Research Progress of Non-oxide and High Entropy Ceramic Coatings

Ceramic coatings play a keyrole in extending the service life of materials in aerospaceandenergy fields byprotectingmaterials from high temperature,oxidation,corrosion and thermal stress.Non-oxide and high entropy ceramics are new emerging coating materials which have been researched and developed in recent years.Compared with traditional oxide ceramics,non-oxide ceramics have better high temperature stability,oxidation resistance and erosion resistance.These characteristics make non-oxide ceramics perform well in extreme environments.It is particularly noteworthy that the non-oxide high entropy ceramic is a uniform solid solution composed of at least four or fiveatoms.Their unique structure and outstanding propertiesshow great potential application in the field of coating.In this paper,the researches aboutregulating microstructure,preparation technology and properties of nitride and its high entropy system,carbide and its high entropy system and boride and its high entropy system in coating field are summarized,and their future development and prospects are prospected.

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

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

Tribological properties of nanostructured Al_2O_3-40%TiO_2 multiphase ceramic particles reinforced Ni-based alloy composite coatings

The Ni-based alloy composite coatings reinforced by nanostructured Al2O3-40%TiO2 multiphase ceramic particles were prepared on the surface of 7005 aluminum alloy by plasma spray technology. The microstructure and tribological properties of the composite coatings were researched. The results show that the composite coatings mainly consist of γ-Ni, α-Al2O3, γ-Al2O3 and rutile-TiO2 etc, and exhibit lower friction coefficients and wear losses than the Ni-based alloy coatings at different loads and speeds. The composite coating bears low contact stress at 3 N and its wear mechanism is micro-cutting wear. As loads increase to 6-12 N, the contact stress is higher than the elastic limit stress of worn surface, and the wear mechanisms change into multi-plastic deformation wear, micro-brittle fracture wear and abrasive wear. With the increase of speeds, the contact temperature of worn surface increases. The composite coating experiences multi-plastic deformation wear, fatigue wear and adhesive wear.

Effects of current density on microstructure and properties of plasma electrolytic oxidation ceramic coatings formed on 6063 aluminum alloy

Plasma electrolytic oxidation (PEO) ceramic coatings were fabricated in a silicate-based electrolyte with the addition of potassium fluorozirconate (K2ZrF6) on 6063 aluminum alloy, and the effects of current density on microstructure and properties of the PEO coatings were studied. It was found that pore density of the coatings decreased with increasing the current density. The tribological and hardness tests suggested that the ceramic coating produced under the current density of 15 A/dm2showed the best mechanical property, which matched well with the phase analysis. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves proved that the coating obtained under 15 A/dm2 displayed the best anti-corrosion property, which was directly connected with morphologies of coatings.

Interface characteristics of Al_2O_3－13%TiO_2 ceramic coatings prepared by laser cladding

Al2O3-13%TiO2 （mass fraction） coatings, prepared by laser cladding on nickel-based alloy, were heated using high frequency induction sources. The coating microstructure and the interface between bond coating and ceramic coating were characterized by SEM, XRD and EDS. The results show that two-layer substructure exists in the ceramic coating： one layer evolving from fully melted region where the sintered grains grow fully; another layer resembling the liquid-phase-sintered structure consisting of three-dimensional net where the melted Al2O3 particles are embedded in the TiO2-rich matrix. The mechanism of the two-layer substructure formation is also explained in terms of the melting and flattening behavior of the powders during laser cladding processing. The spinel compounds NiAl2O4 and acicular compounds Cr2O3 are discovered in the interface between bond coating and ceramic coating. It proves that the chemical reactions in the laser cladding process will significantly enhance the coating adhesion.

Multilayer ceramic coating for impeding corrosion of sintered NdFeB magnets

Sintered NdFeB magnets have complex microstructure that makes them susceptible to corrosion in active environments.The current paper evaluated the anticorrosion characteristics of multilayer titanium nitride ceramic coating applied through cathodic arc physical vapour deposition(CAPVD) for protection of sintered NdFeB permanent magnets.The performance of ceramic coating was compared to the electrodeposited nickel coating having a copper interlayer.Electrochemical impedance spectroscopy(EIS) and cyclic polar...

Preparation and structure of microarc oxidation ceramic coatings containing ZrO2 grown on LY12 Al alloy

Ceramic coatings containing ZrO2 were prepared in situ on LY12 aluminum alloy by microarc oxidation（MAO） in the mixed solution of zirconate and phosphate solution.The phase composition and morphology of the coatings were studied by XRD and SEM,respectively.The growing mechanism of ceramic coatings was discussed in a preliminary manner.The results show that with an increase in MAO time,the compactness of the coating improved and the thickness increased.From the inner layer to the coating surface,the content of Zr increased,while the content of Al decreased.In addition,the coating was composed of m-ZrO2,t-ZrO2,and a little amount of γ-Al2O3.With an increase in reaction time,the relative content of t-ZrO2 within the coating sharply decreased while the relative content of m-ZrO2 sharply increased,and then both generally kept at a constant level after 60 min.

Characterization of bioactive ceramic coatings prepared on titanium implants by micro-arc oxidation

Micro-arc oxidation （MAO） is an enhanced chemical technology in an electrolyte medium to obtain coating structures on valve-metal surfaces. Titanium oxide films obtained by MAO in the sodium phosphate electrolyte were investigated. The films were composed mainly of TiO2 phases in the form of anatase and mille and enriched with Na and P elements at the surface. Their apafite-inducing ability was evaluated in a simulated body fluid （SBF）. When immersing in SBF for over 30 d, a preferential carbonated-hydroxyapatite was formed on the surfaces of the films, which suggests that the MAO-treated titanium has a promising positive biological response.

Deformation Behavior of Nanostructured Ceramic Coatings Deposited by Thermal Plasma Spray

Al2O3-13 wt pet TiO2 coating deposited by direct current plasma spray consists of nanostructured region and micro-lamellae. Bend test shows that the ceramic coating can sustain some deformation without sudden failure. The deformation is achieved through the movement of nano-particles in the nanostructured region under tensile stress.

Evolution of Residual Stresses in Micro-arc Oxidation Ceramic Coatings on 6061 Al Alloy

Most researches on micro-arc oxidation mainly focus on the application rather than discovering the evolution of residual stresses. However, residual stresses in the surface coatings of structural components have adverse effects on their properties, such as fatigue life, dimensional stability and corrosion resistance, etc. The micro-arc oxidation ceramic coatings are produced on the surfaces of 6061 aluminum alloy by a homemade asymmetric AC type of micro-arc oxidation equipment of 20 kW. A constant current density of 4.4___0.1 A/dm2 and a self-regulated composite electrolyte are used. The micro-arc oxidation treatment period ranges from 10 min to 40 min, and the thickness of the ceramic coatings is more than 20 Bin. Residual stresses attributed to 7-A1203 constituent in the coatings at different micro-arc oxidation periods are analyzed by an X-ray diffractometer using the sin2~u method. The analysis results show that the residual stress in the ceramic coatings is compressive in nature, and it increases first and then decreases with micro-arc oxidation time increase. The maximum stress value is 1 667_＋20 MPa for period of 20 min. Through analyzing the coating thickness, surface morphology and phase composition, it is found that the residual stress in the ceramic coatings is linked closely with the coating growth, the phase composition and the micro cracks formed. It is also found that both the heat treatment and the ultrasonic action release remarkably the residual compressive stress. The heat treatment makes the residual compressive stress value decrease 1 378 MPa. The ultrasonic action even alters the nature of the residual stress, making the residual compressive stress change into a residual tensile stress.

Microstructure and oxidation resistance of reactive plasma clad Cr_7C_3/γ-Fe ceramic composite coating

A new type oxidation resistance in situ Cr7 C3/γ-Fe ceramic composite coating was fabricated on hardened and tempered grade C steel by reactive plasma clad with Fe-Cr-C alloy powders. The oxidation resistance of the ceramic composite coating was investigated under the test condition of 900 ℃ and 50 hours. The results indicate that the coating has a rapidly solidified microstructure consisting of blocky primary Cr7 C3 and the inter-blocky Cr7 C3/γ-Fe eutectics and is metallurgically bonded to the hardened and tempered grade C steel substrate. The high temperature oxidation resistance of the coating is up to 1.9 times higher than that of grade C steel. The oxidation kinetics curve of the coating is conforming to the parabolic-rate law equation. The excellent oxidation resistance of the coating is mainly attributed to the continuous oxide films which consist of Cr203 and Fe203. The continuous oxide films can prevent the inner part of the coating from being further oxidized.

Effect of the Oxidation Time on Properties of Ceramic Coatings Produced on Ti-6Al-4V by Micro-Arc Oxidation

Ceramic coatings were prepared on Ti-6AI-4V alloy using ac micro-arc oxidation (MAO) in silicate-hypophosphate solution. Growth regularity and formation mechanism of ceramic coatings were discussed. It was found that during the first stage the growth rate of coatings toward the external surface was larger than that toward substrate and then the coating began to grow mainly towards Ti alloy. When the total coating thickness reaches a certain value, it would no longer increase. In addition, the variations of the composition and microstructure of ceramic coatings according to the depositing time were also investigated with X-ray diffraction (XRD) and scanning electron microscope (SEM). The amount of rutile TiO2 gradually increased, whereas the amounts of the anatase TiO2 and amorphous phases first increased and then decreased slightly.

Salt spray corrosion test of micro-plasma oxidation ceramic coatings on Ti alloy

Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation （MPO）. The salt spray tests of the coated samples and the substrates were carded out in a salt spray test machine. The phase composition and surface morphology of the coatings were investigated by XRD and SEAM. Severe corrosion occurred on the substrate surface, while there were no obvious corrosion phenomena on the coated samples. The coatings were composed of Al2TiO5 and a little α-Al2O3 and mille TiO2, and the salt spray test did not change the composition of the coatings. The weight loss rate of the coatings decreased with increasing MPO time because of the increase in density and thickness of the coatings. The surface morphology of the coatings was influenced by salt spray corrosion test. Among the coated samples, the coating prepared for 2 h has the best corrosion resistance under salt spray test.

Effects of Yttrium Ion on Formation Mechanism of ZrO_2-Y_2O_3 Ceramic Coatings Formed by Plasma Electrolytic Oxidation on Al-12Si Alloy

ZrO2-Y2O3 ceramic coating was produced by plasma electrolytic oxidation （PEO） on ZAlSil2Cu3Ni2 alloy. The microstructure and phase composition of the coating were investigated by SEM and XRD.： The results show that adding an appropriate amount of yttrium ion can improve the growing rate of ceramic coating at different oxidation stages and decrease arc voltage. The thickness of ZrO2-Y2O3 coating is 16 μn thicker than that of ZrO2 coating and the maximum oxidation rate improves by 0.6 μm/min. In addition, the arc voltage decreases from 227 to 172 V. It can be seen that the rate of oxidation firstly increases to some extent and then decreases with the content of yttrium ion increasing. The growth rate reaches the maximum while the content of yttrium ion is 0.05 g-L-1The maximum thickness is 90 μm.Compared to ZrO2 coating, the micropores of ZrO2-Y2O3 coating are less and the ceramic layer is repeatedly deposited by ZrO2 and Y2O3 ceramic particles. Meanwhile, the binding force between coating and substrate is better and the coating is uniform and compact. The ceramic layer is mainly composed of c-Y0.15Zr0.85O1.93□0.07, m-ZrO2, α-Al2O3, ,γ-Al2O3 and Y2O3. It is indicated that ZrO2 has beert fully stabilized by yttrium ion through the formation of solid solution.

Ceramic-Metal Composite Coating by Laser Cladding

Four kinds of ceramics (silicon carbide, boron carbide, aluminum oxide and tungsten carbide) were added into Ni base self-fluxing alloy as reinforcing materials in order to obtain metalceramic composite coating by means of laser cladding. A lot of experiments have been carried out to test the processability of the four kinds of ceramics with different sizes and contents. The microstructures of sintered tungsten carbide (S-WC) and cast tungsten carbide (C-WC) reinforced Ni base alloy coatings were analysed, the distortion regulation of laser clad specimens was revealed. The wear resistance of the composite coating has been tested.

Flame Pyrolysis Spraying of Alumina-Yttria Ceramic Coating

Alumina yttria composite oxide coating was obtained on the stainless steel through the pyrolysis of aluminium nitrate and yttrium nitrate by flame spraying in the open atmospheric environment. The isothermal oxidation behaviour of the specimens coated with alumina yttria was investigated in air at the temperature of 1273 K. The results show that coating can promote the selective oxidation of chromium in the alloy and improve the high temperature corrosion resistance of the stainless steel.

Characteristics of a multi-component MgO-based bioceramic coating synthesized in-situ by plasma electrolytic oxidation

Plasma electrolytic oxidation(PEO)has held great potential for the advancement of biodegradable implants,as it helps in developing porous bioceramic coatings on the surface of magnesium alloys.In this research work,MgO-based bioceramic coatings containing the Si,P,Ca,Na,and F elements have been successfully fabricated on an AZ31 magnesium alloy plate utilizing the PEO method.The characteristic current-voltage behavior of the samples during the process was surveyed in an electrolyte containing Ca(H_(2)PO_(4))_(2),Na_(2)SiO_(3)·9H_(2)O,Na_(3)PO_(4)·12H_(2)O,NaF,and KOH with a pH of 12.5 and electrical conductivity of 20 mS/cm^(-1).The results revealed that applying a voltage of 350-400 V(that is 50-100 V higher than the breakdown limit)could greatly facilitate the synthesis of a PEO ceramic coating with fewer defects and more uniform morphology.The resulting coating was a compositionally graded bioceramic layer with a thickness in the range of 3.5±0.4 to 6.0±0.7µm,comprising the above-mentioned elements as promising bioactive agents.The synthesized ceramic features were investigated in terms of the elemental distribution of components through the thickness,which indicated a gradual rise in the Si and P contents and,conversely,a decline in the F content towards the outer surface.The growth mechanism of the PEO coating has been discussed accordingly.

Fabrication of in-situ synthesized ceramic reinforced Ni-based alloy composite coatings by reactive braze coating processing

In-situ synthesized ceramic such as TiC,Cr7C3 and Cr5B3 reinforced Ni-based alloy composite coating was fabricated on the surface of mild steel substrate by reactive braze coating processing with colloidal graphite,Cr,Ni,ferro-boron,Si and titanium powders as the raw materials at low temperature of 1000℃,and a new kind of coating materials was developed.By means of SEM,EDS,XRD and surface hardness tester,the microstructures,phases,hardness and wear-resistance of the coating were analyzed,respectively.The results revealed that the coating was mainly composed of the ceramic in-situ synthesized reinforcement phases of TiC,Cr7C3 and Cr5B3 and the binder phases in-situ synthesized of Ni31Si12 and(Ni,Fe)solid solution;The ceramic reinforcement phases of TiC,Cr7C3 and Cr5B3 were randomly distributed in the binder phases of Ni31Si12 and(Ni,Fe)solid solution;The coating had about 15vol%pores and can possibly be applied as a self-lubrication coating;The coating and the substrate were integrated together by metallurgical bonding;The coating had a hardness up to 91-94HR15N.

Element Analysis of Ceramic Coatings under Spherical Indentation with Metallic Interlayer: PartⅡRing Crack

Spherical indentation of ceramic coatings with metallic interlayer was performed by means of axisymmetric finite element analysis （FEA）. Two typical ceramic coatings with relatively high and low elastic modulus deposited on aluminum alloy and carbon steel were considered. The fracture mechanics of the ceramic coatings mechanisms due to occurrence of surface ring cracks extending traverse the coating thickness under spherical indentation are investigated within the framework of linear fracture mechanics. The J-integral associated to such cracks was computed. The evolution of J-integral vs the crack length and the indentation depth was studied. The effects of the interlayer, the coating and the substrate on the J-integral evolution were discussed. The results show that a suitable metallic interlayer can improve the fracture resistance of the coating systems under the same indentation conditions through reducing the J-integral.

Reactive synthesis Ti （CN） -based metal ceramic coating by electric-spark deposition

Electric-spark deposition （ESD） was adopted for depositing a Ti（ CN） -based ceramic coating on the TC4 titanium alloy substrate using a laboratory-developed electric-spark deposition system, a nitrogen-sealed atmosphere and graphite electrode. The surface morphology, microstructure, interfacial behavior between the coatings and substrate, phase and element composition of the coatings were investigated by scanning electron microscope （ SEM ） , X-ray diffraction （ XRD ） , X-ray photoelectron spectroscopy （ XPS ） and Auger electron spectroscopy （ AES ） . Microhardness profile was measured with a Vickers microhardness tester. The results show that metallurgical bond between the coating and substrate is realized and the phase of coatings are made up of Ti（ CN ） spherocrystal and dendritic crystal, TiV and C. Ti（ CN） ceramic particles, which is in-situ synthesized by the reaction among titanium from the substrate, carbon from the graphite electrode and nitrogen from the shielding nitrogen gas, is about 600 mn and distributes dispersively among the coatings. Microharduess profile falls off with the coatings thickness increasing and the highest microhardness values of the superficial coating could be up to 1 496HV, which is six times more than that of the substrate.