CN120026273A - A high-performance ScYSZ thermal barrier coating with a continuously prepared double-gradient structure and a preparation method thereof - Google Patents
A high-performance ScYSZ thermal barrier coating with a continuously prepared double-gradient structure and a preparation method thereof Download PDFInfo
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- CN120026273A CN120026273A CN202510227311.XA CN202510227311A CN120026273A CN 120026273 A CN120026273 A CN 120026273A CN 202510227311 A CN202510227311 A CN 202510227311A CN 120026273 A CN120026273 A CN 120026273A
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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Abstract
本发明公开了一种连续制备双渐变结构的高性能ScYSZ热障涂层及其制备方法，包括如下步骤：将团聚ScYSZ陶瓷粉末采用超音速等离子喷涂工艺，在高温合金基体上制备ScYSZ层状结构层；将纳米晶钪钇共稳氧化锆陶瓷粉末与含分散剂的无水乙醇进行球磨，得到悬浮液；将悬浮液利用超音速悬浮液等离子喷涂工艺，在ScYSZ层状结构层上制备垂直裂纹结构层，形成双渐变结构的高性能ScYSZ热障涂层。本发明中含有层状组织结构的ScYSZ涂层中的纳米组织可大大降低涂层的热导率，以进一步地增强涂层的隔热效果；且具有垂直裂纹结构的ScYSZ涂层增大了涂层的应力损伤容限，降低了涂层在冷热交变循环服役条件下的热应力积累，易于热应力的释放。
The present invention discloses a high-performance ScYSZ thermal barrier coating with a continuous double-gradient structure and a preparation method thereof, comprising the following steps: agglomerated ScYSZ ceramic powder is subjected to a supersonic plasma spraying process to prepare a ScYSZ layered structure layer on a high-temperature alloy substrate; nanocrystalline scandium-yttrium co-stabilized zirconia ceramic powder is subjected to ball milling with anhydrous ethanol containing a dispersant to obtain a suspension; the suspension is subjected to a supersonic suspension plasma spraying process to prepare a vertical crack structure layer on the ScYSZ layered structure layer to form a high-performance ScYSZ thermal barrier coating with a double-gradient structure. The nanostructure in the ScYSZ coating containing a layered structure in the present invention can greatly reduce the thermal conductivity of the coating to further enhance the thermal insulation effect of the coating; and the ScYSZ coating with a vertical crack structure increases the stress damage tolerance of the coating, reduces the thermal stress accumulation of the coating under the service conditions of hot and cold alternating cycles, and is easy to release thermal stress.
Description
Technical Field
The invention belongs to the technical field of high-temperature protective coatings, and particularly relates to a high-performance ScYSZ thermal barrier coating with a continuously prepared double-gradual-change structure and a preparation method thereof.
Background
The thermal barrier coating has good high temperature resistance and corrosion resistance due to its low thermal conductivity, and is widely used in hot end components of aeroengines and heavy duty gas turbines. With the development of aeroengines and gas turbines to high thermal efficiency, low emission, high thrust-weight ratio, high power and the like, the temperature of the gas inlet at the front end of the turbine is higher and higher, and the highest temperature is far higher than the temperature bearing capacity of nickel-based superalloy. The most widely applied 8YSZ thermal barrier coating system is easy to sinter, phase change, corrode and the like under the high-temperature environment of 1200 ℃ for a long time, and the strain tolerance is reduced. Whereas scandium yttrium co-stabilized zirconia (ScYSZ) ceramic coatings have low thermal conductivity and excellent high temperature tetragonal phase structural stability compared to conventional 8YSZ ceramic thermal barrier coatings.
In the coating structure system, a coating with a typical lamellar tissue structure can be prepared through a supersonic plasma spraying process, and a coating with a vertical crack structure can be prepared through a supersonic suspension plasma spraying process, but a large number of interlayer interfaces in the lamellar tissue structure are frequently nucleation points of cracks, so that interlayer cracking and premature failure are easy to occur in the coating service process. The vertical crack structure can greatly improve the service life of the thermal barrier coating under the service condition of cold-hot alternating cycle due to the high strain tolerance, but the heat insulation effect of the coating is far inferior to that of a plasma sprayed lamellar structure coating due to the introduction of the vertical crack.
Disclosure of Invention
In order to solve the problem that an 8YSZ ceramic thermal insulation coating is difficult to be used in a high-temperature thermal chemistry multi-field coupling environment at a temperature of more than 1200 ℃ for a long time in the prior art, the invention aims to provide a high-performance ScYSZ thermal insulation coating with a low thermal conductivity, good strain tolerance and high thermal cycle life, which is continuously prepared in a double gradual change structure, and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method for continuously preparing a high-performance ScYSZ thermal barrier coating with a double gradual change structure comprises the following steps:
preparing a ScYSZ layered structure layer on a high-temperature alloy matrix by adopting a supersonic plasma spraying process to agglomerate ScYSZ ceramic powder;
Ball milling is carried out on nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder and absolute ethyl alcohol containing a dispersing agent to obtain suspension;
And preparing a vertical crack structure layer on the ScYSZ lamellar structure layer by using the suspension liquid through a supersonic suspension liquid plasma spraying process, so as to form the high-performance ScYSZ thermal barrier coating with a double gradual change structure.
A further improvement of the invention is that the ScYSZ layer structure has a thickness of 100 μm.
The invention is further improved in that the supersonic plasma spraying process parameters are 430-450A of current, 125-140V of voltage, 110-120L/min of main gas argon flow, 15-17L/min of secondary gas hydrogen flow, 90-110 mm of spraying distance and 14-18 g/min of powder feeding amount.
The invention is further improved in that the dispersing agent is polyethylene glycol.
The invention is further improved in that the mass ratio of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder to the dispersing agent is 20-40:1-4.
The invention is further improved in that the coating thickness of the vertical crack structure layer is 100 μm.
The invention is further improved in that the plasma spraying process parameters of the supersonic suspension are 380-420A current, 110-150V voltage, 60-70L/min main gas argon flow, 16-22L/min secondary gas hydrogen flow, 40mm spraying distance and 15-25 mL/min suspension powder feeding rate.
The invention is further improved in that the suspension is preheated to 180 ℃ before the vertical crack structure layer is prepared on the ScYSZ lamellar structure layer by utilizing a supersonic suspension plasma spraying process.
The invention further improves that the agglomerated ScYSZ ceramic powder is prepared by mixing nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder, a binder and water to obtain slurry, ball-milling the slurry, and then carrying out centrifugal spray granulation to agglomerate the powder to obtain the agglomerated ScYSZ ceramic powder.
A high-performance ScYSZ thermal barrier coating with a double gradual change structure comprises a ScYSZ layered structure layer and a vertical crack structure layer which are arranged on a high-temperature alloy substrate from bottom to top.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts a supersonic plasma spraying technology to prepare the ScYSZ coating containing the lamellar structure, and also adopts a supersonic suspension plasma spraying technology to continuously prepare the ScYSZ coating with a vertical crack structure on the ScYSZ coating with the lamellar structure. The nano-structure in the ScYSZ coating containing the lamellar structure can greatly reduce the heat conductivity of the coating so as to further enhance the heat insulation effect of the coating; the ScYSZ coating with the vertical crack structure increases the stress damage tolerance of the coating, reduces the thermal stress accumulation of the coating under the service condition of cold-hot alternation circulation, is easy to release the thermal stress, can effectively improve the defect of poor heat insulation performance of the layer with the vertical crack structure, has low heat conductivity and excellent high-temperature tetragonal phase stability, and is beneficial to prolonging the service life of the hot end part in higher temperature and more complex harsh environments.
Furthermore, in the preparation process of the ScYSZ coating with the double gradual change structure, the formation of a vertical crack structure of the coating is realized by adjusting the concentration of supersonic suspension slurry, the suspension powder feeding rate, the power and other preparation factors, and finally the thermal stress release of the coating under the service condition of cold-hot alternating circulation is influenced.
Drawings
FIG. 1 is a schematic structural diagram of a dual graded structural high performance ScYSZ thermal barrier coating of example 1;
FIG. 2 is an SEM image of a dual graded structure high performance ScYSZ thermal barrier coating of example 1;
FIG. 3 is a TEM morphology of the nanocrystalline ScYSZ powder of example 1;
FIG. 4 is an agglomerated ScYSZ ceramic powder of example 1;
Fig. 5 is a graph of the variation of the heat insulation temperature at 1200 ℃ for the dual graded structure coating of example 1.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The invention discloses a preparation method for continuously preparing a high-performance ScYSZ thermal barrier coating with a double gradual change structure, which comprises the following steps:
Step 1, scandium chloride hexahydrate, yttrium chloride hexahydrate, zirconium oxychloride octahydrate and citric acid are dissolved in deionized water according to the molar ratio of 0.14:0.01:0.925:1.075 to form a colorless transparent solution, then the prepared solution is placed in a water bath at 60 ℃ to be stirred for 24 hours for sol-gel reaction to obtain wet gel, and the gel product after the reaction is placed in a baking oven at 60 ℃ to be dried, so that a xerogel precursor is finally obtained.
And 2, setting the xerogel precursor in a muffle furnace at 1100 ℃ for 4 hours, and obtaining the nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder.
Mixing nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder, a binder (polyvinyl alcohol PVA) and water to obtain slurry, wherein the weight concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 50 wt%, the weight concentration of the binder polyvinyl alcohol PVA is 1 wt% and the weight concentration of deionized water is 49 wt%, ball milling the slurry through a planetary ball mill at 400r/min for 8 hours, and agglomerating the powder through a centrifugal spray granulation dryer to obtain agglomerated ScYSZ ceramic powder, wherein the agglomerated ScYSZ ceramic powder is suitable for the requirements of a supersonic plasma spraying process and has good fluidity, and the centrifugal spray granulation dryer has the technological parameters of 220 ℃ of air inlet temperature, 250Hz of centrifugal frequency and 20mL/min of feeding rate.
And 3, placing the agglomerated ScYSZ ceramic powder obtained in the step 2 into a supersonic plasma spraying powder feeding device, adopting a supersonic plasma spraying process, and adjusting supersonic plasma spraying process parameters to prepare a ScYSZ layered structure layer on the high-temperature alloy substrate, wherein the thickness of the coating is 100 mu m. The supersonic plasma spraying process parameters are 430-450A of current, 125-140V of voltage, 110-120L/min of main gas and argon flow, 15-17L/min of secondary gas and hydrogen flow, 90-110 mm of spraying distance and 14-18 g/min of powder feeding amount.
And 4, performing ball milling and dispersing on the nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder in the step 2 and absolute ethyl alcohol containing polyethylene glycol (PEG) serving as a dispersing agent to obtain a suspension, wherein the mass concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 20-40 wt%, the mass concentration of the dispersing agent is 1-4 wt%, transporting the suspension to an atomizer by using a peristaltic pump, atomizing the suspension by using the atomizer, then sending the atomized suspension into jet flow of a supersonic plasma spray gun, preparing a vertical crack structural layer on the ScYSZ lamellar structural layer by using a supersonic suspension plasma spray process, and forming the high-performance ScYSZ thermal barrier coating with a double gradual change structure, wherein the thickness of the coating is 100 mu m.
The supersonic suspension plasma spraying process parameters are that the current is 380-420A, the voltage is 110-150V, the flow of main gas and argon is 60-70L/min, the flow of secondary gas and hydrogen is 16-22L/min, the spraying distance is 40mm, the powder feeding rate of the suspension is 15-25 mL/min, and the substrate is preheated to 180 ℃ before spraying.
Example 1
The preparation method of the high-performance ScYSZ thermal barrier coating with the double gradual change structure comprises the following steps:
Step1, scandium chloride hexahydrate, yttrium chloride hexahydrate, zirconium oxychloride octahydrate and citric acid are dissolved in deionized water according to a molar ratio of 0.14:0.01:0.925:1.075 to form a colorless transparent solution, then the prepared solution is placed in a water bath at 60 ℃ to be stirred for 24 hours for sol-gel reaction to obtain wet gel, and the gel product after the reaction is placed in a baking oven at 60 ℃ to be dried, so that a xerogel precursor is finally obtained.
And 2, setting the xerogel precursor in a muffle furnace at 1100 ℃ for 4 hours, and obtaining the nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder. The TEM morphology of the powder is shown in fig. 3, and the grain size of the powder is in the range of 10-40 nm, so that the grain size is uniformly distributed.
Mixing nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder, a binder polyvinyl alcohol and water to obtain slurry, wherein the weight concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 50 wt%, the weight concentration of the binder polyvinyl alcohol PVA is 1wt% and the weight concentration of deionized water is 49 wt%, ball milling the slurry through a planetary ball mill at 400r/min for 8 hours, and agglomerating the powder through a centrifugal spray granulation dryer to obtain agglomerated ScYSZ ceramic powder, wherein the agglomerated ScYSZ ceramic powder is suitable for the requirements of a supersonic plasma spraying process and has good flowability, and as can be seen in fig. 4, the agglomerated ScYSZ ceramic powder has good sphericity and particle size within a range of 10-50 mu m. Wherein, the technological parameters of the centrifugal spray granulation dryer are that the air inlet temperature is 220 ℃, the centrifugal frequency is 250Hz, and the feeding rate is 20mL/min.
And 3, placing the agglomerated ScYSZ ceramic powder obtained in the step 2 into a supersonic plasma spraying powder feeding device, adopting a supersonic plasma spraying process, and adjusting supersonic plasma spraying process parameters to prepare a ScYSZ layered structure layer on the high-temperature alloy substrate, wherein the thickness of the coating is 100 mu m. The supersonic plasma spraying process parameters are 430A current, 138V voltage, 120L/min main gas argon flow, 16L/min secondary gas hydrogen flow, 100mm spraying distance and 16g/min powder feeding.
And 4, performing ball milling and dispersing on the nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder in the step 2 and absolute ethyl alcohol containing polyethylene glycol (PEG) serving as a dispersing agent to obtain a suspension, wherein the mass concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 20 wt%, the mass concentration of the dispersing agent is 1 wt%, transporting the suspension to an atomizer by using a peristaltic pump, atomizing the suspension by using the atomizer, then sending the atomized suspension into jet flow of a supersonic plasma spray gun, and preparing a coating with a vertical crack structure on the ScYSZ lamellar structure layer by using a supersonic suspension plasma spraying process, wherein the thickness of the coating is 100 mu m, thereby forming the high-performance ScYSZ thermal barrier coating with a double gradual change structure.
The supersonic suspension plasma spraying process parameters are that the current is 420A, the voltage is 150V, the flow of main gas and argon is 70L/min, the flow of secondary gas and hydrogen is 22L/min, the spraying distance is 40mm, the powder feeding rate of the suspension is 25mL/min, and the substrate is preheated to 180 ℃ before spraying.
The structure of the double-gradual-change-structure high-performance ScYSZ thermal barrier coating is shown in figure 1, and a layered structure layer and a vertical crack structure layer are sequentially arranged on a high-temperature alloy substrate from bottom to top.
An SEM image of the dual-graded-structure high-performance ScYSZ thermal barrier coating provided in embodiment 1 of the present invention is shown in fig. 2, and it can be seen that gray is a superalloy substrate portion, a layered-structure ScYSZ ceramic layer is formed in the middle of the drawing, and a vertical-crack-structure ScYSZ ceramic layer is formed as the uppermost layer.
Referring to the device in document (Y.Wang,Y.Bai,G.H.Liu,et al.,Wide-velocity range high-energy plasma sprayed yttria-stabilized zirconia thermal barrier coating—Part II:Structural defects and thermal-bonding properties,Surface and Coatings Technology,476(2024)130203.) for heat insulation effect test, it can be seen from the heat insulation effect curves of the coating of the double gradient structure in fig. 5 that the curves T1 and T3 respectively represent the surface temperature of the uncoated substrate and the surface temperature of the coated substrate, the curves T2 and T4 respectively represent the back surface temperature of the uncoated substrate and the back surface temperature of the coated substrate, the difference between the curve stabilization stages, i.e., (T3-T4) - (T1-T2), is the heat insulation effect of the coating, and the calculated heat insulation temperature of the obtainable coating is about 96 ℃, which indicates that the heat insulation effect of the coating of the double gradient structure is good at 1200 ℃.
Example 2
Step1, same as in example 1;
step 2, same as in example 1;
Step 3, same as in example 1;
And 4, ball-milling and dispersing nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder and absolute ethyl alcohol containing polyethylene glycol (PEG) serving as a dispersing agent to obtain a suspension, wherein the mass concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 20 wt%, the mass concentration of the dispersing agent is 1wt%, transporting the suspension to an atomizer by using a peristaltic pump, atomizing the suspension by using the atomizer, then sending the atomized suspension into jet flow of a supersonic plasma spray gun, preparing a coating with a vertical crack structure on the ScYSZ lamellar structure layer by using a supersonic suspension plasma spray process, and forming the high-performance ScYSZ thermal barrier coating with a double gradual change structure, wherein the thickness of the coating is 100 mu m.
The supersonic suspension plasma spraying process parameters are 380A current, 110V voltage, 60L/min main gas and argon flow, 16L/min secondary gas and hydrogen flow, 40mm spraying distance, 25mL/min suspension powder feeding rate, and preheating the substrate to 180 ℃ before spraying.
Example 3
Step1, same as in example 1;
step 2, same as in example 1;
Step 3, same as in example 1;
And 4, ball-milling and dispersing nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder and absolute ethyl alcohol containing polyethylene glycol (PEG) serving as a dispersing agent to obtain a suspension, wherein the mass concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 20 wt%, the mass concentration of the dispersing agent is 1wt%, transporting the suspension to an atomizer by using a peristaltic pump, atomizing the suspension by using the atomizer, then sending the atomized suspension into jet flow of a supersonic plasma spray gun, preparing a coating with a vertical crack structure on the ScYSZ lamellar structure layer by using a supersonic suspension plasma spray process, and forming the high-performance ScYSZ thermal barrier coating with a double gradual change structure, wherein the thickness of the coating is 100 mu m.
The supersonic suspension plasma spraying process parameters are that the current is 400A, the voltage is 130V, the flow of main gas and argon is 70L/min, the flow of secondary gas and hydrogen is 22L/min, the spraying distance is 40mm, the powder feeding rate of the suspension is 20mL/min, and the substrate is preheated to 180 ℃ before spraying.
Example 4
Step1, same as in example 1;
step 2, same as in example 1;
Step 3, same as in example 1;
And 4, ball-milling and dispersing nanocrystalline scandium yttrium co-stabilized zirconia (ScYSZ) ceramic powder and absolute ethyl alcohol containing polyethylene glycol (PEG) serving as a dispersing agent to obtain a suspension, wherein the mass concentration of the nanocrystalline scandium yttrium co-stabilized zirconia ceramic powder is 20 wt%, the mass concentration of the dispersing agent is 1wt%, transporting the suspension to an atomizer by using a peristaltic pump, atomizing the suspension by using the atomizer, then sending the atomized suspension into jet flow of a supersonic plasma spray gun, preparing a coating with a vertical crack structure on the ScYSZ lamellar structure layer by using a supersonic suspension plasma spray process, and forming the high-performance ScYSZ thermal barrier coating with a double gradual change structure, wherein the thickness of the coating is 100 mu m.
The supersonic suspension plasma spraying process parameters are 390A current, 110V voltage, 70L/min main gas and argon flow, 16L/min secondary gas and hydrogen flow, 40mm spraying distance, 15mL/min suspension powder feeding rate, and the substrate is preheated to 180 ℃ before spraying.
According to the method for continuously preparing the double-gradual-change-structure thermal barrier coating, the obtained layered and vertical crack double-structure ScYSZ coating has excellent structural stability and excellent high-temperature thermal shock resistance and heat insulation performance, and the thermal protection coating prepared by the method has a wide application prospect in the use of high-end equipment metal hot end parts of aeroengines and heavy gas turbines.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. It is intended that all such variations as fall within the scope of the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Claims (10)
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