CN114032506A - Thermal barrier coating with melting CMAS erosion resistance and preparation method thereof - Google Patents
Thermal barrier coating with melting CMAS erosion resistance and preparation method thereof Download PDFInfo
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- CN114032506A CN114032506A CN202111323518.5A CN202111323518A CN114032506A CN 114032506 A CN114032506 A CN 114032506A CN 202111323518 A CN202111323518 A CN 202111323518A CN 114032506 A CN114032506 A CN 114032506A
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
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Abstract
A thermal barrier coating with resistance to corrosion of molten CMAS and a preparation method thereof relate to the technical field of surface corrosion and protection of thermal barrier coatings. In the invention, a structure with micro mastoids is prepared on the surface of the thermal barrier coating in the early stage, and then a layer of nano villus with hydrophobicity is prepared on the micro mastoid structure. The contact angle of the molten CMAS on the surface of the thermal barrier coating is improved, and the wettability of the molten CMAS on the surface of the thermal barrier coating is reduced, so that the CMAS is prevented from invading the coating, and the thermal barrier coating is protected.
Description
Technical Field
The invention relates to the technical field of surface corrosion and protection of thermal barrier coatings, in particular to a thermal barrier coating with CMAS corrosion resistance and a preparation method thereof.
Background
In the development history of aircraft engines, the thrust-weight ratio is the most important ring. With the continuous improvement of the thrust-weight ratio, the gas inlet temperature in front of the turbine can be greatly improved, and when the fourth generation fighter plane is reached, the gas inlet temperature reaches 1650 ℃, and the requirement of aviation development is difficult to meet by simply depending on the improvement of a high-temperature alloy technology. In the sixty years of the last century, the united states aviation and space agency proposed the concept of thermal barrier coating, namely, coating a protective coating with high temperature resistance and good heat insulation performance on the surface of a high-temperature alloy substrate to achieve the purpose of reducing the surface temperature of the alloy.
During the operation of the aircraft, sand dust, dirt and the like are inevitably sucked in, and the substances are mainly calcium oxide, magnesium oxide, and a mixture of aluminum oxide and silicon oxide (CMAS). Under the high temperature environment of the engine, such mixtures may melt and penetrate the thermal barrier coating surface. As the thermal expansion coefficients of the CMAS and the thermal barrier coating are not consistent, the thermal barrier coating can crack and fail in the running process of an engine.
At present, the corrosion protection measures of CMAS mainly include the following three modes:
(1) and (4) physical protection, namely adding a compact layer on the surface of the thermal barrier coating to prevent CMAS from penetrating into the thermal barrier coating. The technical problem is that the compact layer has low thermal expansion coefficient and is often peeled off due to excessive thermal stress in the service process.
(2) Chemical protection, namely coating a chemical protective layer on the surface of the thermal barrier coating, wherein the protective material can react with the CMAS to generate a compact new phase to prevent the CMAS from permeating into the thermal barrier coating. The current technical problem is that CMAS can accumulate on the surface of the thermal barrier coating, and the thickness is increased continuously, which can reduce the service life of the coating.
(3) Improving the composition of YSZ coating, doping with substances capable of crystallizing CMAS, and blocking CMAS melt infiltration. The current technical problem is that the CMAS cannot be completely blocked from penetrating due to the pores and cracks still existing inside the coating.
Aiming at the defects of the method, the invention prepares a structure with micro mastoid on the surface of the thermal barrier coating in the early stage, and then prepares a layer of nano villus with hydrophobicity on the micro mastoid structure. The contact angle of the molten CMAS on the surface of the thermal barrier coating is improved, and the wettability of the molten CMAS on the surface of the thermal barrier coating is reduced, so that the CMAS is prevented from invading the coating, and the thermal barrier coating is protected.
Disclosure of Invention
In order to effectively solve the problems of failure and the like caused by corrosion of molten CMAS to the thermal barrier coating, the invention provides a novel CMAS corrosion resistant thermal barrier coating and a preparation method thereof, which can effectively improve the CMAS corrosion resistance of the thermal barrier coating and improve the stability of the thermal barrier coating.
The technical scheme of the invention is that a micrometer mastoid array structure with the diameter of 10-120 mu m, the height of 20-50 mu m and the distance of 30-120 mu m is prepared on the surface of a ceramic layer of a thermal barrier coating in the early stage, and a layer of yttria-graphene composite coating or zirconia-graphene composite coating is prepared on the surface of the ceramic layer by deposition by using a dipping technology or a spin coating technology. The graphene has a hydrophobic characteristic, is embedded on the surface of the mastoid to form nano fluff, and is similar to a lotus leaf structure with a self-cleaning bionic function, so that the molten CMAS can be effectively prevented from being attached to the surface of the ceramic layer, and the CMAS erosion resistance of the thermal barrier coating is improved.
A thermal barrier coating having resistance to CMAS erosion, characterized by: the thermal barrier coating is sequentially composed of a high-temperature alloy substrate to be processed, a bonding layer, a ceramic layer, an yttrium oxide-graphene composite coating or a zirconium oxide-graphene composite coating from bottom to top; the surface of the ceramic layer is provided with a micron-sized mastoid array structure;
the modified structure of the special yttrium oxide-graphene composite coating or zirconium oxide-graphene composite coating has the characteristic of a nano villus structure formed by graphene; meanwhile, the yttrium oxide-graphene composite coating or the zirconium oxide-graphene composite coating extends the mastoid array structure on the surface of the ceramic layer, namely the yttrium oxide-graphene composite coating or the zirconium oxide-graphene composite coating is in the mastoid array structure.
The invention relates to a thermal barrier coating with CMAS erosion resistance and a preparation method thereof, which are characterized by comprising the following specific preparation steps:
(1) preparing a micrometer mastoid array structure with the diameter of 10-120 mu m, the height of 20-50 mu m and the distance of 30-120 mu m on the surface of the thermal barrier coating ceramic layer; or preparing a micrometer mastoid array structure with the diameter of 10-120 μm, the height of 20-50 μm and the distance of 30-120 μm on the surface of the bonding layer, then preparing a thermal barrier coating ceramic layer, and obtaining the micrometer mastoid array structure by extending on the surface of the thermal barrier coating ceramic layer;
(2) uniformly coating the yttrium oxide-graphene or zirconium oxide-graphene dispersion liquid on the surface of the ceramic layer in the step (1) by adopting a dip coating or spin coating method, wherein the thickness of the coating is 10-3000 nm; a micrometer mastoid array structure is also obtained on the surface of the obtained yttrium oxide-graphene or zirconium oxide-graphene coating;
(3) putting the coated sample in the step (2) into a drying box for drying;
wherein the components of the yttrium oxide-graphene or zirconium oxide-graphene dispersion liquid in the step (2) are 16g/L yttrium oxide or zirconium oxide, 0.1g/L graphene oxide, 1.04g/L sodium dodecyl benzene sulfonate, 0.14g/L hexadecyl dimethyl ammonium bromide and 0.24g/L polyvinylpyrrolidone.
And (4) keeping the temperature of the drying oven in the step (3) at 120 ℃ for 3 min.
The invention has the advantages that:
1. the prepared yttrium oxide-graphene composite coating or zirconium oxide-graphene composite coating is similar to a lotus leaf structure in structure and has hydrophobicity, and the molten CMAS is difficult to attach to the surface of the thermal barrier coating, so that the erosion resistance of the molten CMAS of the thermal barrier coating is improved.
2. The preparation method of the coating is simple in process and low in cost.
Drawings
FIG. 1 is a schematic representation of a thermal barrier coating having resistance to erosion by molten CMAS;
FIG. 2 is a schematic structural diagram of a thermal barrier coating with resistance to erosion by molten CMAS
FIG. 3. Yttrium oxide-graphene dispersion
FIG. 4 thermal barrier coating micrographs
FIG. 5 is a three-dimensional topography of a thermal barrier coating
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings, which are illustrated in the appended drawings. It is to be noted that the examples of the present invention and the features of the examples may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
The invention relates to the technical field of surface corrosion and protection of thermal barrier coatings, in particular to a thermal barrier coating with melting-resistant CMAS corrosion and a preparation method thereof. Preparing a bonding layer by adopting an electron beam physical vapor deposition method, preparing a micrometer mastoid array structure with the diameter of 100 micrometers, the height of 20-30 micrometers and the distance of 80 micrometers on the surface of the bonding layer by adopting an etching process, preparing a ceramic layer by adopting the electron beam physical vapor deposition process, and transferring the structural characteristics of the bonding layer to the ceramic layer by utilizing the process characteristics. And finally, preparing a layer of yttrium oxide mixed graphene layer on the surface of the ceramic layer by using a spin coating method. The columnar bulge structure of the layer is provided with microprotrusions formed by graphene, so that a hydrophobic structure is formed; the structure can effectively prevent the molten CMAS from being attached to the surface of the ceramic layer, thereby improving the CMAS erosion resistance of the thermal barrier coating.
FIG. 1 shows a schematic structural diagram of the present invention, a thermal barrier coating with CMAS erosion resistance and a preparation method thereof, wherein the method comprises the following steps:
the method comprises the following steps: polishing and sand blasting the surface of the high-temperature alloy to be processed;
step two: preparing a MCrAlY bonding layer (M is Ni, Co or Ni and Co) with the thickness of 120 microns on the surface of a sample by adopting an electron beam physical vapor deposition process;
step three: preparing a micrometer mastoid array structure with the diameter of 100 micrometers, the height of 20-30 micrometers and the interval of 80 micrometers on the surface of the bonding layer by adopting an etching process;
step four: carrying out sand blasting treatment on the etched bonding layer;
step five: preparing a YSZ ceramic layer with the thickness of 120 microns on the surface of the bonding layer by adopting an electron beam physical vapor deposition process, and transmitting the characteristics of the surface of the bonding layer to the ceramic layer due to the characteristics of the electron beam physical vapor deposition process;
step six: cleaning the ceramic layer obtained in the fifth step;
step seven: uniformly coating the yttrium oxide-graphene dispersion liquid on the surface of the ceramic layer by using a KW-4A type spin coater; the coating thickness was 2000 nm.
Step eight: putting the coated sample in the step seven into a drying box for drying;
the speed of the spin coater in the seventh step is 3000r/min, and the rotation time is 30 s;
the ingredient of the yttrium oxide-graphene dispersion liquid in the step seven is 4g/l of yttrium oxide,
0.1g/l of graphene oxide, 1.04g/l of sodium dodecyl benzene sulfonate, 0.14g/l of hexadecyl dimethyl ammonium bromide and ethanol are used as solvents;
and eighthly, keeping the temperature of the drying oven at 120 ℃ for 3 min.
And performing a CMAS erosion experiment on the prepared thermal barrier coating with the modified structure and the CMAS with the conventional structure. The matrix operation steps are as follows: at the surface of the thermal barrier coating layer by 8g/cm2Coating CMAS powder (CaO 22%, MgO 19%, Al)2O314％、SiO245%), then transferred to a muffle furnace at 5 deg.C/min up to 1250 deg.C for 30min and then furnace cooled. The spalled area of the thermal barrier coating in the conventional structure under the influence of CMAS erosion accounted for 25% of the total area, and the coating had failed. The thermal barrier coating with the micrometer mastoid array structure of the invention has a unique lotus leaf structure,the thermal barrier coating is intact and has no shedding phenomenon. The experiment proves that the thermal barrier coating with the modified structure has better anti-melting CMAS erosion performance than the conventional structure.
Claims (5)
1. A thermal barrier coating having resistance to CMAS erosion, characterized by: the thermal barrier coating is sequentially composed of a high-temperature alloy substrate to be processed, a bonding layer, a ceramic layer, an yttrium oxide-graphene composite coating or a zirconium oxide-graphene composite coating from bottom to top; the surface of the ceramic layer is provided with a micron-sized mastoid array structure.
2. A thermal barrier coating having resistance to CMAS erosion as claimed in claim 1 wherein: the modified structure of the yttrium oxide-graphene composite coating or the zirconium oxide-graphene composite coating has the characteristic of a nano villus structure formed by graphene; meanwhile, the yttrium oxide-graphene composite coating or the zirconium oxide-graphene composite coating extends the mastoid array structure on the surface of the ceramic layer, namely the yttrium oxide-graphene composite coating or the zirconium oxide-graphene composite coating is in the mastoid array structure.
3. A method of preparing a thermal barrier coating having resistance to CMAS erosion according to claim 1 or 2, characterized in that: the preparation method comprises the following specific steps:
(1) preparing a micrometer mastoid array structure with the diameter of 10-120 mu m, the height of 20-50 mu m and the distance of 30-120 mu m on the surface of the thermal barrier coating ceramic layer; or preparing a micrometer mastoid array structure with the diameter of 10-120 μm, the height of 20-50 μm and the distance of 30-120 μm on the surface of the bonding layer, then preparing a thermal barrier coating ceramic layer, and obtaining the micrometer mastoid array structure by extending on the surface of the thermal barrier coating ceramic layer;
(2) uniformly coating the yttrium oxide-graphene or zirconium oxide-graphene dispersion liquid on the surface of the ceramic layer in the step (1) by adopting a dip coating or spin coating method, wherein the thickness of the coating is 10-3000 nm; a micrometer mastoid array structure is also obtained on the surface of the obtained yttrium oxide-graphene or zirconium oxide-graphene coating;
(3) and (3) drying the coated sample in the step (2) in a drying box.
4. The method according to claim 3, wherein the yttria-graphene or zirconia-graphene dispersion of step (2) comprises 16g/L yttria or zirconia, 0.1g/L graphene oxide, 1.04g/L sodium dodecylbenzenesulfonate, 0.14g/L cetyldimethyl ammonium bromide, and 0.24g/L polyvinylpyrrolidone.
5. The method according to claim 3, wherein the drying oven temperature in the step (3) is 120 ℃ and the holding time is 3 min.
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2021
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