Micro-alloying of Zn and Ca in vacuum induction casted bioresorbable Mg system:Perspectives on corrosion resistance,cytocompatibility,and inflammatory response

There is an increasing interest in biodegradable materials,such as magnesium,for orthopaedic implants.This is driven by their potential to address challenges like stress shielding and the need for secondary removal surgery.In this study,biodegradable magnesium alloys were produced using the Vacuum Induction Casting technique.The impact of micro-alloying Zn and Ca in Mg-xZn-0.2Ca(x=0.1,0.2,0.3,and 0.4 wt%)alloys on corrosion resistance,cytocompatibility,and early-stage inflammatory response was investigated.XRD and SEM-EDS analysis confirmed the presence of Ca_(2)Mg_(6)Zn_(3)secondary phases in all alloys.The Mg-0.3Zn-0.2Ca alloy exhibited the lowest corrosion rate and an elastic modulus of 36.8 GPa,resembling that of natural bone.Electrochemical measurements indicated a correlation between grain size and secondary phase volume fraction in explaining corrosion behaviour.In vitro degradation in simulated body fluid(SBF)for 21 days showed hydroxyapatite formation on alloy surfaces,aligning with electrochemical studies.In vitro cytotoxicity tests demonstrated the cytocompatibility of all alloys,with Mg-0.3Zn-0.2Ca having the highest cell viability over a 6-day cell culture.Investigation into the inflammatory response with RAW-Blue macrophages revealed the anti-inflammatory properties of Mg-0.3Zn-0.2Ca alloys.Micro-alloying with 0.3 wt%Zn and 0.2 wt%Ca enhanced mechanical properties,corrosion resistance,cytocompatibility,and immunomodulatory properties.This positions the Mg-0.3Zn-0.2Ca alloy as a promising biodegradable implant for bone fixation applications.

Corrosion-Resistant Polymer-Derived SiOC Membrane for Effective Organic Removal via Synergistic Adsorption and Peroxymonosulfate Activation

A major challenge is to construct ceramic membranes with tunable structures and functions for water treatment.Herein,a novel corrosion-resistant polymer-derived silicon oxycarbide(SiOC)ceramic membrane with designed architectures was fabricated by a phase separation method and was applied in organic removal via adsorption and oxidation for the first time.The pore structure of the as-prepared SiOC ceramic membranes was well controlled by changing the sintering temperature and polydimethylsiloxane content,leading to a pore size of 0.84–1.62μm and porosity of 25.0–43.8%.Corrosion resistance test results showed that the SiOC membranes sustained minimal damage during 24 h exposure to high-intensity acid–base conditions,which could be attributed to the chemical inertness of SiOC.With rhodamine 6G(R6G)as the model pollutant,the SiOC membrane demonstrated an initial eff ective removal rate of 99%via adsorption;however,the removal rate decreased as the system approached adsorption saturation.When peroxymonosulfate was added into the system,efficient and continuous degradation of R6G was observed throughout the entire period,indicating the potential of the as-prepared SiOC membrane in oxidation-related processes.Thus,this work provides new insights into the construction of novel polymer-derived ceramic membranes with well-defined structures and functions.

GPa-level pressure-induced enhanced corrosion resistance in TiZrTaNbSn biomedical high-entropy alloy

TiZrTaNb-based high-entropy alloys(HEAs)are research frontier of biomedical materials due to their high hardness,good yield strength,excellent wear resistance and corrosion resistance.Sn,as an essential trace element in the human body that plays a significant role in physiological process.It has stable chemical properties and a low elastic modulus.In this study,a new material,TiZrTaNbSn HEAs,was proposed as a potential biomedical alloy.The Ti_(35)Zr_(25)Ta_(15)Nb_(15)Sn_(10)biomedical high-entropy alloys(BHEAs)were successfully prepared through an arc melting furnace and then remelted using a German high-temperature and high-pressure apparatus under GPa-level(4 GPa and 7 GPa).The precipitation behavior of the needle-like HCP-Zr_(5)Sn_(3)phase that precipitates discontinuously at the grain boundary was successfully controlled.The phase constitution,microstructure,and corrosion resistance of the alloy were studied.The results show that the needle-like HCP-Zr_(5)Sn_(3)phase is eliminated and the(Zr,Sn)-rich nano-precipitated phase is precipitated in the microstructure under high pressure,which leads to the narrowing of grain boundaries and consequently improves the corrosion resistance of the alloy.In addition,the formation mechanisms of(Zr,Sn)-rich nanoprecipitates in BHEAs were discussed.More Zr and Sn dissolve in the matrix due to the effect of high pressure,during the cooling process,they precipitate to form a(Zr,Sn)-rich nano-precipitated phase.

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.

Evolution of mechanical properties,localized corrosion resistance and microstructure of a high purity Al-Zn-Mg-Cu alloy during non-isothermal aging

The evolution of mechanical properties,localized corrosion resistance of a high purity Al-Zn-Mg-Cu alloy during non-isothermal aging(NIA)was investigated by hardness test,electrical conductivity test,tensile test,intergranular corrosion test,exfoliation corrosion test,slow strain rate tensile test and electrochemical test,and the mechanism has been discussed based on microstructure examination by optical microscopy,electron back scattered diffraction,scanning electron microscopy and scanning transmission electron microscopy.The NIA treatment includes a heating stage from 40℃to 180℃with a rate of 20℃/h and a cooling stage from 180℃to 40℃with a rate of 10℃/h.The results show that the hardness and strength increase rapidly during the heating stage of NIA since the increasing temperature favors the nucleation and the growth of strengthening precipitates and promotes the transformation of Guinier-Preston(GPI)zones toη'phase.During the cooling stage,the sizes ofη'phase increase with a little change in the number density,leading to a further slight increase of the hardness and strength.As NIA proceeds,the corroded morphology in the alloy changes from a layering feature to a wavy feature,the maximum corrosion depth decreases,and the reason has been analyzed based on the microstructural and microchemical feature of precipitates at grain boundaries and subgrain boundaries.

First Principles Calculations for Corrosion in Mg-Li-Al Alloys with Focus on Corrosion Resistance: A Comprehensive Review

This comprehensive review examines the structural,mechanical,electronic,and thermodynamic properties of Mg-Li-Al alloys,focusing on their corrosion resistance and mechanical performance enhancement.Utilizing first-principles calculations based on Density Functional Theory(DFT)and the quasi-harmonic approximation(QHA),the combined properties of the Mg-Li-Al phase are explored,revealing superior incompressibility,shear resistance,and stiffness compared to individual elements.The review highlights the brittleness of the alloy,supported by B/G ratios,Cauchy pressures,and Poisson’s ratios.Electronic structure analysis shows metallic behavior with varied covalent bonding characteristics,while Mulliken population analysis emphasizes significant electron transfer within the alloy.This paper also studied thermodynamic properties,including Debye temperature,heat capacity,enthalpy,free energy,and entropy,which are precisely examined,highlighting the Mg-Li-Al phase sensitive to thermal conductivity and thermal performance potential.Phonon density of states(PHDOS)confirms dynamic stability,while anisotropic sound velocities reveal elastic anisotropies.This comprehensive review not only consolidates the current understanding of the Mg-Li-Al alloy’s properties but also proposes innovative strategies for enhancing corrosion resistance.Among these strategies is the introduction of a corrosion barrier akin to the Mg-Li-Al network,which holds promise for advancing both the applications and performance of these alloys.This review serves as a crucial foundation for future research aimed at optimizing alloy design and processing methods.

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.

Effect of Rare Earths on Corrosion Resisting Properties of Carbon-Manganese Clean Steels

Electrochemistry experiments were made on carbon-manganese clean steel with rare earths Ce and La respectively to observe corrosion parameters such as corrosion current i_(corr), and characteristic potential of pitting E_b. The results indicate that the rare earths have effect on corrosion resisting properties of carbon-manganese clean steel, and the optimum contents of La is about 0.011% (mass fraction) and Ce about 0.014% (mass fraction) respectively. The change of corrosion resistance is related to the action of rare earths on microstructure and effect on surface state of samples in the process of polarization.

Corrosion resistance of in-situ Mg-Al hydrotalcite conversion film on AZ31 magnesium alloy by one-step formation

In situ growth of nano-sized layered double hydroxides （LDH） conversion film on AZ31 alloy was synthesized by a urea hydrolysis method. The formation mechanism of the film was proposed. Firstly, the dissolved Mg2＋ ions deposited into a precursor film consisted of MgCO3 and Mgs（CO3）4（OH）2·4H2O; secondly, the precursor translated into the crystalline Mg（OH）2 in alkaline conditions; finally, the Mg2＋ ions in Mg（OH）z were replaced by A13＋ ions, Mg（OH）2 translated into the more stable LDH structure, simultaneously, the OH- ions in the interlayer were exchanged by CO32-, thus led to the formation of the LDH （Mg6Alz（OHh6CO3·4H2O） film. The results indicated that the LDH film characterized by interlocking plate-like nanostructures and ion-exchange ability significantly improved the corrosion resistance of the AZ31 Mg alloy.

Reactive HVOF sprayed TiN-matrix composite coating and its corrosion and wear resistance properties

TiN-matrix composite coating was prepared on 45# steel by reactive high-velocity oxy-fuel （HVOF） spraying. Its microstructure, phase composition, micro-hardness, corrosion resistance in 3.5% NaC1 solution and wear resistance were analyzed. The results suggest that the TiN-matrix composite coating is well bonded with the substrate. The micro-hardness measured decreases with the increase of applied test loads. And the micro-hardness of the coating under heavy loads is relatively high. The TiN-matrix composite coating exhibits an excellent corrosion resistance in 3.5% NaC1 solution. The corrosion potential of coating is positive and the passivation zone is broad, which indicates that the TiN-matrix composite coating is stable in the electrolyte and provides excellent protection to the substrate. The wear coefficient of the coating under all loads maintains at 0.49-0.50. The wear mechanism of the coating is revealed to be three-body abrasive wear. Yet the failure forms of TiN-matrix composite coating under different loads have an obvious difference. The failure form of coating under light loads is particle spallation due to the stress concentration while that of coating under heavy loads is crackin~ between inter-lamellae.

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.

Effects of surface nanocrystallization on corrosion resistance of β-type titanium alloy

Surface mechanical attrition treatment (SMAT) was performed on biomedicalβ-type TiNbZrFe alloy for 60 min at room temperature to study the effect of surface nanocrystallization on the corrosion resistance of TiNbZrFe alloy in physiological environment. The surface nanostructure was characterized by TEM, and the electrochemical behaviors of the samples with nanocrystalline layer and coarse grain were comparatively investigated in 0.9% NaCl and 0.2% NaF solutions, respectively. The results indicate that nanocrystallines with the size of 10-30 nm are formed within the surface layer of 30 μm in depth. The nanocrystallized surface behaves higher impedance, more positive corrosion potential and lower corrosion current density in 0.9%NaCl and 0.2%NaF solutions as compared with the coarse grain surface. The improvement of the corrosion resistance is attributed to the rapid formation of stable and dense passive film on the nanocrystallized surface of TiNbZrFe alloy.

Study on Seawater Corrosion Resisting Properties ofAl-Mg-RE Alloy Gauze

The corrosion resistance of gauzes made of various materials, including Al-Mg-RE alloy with various RE contents, Al-Mg alloy, low-carbon steel and plastic, was evaluated and compared. The experimental methods used include immersion method, salt spray test, weight loss test, electrode potential analysis and metallographic method, etc. The corrosion resistance of Al-Mg-RE alloy gauzes in mediums such as running water, natural seawater, NaCl solution with various concentrations, 0.05 mol.L-1 Na2SO4 solution, and 10% H2SO4 solution etc., is superior to those of Al-Mg alloy gauzes made in either China or U.S.A., and much superior to those of gauzes made of low-carbon steel and plastic. The electrode potentials of the Al-Mg-RE alloy in both the natural seawater and 0.05 mol.L-1 Na2SO4 solution increase linearly with increasing RE content in the alloy. The microstructure in the Al-Mg-RE alloy has been refined and the shape of compounds has been obviously changed comparing with those in Al-Mg alloy without RE elements. AU these microstructural changes are favorable to the corrosion resistance of the alloy. The Al-Mg-RE alloy gauze may be used as a substitute for those made df Al-Mg alloy, low-carbon steel and plastic in moisture marine or industrial environment for better serviceability.

Electrodeposition and corrosion resistance of Ni-P-TiN composite coating on AZ91D magnesium alloy

In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were addedto fabricate Ni-P-TiN composite coating by electrodeposition. The surface, cross-section morphology and composition wereexamined using SEM, EDS and XRD, and the corrosion resistance was checked by electrochemical technology. The results indicatethat TiN nanoparticles were doped successfully in the Ni-P matrix after a series of complex pretreatments including activation, zincimmersion and pre-electroplating, which enhances the stability of magnesium alloy in electrolyte and the adhesion betweenmagnesium alloy and composite coating. The microhardness of the Ni-P coating increases dramatically by adding TiN nanoparticlesand subsequent heat treatment. The corrosion experimental results indicate that the corrosion resistance of Ni-P-TiN compositecoating is much higher than that of uncoated AZ91D magnesium alloy and similar with Ni-P coating in short immersion time.However, TiN nanoparticles play a significant role in long-term corrosion resistance of composite coatings.

Effect of purification treatment on corrosion resistance of Mg-Gd-Y-Zr alloy

Mg-Gd-Y-Zr alloys were purified by filtering purification with and without vacuum. The type, morphology, size distribution and volume fraction of inclusion were analyzed with OM and SEM. The effect of inclusion in Mg-Gd-Y-Zr alloys on anticorrosion ability was investigated with salt spray test and electrochemical test. The results show that the inclusions in the alloy can be removed effectively by filtering purification. The average size of inclusions in the alloys is decreased from 12.7 μm to 2.0 μm and the volume fraction of inclusions is reduced from 0.30% to 0.04%. With the decrease of the size of inclusions in the alloys, the corrosion rate of the alloys decreases dramatically from 38.8 g/（m 2 ·d） to 2.4 g/（m 2 ·d） in the salt spray test. The corrosion potential increases while the corrosion current decreases and the polarization resistance increases in the electrochemical tests, which indicates that the anticorrosion ability is improved.

Corrosion resistance of Fe-based amorphous metallic matrix coating fabricated by HVOF thermal spraying

The Fe-based amorphous metallic matrix coating （Fe-AMMC） was fabricated with the powder mixtures of Fe-based metallic glass synthesized with industrial raw materials, NiCr alloy and WC particle by high velocity oxy-fuel （HVOF） spraying. The corrosion resistance of Fe-AMMC was investigated by potentiodynamic polarization tests in 1 mol/L HCl, NaCl, H2SO4 and NaOH solutions, respectively. The surface morphologies corroded were observed by SEM. The results indicate that Fe-AMMC exhibits excellent corrosion resistance, higher corrosion resistance than 304L stainless steel in the chloride solutions. The low corrosion current density and passive current density of Fe-AMMC with a wide spontaneous passivation region are about 132.0μA/cm2 and 9.0 mA/cm2 in HCl solution, and about 2.5 μA/cm2 and 2.3 mA/cm2 in NaCl solution. The excellent corrosion resistance demonstrates that Fe-based amorphous metallic matrix powder is a viable engineering material in practical anti-corrosion and anti-wear coating applications.

Effect of additive BaO on corrosion resistance of xCu/(10NiO-NiFe_2O_4) cermet inert anodes for aluminum electrolysis

xCu/（10NiO-NiFe2O4） cermet and 1BaO-xCu/（10NiO-NiFe2O4） cermet（x=5,10,17） inert anodes were prepared as potential inert anodes for aluminum electrolysis and their corrosion resistance to traditional electrolyte was studied with anodic current density of 1.0 A/cm2 in laboratory electrolysis.The substantial corrosion of metal Cu was observed,many pores appeared on the surface of anode and electrolytes infiltrated inside anodes during the electrolysis.The wear rates of 5Cu/（10NiO-NiFe2O4）,10Cu/（10NiO-NiFe2O4）,17Cu/（10NiO-NiFe2O4）,1BaO-5Cu/（10NiO-NiFe2O4）,1BaO-10Cu/（10NiO-NiFe2O4） and 1BaO-17Cu/（10NiO-NiFe2O4） are 2.15,6.50,8.30,4.88,4.70 and 4.48 cm/a,respectively.The addition of BaO to 10Cu/（10NiO-NiFe2O4） cermet and 17Cu/（10NiO-NiFe2O4） cermet is advantageous because BaO can effectively promote densification and thus improve corrosion resistance.But the addition of BaO to 5Cu/（10NiO-NiFe2O4） cermet is unfavorable to corrosion resistance because additive BaO at the grain boundary of anode accelerates possibly the corrosion of cermet.

Effect of sintering atmosphere on corrosion resistance of Ni/(NiFe_2O_4-10NiO) cermet inert anode for aluminum electrolysis

A comparative study on the corrosion resistance of 17Ni/（NiFe2O4-10NiO） cermet inert anode prepared in differentsintering atmospheres was conducted in Na3AlF6-Al2O3 melt. The results indicate that the corrosion rates of NiFe2O4-based cermetanodes prepared in the vacuum and the atmosphere with oxygen content of 2×10^-3 （volume fraction） are 6.46 and 2.71 cm/a,respectively. Though there is a transition layer with lots of holes or pores, a densified layer is formed on the surface of anode due tosome reactions producing aluminates. For the anode prepared in the atmosphere with oxygen content of 2×10^-3, the thickness of thedensification layer （about 50 μm） is thicker than that （about 30 μm） formed on the surface of anode prepared in the vacuum. Thecontents of NiO and Fe（II） in NiFe2xO4-y-z increase with the decrease of oxygen content in sintering atmosphere, which reduces thecorrosion resistance of the material.

Structure and corrosion resistance of modified micro-arc oxidation coating on AZ31B magnesium alloy

A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investigated using the contact angle measuring device. The surface morphologies and structure of the coatings were evaluated using SEM, XRD and FT-IR. The corrosion resistance was investigated by potentiodynamic polarization curves and long-term immersion test. The results showed that the water contact angle (CA) increases gradually with modification time from 0 to 5 h, the highest CA reaches 138° after being modified for 5 h, and the number and size of the micro pores are decreased. The modification method hardly alters crystalline structure of the MAO coating, but improves the corrosion resistance based on the much positive potential and low current density. Moreover, the corrosion resistance and hydrophobicity can be enhanced with increasing the alkyl chain. The wetting and spreading for the alkylcarboxylate with low surface energy become easier on the micro-porous surface, and alkylcarboxylate monolayer will be formed through bidentate bonding, which changes the surface micropores to a sealing or semi-sealing structure and makes the MAO coating dense and hydrophobic. All the results demonstrate that the modification process improves the corrosion protection ability of the MAO coating on AZ31B Mg alloy.

Electrodeposition of Cu coating with high corrosion resistance on Mg-3.0Nd-0.2Zn-0.4Zr magnesium alloy

To improve the corrosion resistance, electrodeposition of Cu coating on Mg-3.0Nd-0.2Zn-0.4Zr （mass fraction, %NZ30K） magnesium alloy via an appropriate pretreatment was investigated. The surface morphologies, compositions and microstructures of the pretreated films and Cu coating were characterized in detail. The results show that the activation film consists of fluoride and phosphates and Zn immersion film forms preferentially on the eutectic compound Mg12Nd phase region. A smooth, uniform and dense Cu coating is successfully obtained. Potentiodynamic polarization tests reveal that Cu coating can greatly improve the corrosion resistance of NZ30K magnesium alloy. Open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS） tests during long-term immersion further demonstrate that Cu coating can provide an effective protection for NZ30K magnesium alloy from corrosion up to ~60 h, due to its dense structure and a stable passive film formed. In addition, Cu coating exhibits good adhesion to substrate as confirmed by thermal shock test.