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.

A super wear-resistant coating for Mg alloys achieved by plasma electrolytic oxidation and discontinuous deposition

Magnesium alloys are lightweight materials with great potential,and plasma electrolytic oxidation(PEO)is effective surface treatment for necessary improvement of corrosion resistance of magnesium alloys.However,the∼14µm thick and rough PEO protection layer has inferior wear resistance,which limits magnesium alloys as sliding or reciprocating parts,where magnesium alloys have special advantages by their inherent damping and denoising properties and attractive light-weighting.Here a novel super wear-resistant coating for magnesium alloys was achieved,via the discontinuous sealing(DCS)of a 1.3µm thick polytetrafluoroethylene(PTFE)polymer layer with an initial area fraction(A_(f))of 70%on the necessary PEO protection layer by selective spraying,and the wear resistance was exceptionally enhanced by∼5500 times in comparison with the base PEO coating.The initial surface roughness(Sa)under PEO+DCS(1.54µm)was imperfectly 59%higher than that under PEO and conventional continuous sealing(CS).Interestingly,DCS was surprisingly 20 times superior for enhancing wear resistance in contrast to CS.DCS induced nano-cracks that splitted DCS layer into multilayer nano-blocks,and DCS also provided extra space for the movement of nano-blocks,which resulted in rolling friction and nano lubrication.Further,DCS promoted mixed wear of the PTFE polymer layer and the PEO coating,and the PTFE layer(HV:6 Kg·mm^(−2),A_(f):92.2%)and the PEO coating(HV:310 Kg·mm^(−2),A_(f):7.8%)served as the soft matrix and the hard point,respectively.Moreover,the dynamic decrease of Sa by 29%during wear also contributed to the super wear resistance.The strategy of depositing a low-frictional discontinuous layer on a rough and hard layer or matrix also opens a window for achieving super wear-resistant coatings in other materials.

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

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

Enhanced corrosion resistance of epoxy resin coating via addition of CeO_(2) and benzotriazole

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.

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

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

Investigation on Interface Structure and Wear-resistant Properties of HVOF Sprayed Carbides Coating onto Copper Substrate

In this paper, we deposited carbides on copper substrate by High velocity oxy-fuel (HVOF) spraying. The structure of the coating and microstructure of the substrate-coating interface have been investigated by means of scanning electron microscope (SEM) and transmission electron microscopy (TEM). We observed the worn surface of the coating and investigated the wear mechanism. The results show that the microstructure of the interface between HVOF sprayed coating and substrate which consists of the amorphous layers, nanocrystalls in the coating and dislocation cells in copper substrate, etc. is complex. The amorphous layers are formed from heated adhesion after rapidly cooling, while the nanocrystalls come from the fragmentation of half-molten carbides. At the same time we found that the wear-resistant properties of the WC-Co coating is better than that of Cr3C2-NiCr coating at room temperature. The early wear-resistance of the HVOF sprayed coating is poor because of the roughness of its surface or bad bond of hard composite particles. The high velocity of molten droplets is propitious to fill up the interspaces between carbides, so as to make the coating more compact and reduce its porosities, thus the wear-resistance of carbides coatings is improved.

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

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

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

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

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.

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.

Protective Graphite Coating for Two-Dimensional Carbon/Carbon Composites

Two-dimensional carbon/carbon(2D C/C)composites are a special class of carbon/carbon composites,generally obtained by combining resin-impregnated carbon fiber clothes,which are then cured and carbonized.This study deals with the preparation of a protective coating for these materials.This coating,based on graphite,was prepared by the slurry method.The effect of graphite and phenolic resin powders with different weight ratios was examined.The results have shown that the coating slurry can fill the pores and cracks of the composite surface,thereby densifying the surface layer of the material.With the increase of the graphite powder/phenolic resin weight ratio,the coating density is enhanced while the coating surface flatness decreases;moreover,the protective ability of coating against erosion first increases(from 1:3 to 2:2)and then decreases(from 2:2 to 3:1).When the weight ratio is about 1:1,the coating for 2D C/C composites exhibits the best erosion resistance,which greatly aids these materials during gas quenching.In this case,the erosion rate is decreased by approximately 41.5%at the impact angle of 30°and 52.3%at normal impact,respectively.This can be attributed to the ability of the coating slurry to infiltrate into the substrate,thereby bonding the fibers together and increasing the compactness of the 2D C/C composites.

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

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

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

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

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.

Effect of manganese on the formation of hybrid zirconiumbased conversion coating on low carbon steel surface

This study revealed the effect of Mn on the formation of hybrid zirconium-based conversion coatings(HZCC)on low carbon steel.The XPS results indicated that the Mn compounds on the surface of low carbon steel were mainly MnO and Mn_(2)SiO_(4).Combined with the electrochemical measurements,the corrosion resistance of HZCC showed an increase followed by a decrease with increasing Mn concentration,which was related to the Mn_(2)SiO_(4) and SiO_(2) on the surface of low carbon steel.The excessive Mn concentration resulted in the loss of SiO_(2) and aggregation of Mn_(2)SiO_(4) on the low carbon steel surface,which caused the aggregation of Zr compounds on the surface and reduced the uniformity of the coating.Meanwhile,a moderate amount of Mn addition would be beneficial to increase the adhesion of organic coatings.

Insights into the oxidation resistance mechanism and tribological behaviors of multilayered TiSiN/CrVxN hard coatings

In the last decades,vanadium alloyed coatings have been introduced as potential candidates for self-lubrication due to their perfect tribological properties.In this work,the influence of V incorporation on the wear performance and oxidation resistance of TiSiN/CrN film coatings deposited by direct current(DC)reactive magnetron sputtering is investigated.The results show that vanadium incorporation significantly decreases the oxidation resistance of the coatings.In general,two layers are formed during the oxidation process:i)Ti(V)O_(2) on top,followed by a protective layer,which is subdivided into two layers,Cr_(2)O_(3) and Si-O.ii)The diffusion of V controls the oxidation of V-containing coatings.The addition of vanadium improves the wear resistance of coatings,and the wear rate decreases with increasing V content in the coatings;however,the friction coefficient is independent of the chemical composition of the coatings.The wear of the V-containing coatings is driven by polishing wear.

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

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

Two-Dimensional Co_(2)(OH)1,4-Benzenedicarboxylate-Halloysite Nanotube Nanocomposite-Epoxy Coating with High Corrosion Resistance

Introducing inorganic nanomaterials into a polymer matrix greatly improves the anticorrosion performance of epoxy coatings(EP);however,poor compatibility between the materials can limit the improvement in properties.In this work,based on the high interface compatibility of two-dimensional(2D)Co_(2)(OH)_(2)BDC(BDC=1,4-benzenedicarboxylate)in the epoxy coating that we reported in previous work,we fabricated a 2D Co_(2)(OH)_(2)BDC-halloysite nanotube(HNT)nanocomposite have a structure consisting of alternating of nanosheets and nanotube by in situ synthesis.The nanocomposite was characterized by Fourier transform infrared spectroscopy,X-ray diffraction,and scanning electron microscopy.The mechanical and anticorrosion performance of the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was evaluated by mechanical tests and electrochemical impedance spectroscopy spectra.Compared with a conventional unreinforced epoxy coating,the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating had higher mechanical strength and toughness,and the low-frequency impedance modulus of 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was increased by three orders of magnitude,demonstrating the high corrosion resistance of our reinforced coating.

Performance study of a complex thermal barrier functional coating with an electro-spark deposited burn-resistant layer

It is necessary to develop burn-resistant and thermal barrier complex functional coatings on the titanium alloys surface due to the poor high temperature performance for titanium materials and the problem of“titanium fire”which is easily happened.MTU Aero Engines GmbH has developed a complex functional coating which has great performance of burn resistant and sealing,the coatings has already been applied on compressor blades and casing for aero-engines and showed great performance.In this study,the complex functional coating which is composed of an electro-spark deposited amorphous Ti40Zr25Ni3 burn-resistant layer and a high-energy plasma spraying prepared YSZ thermal barrier layer was prepared on titanium alloys surface.Then the heat insulation ability,burn resistant performance and the bonding strength were investigated.The experimental results showed that the interface between the coating and the matrix was typical metallurgical bonded,and the average bonding strength was 36.335 MPa;when the temperature of the flame on the one side of the specimen reached 600℃,the average insulated temperature of the coating samples was 70.67℃;when the flame temperature was 350℃,the titanium samples without the complex functional coatings were burned,while the samples with the coating showed great performance of burn resistant even when the temperature was 750℃.This indicates that the new functional coating has good heat-insulating and burn-resistant performance.

Microstructure and properties of a wear resistant Al-25Si-4Cu-1Mg coating prepared by supersonic plasma spraying

A high content silicon aluminum alloy(Al-25Si-4Cu-1Mg)coating was prepared on a 2A12 aluminum alloy by supersonic plasma spraying.The morphology and microstructure of the coating were observed and analyzed.The hardness,elastic modulus,and bonding strength of the coating were measured.The wear resistance of the coating and 2A12 aluminum alloy was studied by friction and wear test.The results indicated that the coating was compact and the porosity was only 1.5%.The phase of the coating was mainly composed ofα-Al andβ-Si as well as some hard particles(Al9Si,Al3.21Si0.47,and CuAl2).The average microhardness of the coating was HV 242,which was greater than that of 2A12 aluminum alloy(HV 110).The wear resistance of the coating was superior to 2A12 aluminum alloy.The wear mechanism of the 2A12 aluminum alloy was primarily adhesive wear,while that of the coating was primarily abrasive wear.Therefore,it is possible to prepare a high content silicon aluminum alloy coating with good wear resistance on an aluminum alloy by supersonic plasma spraying.