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.

Comparative investigation of microstructure and high-temperature oxidation resistance of high-velocity oxy-fuel sprayed CoNiCrAlY/nano-Al_(2)O_(3) composite coatings using satellited powders

Satellited CoNiCrAlY–Al_(2)O_(3)feedstocks with 2wt%, 4wt%, and 6wt% oxide nanoparticles and pure CoNiCrAlY powder were deposited by the high-velocity oxy fuel process on an Inconel738 superalloy substrate. The oxidation test was performed at 1050℃ for 5, 50, 100,150, 200, and 400 h. The microstructure and phase composition of powders and coatings were characterized by scanning electron microscopy and X-ray diffraction, respectively. The bonding strength of the coatings was also evaluated. The results proved that with the increase in the percentage of nanoparticles(from 2wt% to 6wt%), the amount of porosity(from 1vol% to 4.7vol%), unmelted particles, and roughness of the coatings(from 4.8 to 8.8 μm) increased, and the bonding strength decreased from 71 to 48 MPa. The thicknesses of the thermally grown oxide layer of pure and composite coatings(2wt%, 4wt%, and 6wt%) after 400 h oxidation were measured as 6.5, 5.5, 7.6, and 8.1 μm, respectively.The CoNiCrAlY–2wt% Al_(2)O_(3)coating showed the highest oxidation resistance due to the diffusion barrier effect of well-dispersed nanoparticles. The CoNiCrAlY–6wt% Al_(2)O_(3)coating had the lowest oxidation resistance due to its rough surface morphology and porous microstructure.

A Novel Fracturing Fluid with High-Temperature Resistance for Ultra-Deep Reservoirs

Ultra-deep reservoirs play an important role at present in fossil energy exploitation.Due to the related high temperature,high pressure,and high formation fracture pressure,however,methods for oil well stimulation do not produce satisfactory results when conventional fracturing fluids with a low pumping rate are used.In response to the above problem,a fracturing fluid with a density of 1.2~1.4 g/cm^(3)was developed by using Potassium formatted,hydroxypropyl guanidine gum and zirconium crosslinking agents.The fracturing fluid was tested and its ability to maintain a viscosity of 100 mPa.s over more than 60 min was verified under a shear rate of 1701/s and at a temperature of 175℃.This fluid has good sand-carrying performances,a low viscosity after breaking the rubber,and the residue content is less than 200 mg/L.Compared with ordinary reconstruction fluid,it can increase the density by 30%~40%and reduce the wellhead pressure of 8000 m level reconstruction wells.Moreover,the new fracturing fluid can significantly mitigate safety risks.

Performance Assessment on Corrosion Resistance of Refractory Materials Based on High-temperature Machine Vision Technology

Refractory materials,as the crucial foundational materials in high-temperature industrial processes such as metallurgy and construction,are inevitably subjected to corrosion and penetration from high-temperature media during their service.Traditionally,observing the in-situ degradation process of refractory materials in complex high-temperature environments has presented challenges.Post-corrosion analysis are commonly employed to assess the slag resistance of refractory materials and understand the corrosion mechanisms.However,these methods often lack information on the process under the conditions of thermal-chemical-mechanical coupling,leading to potential biases in the analysis results.In this work,we developed a non-contact high-temperature machine vision technology by the integrating Digital Image Correlation(DIC)with a high-temperature visualization system to explore the corrosion behavior of Al2O3-SiO2 refractories against molten glass and Al2O3-MgO dry ramming refractories against molten slag at different temperatures.This technology enables realtime monitoring of the 2D or 3D overall strain and average strain curves of the refractory materials and provides continuous feedback on the progressive corrosion of the materials under the coupling conditions of thermal,chemical,and mechanical factors.Therefore,it is an innovative approach for evaluating the service behavior and performance of refractory materials,and is expected to promote the digitization and intelligence of the refractory industry,contributing to the optimization and upgrading of product performance.

A high-temperature resistant and high-density polymeric saturated brine-based drilling fluid

Three high-temperature resistant polymeric additives for water-based drilling fluids are designed and developed:weakly cross-linked zwitterionic polymer fluid loss reducer(WCZ),flexible polymer microsphere nano-plugging agent(FPM)and comb-structure polymeric lubricant(CSP).A high-temperature resistant and high-density polymeric saturated brine-based drilling fluid was developed for deep drilling.The WCZ has a good anti-polyelectrolyte effect and exhibits the API fluid loss less than 8 mL after aging in saturated salt environment at 200°C.The FPM can reduce the fluid loss by improving the quality of the mud cake and has a good plugging effect on nano-scale pores/fractures.The CSP,with a weight average molecular weight of 4804,has multiple polar adsorption sites and exhibits excellent lubricating performance under high temperature and high salt conditions.The developed drilling fluid system with a density of 2.0 g/cm^(3)has good rheological properties.It shows a fluid loss less than 15 mL at 200°C and high pressure,a sedimentation factor(SF)smaller than 0.52 after standing at high temperature for 5 d,and a rolling recovery of hydratable drill cuttings similar to oil-based drilling fluid.Besides,it has good plugging and lubricating performance.

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.

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.

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.

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.

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.

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.

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.

Micro-analysis of high-temperature oxidation-resistance of a new kind of heat-resistant grid plate in grate-kiln

To further improve the oxidation-resistance of materials and reduce the cost of grid plates in grate-kiln, a new kind of heat-resistant grid plate was developed. The microstructure of this grid plate with a life more than 18 months was studied by XRD, SEM and EDS techniques. The results show that high hardness, high intensity and good impact property make the new kind of heat-resistant grid plate and its oxide film have a higher resistance to deformation and abrasion at 900-1000℃ Besides, small grain size is beneficial to form a complete protective oxide film. The oxide film composed of SiO2 layer, Cr2O3 layer and Fe2O3 layer is rather thin and bonds closely with the backing. The forming of the chemical stable nickel-rich layer increases the density of Cr2O3 layer.

Microstructure studies of air-plasma-spray-deposited CoNiCrAlY coatings before and after thermal cyclic loading for high-temperature application

In the present study, bond-coats for thermal barrier coatings were deposited via air plasma spraying（APS） techniques onto Inconel 800 and Hastelloy C-276 alloy substrates. Scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, X-ray diffraction（XRD）, and atomic force microscopy（AFM） were used to investigate the phases and microstructure of the as-sprayed, APS-deposited Co Ni Cr Al Y bond-coatings. The aim of this work was to study the suitability of the bond-coat materials for high temperature applications. Confirmation of nanoscale grains of the γ/γ′-phase was obtained by TEM, high-resolution TEM, and AFM. We concluded that these changes result from the plastic deformation of the bond-coat during the deposition, resulting in Co Ni Cr Al Y bond-coatings with excellent thermal cyclic resistance suitable for use in high-temperature applications. Cyclic oxidative stability was observed to also depend on the underlying metallic alloy substrate.

Flexural behavior of composite beams after the ultimate limit state externally strengthened with CFRP sheets bonded with high-temperature resistant matrix

In this paper the alkali-activated slag cementitious materials(AASCM)which strength at 600 ℃ is larger than that of AASCM at room temperature,were prepared to paste CFRP sheets to strengthen four simply supported unbonded prestressed composite beams encased circular steel tube truss after ultimate limit state.Test on flexural behavior of these four beams was performed.Moreover,normal section load-bearing capacity of these beams and the curve load-deflection at mid-span were obtained.Experimental results show that it is feasible to strengthen concrete members with CFRP sheets bonded with AASCM.Based on the experimental results and theoretical study,computational method of stiffness is proposed for calculating bending rigidity and normal section load-bearing capacity of concrete simply supported beams strengthened with CFRP sheets bonded with AASCM.Formula of bending rigidity calculation was founded which results are in good agreement with testing data.

High-Temperature Corrosion of Protective Coatings for Boiler Tubes in Thermal Power Plants

High-temperature corrosion is a serious problem for the water-wall tubes of boilers used in thermal power plants. Oxidation, sulfidation and molten salt corrosion are main corrosion ways.Thereinto, the most severe corrosion occurs in molten salt corrosion environment. Materials rich in oxides formers, such as chromium and aluminum, are needed to resist corrosion in high-temperature and corrosive environment, but processability of such bulk alloys is very limited. High velocity electric arc spraying (HVAS) technology is adopted to produce coatings with high corrosion resistance. By comparison, NiCr (Ni-45Cr-4Ti) is recommended as a promising alloy coating for the water-wall tubes, which can even resist molten salt corrosion attack. In the study of corrosion mechanism, the modern material analysis methods, such as scanning electron microscopy (SEM), X-ray diffractometry (XRD) and energy dispersive spectrometry (EDS), are used. It is found that the corrosion resistances of NiCr and FeCrAI coatings are much better than that of 20g steel, that the NiCr coatings have the best anti-corrosion properties, and that the NiCr coatings have slightly lower pores than FeCrAI coatings.It is testified that corrosion resistance of coatings is mainly determined by chromium content, and the microstructure of a coating is as important as the chemical composition of the material. In addition, the fracture mechanisms of coatings in the cycle of heating and cooling are put forward. The difference of the thermal physical properties between coatings and base metals results in the thermal stress inside the coatings. Consequently, the coatings spall from the base metal.

Formation Mechanism of a Y-modified Cr-Al Coating Co-deposited on DZ125 Alloy and Its High-temperature Oxidation Resistance

Y-modified Cr-Al coatings were co-deposited on DZ125 alloy by a pack cementation process,and the microstructures,constituent phases,and formation mechanisms of the obtained coatings were studied.The oxidation resistance of the coatings was also investigated.The experimental results show that the coating prepared by co-depositing Cr-Al-Y at 1050℃for 2 h has a multi-layered structure with an outer layer composed of Cr and Ni_(3)Cr_(2),a middle layer composed of Ni_(3)Cr_(2) and Al_(13)Co_(4),and an inner layer composed of Ni_(3)Al.The co-deposited Y is mainly present in the outer and middle layers of the coating.The coating formation process follows a sequential deposition mechanism in which Al is deposited during the initial stage,followed by Cr deposition.After oxidation at 1100℃for 100 h,a dense Cr_(2)O_(3)·Al_(2)O_(3) scale forms on the obtained coating,which effectively protects the DZ125 alloy from oxidation by preventing the inward diffusion of oxygen.

High-temperature oxidation behavior of heat resistant stainless steel 1.4828

The kinetic curves of the high-temperature oxidation of austenitic heat resistant stainless steel 1. 4828 at 1 050 ℃ were measured using a weighing method. It is shown that the oxidation curves at 1 050 ℃ followed the parabolic line law, and after 250 h of oxidation, the mass gain was about 80 g/m2. The surface morphology and structure of the oxide layers were studied by scanning electron microscopy and X-ray diffraction. A complicated oxide layer obtained at 1 050 ℃ was mainly composed, from inner to outer, of （FeSi） 3 04, Cr2 03, Fe2 03, and spinel oxides FeCr204 and NiMn204.

Corrosion resistance of cerium-doped zinc calcium phosphate chemical conversion coatings on AZ31 magnesium alloy

Zinc calcium phosphate （Zn-Ca-P） coating and cerium-doped zinc calcium phosphate （Zn-Ca-Ce-P） coating were prepared on AZ31 magnesium alloy. The chemical compositions, morphologies and corrosion resistance of coatings were investigated through energy-dispersive X-ray spectroscopy （EDS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, electron probe micro-analysis （EPMA） and scanning electron microscopy （SEM） together with hydrogen volumetric and electrochemical tests. The results indicate that both coatings predominately contain crystalline hopeite （Zn3（PO4）2·4H2O）, Mg3（PO4）2 and Ca3（PO4）2, and traces of non-crystalline MgF2 and CaF2. The Zn-Ca-Ce-P coating is more compact than the Zn-Ca-P coating due to the formation of CePO4, and displays better corrosion resistance than the Zn-Ca-P coating. Both coatings protect the AZ31 Mg substrate only during an initial immersion period. The micro-galvanic corrosion between the coatings and their substrates leads to an increase of hydrogen evolution rate （HER） with extending the immersion time. The addition of Ce promotes the homogenous distribution of Ca and formation of hopeite. The Zn-Ca-Ce-P coating has the potential for the primer coating on magnesium alloys.