CN117987759A - Anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder and preparation method thereof - Google Patents
Anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder and preparation method thereof Download PDFInfo
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- CN117987759A CN117987759A CN202410186273.3A CN202410186273A CN117987759A CN 117987759 A CN117987759 A CN 117987759A CN 202410186273 A CN202410186273 A CN 202410186273A CN 117987759 A CN117987759 A CN 117987759A
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- 239000000843 powder Substances 0.000 title claims abstract description 89
- 238000005245 sintering Methods 0.000 title claims abstract description 57
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 239000012720 thermal barrier coating Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 238000007750 plasma spraying Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
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- 239000007787 solid Substances 0.000 claims description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 abstract description 82
- 230000004888 barrier function Effects 0.000 abstract description 12
- 238000009413 insulation Methods 0.000 abstract description 4
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- 230000003247 decreasing effect Effects 0.000 description 4
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Abstract
The invention belongs to the technical field of coatings, and particularly relates to an anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder and a preparation method thereof. The powder inner shell is Yttria Stabilized Zirconia (YSZ) and the outer shell is La 2Zr2O7 (LZO). The ceramic layer takes YSZ as a framework and LZO as a barrier group for resisting sintering. The invention prepares the sandwich type sheet microstructure barrier group ceramic layer of LZO+YSZ+LZO based on a plasma spraying process, blocks the sintering mass transfer path between YSZ sheets and greatly improves the sintering resistance of the ceramic layer. The sandwich type lamellar microstructure 'barrier group' ceramic layer can keep high sintering resistance, high heat insulation and high strain tolerance at a high temperature higher than the traditional service temperature, and can remarkably improve the service temperature of the thermal barrier coating and further improve the efficiency of the gas turbine.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder and a preparation method thereof.
Background
Thermal Barrier Coatings (TBCs) are a high temperature, high thermal and corrosion resistant ceramic coating material that is applied to the surface of an aircraft engine turbine blade. With the rapid development of aerospace technology, the requirements on the inlet air temperature of an engine combustion chamber and a gas turbine are continuously increased. The main challenges faced by thermal barrier coatings are sintering problems at high temperatures, which can lead to reduced porosity, increased thermal conductivity, and increased elastic modulus of the coating, which can lead to changes in residual stresses within the coating and promote the propagation of microcracks. The reduction of microscopic gaps can significantly impair the thermal insulation capability and strain tolerance of the ceramic layer, affecting the service life of the ceramic coating.
In a high temperature working environment, the particle surface of YSZ changes due to sintering, and protrusions between particles increase, resulting in the joining of adjacent sheets. In order to improve the sintering resistance, a method for preventing such inter-sheet diffusion bridging is required. However, the existing research has not effectively solved the problem from the sintering mechanism. Rare earth zirconate is a novel thermal barrier ceramic material which is expected to replace YSZ at present, has excellent sintering resistance and phase stability, but has lower fracture toughness than YSZ. To overcome this problem, it is contemplated to combine the good coefficient of thermal expansion and fracture toughness of YSZ with La 2Zr2O7 high temperature thermal stability and low thermal conductivity to effectively improve the sintering resistance of the YSZ layer and the overall performance of the thermal barrier coating, and thus the gas turbine efficiency.
In recent years, core-shell nanostructured materials have received attention for their unique properties and controllable physicochemical properties, in which the core is surrounded by a shell, and performance optimization is achieved by controlling the composition between the shell and the core. Based on the above, it is necessary to develop an anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder to improve the service problem of TBCs.
Disclosure of Invention
The invention aims to provide an anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder and a preparation method thereof, wherein a ceramic layer of the anti-sintering thermal barrier coating is prepared by adopting the double-shell microstructure composite ceramic powder, an inner shell of the powder is Yttria Stabilized Zirconia (YSZ), and an outer shell of the powder is La 2Zr2O7 (LZO). The ceramic layer of the anti-sintering thermal barrier coating is prepared by adopting a plasma spraying process, takes YSZ as a framework, takes LZO as an anti-sintering barrier group and consists of a plurality of sandwich type lamellar microstructures of LZO+YSZ+LZO. Based on the principle of blocking the mass transfer path of the interlayer sintering of the YSZ sheet, the method aims to block the bridging path between YSZ flat particles in the high temperature process through the LZO barrier group, achieve the purposes of resisting sintering and improving service temperature, and realize the preparation of a new generation of high-efficiency gas turbine thermal barrier coating.
The invention aims at realizing the following technical scheme:
The invention provides a sintering-resistant thermal barrier coating, wherein a ceramic layer of the sintering-resistant thermal barrier coating consists of a plurality of sandwich-type lamellar microstructures of LZO+YSZ+LZO, and is prepared by adopting double-shell microstructure composite ceramic powder, wherein the inner shell of the double-shell microstructure composite ceramic powder is YSZ particles, the outer shell of the double-shell microstructure composite ceramic powder is La 2Zr2O7 particles, and the mass percentage of YSZ is 8 wt%.
The invention also provides a preparation method of the anti-sintering thermal barrier coating, which comprises the following steps:
(1) Drying YSZ powder and La 2Zr2O7 powder respectively in a hot oven, wherein the temperature of the oven is set to 100 ℃, and the drying time is set to 2h so as to remove water in the powder;
(2) And spraying the fused La 2Zr2O7 powder by using an atmospheric plasma spraying device by using plasma as a heat source, and colliding the solid YSZ powder with the sprayed fused La 2Zr2O7 particles by using a powder feeder to form YSZ@La 2Zr2O7 double-shell microstructure powder with YSZ as an inner shell and La 2Zr2O7 as an outer shell, so that the mechanical coating state is realized.
Further, in the step (2), spraying the melted La 2Zr2O7 powder by using the atmospheric plasma spraying device further includes setting a plasma spraying process parameter, setting a powder feeding speed and a spraying time, and performing a spraying treatment.
Furthermore, the atmosphere plasma spraying equipment adopts argon as main flow gas, hydrogen as auxiliary gas and nitrogen as powder feeding gas for spraying powder.
Further, the plasma spraying process parameters are that the current is 600-650A, the voltage is 60-70V, the argon flow is 45.2 SLM, and the hydrogen flow is 5.6 SLM.
Further, the powder feeding speed is 6.0 r/min, and the thickness of the ceramic layer is 300-600 mu m.
Further, in the step (2), the angle formed by the gun head of the atmospheric plasma spraying device and the spray head of the powder feeder in the mixing process is any angle of 60-120 degrees, and the distance is 7-10 cm.
The invention has the beneficial effects that:
The invention discloses an anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder and a preparation method thereof, wherein an LZO+YSZ+LZO sandwich type lamellar microstructure barrier group ceramic layer is prepared based on a plasma spraying process, the thought of a sintering mass transfer path between YSZ sheets is blocked, and the sintering resistance of the ceramic layer is greatly improved. The structure can maintain high heat insulation performance and strain tolerance at high temperature, and is beneficial to improving the stability and reliability of the coating under extreme environments. The lifetime of this new thermal barrier coating will be longer than conventional coatings due to reduced performance degradation caused by sintering, which design provides new possibilities for high performance development of the thermal barrier coating. The preparation of the composite ceramic powder based on the double-shell microstructure not only optimizes the microcosmic appearance and structural characteristics of the thermal barrier coating, such as porosity and shrinkage, so that the sintering resistance of the YSZ layer is obviously improved, and the performance and stability of the thermal barrier ceramic coating in a high-temperature environment are enhanced. The application of such powder thermal barrier coatings to engine components will help to significantly extend the useful life of these components in high temperature environments, particularly for use in aircraft engines and other high performance combustion equipment.
Drawings
FIG. 1 is a schematic view of a La 2Zr2O7 coated YSZ flat particle film barrier group, wherein FIG. 1a is a schematic view, and FIG. 1b is a cross-sectional view of an actual spray coating;
FIG. 2 is a coating mechanism diagram of a product prepared by a mechanical coating method;
FIG. 3 is a graph of the surface topography of YSZ subjected to high temperature heat treatment;
FIG. 4 is a surface topography of a YSZ@LZO structural specimen subjected to high temperature heat treatment;
FIG. 5 is a graph showing the comparison of the porosity and shrinkage changes induced by sintering after heat treatment;
FIG. 6 is a graph showing the microhardness of a test specimen according to the heat treatment time.
Detailed Description
The invention aims to provide a preparation method of an anti-sintering thermal barrier coating based on double-shell microstructure composite ceramic powder, which comprises the following steps: mixing 8YSZ and La 2Zr2O7 powder, performing high-temperature heat treatment by using an atmospheric plasma spraying device after a mechanical coating method to obtain powder, wherein the inner shell is yttria-stabilized zirconia (YSZ), the outer shell is La 2Zr2O7 (LZO), the ceramic layer takes YSZ as a framework, and LZO is an anti-sintering barrier group. The method specifically comprises the following steps:
Step one: using plasma as a heat source, and spraying melted LZO powder at a proper angle and distance through a powder feeder;
step two: mixing YSZ powder with the sprayed molten LZO particles by using another powder feeder to form YSZ@LZO ceramic layer powder, and taking on a mechanical coating state;
step three: carrying out high-temperature heat treatment on the prepared YSZ@LZO ceramic layer powder, and simulating a sintering process;
step four: performance tests, including phase and microstructure analysis, porosity, shrinkage and microhardness tests, were performed to evaluate their resistance to sintering.
The following examples serve to further illustrate the invention but are not limited thereto.
Example 1
A composite ceramic powder based on a double-shell microstructure is prepared by adopting plasma spraying equipment to carry out mechanical cladding, setting proper plasma spraying technological parameters, placing YSZ powder in a common powder feeder, placing La 2Zr2O7 powder in a forced powder feeder, changing the angle between a plasma spray gun and the YSZ powder feeder, and preparing 60 DEG, 90 DEG and 120 DEG YSZ@LZO powder. The preparation process comprises the following steps:
(1) Drying YSZ powder and La 2Zr2O7 powder respectively in a hot oven, wherein the temperature of the oven is set to 100 ℃, and the drying time is set to 2h so as to remove water in the powder;
(2) Using plasma as a heat source, spraying melted La 2Zr2O7 powder by using an atmospheric plasma spraying device, adopting argon as main flow gas, adopting auxiliary gas as hydrogen gas and adopting nitrogen as powder feeding gas in the spraying process, setting parameters of the atmospheric plasma spraying device as current 650A, voltage 69V, argon speed of 45.2 SLM, hydrogen speed of 5.6 SLM and powder feeding speed of 6.0 r/min,
(3) And mixing YSZ powder with sprayed fused La 2Zr2O7 particles by using a powder feeder, controlling the angles of a gun head of the atmospheric plasma spraying equipment and a spray head of the powder feeder to be 60 degrees, 90 degrees and 120 degrees, the distance to be 7-8 cm, and the spraying time to be 10 min, and respectively preparing three-angle YSZ@La 2Zr2O7 powder, wherein the mass percent of YSZ is 8 wt%.
After the prepared YSZ@La 2Zr2O7 powder is pressed, high-temperature heat treatment is carried out on the prepared YSZ@La 2Zr2O7 powder in a box-type resistance furnace, the surface microscopic morphology of a sintered sample is observed, and the prepared YSZ@LZO sample is compared with the result of 8YSZ, so that the high-temperature sintering performance of the powder is further studied. The schematic diagram of the La 2Zr2O7 coated YSZ flat particle film barrier group is shown in fig. 1a, the cross-sectional morphology of the thermal barrier coating is shown in fig. 1b, the white contrast in the diagram is La 2Zr2O7, and the gray contrast is YSZ. La 2Zr2O7 is inserted between YSZ to prevent YSZ sintering. The coating mechanism diagram of the mechanical coating method for preparing the ceramic layer taking La 2Zr2O7 as a sintering barrier by using the powder with the double-shell structure is shown in figure 2.
After 200 hours of high temperature treatment (1200 ℃) significant interconnections between grains of conventional YSZ material occurred, transitioning from the original network structure to a more dense morphology. This change indicates that YSZ materials undergo severe densification after prolonged heat treatment, showing significant sintering phenomena. Densification by sintering is one of the main reasons for degradation of material properties under high temperature conditions, especially in applications where it is desirable to maintain a certain porosity to maintain thermal insulation properties. In contrast, ysz@la 2Zr2O7 samples prepared by the mechanical cladding method and sprayed at angles of 60 °, 90 ° and 120 °, respectively, did not exhibit a severe sintering phenomenon similar to YSZ under the same heat treatment conditions. These structural samples did not undergo dense inter-grain bonding or large-area grain-tight agglomeration after heat treatment. This result clearly indicates that ysz@la 2Zr2O7 powder exhibits a stronger sintering resistance at high temperatures than conventional YSZ powder. The microscopic morphologies of the YSZ and ysz@la 2Zr2O7 samples after the high temperature heat treatment are shown in fig. 3 and 4.
Example 2
After the YSZ@La 2Zr2O7 powder prepared in the example 1 is pressed, the powder is subjected to high-temperature heat treatment in a box-type resistance furnace, the porosity of a sintered sample is analyzed, and the sample for preparing the YSZ@La 2Zr2O7 is compared with the result of 8YSZ, so that the high-temperature sintering performance of the composite ceramic powder based on the double-shell microstructure is further studied.
The porosity of the sample of this example was distributed between 17-31% before and after 200 h heat treatment, and the porosity of all three samples was substantially uniform in decreasing trend, with an average decreasing amplitude of about 10%. In contrast, the conventional YSZ coating porosity overall decreases by about 18%, with sample porosity decreasing by only about 55% of YSZ. The porosity of the YSZ samples was higher than that of all three samples at the first 20 hours of heat treatment, but then the porosity of YSZ was rapidly decreased, indicating that densification of the tissue was very severe. In sharp contrast, the samples did not exhibit significant densification even after prolonged heat treatment. This result clearly shows that the ceramic samples of the present invention have better sintering resistance in high temperature environments than conventional YSZ coatings. The porosity vs. graph is shown in FIG. 5 (a).
Example 3
After the YSZ@La 2Zr2O7 powder prepared in the example 1 is pressed, the powder is subjected to high-temperature heat treatment in a box-type resistance furnace, the shrinkage rate of a sintered sample is analyzed, and the sample for preparing the YSZ@La 2Zr2O7 is compared with the result of 8YSZ, so that the high-temperature sintering performance of the composite ceramic powder based on the double-shell microstructure is further studied.
The final shrinkage rates of YSZ/LZO of the invention were 2.56%, 2.41% and 2.38%, respectively. The significant difference in the shrinkage of conventional YSZ is as high as 4.62%, which reveals the superiority of the coating prepared according to the present invention over conventional YSZ coatings in terms of anti-sintering properties. The lower shrinkage indicates that the bond strength between YSZ particles is relatively weak in YSZ/LZO structures. This is because the outer LZO film effectively prevents bridging and incorporation between YSZ particles, a common phenomenon in sintering processes. During sintering, the material generally undergoes density increase and porosity reduction, while YSZ/LZO structures can effectively slow down the process due to their unique construction. The shrinkage ratio of the two ceramic powders after the high temperature heat treatment is compared with that shown in FIG. 5 (b).
Example 4
After the YSZ@La 2Zr2O7 powder prepared in the example 1 is pressed, the powder is subjected to high-temperature heat treatment in a box-type resistance furnace, the microhardness of a sintered sample is analyzed, and the sample for preparing the YSZ@La 2Zr2O7 is compared with the result of 8YSZ, so that the high-temperature sintering performance of the composite ceramic powder based on the double-shell microstructure is further studied.
The hardness of the samples prepared in three different spraying directions in the invention shows positive correlation increase in the heat treatment process, the hardness range is 400-800 HV 0.5, the hardness increases along with the extension of the heat treatment time, and particularly the microhardness values of the three samples are respectively increased by 183%, 169% and 167%. In contrast, the hardness range of the traditional YSZ coating under the same heat treatment condition is 700-1100 HV 0.5, and the hardness value of the traditional YSZ coating in each time period is obviously higher than that of the YSZ@LZO structure although the variation amplitude of the traditional YSZ coating is similar to that of a sample. The sample tissue keeps more pores in the heat treatment process and resists densification, so that the tissue structure is more loose relative to YSZ, the hardness value is obviously lower than YSZ, the serious densification is caused by serious decrease of the porosity of YSZ and increase of the volume shrinkage, and the increase of the grain size continuously increases the compactness of YSZ, so that the higher microhardness value is brought. In conclusion, compared with YSZ in the heat treatment process, the YSZ@La 2Zr2O7 powder provided by the invention has obvious heat stability and sintering resistance. The hardness of the two ceramic powders after the high temperature heat treatment is compared with that shown in FIG. 6.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (7)
1. The sintering-resistant thermal barrier coating is characterized in that a ceramic layer of the sintering-resistant thermal barrier coating consists of a plurality of sandwich-type lamellar microstructures of LZO+YSZ+LZO, and is prepared by adopting double-shell microstructure composite ceramic powder, wherein the inner shell of the double-shell microstructure composite ceramic powder is YSZ particles, the outer shell of the double-shell microstructure composite ceramic powder is La 2Zr2O7 particles, and the mass percentage of YSZ is 8 wt%.
2. The method for preparing the anti-sintering thermal barrier coating as claimed in claim 1, comprising the steps of:
(1) Drying YSZ powder and La 2Zr2O7 powder respectively in a hot oven, wherein the temperature of the oven is set to 100 ℃, and the drying time is set to 2h so as to remove water in the powder;
(2) And spraying the fused La 2Zr2O7 powder by using an atmospheric plasma spraying device by using plasma as a heat source, and colliding the solid YSZ powder with the sprayed fused La 2Zr2O7 particles by using a powder feeder to form YSZ@La 2Zr2O7 double-shell microstructure powder with YSZ as an inner shell and La 2Zr2O7 as an outer shell, so that the mechanical coating state is realized.
3. The method for preparing a sintering-resistant thermal barrier coating according to claim 2, wherein in the step (2), spraying the melted La 2Zr2O7 powder by using an atmospheric plasma spraying device further comprises setting a plasma spraying process parameter, setting a powder feeding speed and a spraying time for spraying.
4. The method for preparing the anti-sintering thermal barrier coating according to claim 3, wherein the atmospheric plasma spraying equipment sprays powder by using argon as main flow gas, hydrogen as auxiliary gas and nitrogen as powder feeding gas.
5. The method for preparing the anti-sintering thermal barrier coating according to claim 4, wherein the plasma spraying process parameters are 600-650A current, 60-70V voltage, 45.2 SLM argon flow and 5.6 SLM hydrogen flow.
6. The method for preparing the anti-sintering thermal barrier coating according to claim 3, wherein the powder feeding speed is 6.0 r/min, and the thickness of the ceramic layer is 300-600 μm.
7. The method for preparing the anti-sintering thermal barrier coating according to claim 2, wherein in the step (2), the angle formed by the gun head of the atmospheric plasma spraying device and the spray head of the powder feeder in the mixing process is any angle of 60-120 degrees, and the distance is 7-10 cm.
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