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.

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.

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.

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.

Structures of ceramics coatings on steel fabricated by hot-dipping and micro-arc oxidation

Firstly, an aluminum coating was produced metallurgically on mild steel by hot-dipping, then an aluminum oxide coating was formed self-growingly from the aluminum coating by micro-arc oxidation treatment. The structures of the composite coatings were investigated by means of SEM, TEM and XRD. The results show that the composite coating consists of three layers which are Fe-Al alloy, aluminum coating and aluminum oxide orderly outward from the steel substrate. There are amorphous phases, k-Al2O3 and θ-Al2O3 mainly in the aluminum oxide.

Stability of aqueous nano-ceramic coatings with two different dispersants

The effects of sodium carboxymethyl cellulose and sodium citrate as dispersants on nano-ceramic aqueous suspension were examined by the measurements of ζ -potential and the sedimentation test. The results show that proper addition of sodium carboxymethyl cellulose or sodium citrate into nano-ceramic coating, exhibits an enhanced dispersion and stability compared with the coating without dispersants. The negative ζ -potential of the particles in the nano-coating increases with the increase of pH value of the coating, and the curve of ζ -pH moves to lower pH range when the dispersants are added into the coating. To ensure that the coating has not only good stability and dispersibility but also no corrosivity to substrate alloy, adding 1.00% sodium citrate into coating with pH value of 7-8 is preferable to adding sodium carboxymethyl cellulose.

Structure and Properties Characterization of Ceramic Coatings Produced on Steel Using a Combined Technique

Metallurgically bonded ceramic coatings were prepared on a steel surface with a combined method of arc spraying and micro-arc oxidation for the first time. Coatings were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Point and line distribution of elements of the ceramic coatings were determined using energy dispersive spectroscopy (EDS). Coatings abrasive wear resistance, corrosion resistance and hot impact property were assessed respectively. The property test results show that metallurgically bonded ceramic coatings were formed on aluminum coatings and the ceramic coatings is mainly composed of a-Al2O3, y-A!2O3^ #-Al2O3 and a little amorphous. The coatings possess excellent abrasive wear, corrosion and hot shock resistance, which can in part be attributed to the gradual distribution of different phases from surface to the substrate.

Finite Element Analysis of Ceramic Coatings under Spherical Indentation with Metallic Interlayer: PartⅠUncracked Coatings

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. Various combinations of indenter radius-coating thickness ratios and interlayer thickness-coating thickness ratios were used in the modeling. The effects of the interlayer, the coating and the substrate on the indentation behavior, such as the radial stress distribution along the coating surface as well as the coating interface, and the plastic deformation zone evolution in the substrate were investigated in connection with the above mentioned ratios. The coating cracking dominant modes were also discussed within the context of the peak tensile stresses on the coating surface and on the coating interface.

Residual Thermal Stresses of Laser Cladding of Intermetallic-Ceramic Composite Coatings

The stresses in laser cladding of Ni3Al-WC composite coating co and in heat affect zone (HAZ) σh have been induced based on considering the influences of laser processing parameters power P and beam traverse speed v.According to the calculated results, certain limits of P and v are necessary in order to obtain crack free coatings. It agrees well with the experimental results.

Compound Ceramic Coatings Grown by Micro-plasma Oxidation on Ti-6Al-4V Alloy

Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation （MPO） in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffraction （XRD） and the scanning electron microscopy （SEM）, respectively. Inductively coupled plasma atomic emission spectrometer technique was used to analyze the solution features of Ti-6Al-4V alloy in the process of preparation. The results reveal that Al2TiO5 forms in the coatings at the initial stages of MPO reaction, and its content changes rapidly with the reaction continuing： after 20 min, the ceramics coatings are composed of α-Al2O3, 7-Al2O3 and Al2TiO5, but after 40 min, its main composition is of α-Al2O3. The content of Ti in the solution will increase when the MPO time extends, and as will Al in the anode area until, after 30 min, it reaches the maximum and keeps constant from then on. Both substrata of Ti and Al in the electrolyte join the MPO reaction at the initial stage, where the formation of Al2TiO5 happens; but as the MPO reaction prolongs, more and more Al in the electrolyte will take part in the reaction, leading to the appearance of a large amount ofAl2O3.