CN111850454A - CMAS erosion resistant thermal barrier coating and preparation method thereof - Google Patents
CMAS erosion resistant thermal barrier coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of surface corrosion and protection of thermal barrier coatings, in particular to a CMAS corrosion resistant thermal barrier coating and a preparation method thereof. The technical scheme of the invention is that a prefabricated CMAS suspension is uniformly coated on the surface of a thermal barrier coating, and then is sintered for a period of time in a high-temperature furnace to form a compact apatite phase barrier layer on the surface. The layer has the characteristics of high melting point, high density, good phase stability and strong binding force, can fill inevitable holes and cracks on the surface of the ceramic layer in the spraying process, can plug CMAS diffusion channels in the ceramic layer, and effectively improves the CMAS erosion resistance of the thermal barrier coating.
Description
Technical Field
The invention relates to the technical field of surface corrosion and protection of thermal barrier coatings, in particular to a CMAS corrosion resistant thermal barrier coating and a preparation method thereof.
Background
The turbine engine being a turbineThe core components of aeronautical equipment such as a machine and the like have the working temperature of 1650 ℃ at most along with the continuous improvement of the thrust-weight ratio, and the maximum bearing temperature of the common single crystal superalloy blade is only 1150 ℃. Thermal Barrier coating (tbcs) and air cooling techniques are commonly used to reduce the blade surface temperature to ensure long-term engine operation at temperatures above the melting point of the blade alloy. However, with increasingly severe service environment, one of the main components is CaO, MgO and Al2O3And SiO2(CMAS) silicate corrosion substances are inevitably deposited on the surface of the blade of the turbine engine, on one hand, the silicate corrosion substances can block the film cooling hole on the surface of the blade, so that the cooling failure is caused, and the temperature field and the stress field distribution on the surface of the blade are changed; on the other hand, the CMAS molten at high temperature reacts with the ceramic layer material of the thermal barrier coating and permeates into the coating, so that the sintering rate of the coating is accelerated, phase change instability and volume change are caused, further, great internal stress is generated, the coating is cracked and even peeled off, the protection failure of the thermal barrier coating is caused, and the service life of the engine is finally shortened rapidly. Furthermore, deposition of CMAS may cause weight gain in the blades, leading to increased engine power consumption.
Common protection methods for resisting CMAS corrosion mainly comprise; spraying a compact aluminum oxide coating on the surface of the thermal barrier coating ceramic layer, and sintering at high temperature to form a compact physical barrier layer; spraying a protective coating which is not wetted by molten CMAS on the surface of the thermal barrier coating ceramic layer; cladding the surface of the ceramic layer of the thermal barrier coating by means of laser processing and the like, so as to block gaps and cracks on the surface of the coating and improve the surface density of the coating; in addition, the method for optimizing the spraying process and avoiding the vertical growth of columnar crystals in the coating is also provided. Although the methods have the beneficial effects, the methods have the limitations of weak binding force, complicated process, poor stability, high cost, easy change of the heat insulation performance of the coating, use of expensive equipment and the like, and most of the methods still stay in the laboratory stage.
Disclosure of Invention
In order to effectively solve the problems of failure and the like of the thermal barrier coating caused by CMAS corrosion in service, 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 device for implementing the invention mainly comprises plasma spraying equipment and a high-temperature furnace, and different equipment for implementing different subsequent treatments.
The technical scheme of the invention is that a prefabricated CMAS suspension is uniformly coated on the surface of a thermal barrier coating, and then is sintered for a period of time in a high-temperature furnace to form a compact apatite phase barrier layer on the surface. The layer has the characteristics of high melting point, high density, good phase stability and strong binding force, can fill inevitable holes and cracks on the surface of the ceramic layer in the spraying process, can plug CMAS diffusion channels in the ceramic layer, and effectively improves the CMAS erosion resistance of the thermal barrier coating.
A thermal barrier coating resistant to CMAS erosion, characterized by: the thermal barrier coating is made of a bonding layer CoCrAlYTaSi material from bottom to top, and the ceramic layer is made of a rare earth zirconate material (the chemical formula of the ceramic layer is RE)2Zr2O7RE is 1-2 different elements of Yb, La, Ce and Gd, the mole ratio of RE element to total elements is less than 20 percent), and the apatite phase barrier layer. Wherein the thickness of the bonding layer is 50-150 μm, the thickness of the ceramic layer is 100-300 μm, and the thickness of the apatite phase barrier layer is 5-10 μm.
The invention relates to a preparation method of a CMAS erosion resistant thermal barrier coating, which is characterized by comprising the following specific preparation steps:
the method comprises the following steps: grinding, polishing and sand blasting the surface of a high-temperature alloy sample to be processed;
step two: preparing a CoCrAlYTaSi bonding layer on the surface of a sample by adopting a plasma spraying process, and controlling the thickness of the bonding layer to be 50-150 mu m by optimizing parameters of the spraying process;
step three: carrying out vacuum heat treatment and surface sand blasting treatment on the sample sprayed with the bonding layer;
step four: spraying ceramic layer rare earth zirconate materials (with the chemical formula of RE) on the surface of the sample treated in the step three by adopting a plasma spraying method2Zr2O7RE is 1-3 different elements of Yb, La, Ce and Gd, the mole ratio of the RE element to the total elements is less than 20 percent, and the thickness of the ceramic layer is controlled to be 100-300 mu m by optimizing spraying process parameters;
step five: grinding and polishing the surface of the ceramic layer prepared in the step four;
step six: the weighed proportions are 22% CaO, 19% MgO, 14% Al2O3And 45% SiO2Adding absolute ethyl alcohol according to the mass ratio of the powder to the absolute ethyl alcohol of 1:10, and ball-milling for 6-8 hours in a ball mill to ensure that the powder and the absolute ethyl alcohol are uniformly mixed to obtain mixed slurry;
step seven: putting the mixed slurry obtained in the step six into a drying oven at the temperature of 120 ℃, and drying for 6-10 hours to obtain dry powder;
step eight: putting the dry powder in the step seven into a high-temperature furnace at 1300 ℃ to calcine for 8 hours to obtain a block product;
step nine: adding absolute ethyl alcohol into the block product obtained in the step eight according to the mass ratio of the block to the absolute ethyl alcohol of 1:10, and performing ball milling for 24 hours in a ball mill to obtain mixed slurry:
step ten: and (4) putting the mixed slurry obtained in the step nine into a drying oven at the temperature of 120 ℃, and drying for 10 hours to obtain dry powder.
Step eleven: grinding the dried powder obtained in the step ten, and sieving the ground powder with a 200-mesh sieve to obtain the required CMAS powder;
step twelve: mixing the CMAS powder and absolute ethyl alcohol according to the mass ratio of 1:10, and continuously stirring until the mixture is uniform to obtain a required suspension;
step thirteen: mixing the suspension liquid in the step twelve with the concentration of 10-30 mg/cm2Coating density, namely coating the coating density on the surface of the coating sample prepared in the step five;
fourteen steps: and calcining the sample obtained in the step thirteen at 1180-1280 ℃ for 0.5-2 hours, cooling to room temperature, and taking out to obtain the multilayer thermal barrier coating.
The invention has the advantages that:
1. after the CMAS suspension prepared by the invention is calcined at 1180-1280 ℃ for 0.5-2 hours, only an apatite phase barrier layer is generated on the surface layer of the ceramic layer, and the apatite phase barrier layer cannot permeate into pores of the ceramic coating and cannot cause the peeling of the ceramic coating; the apatite phase barrier layer is CaO or SiO2Reaction products with the ceramic layer material of the thermal barrier coating. Such as Ca2Gd8(SiO4)6O and the like
2. The CMAS-resistant layer has a compact structure, a high melting point and good high-temperature phase stability, and can effectively block a CMAS diffusion channel in a thermal barrier coating ceramic layer and prevent CMAS from further corroding the thermal barrier coating;
3. the CMAS-resistant layer has good interface compatibility with a ceramic layer, strong binding force and high interface matching degree, and has no influence on the heat-insulating property and the service life of the original thermal barrier coating;
4. although the thermal barrier coating has a multi-layer thermal barrier coating structure, the weight gain is small, and the conventional spraying technology such as atmospheric plasma spraying and an electron beam vapor deposition method can be adopted;
5. the invention has simple process, low cost, simple related equipment and convenient practice.
Drawings
FIG. 1 is a partial scan of a ceramic layer and a CMAS-resistant layer of a thermal barrier coating according to example 1, and an apatite phase barrier layer having a thickness of 5.8 μm was prepared.
FIG. 2 is a partial scan of a ceramic layer and a CMAS-resistant layer of a thermal barrier coating in example 2,
the thickness of the prepared apatite phase barrier layer was 7.2 μm. .
FIG. 3 is a partial scan of a ceramic layer and a CMAS-resistant layer of a thermal barrier coating in example 3,
the thickness of the prepared apatite phase barrier layer was 9.6 μm. .
Detailed Description
Embodiments of the present invention will now be described.
Example 1
(1) The surface scratches of 5 samples of the high-temperature alloy GH4586 are respectively ground by 100-mesh, 500-mesh and 1000-mesh sand paper to remove, then a diamond polishing agent is used for polishing the samples to a mirror surface, then surface sand blasting treatment is carried out to form roughness on the surfaces, a CoCrAlYTaSi bonding layer is prepared by adopting a plasma spraying method, a spraying process (power is 40kW, main gas flow is 50L/min, auxiliary gas flow is 25L/min, powder delivery rate is 2r/min, carrier gas flow is 7L/min, spraying distance is 80 mu m) is optimized, spraying time is 30s, the thickness of the bonding layer is controlled to be 80 mu m, and then vacuum diffusion heat treatment (900 ℃) and surface sand blasting treatment are carried out on the prepared bonding layer to improve the surface roughness.
(2) Gd is sprayed on the surface of the sample with the prepared bonding layer by adopting a plasma spraying method2Zr2O7And controlling the thickness of the ceramic layer to be 150 microns by optimizing spraying process parameters (power is 60kW, main gas flow is 60L/min, auxiliary gas flow is 30L/min, powder delivery rate is 5r/min, carrier gas flow is 10L/min, spraying distance is 60 microns) and spraying time is 60s, and then grinding and polishing the surface of the prepared ceramic layer to a mirror surface.
(3) Weighing 22% of CaO, 19% of MgO and 14% of Al in percentage by mass2O3And 45% SiO2Adding 2000g of absolute ethyl alcohol into 200g of the mixed powder, ball-milling for 6 hours in a ball mill to ensure that the mixed powder is uniformly mixed to obtain mixed slurry, and then putting the mixed slurry into a drying oven at 120 ℃ to dry for 6 hours to obtain dry powder. And calcining the obtained dry powder in a high-temperature furnace at 1300 ℃ for 8h, cooling to room temperature along with the furnace, adding 2000g of absolute ethyl alcohol, ball-milling in a ball mill for 24h, taking out, and drying in a drying oven at 120 ℃ for 10h to obtain the dry powder. The powder is subsequently milled. And sieving with a 200-mesh sieve to obtain uniform and fine CMAS powder. And mixing the prepared CMAS powder with absolute ethyl alcohol according to the mass ratio of 1:10, and continuously stirring until the mixture is uniform to obtain CMAS suspension.
(4) The CMAS suspension was suspended at 20mg/cm2The coating density of (a) was applied to the surface of the polished ceramic layer sample. The sample was then calcined in a high temperature furnace at 1180 ℃ for 0.6h and then cooled in the furnace to room temperature to give a dense apatite phase CMAS corrosion resistant layer of 5.8 μm thickness.
(5) And carrying out a CMAS corrosion test on the prepared thermal barrier coating. Experiments show that: after 24h, 1250 ℃ CMAS corrosion testing, the mean depth of diffusion of the CMAS was only 41.2 μm, a significant improvement over 80 μm for the untreated thermal barrier coating.
Example 2
(1) The surface scratches of 5 samples of the high-temperature alloy GH4586 are respectively ground by 100-mesh, 500-mesh and 1000-mesh sand paper to remove, then a diamond polishing agent is used for polishing the samples to a mirror surface, then surface sand blasting treatment is carried out to form roughness on the surfaces, a CoCrAlYTaSi bonding layer is prepared by adopting a plasma spraying method, a spraying process (power is 40kW, main gas flow is 50L/min, auxiliary gas flow is 25L/min, powder delivery rate is 2r/min, carrier gas flow is 7L/min, spraying distance is 80 mu m) is optimized, spraying time is 30s, the thickness of the bonding layer is controlled to be 80 mu m, and then vacuum diffusion heat treatment (900 ℃) and surface sand blasting treatment are carried out on the prepared bonding layer to improve the surface roughness.
(2) Spraying (La) on the prepared bonding layer surface by adopting a plasma spraying method0.5Gd0.5)2Zr2O7And controlling the thickness of the ceramic layer to be 180 mu m by optimizing spraying process parameters (power is 60kW, main gas flow is 60L/min, auxiliary gas flow is 30L/min, powder feeding rate is 5r/min, carrier gas flow is 10L/min, spraying distance is 60 mu m) and spraying time is 80s, and then grinding and polishing the surface of the prepared ceramic layer to a mirror surface.
(3) Weighing 22% of CaO, 19% of MgO and 14% of Al in percentage by mass2O3And 45% SiO2Adding 2000g of absolute ethyl alcohol into 200g of the mixed powder, ball-milling for 6 hours in a ball mill to ensure that the mixed powder is uniformly mixed to obtain mixed slurry, and then putting the mixed slurry into a drying oven at 120 ℃ to dry for 6 hours to obtain dry powder. And calcining the obtained dry powder in a high-temperature furnace at 1300 ℃ for 8h, cooling to room temperature along with the furnace, adding 2000g of absolute ethyl alcohol, ball-milling in a ball mill for 24h, taking out, and drying in a drying oven at 120 ℃ for 10h to obtain the dry powder. The powder is subsequently milled. And sieving with a 200-mesh sieve to obtain uniform and fine CMAS powder. Mixing the prepared CMAS powder with absolute ethyl alcohol according to the mass ratio of 1:10The mixture was stirred continuously until homogeneous to give a CMAS suspension.
(4) The CMAS suspension was suspended at 20mg/cm2The coating density of (a) was applied to the surface of the polished ceramic layer sample. The sample was then calcined in a 1240 ℃ high temperature furnace for 1h and then furnace cooled to room temperature to give a dense apatite phase CMAS corrosion resistant layer of 7.2 μm thickness.
(5) And carrying out a CMAS corrosion test on the prepared thermal barrier coating. Experiments show that: after 24h, 1250 ℃ CMAS corrosion testing, the mean depth of diffusion of the CMAS was only 30.2 μm, a significant improvement over the 80 μm of the untreated thermal barrier coating.
Example 3
(1) The surface scratches of 5 samples of the high-temperature alloy GH4586 are respectively ground by 100-mesh, 500-mesh and 1000-mesh sand paper to remove, then a diamond polishing agent is used for polishing the samples to a mirror surface, then surface sand blasting treatment is carried out to form roughness on the surfaces, a CoCrAlYTaSi bonding layer is prepared by adopting a plasma spraying method, a spraying process (power is 40kW, main gas flow is 50L/min, auxiliary gas flow is 25L/min, powder delivery rate is 2r/min, carrier gas flow is 7L/min, spraying distance is 80 mu m) is optimized, spraying time is 30s, the thickness of the bonding layer is controlled to be 80 mu m, and then vacuum diffusion heat treatment (900 ℃) and surface sand blasting treatment are carried out on the prepared bonding layer to improve the surface roughness.
(2) Spraying (Gd) on the surface of the prepared bonding layer by adopting a plasma spraying method0.7Yb0.3)2Zr2O7And controlling the thickness of the ceramic layer to be 200 mu m by optimizing spraying process parameters (power is 60kW, main gas flow is 60L/min, auxiliary gas flow is 30L/min, powder feeding rate is 5r/min, carrier gas flow is 10L/min, spraying distance is 60 mu m) and spraying time is 100s, and then grinding and polishing the surface of the prepared ceramic layer to a mirror surface.
(3) Weighing 22% of CaO, 19% of MgO and 14% of Al in percentage by mass2O3And 45% SiO2Adding 2000g of absolute ethyl alcohol into 200g of the mixed powder, ball-milling for 6h in a ball mill to ensure that the mixed powder is uniformly mixed to obtain mixed slurry, and then putting the mixed slurry into a drying oven at 120 ℃ to dry for 6h to obtain dried powderAnd (3) powder. And calcining the obtained dry powder in a high-temperature furnace at 1300 ℃ for 8h, cooling to room temperature along with the furnace, adding 2000g of absolute ethyl alcohol, ball-milling in a ball mill for 24h, taking out, and drying in a drying oven at 120 ℃ for 10h to obtain the dry powder. The powder is subsequently milled. And sieving with a 200-mesh sieve to obtain uniform and fine CMAS powder. And mixing the prepared CMAS powder with absolute ethyl alcohol according to the mass ratio of 1:10, and continuously stirring until the mixture is uniform to obtain CMAS suspension.
(4) The CMAS suspension was suspended at 20mg/cm2The coating density of (a) was applied to the surface of the polished ceramic layer sample. The sample was then calcined in a high temperature furnace at 1280 ℃ for 2h and then furnace cooled to room temperature to give a dense apatite phase CMAS corrosion resistant layer of 9.6 μm thickness.
(5) And carrying out a CMAS corrosion test on the prepared thermal barrier coating. Experiments show that: after 24h, 1250 ℃ CMAS corrosion testing, the mean depth of diffusion of the CMAS was only 23.6 μm, a significant improvement over the 80 μm of the untreated thermal barrier coating.
Claims (10)
1. The thermal barrier coating is characterized by consisting of a bonding layer, a ceramic layer and an apatite phase barrier layer from bottom to top.
2. The CMAS erosion resistant thermal barrier coating of claim 1, wherein the bond layer is a CoCrAlYTaSi material; the ceramic layer is made of rare earth zirconate materials with a chemical formula of RE2Zr2O7RE is 1-2 different elements of Yb, La, Ce and Gd, and the molar ratio of RE element to the total elements is less than 20%; the thickness of the bonding layer is 50-150 μm, the thickness of the ceramic layer is 100-300 μm, and the thickness of the apatite phase barrier layer is 5-10 μm.
3. The method of claim 1, wherein the CMAS erosion resistant thermal barrier coating is prepared by a thermal barrier coating process,
the method comprises the following steps: grinding, polishing and sand blasting the surface of a high-temperature alloy sample to be processed;
step two: preparing a CoCrAlYTaSi bonding layer on the surface of a sample by adopting a plasma spraying process, and controlling the thickness of the bonding layer to be 50-150 mu m by optimizing parameters of the spraying process;
step three: carrying out vacuum heat treatment and surface sand blasting treatment on the sample sprayed with the bonding layer;
step four: spraying a ceramic layer rare earth zirconate material on the surface of the sample treated in the step three by adopting a plasma spraying method, and controlling the thickness of the ceramic layer to be 100-300 mu m by optimizing spraying process parameters;
step five: grinding and polishing the surface of the ceramic layer prepared in the step four;
step six: the weighed proportions are 22% CaO, 19% MgO, 14% Al2O3And 45% SiO2Adding absolute ethyl alcohol into the mixed powder, and performing ball milling in a ball mill to ensure that the mixed powder is uniformly mixed to obtain mixed slurry;
step seven: drying the mixed slurry obtained in the step six in a drying box to obtain dry powder;
step eight: placing the dry powder in the seventh step into a high-temperature furnace for calcining to obtain a block product;
step nine: adding absolute ethyl alcohol into the block product obtained in the step eight, and performing ball milling in a ball mill to obtain mixed slurry:
step ten: drying the mixed slurry obtained in the step nine in a drying oven to obtain dry powder;
step eleven: grinding and sieving the dried powder obtained in the step ten to obtain the required CMAS powder;
step twelve: mixing the CMAS powder and absolute ethyl alcohol, and continuously stirring until the mixture is uniform to obtain a required suspension;
step thirteen: coating the suspension liquid prepared in the step twelve on the surface of the coating sample prepared in the step five;
fourteen steps: and cooling the calcined sample to room temperature, and taking out to obtain the CMAS corrosion resistant thermal barrier coating.
4. The preparation method of the CMAS erosion resistant thermal barrier coating as claimed in claim 3, wherein in the sixth step, the mass ratio of the mixed powder to the absolute ethyl alcohol is 1:10, and the ball milling time is 6-8 h.
5. The method for preparing a thermal barrier coating resistant to CMAS erosion of claim 3, wherein in step seven, the drying temperature is 120 ℃ and the drying time is 6-10 h.
6. The method for preparing a thermal barrier coating resistant to CMAS erosion of claim 3, wherein in step eight, the calcination temperature is 1300 ℃ and the calcination time is 8 hours.
7. The method for preparing a thermal barrier coating resistant to CMAS erosion of claim 3, wherein in step nine, the mass production is in a mass ratio of 1:10 with absolute ethanol and the ball milling time is 24 h.
8. The method for preparing a thermal barrier coating resistant to CMAS erosion of claim 3, wherein in the tenth step, the drying temperature is 120 ℃ and the drying time is 10 hours; in the eleventh step, 200 mesh sieve is sieved.
9. The method of claim 3, wherein in step twelve, the CMAS powder to absolute ethyl alcohol mass ratio is 1: 10.
10. The method for preparing a thermal barrier coating resistant to CMAS erosion as claimed in claim 3, wherein in step thirteen, the coating density is 10-30 mg/cm2(ii) a In the fourteenth step, the calcination temperature is 1180-1280 ℃, and the calcination time is 0.5-2 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113773075A (en) * | 2021-09-22 | 2021-12-10 | 湘潭大学 | CMAS erosion resistant zirconium-tantalum thermal barrier coating material and preparation method thereof |
| CN114671686A (en) * | 2022-04-21 | 2022-06-28 | 昆明理工大学 | Preparation method of anti-permeation ceramic material capable of rapidly reacting with low-melting-point oxide |
| CN114920558A (en) * | 2022-04-24 | 2022-08-19 | 昆明理工大学 | Low-melting-point oxide permeation resistant ceramic and preparation method and application thereof |
| CN116477970A (en) * | 2023-03-05 | 2023-07-25 | 广西大学 | Preparation method of CMAS corrosion-resistant in-situ generated rare earth apatite phase compact reaction layer |
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| CN114671686B (en) * | 2022-04-21 | 2023-09-22 | 昆明理工大学 | Preparation method of ceramic material capable of fast reacting with low-melting-point oxide and resisting permeation |
| CN114920558A (en) * | 2022-04-24 | 2022-08-19 | 昆明理工大学 | Low-melting-point oxide permeation resistant ceramic and preparation method and application thereof |
| CN116477970A (en) * | 2023-03-05 | 2023-07-25 | 广西大学 | Preparation method of CMAS corrosion-resistant in-situ generated rare earth apatite phase compact reaction layer |
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