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.

Ceramics Surface Modification by Excimer Laser Metal Coating

Thin metallic layers (~ 2 μm) of Ni were deposited on polycrystalline Al2O3. ZrO2 and (Ce-TZP)+Al2O3 ceramic substrates. and further irradiated with pulsed excimer (Xeno chloride) laser pulses. The laser energy density was varied from 0.21 to 0.81 J / cm2 to optimize bending strength. For ZrO2 ceramic, it was found that the strength increases from 530 to 753 MPa at 0.51 J / cm2 irradiation. For Al2O3 and (Ce-TZP)+ Al2O3 the fracture strength also increases in varying degree. The causes of strength increment were discussed.

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...

Characterization of microarc oxidation coatings on pure titanium

Key Laboratory for Beam Technology and Materials Modification, Institute ofLow Energy Nuclear Physics, Beijing Normal UniversityThe morphology, composition, and phase structure of the oxide coatings produced on the surface ofpure titanium by alternating-current microarc discharge in aluminate solution were investigated byX-ray diffraction and scanning electron microscopy. The profiles of the hardness H and the elasticmodulus E in the coatings were determined using a nanoindentation method. The concentrationdistributions of Ti, Al, and O in the coating show that this coating over 30 mu m thick contains twolayers: an outer layer and an inner layer. The oxide coating is mainly composed of TiO_2 rutile andAl_2TiO_5 compounds. During oxidation, the temperature in the microarc discharge channel was veryhigh to make the local coating molten. From the surface to the interior of the coating, H and Eincrease gradually, and then reach maximum values of 9.78 GPa and 176 GPa respectively at a distanceof 7 mu m from the coating/titanium interface. They are also rather high near the interface.

Micro-arc oxidation coatings on Mg-Li alloys

Micro-arc oxidation (MAO) method was used for the surface modification of an Mg-5wt.%Li alloy. Ceramic coatings were in-situ fabricated on the Mg-Li alloy. The morphology feature,phase composition,and corrosion-resistance of the formed ceramic coatings were studied by SEM,XRD,and electrochemical methods,respectively. The results showed that the coatings produced in a sodium silicate solution system were composed of MgO and Mg2SiO4. The ceramic coating became thicker and the content of Mg2SiO4 phase increased as the concentration of Na2SiO3 increased in the solution. The coating was loose at the low concentration of Na2SiO3 and was compact at the high concentration of Na2SiO3. The coated samples had a better corrosion resistance than the Mg-Li substrate in terms of the Tafel polarization curves and the cyclic voltammetry curves (CV).

Preparation of micro-arc oxidation coatings on magnesium alloy and its thermal shock resistance property

In the NaAlO2-Na2SiO3 compound system, the ceramic coatings were prepared on magnesium alloy by micro-arc oxidation. The morphology, phase composition, and thermal shock resistance of the ceramic coatings were studied by scanning electron microscope, X-ray diffraction and thermal shock tests, respectively. The results showed that the ceramic coating contains MgO, MgAl2O4, as well as a little amount of MgESiO4. The thickness of the ceramic coatings increases with the current density increasing, when the current density is 12 A·dm^-2, the thermal shock resistance of the produced ceramic coating is the best. The hardness of the ceramic coating is up to 10 GPa or so.

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.

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.

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.

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.

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.

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.

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.

Microstructure and Corrosion Resistance of Cr_7C_3/γ-Fe Ceramal Composite Coating Fabricated by Plasma Cladding

A new type in situ Cr7C3/γ-Fe ceramal composite coating was fabricated on substrate of hardened and tempered grade C steel by plasma cladding with Fe-Cr-C alloy powders. The ceramal composite coating has a rapidly solidified microstructure consisting of primary Cr7C3/γ- and the Cr7C3/γ-Fe eutectics, and is metallurgically bonded to the degree C steel substrate. The corrosion resistances of the coating in water solutions of 0.5 mol/L H2SO4 and 3.5% NaCl were evaluated utilizing the electrochemical polarization corrosion-test method. Because of the inherent excellent corrosion-resisting properties of the constituting phase and the rapidly solidified homogeneous microstructure, the plasma clad ceramal composite coating exhibits excellent corrosion resistance in the water solutions of 0.5 mol/L H2SO4 and 3.5% NaCl.

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.

Moisture-proof and Enhanced Effect of Inorganic Coating on Porous Si_3N_4 Ceramic

Inorganic coating was fabricated on the surface of the porous Si3N4 ceramic by polymer derived（PD） and spraying technology, via using vinyl-polysilazane（PSN-1） as a preceramic polymer and Si3N4 and lithium aluminosilicate（LAS） powders as fillers. The phase and microstructure of the coatings were analyzed by X-ray diffraction（XRD） analysis and scanning electron microscopy（SEM）, respectively. The effect of the coatings on mechanical property and humidity resistance of the porous Si3N4 ceramic was investigated. The experimental results showed that we successfully fabricated the uniform and dense coating which preferably combined with the substrate upon the addition of fillers. The bending strength of the porous Si3N4 ceramic sprayed the coating increased by more than 18%, and the surface hardness increased by 1.7 times. The apparent porosity of the materials reduced by an average of 97.7%, and water absorption was below 0.5%. Therefore, the prepared coating with preferable density had an obviously moisture-proof and enhanced effect on the porous Si3N4 ceramic.

Effects of Additive CeO_2 on Thermal Shock Resistance of Plasma-Sprayed Cr_2O_3 Coating

The influence of CeO2 with different content on the thermal shock resistance of plasmasprayed Cr2O3 coating was investigated. The thermal shock failure mechanism of coating was also studied. It is found that the thermal shock failure mechanism of coating is thermal stress fatigue destruction, and the destruction takes place at interface of ceramic and bond coating. The experimental results show that the lifetime of coating fracture and failure increase considerably when 3% CeO2 is added into the plasma-sprayed Cr2O3 coating. The suitable content of CeO2 makes the microcracks exist in network form. The microcrack net can release internal stress in coating, delay the crack forming and expanding and decrease holes in coating. Thus the thermal shock resistance increase largely.

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.