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).

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.

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.

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.

Microstructure and properties of induction brazing nickel base/WC composite coating

BNi-2/WC composite wear-resisting coating was prepared on carbon steel by the method of induction brazing.The microstructure and phase composition of the composite coating were analyzed,and the bonding strength and wear-resisting performance of the coating were tested.During the process of induction brazing,the tungsten carbide partially dissolves and reacts with the filler metal alloy to form NiW compound phase,which realizes the metallurgical combination of tungsten carbide and filler metal alloy.The matrix of the filler metal alloy consists of Ni solid solution and Ni_(3)B/Ni_(3)Si eutectic phase,and the metallurgical diffusion reaction occurs between the filler metal alloy and the steel matrix.The mechanical analysis results show that the self-strength of the composite coating reaches 140 MPa and the bonding strength of the filler metal alloy to the steel matrix reaches 360 MPa.The dry sand rubber wheel wear testing machine showed that the coating weight loss was only 0.2824 g,which was only 1/5 of the weight loss of 65 Mn matrix under the same conditions.

New superhydrophobic composite coatings on Mg-Mn-Ce magnesium alloy

A novel combined method for the formation of composite coatings on the Mg-Mn-Ce alloy is developed.Ceramic like matrix was formed on the Mg alloy surface by the plasma electrolytic oxidation.Then the samples were subsequently processed by dip-coating in an alcohol suspension of superdispersed polytetrafluoroethylene and spraying with the tetrafluoroethylene telomers solution.SEM,OSP,and SPM was used to study structure of formed surfaces.It was established by measurements of CA and CAH,as well as surface free energy calculations that formed coatings demonstrate superhydrophobic properties due to the presence of an irregular hierarchical surface structure and low surface free energy of fluoropolymers.The coating preserves its hydrophobic properties after exposure to high and low temperatures,for a long time as well as being in corrosive environments.EDS and XRD data analysis confirmed the presence of organofluorine compounds in the composite layers,including in the form of crystalline polytetrafluoroethylene.Using potentiodynamic polarization test and EIS,it was found that the resulting coatings significantly increase the corrosion resistance of Mg material.These data are also confirmed by salt spray tests for 40 days.Incorporation of fluoropolymers additionally decrease coatings coefficient of friction.

One-step hydrothermal synthesis of 2,5-PDCA-containing MgAl-LDHs three-layer composite coating with high corrosion resistance on AZ31

The addition of 2,5-pyridinedicarboxylic acid(2,5-PDCA)to the Mg-Al LDH coating,which was prepared by one-step hydrothermal synthesis,had extremely enhanced the corrosion protection of AZ31 Mg alloy,although the 2,5-PDCA could not be intercalated into the interlayer spacing.The corrosion current density of 0.05 mol L^(−1)2,5-PDCA LDH containing LDH coating is 3.18 nA cm^(−2),reduced by two orders of magnitude compared to the LDH coating without inhibitor,and the corrosion inhibition efficiency of the coating is 98.05%.The coating formed on the surface of AZ31 was peeled off from the substrate by using a mechanical method and SEM observation of the cross-section showed that the coating consisted of three different layers.The innermost layer is a thick layer that consists of Mg(OH)_(2)and the intermediate layer is LDH,which is vertical to the substrate and the outmost layer is a thin but very dense deposit layer of LDH agglomerates with complexes of 2,5-PDCA and Mg.This kind of sediment/LDH/Mg(OH)_(2)three-layer composite structure was accountable for the increase in the corrosion resistance of AZ31 Mg alloy.

Corrosion behavior of composite coatings containing hydroxyapatite particles on Mg alloys by plasma electrolytic oxidation: A review

Mg and its alloys have been introduced as promising biodegradable materials for biomedical implant applications due to their excellent biocompatibility, mechanical behavior, and biodegradability. However, their susceptibility to rapid corrosion within the body poses a significant challenge and restricts their applications. To overcome this issue, various surface modification techniques have been developed to enhance the corrosion resistance and bioactivity of Mg-based implants. PEO is a potent technique for producing an oxide film on a surface that significantly minimizes the tendency to corrode. However, the inevitable defects due to discharges and poor biological activity during the coating process remain a concern. Therefore, adding suitable particles during the coating process is a suitable solution. Hydroxyapatite(HAp)has attracted much attention in the development of biomedical applications in the scientific community. HAp shows excellent biocompatibility due to its similarity in chemical composition to the mineral portion of bone. Therefore, its combination with Mg-based implants through PEO has shown significant improvements in their corrosion resistance and bioactivity. This review paper provides a comprehensive overview of the recent advances in the preparation, characterization, corrosion behavior and bioactivity applications of HAp particles on Mg-based implants by PEO.

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.

Oxidation and Electrical Properties of Cu-Mn_(3)O_(4)Composite Coating Obtained by Electrodeposition on SOFC Interconnects

Cu-Mn_(3)O_(4)composite coating was prepared on the SUS 430 ferritic stainless steel by electrodeposition and then exposed in air at 800℃corresponding to the cathode atmosphere of solid oxide fuel cell(SOFC).A dual-layer oxide structure mainly comprising an external layer of CuO followed by(Cu,Mn,Fe)_(3)O_(4)spinel and an internal layer of Cr-rich oxide was thermally developed on the coated steel.The scale area-specific resistances(ASRs)of the coated steels were lower than the scale ASR of the uncoated steel after identical thermal exposure.The external layer of CuO/(Cu,Mn,Fe)_(3)O_(4)spinel not only served as a barrier to reduce the growth rate of Cr-rich oxide internal layer and to suppress the outward diffusion of Cr,but also lowered the surface scale ASRs considerably.

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.

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.

Microstructure and mechanical properties of Ni-based composite coatings reinforced by in situ synthesized TiB_2 + TiC by laser cladding

A Ni-based composite coating reinforced by in situ synthesized TiB2 and TiC particles was fabricated on Ti6A14V by laser cladding. An attempt was made to correlate the thermodynamic predictions and experimental observation. The micro- structure and the microhardness profile across the coating were investigated by means of X-ray diffraction （XRD）, scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, and a hardness tester. It is found that the coating mainly consists of a large number of reinforcements （black blocky TiB2, flower-like or equiaxial TiC, and fine acicular CrB） and the 7 matrix. The hardness of TiB2, TiC, and CrB reinforcements is much higher than that of the 7 matrix. The dispersive distribu- tion of such high hardness reinforcements causes the increase in hardness of the whole coating. The average value of the hard- ness is approximately Hv0.2 700 in the coating. The hardness of the coating is obviously higher than that of the substrate due to the dispersion strengthening of reinforcements.

Microstructural characterization of titanium matrix composite coatings reinforced by in situ synthesized TiB + TiC fabricated on Ti6Al4V by laser cladding

Titanium-based composite coatings reinforced by in situ synthesized TiB and TiC particles between titanium and B4C were successfully fabricated on Ti6Al4V by laser cladding. Phase constituents of the coatings were predicted by thermodynamic calculations in the Ti-BnC-Al and Ti-B-C-Al systems, respectively, and were validated well by X-ray diffraction （XRD） analysis results. Microstructural and metallographic analyses were made by scanning electron microscopy （SEM） and electron probe micro-analysis （EPMA）. The results show that the coatings are mainly composed of α-Ti cellular dendrites and the eutecticum in which a large number of needle-shaped TiB and a few equiaxial TiC particles are embedded. C is enriched in α-Ti cellular dendrites and far exceeds the theoretical maximum dissolubility, owing to the extension of saturation during laser cladding. The coatings have a good metallurgical bond with the substrate due to the existence of the dilution zone, in which a great amount of lamella β-Ti grains consisting of a thin needle-shaped martensitic microstructure are present and grow parallel to the heat flux direction; a few TiB and TiC reinforcements are observed at the boundaries of initial β-Ti grains.

MICROSTRUCTURE OF ELECTRODEPOSITED Ni-W-P-SiC COMPOSITE COATINGS

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Microstructure and formation mechanism of titanium matrix composites coating on Ti-6Al-4V by laser cladding

Laser cladding experiments were done on a 5-kW continuous wave CO2 laser to synthesize TiC and TiB rein- fowed titanium matrix composite coatings on Ti-6AI-4V alloy with a mixture of Ti and B4C precursor powder. The ther- modynamics of the reactions were calculated and analyzed. The microstructure and phase evolution of TiB and TiC com- posites were investigated. The results showed that the chemical reaction between Ti and B4C would release much heat, and these compounds, TiC, TiB, and small amount of TiB2, can be formed on the surface of Ti-6AI-4V alloy if the supplied en- ergy is sufficient to excite the reaction among the initial products. A good metallurgical bond between the coating and the substrate can be achieved. The microhardness of coating was irregular and the maximum value was approximately HV600.

CATHODIC PROCESS AND WEAR RESISTANCE OF ELECTRO-DEPOSITED RE-Ni-W-P-SiC COMPOSITE COATING

Cathodic deposition current density of the composite coatings increases when SiC par-ticles and rare earth (RE) were added in the bath, which is profitable for Ni- W-P alloy to deposit in the cathod, forming Ni-W-P-SiC and RE-Ni-W-P-SiC composite coatings. On the contrary, the addition of PTFE in the bath decreases cathodic deposition current density of the coatings. The current density increases a little when the amount of RE is 7-9g/l; however, the current density increases greatly when the amount of RE is increased to 11-13g/l. Bui ij the amount of RE is raised further, the current density decreases. Hardness and wear resistance of RE-Ni-W-P-SiC composite coating have been studied, and the results show that the hardness and wear resistance of RE-Ni-W-P-SiC composite coating increase with increasing heat treatment tempera-ture, which reach peak values at 400℃; while the hardness and wear resistance of the coating decrease with the rise of heat treated temperature continuously.

Microstructure and corrosion resistance of Fe/Mo composite amorphous coatings prepared by air plasma spraying

Fe/Mo composite coatings were prepared by air plasma spraying （APS） using Fe-based and Mo-based amorphous and nanocrys- talline mixed powders. Microstructural studies show that the composite coatings present a layered structure with low porosity due to adding the self-bonded Mo-based alloy. Corrosion behaviors of the composite coatings, the Fe-based coatings and the Mo-based coatings were in- vestigated by electrochemical measurements and salt spray tests. Electrochemical results show that the composite coatings exhibit a lower polarization current density and higher corrosion potentials than the Fe-based coating when tested in 3.5wt% NaC1 solutions, indicating supe- rior corrosion resistance compared with the Fe-based coating. Also with the increase in addition of the Mo-based alloy, a raised corrosion re- sistance, inferred by an increase in corrosion potential and a decrease in polarization current density, can be found. The results of salt spray tests again show that the corrosion resistance is enhanced by adding the Mo-based alloy, which helps to reduce the porosity of the composite coatings and enhance the stability of the passive films.

MoSi_2 oxidation resistance coatings for Mo_5Si_3/MoSi_2 composites

In order to improve the oxidation resistance properties of 30 at.% Mo5Si3/MoSi2 composite at high temperature in air, a molybdenum disilicide coating was prepared on its surface by a molten salt technology. XRD and SEM analysis showed that only tetragonal MoSi2 phase existed in the coating after being siliconized for 5 h at 900℃. The oxidation film formed on the uncoated sample was not dense, so that oxygen diffused easily through it. The volatilization of MoO3 resulted in the oxidation film separating from the substrate. The MoSi2 coating was proved to be an effective method to prevent 30 at.% Mo5Si3/MoSi2 composites from being oxidized at 1200℃. A dense glassy SiO2 film was formed on the MoSi2 coating surface, which acted as a barrier layer for the diffusion of oxygen atoms to the substrate. The 30at.% MosSi3/MoSi2 composites with a MoSi2 coating showed much better oxidation resistance at high temperature.

Microstructure and mechanical properties of twin-wire arc sprayed Ni-Al composite coatings on 6061-T6 aluminum alloy sheet

We have systematically studied the microstructure and mechanical properties of Ni-5wt%Al and Ni-20wt%Al composite coat- ings fabricated on 6061-T6 aluminum alloy sheet by twin-wire arc spraying under different experimental conditions. The abrasive wear be- havior and interface diffusion behavior of the composite coatings were evaluated by dry/wet rubber wheel abrasive wear tests and heat treat- ment, respectively. Experimental results indicate that the composite coatings exhibit features of adhesive wear. Besides, the Vickers micro- hardness of NiA1 and Ni3AI intermetallic compounds is relatively larger than that of the substrate, which is beneficial for enhancing the wear resistance. With the increase of annealing temperature and time, the interface diffusion area between the Ni-Al coating and the substrate gradually expands with the formation of NiAl3 and Ni2Al3 phases, and is controlled by diffusion of aluminum atoms. The grain growth ex- ponent n of diffusion kinetics of the Ni-Al coating, calculated via a high-temperature diffusion model at 400, 480, and 550℃, is between 0.28 and 0.38. This satisfies the cubic law, which is consistent with the general theoretical relationship of high-temperature diffusion.