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.

Design of multilayer hybrid sol-gel coatings with bifunctional barrier-bioactive response on the Elektron 21 magnesium alloy for biomedical applications

The present study aims to develop multilayer barrier-bioactive hybrid sol-gel coatings from a mixture of the silane precursors tetraethylorthosilicate(TEOS)and glycidoxypropyltriethoxysilane(GPTMS)deposited on the Elektron 21 magnesium alloy.The purpose of the inner layer(barrier coating)was to provide corrosion protection to the magnesium alloy,whereas the outer layer(bioactive coating)was doped with different Ca and Mg contents to produce a bioactive material.The coatings were characterised using scanning electron microscopy(SEM)and their corrosion behaviour was evaluated by anodic polarisation and electrochemical impedance spectroscopy after immersion in simulated body fluid(SBF)at 37±0.5°C.The experimental results showed that the multilayer coatings increased the corrosion resistance of the alloy up to three orders of magnitude during immersion in SBF solution.On the other hand,the presence of Ca and Mg in the bioactive coating promoted the growth of apatite-like phases.However,an increment of salt content favoured the formation of porous coatings,which allowed the access of the electrolyte to the substrate leading to their rapid deterioration.Despite the latter,this research endorses the premise that the TEOS-GPTMS hybrid system represents a promising alternative to produce bifunctional barrier-bioactive coatings.

The Role of the Chelating Agent on the Structure and Anticorrosion Performances of an Organosilane—Zirconium Sol-Gel Coatings

This work investigates the role of the structure of a zirconium complex (ZC) on the condensation and anticorrosion properties of an organosilane sol-gel coating. The structure and reactivity of the ZC were modified by varying the content of methacrylic acid employed as a chelating agent. The structures of the developed materials were characterised by Dynamic Light Scattering, Fourier Transform Infrared Spectroscopy, Differential Scanning Calorimetry and Scanning Electron Microscopy. The passive anticorrosion properties were evaluated by Electrochemical Impedance Spectroscopy of the sol-gel coatings deposited on AA2024-T3 substrates. It was highlighted, that a competition in the condensation process of the silicate (Si-O-Si) and silicon-ZC oxides (Si-O-Zr) species can be tailored by the structure of the ZC, with the least chelated ZC exhibiting the highest content of Si-O-Zr bonds. At the same time, it was also found that the coatings containing the highest content of Si-O-Zr groups exhibited the best anticorrosion barrier performances amongst all sol-gel coatings investigated here, therefore presenting the highest condensation degree. This suggested that Si-O-Zr bonds were the essential chemical species responsible for the formation of condensed coatings. A direct correlation between the structure of the coatings and their anticorrosion performances is proposed.

Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel

Sol-gel titania films were deposited on 316L stainless steel using titanium isopropoxide as a chemical precursor. Dip-coating was performed at withdrawal speeds of 6 mm/min, 30 mm/min, and 60 mm/min. Deposited gel films were heat treated in air at 80℃, 100℃, 300℃, and 400℃. The structural evolution of the coatings was evaluated by infrared reflection-absorption spectroscopy. The influence of the withdrawal speed and the heat treatment temperature on the structure of the films was studied by varying the reflectance incidence angle during the infrared experiments and by Glow Discharge Spectrometry. Free functional groups were detected. The results indicate the formation of bidendate bridging coordination of carboxylic acid to titanium. Titanium atoms can also be pentacoordinated according to the processing conditions of the films. We observed a tendency of increasing amounts of OH groups with decreasing reflectance incidence angle. The film hardness was measured via Knoop microindenation hardness test.

Development of Modified Glasses by Transparent, Functional Hybrid Sol-Gel Nano-Ceramic Coatings, a Comparative Study

This paper concentrates on the development of glasses with self-cleaning surfaces exhibiting high water contact angles. In this study, we prepared super-hydrophobic nano-ceramic coated glass based on titania & silica using simple sol-gel & dip coating methods and studied the best composition of the coatings by altering ratios of titanium tetraisopropoxide (TTIP)/tetraethyl orthosilicate (TEOS) with different homogenizing agents. We characterized the coatings by surface roughness measurement, percentage of optical transmission, static contact angle, near-infrared (NIR) transmission, and diffuse reflectance. The fabrication of coatings on glass substrates played an important role in increasing the water contact angle of about 95° and visible & NIR transmission of about 90%. We compared our modified glass substrate with commercial low emissivity (Low E) glass using X-ray diffraction (XRD) analysis, which showed pure amorphous surface claiming excellent wettability and thus the prepared glass substrate could have a variety of applications in different fields.

High corrosion and wear resistant electroless Ni–P gradient coatings on aviation aluminum alloy parts

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.

Surface Metallization of Glass Fiber(GF)/Polyetheretherketone(PEEK) Composite with Cu Coatings Deposited by Magnetron Sputtering and Electroplating

Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.

Bio-Based Waterborne Poly(Vanillin-Butyl Acrylate)/MXene Coatings for Leather with Desired Warmth Retention and Antibacterial Properties

This study presents a solvent-free,facile synthesis of a bio-based green antibacterial agent and aromatic monomer methacrylated vanillin(MV)using vanillin.The resulting MV not only imparted antibacterial properties to coatings layered on leather,but could also be employed as a green alternative to petroleum-based carcinogen styrene(St).Herein,MV was copolymerized with butyl acrylate(BA)to obtain waterborne bio-based P(MV-BA)miniemulsion via miniemulsion polymerization.Subsequently,MXene nanosheets with excellent photothermal conversion performance and antibacterial properties,were introduced into the P(MV-BA)miniemulsion by ultrasonic dispersion.During the gradual solidification of P(MV-BA)/MXene nanocomposite miniemulsion on the leather surface,MXene gradually migrated to the surface of leather coatings due to the cavitation effect of ultrasonication and amphiphilicity of MXene,which prompted its full exposure to light and bacteria,exerting the maximum photothermal conversion efficiency and significant antibacterial efficacy.In particular,when the dosage of MXene nanosheets was 1.4 wt%,the surface temperature of P(MV-BA)/MXene nanocomposite miniemulsioncoated leather(PML)increased by about 15℃ in an outdoor environment during winter,and the antibacterial rate against Escherichia coli and Staphylococcus aureus was nearly 100%under the simulated sunlight treatment for 30 min.Moreover,the introduction of MXene nanosheets increased the air permeability,water vapor permeability,and thermal stability of these coatings.This study provides a new insight into the preparation of novel,green,and waterborne bio-based nanocomposite coatings for leather,with desired warmth retention and antibacterial properties.It can not only realize zerocarbon heating based on sunlight in winter,reducing the use of fossil fuels and greenhouse gas emissions,but also improve ability to fight off invasion by harmful bacteria,viruses,and other microorganisms.

Developing an atmospheric aging evaluation model of acrylic coatings:A semi-supervised machine learning algorithm

To study the atmospheric aging of acrylic coatings,a two-year aging exposure experiment was conducted in 13 representative climatic environments in China.An atmospheric aging evaluation model of acrylic coatings was developed based on aging data including11 environmental factors from 567 cities.A hybrid method of random forest and Spearman correlation analysis was used to reduce the redundancy and multicollinearity of the data set by dimensionality reduction.A semi-supervised collaborative trained regression model was developed with the environmental factors as input and the low-frequency impedance modulus values of the electrochemical impedance spectra of acrylic coatings in 3.5wt%NaCl solution as output.The model improves accuracy compared to supervised learning algorithms model(support vector machines model).The model provides a new method for the rapid evaluation of the aging performance of acrylic coatings,and may also serve as a reference to evaluate the aging performance of other organic coatings.

Multiscale Simulation of Microstructure Evolution during Preparation and Service Processes of Physical Vapor Deposited c-TiAlN Coatings

Physical Vapor Deposited(PVD)TiAlN coatings are extensively utilized as protective layers for cutting tools,renowned for their excellent comprehensive performance.To optimize quality control of TiAlN coatings for cutting tools,a multi-scale simulation approach is proposed that encompasses the microstructure evolution of coatings considering the entire preparation and service lifecycle of PVD TiAlN coatings.This scheme employs phase-field simulation to capture the essential microstructure of the PVD-prepared TiAlN coatings.Moreover,cutting simulation is used to determine the service temperature experienced during cutting processes at varying rates.Cahn-Hilliard modeling is finally utilized to consume the microstructure and service condition data to acquaint the microstructure evolution of TiAlN coatings throughout the cutting processes.This methodology effectively establishes a correlation between service temperature and its impact on the microstructure evolution of TiAlN coatings.It is expected that the present multi-scale numerical simulation approach will provide innovative strategies for assisting property design and lifespan prediction of TiAlN coatings.

Degradation and biocompatibility of one-step electrodeposited magnesium thioctic acid/magnesium hydroxide hybrid coatings on ZE21B alloys for cardiovascular stents

Constructing a functional hybrid coating appears to be a promising strategy for addressing the poor corrosion resistance and insufficient endothelialization of Mg-based stents.Nevertheless,the steps for preparing composite coatings are usually complicated and time-consuming.Herein,a novel composite coating,composed of bioactive magnesium thioctic acid(MTA)layer formed by deposition and corrosion-resistant magnesium hydroxide(Mg(OH)_(2))layer grown in situ,is simply fabricated on ZE21B alloys via one-step electrodeposition.Scanning electron microscopy(SEM)shows that the electrodeposited coating has a compact and uniform structure.And the high adhesion of the MTA/Mg(OH)_(2)hybrid coating is also confirmed by the micro-scratch test.Electrochemical test,scanning kelvin probe(SKP),and hydrogen evolution measurement indicate that the hybrid coating effectively reduces the degradation rate of Mg substrates.Haemocompatibility experiment and cell culture trial detect that the composite coating is of fine biocompatibility.Finally,the preparation mechanism of MTA/Mg(OH)_(2)hybrid coatings is discussed and proposed.This coating shows a great potential application for cardiovascular stents.

HVOF-sprayed HAp/S53P4 BG composite coatings on an AZ31 alloy for potential applications in temporary implants

Bioactive thermal spray coatings produced via high-velocity oxygen fuel spray(HVOF)from hydroxyapatite(HAp)and bioactive glasses(BG)have the potential to be employed on temporary implants due to the ability of both HAp and BG to dissolve and promote osseointegration,considering that both phases have different reaction and dissolution rates under in-vitro conditions.In the present work,75%wt.HAp-25%wt.S53P4 bioactive glass powders were HVOF-sprayed to obtain HAp/S53P4 BG composite coatings on a bioresorbable AZ31 alloy.The study is focused on exploring the effect of the stand-off distance and fuel/oxygen ratio variation as HVOF parameters to obtain stable structural coatings and to establish their effect on the phases and microstructure produced in those coatings.Different characterization techniques,such as scanning electron microscopy,X-ray diffraction,and Fourier transform infrared spectroscopy,were employed to characterize relevant structural and microstructural properties of the composite coatings.The results showed that thermal gradients during coating deposition must be managed to avoid delamination due to the high temperature achieved(max 550℃)and the differences in coefficients of thermal expansion.It was also found that both spraying distance and oxygen/fuel ratio allowed to keep the hydroxyapatite as the main phase in the coatings.In addition,in-vitro electrochemical studies were performed on the obtained HAp/S53P4 BG composite coatings and compared against the uncoated AZ31 alloy.The results showed a significant decrease in hydrogen evolution(at least 98%)when the bioactive coating was applied on the Mg alloy during evaluation in simulated body fluid(SBF).

Design multifunctional Mg–Zr coatings regulating Mg alloy bioabsorption

Magnesium(Mg)alloys are widely used for temporary bone implants due to their favorable biodegradability,cytocompatibility,hemocompatibility,and close mechanical properties to bone.However,rapid degradation and inadequate strength limit their applicability.To overcome this,the direct current magnetron sputtering technique is employed for surface coating in Mg-based alloys using various zirconium(Zr)content.This approach presents a promising strategy for simultaneously improving corrosion resistance,maintaining biocompatibility,and enhancing strength without compromising osseointegration.By leveraging Mg’s inherent biodegradability,it has the potential to minimize the need for secondary surgeries,thereby reducing costs and resources.This paper is a systematic study aimed at understanding the corrosion mechanisms of Mg–Zr coatings,denoted Mg-xZr(x=0–5 at.%).Zr-doped coatings exhibited columnar growth leading to denser and refined structures with increasing Zr content.XRD analysis confirmed the presence of the Mg(00.2)basal plane,shifting towards higher angles(1.15°)with 5 at.%Zr doping due to lattice parameter changes(i.e.,decrease and increase of“c”and“a”lattice parameters,respectively).Mg–Zr coatings exhibited“liquidphilic”behavior,while Young’s modulus retained a steady value around 80 GPa across all samples.However,the hardness has significantly improved across all samples’coating,reaching the highest value of(2.2±0.3)GPa for 5 at.%Zr.Electrochemical testing in simulated body fluid(SBF)at 37℃ revealed a significant enhancement in corrosion resistance for Mg–Zr coatings containing 1.0–3.4 at.%Zr.Compared with the 5 at.%Zr coating which exhibited a corrosion rate of 32 mm/year,these coatings displayed lower corrosion rates,ranging from 1 to 12 mm/year.This synergistic enhancement in mechanical properties and corrosion resistance,achieved with 2.0–3.4 at.%Zr,suggests potential ability for reducing stress shielding and controlled degradation performance,and consequently,promising functional biodegradable materials for temporary bone implants.

Antibacterial HA-coatings on bioresorbable Mg alloy

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

Structure and corrosion behavior of FeCoCrNiMo high-entropy alloy coatings prepared by mechanical alloying and plasma spraying

FeCoCrNiMox composite powders were prepared using the mechanical alloying technique and made into high-entropy alloy(HEA)coatings with the face-centered cubic phase using plasma spraying to address the element segregation problem in HEAs and pre-pare uniform HEA coatings.Scanning electron microscopy,transmission electron microscopy,and X-ray diffractometry were employed to characterize these coatings’microstructure and phase composition.The hardness,elastic modulus,and fracture toughness of coatings were tested,and the corrosion resistance was analyzed in simulated seawater.Results show that the hardness of the coating is HV0.1606.15,the modulus of elasticity is 128.42 GPa,and the fracture toughness is 43.98 MPa·m^(1/2).The corrosion potential of the coating in 3.5wt%NaCl solution is-0.49 V,and the corrosion current density is 1.2×10^(−6)A/cm^(2).The electrochemical system comprises three parts:the electrolyte,the adsorption and metallic oxide films produced during immersion,and the FeCoNiCrMo HEA coating.Over in-creasingly long periods,the corrosion reaction rate increases first and then decreases,the corrosion product film comprising metal oxides reaches a dynamic balance between formation and dissolution,and the internal reaction of the coating declines.

Optical facet coatings for high-performance LWIR quantum cascade lasers atλ∼8.5μm

We report on the performance improvement of long-wave infrared quantum cascade lasers(LWIR QCLs)by studying and optimizing the anti-reflection(AR)optical facet coating.Compared to the Al2O3 AR coat⁃ing,the Y_(2)O_(3)AR coating exhibits higher catastrophic optical mirror damage(COMD)level,and the optical facet coatings of both material systems have no beam steering effect.A 3-mm-long,9.5-μm-wide buried-heterostruc⁃ture(BH)LWIR QCL ofλ~8.5μm with Y_(2)O_(3)metallic high-reflection(HR)and AR of~0.2%reflectivity coating demonstrates a maximum pulsed peak power of 2.19 W at 298 K,which is 149%higher than that of the uncoated device.For continuous-wave(CW)operation,by optimizing the reflectivity of the Y_(2)O_(3)AR coating,the maximum output power reaches 0.73 W,which is 91%higher than that of the uncoated device.

Effects of plasma spraying process on microstructure and mechanical properties of Cr_(2)AlC/410 composite coatings

To investigate the influences of Cr_(2)AlC mass fraction and supersonic plasma spraying process on the microstructure and mechanical properties of Cr_(2)AlC reinforced 410 stainless steel composite coatings,the coatings containing different mass fractions of Cr_(2)AlC were prepared and investigated.The composite coating exhibited low porosity and high adhesion strength.The addition of Cr_(2)AlC significantly enhanced the hardness of the composite coatings through particle strengthening.However,when the mass fraction of Cr_(2)AlC was 20%,the aggregation of Cr_(2)AlC resulted in a strong decrease in the coating preparation efficiency,as well as a decline in adhesion strength.In the supersonic plasma spraying process,the Ar flow rate mainly influenced the flight velocity of the particles,while the H_(2) flow rate and the current mainly affected the temperature of the plasma torch.Consequently,all of them influenced the melting degree of particles and the quality of the coating.The lowest porosity and the highest hardness and adhesion strength could be obtained when the Ar flow rate is 125 L/min,the H_(2) flow rate is 25 L/min,and the current is 385 A.

Comparative review of corrosion-resistant coatings on metal bipolar plates of proton exchange membrane fuel cells

In the realm of proton exchange membrane fuel cells(PEMFCs),the bipolar plates(BPs)are indispensable and serve pivotal roles in distributing reactant gases,collecting current,facilitating product water removal,and cooling the stack.Metal BPs,characterized by outstanding manufacturability,cost-effectiveness,higher power density,and mechanical strength,are emerging as viable alternatives to traditional graphite BPs.The foremost challenge for metal BPs lies in enhancing their corrosion resistance and conductivity under acidic conditions,necessitating the application of various coatings on their surfaces to ensure superior performance.This review summarizes and compares recent advancements in the research of eight distinct types of coatings for BPs in PEMFCs,including noble metal,carbide,ni-tride,and amorphous carbon(a-C)/metal compound composite coatings.The various challenges encountered in the manufacturing and fu-ture application of these coatings are also delineated.

Improvement strategy on thermophysical properties of A_(2)B_(2)O_(7)-type rare earth zirconates for thermal barrier coatings applications:A review

The A_(2)B_(2)O_(7)-type rare earth zirconate compounds have been considered as promising candidates for thermal barrier coating(TBC) materials because of their low sintering rate,improved phase stability,and reduced thermal conductivity in contrast with the currently used yttria-partially stabilized zirconia (YSZ) in high operating temperature environments.This review summarizes the recent progress on rare earth zirconates for TBCs that insulate high-temperature gas from hot-section components in gas turbines.Based on the first principles,molecular dynamics,and new data-driven calculation approaches,doping and high-entropy strategies have now been adopted in advanced TBC materials design.In this paper,the solid-state heat transfer mechanism of TBCs is explained from two aspects,including heat conduction over the full operating temperature range and thermal radiation at medium and high temperature.This paper also provides new insights into design considerations of adaptive TBC materials,and the challenges and potential breakthroughs are further highlighted for extreme environmental applications.Strategies for improving thermophysical performance are proposed in two approaches:defect engineering and material compositing.

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

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