones prepared in a high hydrolysis degree of silane. The optimum corrosion resistance of the composite coati ng was LDH/PMTMS-3 coating, which had the lowest value of corrosion current density (5.537×10^-9 A·cm^-2) and a dense surface.Plausible mechanism for coating formation and corrosion process of MTMS-modified Mg(OH)2/Mg-Al-LDH coatings were discussed.

Green corrosion inhibitors intercalated Mg:Al layered double hydroxide coatings to protect Mg alloy

Mg alloy was protected with Mg:Al layered double hydroxide(LDH)coating intercalated with three green corrosion inhibitors(sodium benzoate,3-aminopropyltriethoxysilane and 8-hydroxyquinoline).The in-situ hydrothermal approach was adopted to intercalate corrosion inhibitors into Mg:Al LDH coating.The intercalated Mg:Al LDH coating was successfully acquired,and the crystalline structure of Mg:Al LDH coating was verified with X-ray diffraction(XRD).The organic functional groups of corrosion inhibitors were identified with the help of Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS).The compact and uniform morphology was confirmed by scanning electron microscopy(SEM).The electrochemical measurement revealed better corrosion resistance of corrosion inhibitorintercalated Mg:Al LDH coatings as compared to that of pristine Mg alloy.The corrosion protection mechanism of corrosion inhibitors was described and unearthed the corrosion inhibitor with the best performance.

Effects of the Thickness Ratio of CrN vs Cr_2O_3 Layer on the Properties of Double-layered CrN/Cr_2O_3 Coatings Deposited by Arc Ion Plating

In this study, CrN/Cr2O3 double-layered coatings with various thickness ratios of CrN vs Cr2O3 layer were prepared by arc ion plating technology. The influences of the thickness ratio of CrN vs Cr2O3 layer on the microstructural characteristics as well as the mechanical and tribological properties of the CrN/Cr2O3 doublelayered coatings were investigated. The corresponding mechanisms were also discussed. The results indicated that the insertion of CrN layer between the Cr2O3 layer and substrate can effectively decrease the internal stress level of the coating. With increasing the thickness ratio of CrN vs Cr2O3 layer, the surface roughness of double-layered coatings decreased gradually, which had a certain influence on the friction coefficient. In addition, the microhardness also declined gradually, the adhesive strength almost increased linearly, whereas the wear rate declined firstly and then increased slightly. As the thickness ratio was 2：1, the double-layered coating exhibited the best wear resistance.

LDH sealing for PEO coated friction stir welded AZ31/AA5754 materials

The need to combine various metals in light-weight constructions requires the development of coatings that prevent galvanic corrosion.Layered double hydroxides(LDHs)can be an example of such coatings,which were previously successfully obtained in situ on individual materials.In addition,the possibility of LDH growth(including LDH growth in the presence of chelating agents)on the surface of plasma electrolytic oxidation(PEO)-coated metals was previously shown.This PEO+LDH combination could improve both corrosion and mechanical characteristics of the system.The possibility of LDHs formation in situ on the surface of PEO-coated friction stir welded(FSW)magnesium-aluminum materials(AZ31/AA5754 system was selected as a model one)was demonstrated in the presence of 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid(DHPTA)as a chelating agent,which was selected based on analysis of respective metal-ligand compounds stability.LDHs growth was achieved under ambient pressure without addition of carbonates in the electrolyte.The effectiveness of the resulting coating is shown both for corrosion resistance and hardness.

Study on the coating of nano-scale SiO_2 film on the surface of nanocrystalline Mg-Al layered double hydroxides

The coating process of a nano-scale SiO2 film on the nanocrystalline Mg-Al layered double hydroxides via a sol-gel process was investigated. The uniform and dense SiO2film with a thickness of about 5 nm on the nano-LDHs particles was characterized by the solubility test in the dilute HNO3 or HCl acid, TEM and FT-IR, XRD, TG and DSC. The chemical shifts of binding en- ergies of Al 2p, Mg 2p, Si 2s and O 1s on the coated particles indicate that the coating of the SiO2 nano-film on the surface of the nano-LDHs proceeds through the formation of Mg-O-Si and Al-O-Si bonds. The thermal analysis shows that both the SiO2-coated nano-LDHs and the nano-LDHs have a similar mass loss process, in which there are three obvious stages of mass loss in the temperature range of 40—700℃. Furthermore, the more the coatedamount of SiO2on the surface of the nano-LDHs is, the less the mass loss of the samples is at 700℃.The nano- LDHs have two obvious endothermic peaks at 244.67℃ and 430.13℃, whose corresponding heat absorption capacities are 412.28 J/g and 336.30 J/g, respectively. In contrast, the coated nano-LDHs have only one endothermic peak at 243.60℃ with a heat absorption capacity of 221.25 J/g.

Corrosion of in-situ grown Mg Al-LDH coating on aluminum alloy

Mg Al-layered double hydroxides（LDH） coatings were fabricated by the in-situ hydrothermal treatment method on the AA5005 aluminum alloy.The characteristics of the coatings were investigated by XRD,FT-IR,SEM and EDS.The effect of the p H value of the solution on the formation of the LDH coatings was studied.The optimum p H value of the solution was 10.0.The corrosion resistance of the LDH coatings was studied using potentiodynamic polarization tests and electrochemical impedance spectrum（EIS）.The results demonstrate that the LDH coatings,characterized by platelets vertically to the substrate surface possess excellent corrosion resistance.The influence of the hydrothermal crystallization time on the corrosion resistance was evaluated.Prolonging the crystallization time can increase the corrosion resistance of the obtained LDH coatings.The anticorrosion mechanism of the LDH coatings was discussed.

Corrosion resistance of Mg−Al LDH/Mg(OH)2/silane−Ce hybrid coating on magnesium alloy AZ31

An environmentally-friendly hybrid coating on AZ31 magnesium alloy substrates was reported.The synergic effect was studied on Mg−Al-layered double hydroxide Mg−Al LDH/Mg(OH)2-coated AZ31 magnesium alloy via an in-situ steam coating process and a subsequent combined surface modification of bis-[triethoxysilylpropyl]tetrasulfide(BTESPT)silane and Ce(NO3)3.The microstructure and composition characteristics of the hybrid coatings were investigated by means of X-ray diffraction(XRD),scanning electronic microscopy(SEM),Fourier transform infrared spectrophotometry(FT-IR)and X-ray photoelectron spectroscopy(XPS).The corrosion resistance of the coated samples was evaluated by potentiodynamic polarization(PDP),electrochemical impedance spectrum(EIS)and hydrogen evolution rate during immersion in 3.5 wt.%NaCl solution.The results show an improved corrosion resistance of the alloy in the presence of BTESPT silane and Ce(NO3)3.This is most likely due to the synergistic effect of steam coating and silane coating to enhance the barrier properties of hybrid coating.In addition,the formation mechanism and anti-corrosion mechanism of coatings were discussed.

Influence of intermetallic Al-Mn particles on in-situ steam Mg-Al-LDH coating on AZ31 magnesium alloy

The influence of intermetallic Al-Mn particles on the corrosion behavior of in-situ formed Mg-Al layered double hydroxide(Mg-Al-CO32--LDH)steam coating on AZ31 Mg alloy was investigated.The alloy was pretreated with H3PO4,HCl,HNO3or citric acid(CA),followed by hydrothermal treatment,for the fabrication of Mg-Al-LDH coating.The microstructure,composition and corrosion resistance of the coated samples were investigated.The results showed that the surface area fraction of Al-Mn phase exposed on the surface of the alloy was significantly increased after CA pretreatment,which promotes the growth of the Mg-Al-LDH steam coating.Further,the LDH-coated alloy pretreated with CA possessed the most compact surface and the maximum coating thickness among all the coatings.The corrosion current density of the coated alloy was decreased by three orders of magnitude as compared to that of the bare alloy.

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.

Acoustic reflection of rib-stiffened double plates coated with a viscoelastic layer

To predict sound-absorbing performance of anechoic materials,the acoustic reflection problem of a viscoelastic layer backed with periodically rib-stiffened infinite double plates is studied in this paper.The reason why structural theories of plates are not applicable to viscoelastic plates is explained through comparing dispersion and attenuation curves of flexural waves with those of Lamb waves.As a result,（visco-）elastic theory is adopted to deal with（visco-）elastic plates,and ribs are treated by structural theories of plates.The coupling between ribs and plates are solved by Hull＇s method,and solution of the reflected field is obtained.The accuracy of present method is validated by comparing with the results by the structural theories of plates.The influence of a backing on the acoustic reflection of the viscoelatic layer is analyzed by computing reflection coefficients.Performances of different viscoelastic materials are evaluated by the average reflection coefficients.The computational results show that,influence of a backing on the acoustic reflection cannot be suppressed by the viscoelastic materials in low frequencies.The resonance is determined by the coupling of the fluid layer and the double plates.And ribs,which are coupled with the double plates,mainly reduce the acoustic reflection.

A self-healing coating based on facile pH-responsive nanocontainers for corrosion protection of magnesium alloy

The preparation of pH-responsive nanocontainers by typical silane modification of the mesoporous silica nanoparticle(MSN)surface is usually high-cost,complex,and time-consuming,which remains a great challenge for effective corrosion protection of magnesium alloy.Here,a new strategy to construct pH-responsive nanocontainers(MSN-MBT@LDH)is demonstrated.The nanocontainers consist of corrosion inhibitor(2-mercaptobenzothiazole,MBT)loaded MSN core and layered double hydroxide(LDH)nanosheet shell serving as gatekeepers.The successful loading of MBT and encapsulation by LDH nanosheets were confirmed by a series of characterization such as scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy(STEM-EDS)and N2 adsorption/desorption isotherms.The pH-responsive feature of the nanocontainers was demonstrated by determination of the MBT concentration in buffer solutions with different pH values.A smart corrosion protection system on Mg alloy is obtained by incorporating the synthesized nanocontainers into a self-assembled nanophase particle(SNAP)coating.The electrochemical tests and visual observations show that the hybrid coating has the best barrier properties and robustness in corrosion protection in NaCl corrosive solutions in comparison with the control coatings.The present method simplifies the synthesis processes of nanocontainers and eliminates the potential detrimental effect of excess gatekeepers on the coating.The findings provide new insights into the preparation of scalable nanocontainers.The self-healing coatings are expected to have widespread applications for corrosion protection of Mg alloy and other metals.

Superhydrophobic and corrosion-resistant siloxane-modified MgAl-LDHs coatings on magnesium alloy prepared under mild conditions

We have developed a superhydrophobic and corrosion-resistant LDH-W/PFDTMS composite coating on the surface of Mg alloy.This composite comprised a tungstate-intercalated(LDH-W)underlayer that was grown at low temperature(relative to hydrothermal reaction conditions)under atmospheric pressure and an outer polysiloxane layer created from a solution containing perfluorodecyltrimethoxysilane(PFDTMS)using a simple immersion method.The successful intercalation of tungstate into the LDH phase and the following formation of the polysiloxane layer were confirmed through X-ray diffraction(XRD),Fourier transform infrared(FTIR)spectroscopy,and X-ray photoelectron spectroscopy(XPS).The corrosion resistance of the LDH-W film,both before and after the PFDTMS modification,was evaluated using electrochemical impedance spectroscopy(EIS),Tafel curves,and immersion experiments.The results showed that Mg coated with LDH-W/PFDTMS exhibited significantly enhanced corrosion protection compared to the unmodified LDHW film,with no apparent signs of corrosion after exposure to 3.5wt%NaCl solution for 15 d.Furthermore,the LDH-W/PFDTMS coating demonstrated superior superhydrophobicity and self-cleaning properties against water and several common beverages,as confirmed by static contact angle and water-repellency tests.These results offer valuable insights into preparing superhydrophobic and corrosion-resistant LDH-based composite coatings on Mg alloy surfaces under relatively mild reaction conditions.

Corrosion resistance of a silane/ceria modified Mg-Al-layered double hydroxide on AA5005 aluminum alloy

The present work aimed at assessing the electrochemical behavior and the corrosion inhibition performance of Mg-Al-layered double hydroxide(LDH)coatings modified with methyltrimethoxysilane(MTMS)and cerium nitrate on AA5005 aluminum alloy.The chemical compositions and surface morphologies of the coatings were investigated by XRD,FT-IR and FE-SEM,while their corrosion resistance was evaluated by electrochemical and immersion tests.An optimum corrosion resistance of the composite coatings was obtained by adding 10^−2 mol·L^−1 cerium nitrate.An excess addition of cerium nitrate resulted in a loose structure and poor corrosion resistance of the coating.The corrosion mechanism of the composite coatings was proposed and discussed.

微弧氧化后Mg-8Li合金表面MgLiAlY-LDHs@GO膜层的生长及耐蚀性能

目的提高Mg-8Li合金的耐蚀性能。方法首先在Mg-8Li合金表面制备微弧氧化膜(MAO),然后使用原位水热法在微弧氧化膜表面原位生长掺杂氧化石墨烯(GO)的四元(MgLiAlY)层状双羟基金属氧化物(LDHs)智能自修复膜层。采用SEM、XRD、FT-IR、EDS、ICP等手段研究MgLiAlY-LDHs@GO膜层的形貌、结构以及成分。通过EIS、Tafel以及浸泡试验等研究膜层的耐蚀性能,分析膜层的腐蚀行为,阐释其耐蚀机理。结果GO的掺杂可以促使LDHs纳米片生长得更加致密,主体层板中具有缓蚀作用的Y3+可以提高涂层的耐蚀性,四元LDHs的生长所需要的Mg^(2+)、Li^(+)、Al^(3+)等离子来源于镁锂合金基体以及微弧氧化膜的溶解,其中Li+也可以促进LDHs纳米片生长得更为均匀细密。膜层的腐蚀电流密度为6.03×10^(–7)A/cm^(2),比MAO膜层降低了1个数量级,提高了镁锂合金的耐蚀性能。结论GO的负载使LDHs的耐蚀性能和膜层稳定性均有一定程度的提升,引入稀土元素Y会改变LDHs的骨架,造成晶格畸变,使得LDHs微观形貌呈现褶皱状,剩下部分以Y(OH)3形式存在于涂层表面,可进一步提高膜层的耐蚀性能和稳定性。

草酸预处理AM50镁合金表面快速原位制备 蒸汽Mg−Al LDH涂层的耐蚀性

通过暴露合金表面的金属间化合物(β-Mg17Al12和AlMn),研究草酸(OA)酸洗对AM50镁合金表面原位蒸汽Mg−Al层状双氢氧化物(LDH)涂层成膜机制和耐蚀性的影响。结果表明,OA预处理使镁合金表面金属间化合物比例显著增加,Mg−Al LDH在Al−Mn相周围成核并生长。当酸洗时间为45 s时,所得LDH涂层的厚度最大、耐蚀性最佳,与基体相比,其腐蚀电流密度降低3个数量级。最后,提出了AM50镁合金表面Mg−Al LDH涂层的成膜机制。