CN114015963A - Low-thermal-conductivity thermal barrier coating with vertical crack structure and preparation method thereof - Google Patents
Low-thermal-conductivity thermal barrier coating with vertical crack structure and preparation method thereof Download PDFInfo
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- 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
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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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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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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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
- C23C4/06—Metallic material
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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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
- 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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Abstract
The invention discloses a thermal barrier coating with a vertical crack structure and low thermal conductivity and a preparation method thereof, wherein the chemical formula of the thermal barrier coating is Srx(Zr0.9A0.05B0.05)O1.95+xA and B are respectively one of lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium and yttrium, A and B are different, and x is more than or equal to 0.8 and less than or equal to 1.0; the preparation method comprises the following steps: strontium nitrate, zirconium nitrate and A (NO)3)3And B (NO)3)3Adding into water to obtain mixed nitrate solution; dropping the ammonium oxalate solution and ammonia water simultaneously; after titration, aging, washing with water and washing with alcohol to obtain powder slurry; mixing the powder slurry with a dispersantThen adding deionized water and milling beads for ball milling to obtain precursor suspension; the precursor suspension is sprayed onto the base material. The thermal barrier coating has excellent high-temperature phase stability and a uniformly distributed vertical crack structure, and is beneficial to reducing the thermal conductivity of the coating and obtaining long service life.
Description
Technical Field
The invention relates to the technical field of thermal barrier coating material preparation. In particular to a low-heat-conductivity thermal barrier coating with a vertical crack structure and a preparation method thereof.
Background
The high-temperature alloy is a high-temperature metal material which can work for a long time at 760-1150 ℃ under a certain stress condition, has good comprehensive performances of oxidation resistance, hot corrosion resistance, fatigue resistance, fracture toughness and the like, and is a key material of hot-end components of military and civil gas turbine engines. In recent years, as aviation gas turbines have been developed to have high flow rates, high thrust-weight ratios, and high inlet temperatures, the temperature of the combustion gases in the combustion chamber has approached 2000K. In order to ensure the normal operation of the high-temperature alloy, a layer of ceramic coating is deposited on the surface of the high-temperature alloy to form a thermal barrier coating, so that the effects of heat insulation and cooling of the high-temperature alloy material of the substrate are achieved.
The widely used surface ceramic coating at present is 6-8% Y2O3Partially stabilized ZrO2(i.e., YSZ, yttria partially stabilized zirconia), YSZ undergoes a phase change at high temperature, which is exacerbated above 1200 ℃, at which point the metal bond coat is susceptible to oxidation, resulting in coating failure, and thus, the need for further increases in gas temperature is difficult to meet. SrZrO3As a perovskite structure substance, compared with YSZ, the perovskite structure substance has the advantages of high melting point, low thermal expansion coefficient and the like, but phase change still exists in the temperature rising process from room temperature to 1400 ℃. The method of rare earth doping is adopted at presentPreparation of SrZrO3The phase transition of the thermal barrier coating is more obvious in the doping effect of the double rare earth of Yb, Y and Gd, and the thermal cycle life of the thermal barrier coating can be obviously prolonged.
In addition, the regularly distributed pore structures in the thermal barrier coating are beneficial to reducing the thermal conductivity of the thermal barrier coating, particularly the vertical crack structures in the coating, so that the thermal conductivity of the coating is effectively reduced, and the toughness and the thermal cycle life of the coating can be improved. However, most of the traditional thermal barrier coatings are prepared by adopting an Atmospheric Plasma Spraying (APS) process, the process adopts solid agglomerated powder for spraying, the agglomerated powder is large in size, the powder is obviously spread after being melted and impacted on a substrate, the coating tissue is difficult to refine and the coating structure is difficult to change, and cracks are easy to generate among the layered tissues of the prepared coatings during high-temperature service so that the coatings fall off and fail prematurely. If the thermal barrier coating with the vertical crack structure is prepared, when the temperature of the base material and the thickness of single-layer spraying reach a critical value in the spraying process, the accumulated plane stress of the coating under the thickness is larger than the strength of the coating under the temperature; therefore, the formation of vertical crack structures in the coating has extremely strict requirements on the properties of the coating and the control of the coating process, and the preparation of the low-thermal-conductivity thermal barrier coating with the high-density vertical crack structure is more difficult.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a thermal barrier coating with a low thermal conductivity and a vertical crack structure, which has not only low thermal conductivity but also good high-temperature phase stability, so as to solve the problem that the service life of the thermal barrier coating is short due to the fact that phase change is easily generated during the current YSZ high-temperature operation. The invention also provides a preparation method of the low-thermal-conductivity thermal barrier coating with the vertical crack structure, which is characterized in that the double rare earth doped modified SrZrO is prepared3The precursor suspension and the ceramic thermal barrier coating with the vertical crack structure prepared by adopting the suspension plasma spraying process have the advantages of low thermal conductivity and high temperature phase stability due to large density and uniform distribution of the vertical crack structure of the coating, and are beneficial to prolonging the service life of hot-end components of the gas turbine.
In order to solve the technical problems, the invention provides the following technical scheme:
a low thermal conductivity thermal barrier coating having a vertical crack structure, the low thermal conductivity thermal barrier coating having a chemical formula of Srx(Zr0.9A0.05B0.05)O1.95+xA and B are respectively one of lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium and yttrium, A and B are different, and x is more than or equal to 0.8 and less than or equal to 1.0.
The low-thermal-conductivity thermal barrier coating with the vertical crack structure has the chemical formula of Sr1.0(Zr0.9 La0.05B0.05)O2.95B is neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium or yttrium;
alternatively, the chemical formula of the low-thermal-conductivity thermal barrier coating material is Sr0.9(Zr0.9Nd0.05B0.05)O2.85B is samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium or yttrium;
alternatively, the chemical formula of the low-thermal-conductivity thermal barrier coating material is Sr0.8(Zr0.9Sm0.05B0.05)O2.75And B is europium, gadolinium, dysprosium, erbium, ytterbium, lutetium or yttrium.
The low-thermal-conductivity thermal barrier coating with the vertical crack structure has the chemical formula of Sr1.0(Zr0.9 Yb0.05Y0.05)O2.95。
A preparation method of a low-thermal-conductivity thermal barrier coating with a vertical crack structure comprises the following steps:
step A: sr (NO)3)2Powder of Zr (NO)3)2Powder, A (NO)3)3Powder and B (NO)3)3Sequentially adding the powder into water, and uniformly stirring to obtain a mixed nitrate solution; dropping ammonium oxalate (NH) into the mixed nitrate solution and ammonia water simultaneously4)2C2O4In solution; after titration is finished and aging is carried out for 3-6 h, and after the upper layer liquid is clarified, the precipitate obtained by reaction is sequentially washed by water and alcoholWashing to neutrality and centrifuging to obtain powder slurry;
and B: mixing the powder slurry with a dispersant solution, placing the mixture into a container, adding deionized water and grinding beads, and carrying out ball milling to obtain a precursor suspension;
and C: spraying the precursor suspension onto a base material by adopting a suspension plasma spraying process to prepare the low-thermal-conductivity thermal barrier coating with the vertical crack structure;
the chemical formula of the low-thermal-conductivity thermal barrier coating is Srx(Zr0.9A0.05B0.05)O1.95+xA and B are respectively one of lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium and yttrium, A and B are different, and x is more than or equal to 0.8 and less than or equal to 1.0.
The preparation method of the low-thermal-conductivity thermal barrier coating with the vertical crack structure comprises the step A of mixing Sr in a nitrate solution2+The concentration of (A) is 0.1-0.3 mol/L; the invention uses ammonium oxalate (NH)4)2C2O4Ammonium oxalate (NH) in solution4)2C2O4The concentration of the water-soluble organic acid is controlled within the range of 0.2-0.4 mol/L, so that the particle size of powder slurry obtained by washing generated precipitates is less than 3 mu m and the particle size of the powder slurry is relatively uniform; NH in ammonia325-28 wt.%; mixed nitrate solution and ammonium oxalate (NH)4)2C2O4The volume ratio of the solution is 1: 3-5, the pH of the reaction system is kept within the range of 9-12 during titration, and the dropwise adding amount of ammonia water is determined according to the pH of the reaction system which can be controlled within the range of 9-12 during titration; when mixing nitrate solution and ammonium oxalate (NH)4)2C2O4The volume ratio of the solution is 1: 3-5, and when the pH value of the reaction system is controlled within the range of 9-12, the complete reaction of the substances can be ensured, and the precipitation can be uniformly generated in the titration process without agglomeration.
In the step B, in order to ensure the stability of the precursor suspension before spraying and within 3-12 h during spraying and to keep a high deposition rate during spraying, the mass fraction of the powder slurry in the precursor suspension is controlled to be 5-20 wt%, and the mass of the dispersant in the precursor suspension is 0.5-2% of the mass of the powder slurry; the dispersant solution is ammonium polyacrylate aqueous solution, and the mass fraction of ammonium polyacrylate in the ammonium polyacrylate aqueous solution is 50 wt.%. In the test, it is found that when 50 wt.% of ammonium polyacrylate aqueous solution is used as the dispersant, and the amount of ammonium polyacrylate is controlled to be 0.5-2% of the mass of the powder slurry, it is more favorable for spraying to form a relatively uniform vertical crack structure, which may be because the dispersion effect of ammonium polyacrylate on the precursor suspension under the condition is more favorable for the ammonium polyacrylate to uniformly deposit on the base material and form a vertical crack structure with a suitable crack distribution.
In the step B, the ball milling time is 1.5-3 h; in the precursor suspension, the median particle size of the powder slurry particles is less than or equal to 1.2 mu m, and the proportion of the particles with the particle size of less than 2.5 mu m is more than 84 percent, so the powder slurry in the particle grading is more helpful for the thermal barrier coating to obtain a micro-nano pore structure with uniform distribution.
In the step C, the precursor suspension is fed into an atomizing nozzle through an axial liquid feeding device; the liquid feeding speed of the precursor suspension is 24-40 mL/min, and the atomizing air flow rate of the atomizing nozzle is 12-20L/min.
In the step C, the parameters of the suspension plasma spraying process are as follows: the total flow rate of the gas is 240-300L/min, and in the gas, the volume fraction of argon is 75-77%, the volume fraction of hydrogen is 12-13%, and the volume fraction of nitrogen is 11-12%; the current is 200-220A, and the power is 85-90 kW; the transverse moving speed of the spray gun is 700-800 mm/s, and the longitudinal step length of the spray gun is 1-2 mm/step; the spraying distance is 50-100 mm, and the preheating temperature of the matrix material is 200-450 ℃; in order to ensure the long-term effectiveness of the service work of the thermal barrier coating, the thickness of the prepared low-thermal-conductivity thermal barrier coating with the vertical crack structure is within the range of 100-300 mu m.
In the step C, firstly, preparing the NiCoCrAlY metal bonding layer on the surface of the base material by adopting an atmospheric plasma spraying process, and then preparing the low-thermal-conductivity thermal barrier coating with the vertical crack structure on the surface of the NiCoCrAlY metal bonding layer by adopting a suspension plasma spraying process.
The technical scheme of the invention achieves the following beneficial technical effects:
1. the invention adopts the suspension plasma spraying process to prepare Srx(Zr0.9A0.05B0.05)O1.95+xThe thermal barrier coating prepared by the method has excellent high-temperature phase stability (no phase change occurs when the thermal barrier coating is subjected to heat treatment at 1400 ℃ for 300h), and also has a uniformly distributed high-density vertical crack structure, so that the structure is favorable for reducing the thermal conductivity of the coating and obtaining a longer service life. Sr provided by the inventionx(Zr0.9A0.05B0.05)O1.95+xSr at 1000 deg.C or below at the same temperaturex(Zr0.9A0.05B0.05)O1.95+xThermal conductivity ratio SrZrO of thermal barrier coating3The reduction is more than 15 percent.
2. The invention adopts the suspension plasma spraying process to prepare Srx(Zr0.9A0.05B0.05)O1.95+xWhen the thermal barrier coating is used, the thickness of the prepared thermal barrier coating is 100-300 mu m by adjusting the process conditions such as proper liquid feeding rate, spraying parameters and the like, and the prepared thermal barrier coating has a vertical crack structure with high density and uniform distribution, and the vertical crack structure with the density distribution is favorable for ensuring that the thermal barrier coating has excellent high-temperature phase stability and longer service life on the premise of lower thermal conductivity. When the precursor suspension is prepared, the median particle size of powder slurry particles in the precursor suspension is controlled to be below 1.2 mu m, the proportion of particles with the particle size of less than 2.5 mu m is controlled to reach 84%, and the thermal barrier coating is more helpful to obtain a micro-nano pore structure containing uniform distribution under the particle grading.
3. The invention is characterized in that nitrate solution and ammonium oxalate (NH) are mixed by controlling during the process of powder slurry in precursor suspension4)2C2O4The volume ratio of the solution is within the range of 1: 3-5, and the pH value of the reaction system is within the range of 9-12, so that complete reaction of reaction substances can be ensured, and precipitates can be uniformly generated in the titration process without agglomeration. In addition, in tests, the technicians of the present invention find that when an aqueous solution of ammonium polyacrylate with a mass fraction of 50 wt.% is used as a dispersant and the amount of the ammonium polyacrylate is controlled to be 0.5-2% of the mass of the powder slurry, it is more favorable for spraying to form a relatively uniform vertical crack structure, probably because the dispersion effect of the ammonium polyacrylate on the precursor suspension under the conditions is more favorable for the ammonium polyacrylate to uniformly deposit on the base material and form a vertical crack structure with a suitable crack distribution.
Drawings
FIG. 1 Sr in example 1 of the present invention1.0(Zr0.9Yb0.05Y0.05)O2.95A distribution curve diagram of the particle size of the precursor suspension;
FIG. 2 Sr in example 1 of the present invention1.0(Zr0.9Yb0.05Y0.05)O2.95XRD patterns of the thermal barrier coating after heat treatment for different times at 1400 ℃;
FIG. 3 Sr in example 1 of the present invention1.0(Zr0.9Yb0.05Y0.05)O2.95A microscopic topography of a cross section of the thermal barrier coating;
FIG. 4 Sr in example 1 of the present invention1.0(Zr0.9Yb0.05Y0.05)O2.95Thermal conductivity profile of thermal barrier coating.
Detailed Description
Example 1
This example has a low thermal conductivity thermal barrier coating with a vertical crack structure, and has a chemical formula of Sr1.0(Zr0.9Yb0.05Y0.05)O2.95The preparation method comprises the following steps:
step A: according to Sr, Zr, Yb andy is 1.0:0.9:0.05:0.05, Sr (NO) is added3)2Powder of Zr (NO)3)2Powder, Yb (NO)3)3Powder and Y (NO)3)3Sequentially adding the powder into water, stirring and uniformly mixing to obtain mixed nitrate solution, and adding Sr in the mixed nitrate solution2+The concentration of (A) is 0.3 mol/L; mixing the nitrate solution and ammonia water (NH in ammonia water)326 wt.%) was added dropwise to the solution while adding ammonium oxalate (NH)4)2C2O4In solution, ammonium oxalate (NH)4)2C2O4Ammonium oxalate (NH) in solution4)2C2O4The concentration of (A) is 0.35 mol/L; at the time of the titration, the reaction system was kept at pH 9, and in this example, a nitrate solution and ammonium oxalate (NH) were mixed4)2C2O4The volume ratio of the solution to the ammonia water is 1:5: 0.15; after the titration reaction is finished and is aged for 6 hours, clarifying the upper-layer liquid, sequentially washing precipitates obtained by the reaction with water (washing with deionized water) and alcohol (washing with absolute ethyl alcohol), washing to neutrality (pH is 7) and centrifuging to obtain powder slurry;
and B: mixing the powder slurry with a dispersant solution, placing the mixture in a planetary ball mill, adding deionized water and grinding beads for ball milling for 2 hours to obtain a precursor suspension; the dispersant solution is ammonium polyacrylate aqueous solution, and the mass fraction of ammonium polyacrylate in the ammonium polyacrylate aqueous solution is 50 wt.%; in this embodiment, the mass fraction of the powder slurry in the precursor suspension is 15 wt.%, and the mass of the ammonium polyacrylate in the precursor suspension is 1% of the mass of the powder slurry; FIG. 1 is Sr1.0(Zr0.9Yb0.05Y0.05)O2.95The particle size distribution curve of the precursor suspension is shown in the figure, the median particle size of the slurry powder particles is below 1.2 mu m, and the proportion of the slurry powder particles with the particle size of less than 2.5 mu m reaches 84 percent, which is beneficial to obtaining a coating containing uniformly distributed micron and nanometer pore structures;
and C: the precursor suspension was sprayed onto the substrate using a suspension plasma spray process, as used in this exampleThe base material is nickel-based high-temperature alloy, and the low-thermal-conductivity thermal barrier coating with the vertical crack structure is prepared after spraying; the specific method comprises the following steps: sr is1.0(Zr0.9Yb0.05Y0.05)O2.95The precursor suspension is sent into an atomizing nozzle through an axial liquid sending device, the liquid sending speed is 35mL/min, the atomizing gas flow speed is 12L/min [ the atomized suspension is subjected to a series of physical and chemical reactions in plasma flame flow and is deposited on the surface of a base material at a certain speed, and finally the low-thermal-conductivity thermal barrier coating with a vertical crack structure is obtained ].
In this embodiment, the plasma spraying process parameters are as follows: the total gas flow rate was 300L/min (volume ratio of argon Ar in the gas: 77%, hydrogen H)2Is 12% by volume, nitrogen gas N211% by volume); the current is 200A, the power is 90kW, the traversing speed of the spray gun is 750mm/s, the longitudinal step length of the spray gun is 2mm/step, the spraying distance is 60mm, the preheating temperature of the base material is 300 ℃, the spraying times are 20 times, and Sr with the layer thickness of about 200 mu m is prepared1.0(Zr0.9Yb0.05Y0.05)O2.95A thermal barrier coating. In this embodiment, by adjusting a suitable liquid feeding rate and a suitable spraying parameter, the thickness of the prepared thermal barrier coating is thin, and the prepared thermal barrier coating has a uniformly distributed vertical crack structure, and the uniformly distributed vertical crack structure is beneficial to enabling the thermal barrier coating to have excellent high-temperature phase stability and obtain a long service life on the premise of having a low thermal conductivity.
Sr prepared in the example1.0(Zr0.9Yb0.05Y0.05)O2.95The thermal barrier coating is heat treated at 1400 ℃ for at least 300 h. FIG. 2 is Sr1.0(Zr0.9Yb0.05Y0.05)O2.95XRD pattern, Sr of thermal barrier coating after heat treatment at 1400 ℃ for different time1.0(Zr0.9Yb0.05Y0.05)O2.95The coating does not have obvious phase change after being thermally treated at 1400 ℃ for 300h, which shows that the coating has excellent high-temperature phase stability;
FIG. 3 is Sr1.0(Zr0.9Yb0.05Y0.05)O2.95The cross-sectional micro-topography of the thermal barrier coating can be seen from fig. 3: prepared Sr1.0(Zr0.9Yb0.05Y0.05)O2.95The thermal barrier coating has an obvious vertical crack structure, and the distribution density of the vertical crack structure is 0.017 channels/micrometer (the length of the vertical crack is more than two thirds of the coating thickness); the structure is beneficial to reducing the thermal conductivity of the coating and enables the coating to obtain longer service life;
FIG. 4 is Sr1.0(Zr0.9Yb0.05Y0.05)O2.95The thermal conductivity curve of the thermal barrier coating, as can be seen in fig. 4: at 1000 ℃ Sr1.0(Zr0.9Yb0.05Y0.05)O2.95The thermal conductivity of the thermal barrier coating is 1.86W/m.K, and the thermal conductivity is equal to that of SrZrO under the same temperature condition3The thermal conductivity (2.19W/m.K) is reduced by 15.1 percent; it is demonstrated that the thermal barrier coating prepared by the embodiment has a thermal conductivity at high temperature which is obviously lower than that of SrZrO3Thermal conductivity of (2).
As can be seen from FIGS. 2 to 4, Sr produced in this example1.0(Zr0.9Yb0.05Y0.05)O2.95The thermal barrier coating has a vertical crack structure with high density and uniform distribution, and the high-temperature thermal conductivity of the thermal barrier coating is obviously lower than that of SrZrO3Has excellent high-temperature phase stability, so that the coating has longer service life. Therefore, the low-thermal-conductivity thermal barrier coating with the vertical crack structure is prepared by the embodiment.
Example 2
This example has a low thermal conductivity thermal barrier coating with a vertical crack structure, and has a chemical formula of Sr1.0(Zr0.9La0.05Dy0.05)O2.95The preparation process is identical to that of example 1, with the only difference that Yb (NO) is used in step A3)3Powder and Y (NO)3)3The powders were respectively replaced with La (NO)3)3Powder and Dy (NO)3)3And (3) powder.
Sr produced in this example1.0(Zr0.9La0.05Dy0.05)O2.95The thermal barrier coating has good phase stability under the long-term heat treatment condition of room temperature to 1400 ℃; the thermal conductivity at 1000 ℃ is 1.55W/m.K, and the thermal conductivity is the same as that of SrZrO under the same temperature condition3The thermal conductivity (2.19W/m.K) is reduced by 29.2 percent; sr produced in this example1.0(Zr0.9La0.05Dy0.05)O2.95The thermal barrier coating has an obvious vertical crack structure, and the distribution density of the vertical crack structure is 0.014 channel/mu m (the length of the vertical crack is more than two thirds of the coating thickness), so that the coating has a longer service life).
Example 3
This example has a low thermal conductivity thermal barrier coating with a vertical crack structure, and has a chemical formula of Sr0.8(Zr0.9Sm0.05Gd0.05)O2.75The preparation method is the same as that of example 1, except that: the preparation method of the mixed nitrate solution in the step A is as follows: sr (NO) is added according to the molar ratio of Sr, Zr, Sm and Gd of 0.8:0.9:0.05:0.053)2Powder of Zr (NO)3)2Powder Sm (NO)3)3Powder and Gd (NO)3)3And sequentially adding the powder into water, and uniformly stirring to obtain a mixed nitrate solution.
Sr produced in this example0.8(Zr0.9Sm0.05Gd0.05)O2.75The thermal barrier coating has good phase stability under the long-term heat treatment condition of room temperature to 1400 ℃; the thermal conductivity at 1000 ℃ is 1.64W/m.K, and the thermal conductivity is the same as that of SrZrO under the same temperature condition3The thermal conductivity (2.19W/m.K) is reduced by 25.2 percent; sr produced in this example1.0(Zr0.9La0.05Dy0.05)O2.95The thermal barrier coating has an obvious vertical crack structure, and the distribution density of the vertical crack structure is 0.016 tracks/mu m (the vertical crack length is more than two thirds of the coating thickness), so that the coating has a longer service life).
In other embodiments, different A and B are selected from lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium, yttrium by adjusting the molar ratio of Sr, Zr, A, and B, using practiceThe preparation of example 1, respectively, gave: sr1.0(Zr0.9La0.05Nd0.05)O2.95Or Sr1.0(Zr0.9La0.05Sm0.05)O2.95Or Sr1.0(Zr0.9La0.05Eu0.05)O2.95Or Sr1.0(Zr0.9La0.05Gd0.05)O2.95Or Sr1.0(Zr0.9La0.05Er0.05)O2.95Or Sr1.0(Zr0.9La0.05Yb0.05)O2.95Or Sr1.0(Zr0.9La0.05Lu0.05)O2.95Or Sr1.0(Zr0.9La0.05Y0.05)O2.95Or Sr0.9(Zr0.9Nd0.05Sm0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Eu0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Gd0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Dy0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Er0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Yb0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Lu0.05)O2.85Or Sr0.9(Zr0.9Nd0.05Y0.05)O2.85Or Sr0.8(Zr0.9Sm0.05Eu0.05)O2.75Or Sr0.8(Zr0.9Sm0.05Dy0.05)O2.75Or Sr0.8(Zr0.9Sm0.05Er0.05)O2.75Or Sr0.8(Zr0.9Sm0.05Yb0.05)O2.75Or Sr0.8(Zr0.9Sm0.05Lu0.05)O2.75Or Sr0.8(Zr0.9Sm0.05Y0.05)O2.75And the like have a low thermal conductivity thermal barrier coating with a vertical crack structure. And the thermal barrier coating obtained is at room temperatureThe high-temperature phase stability is good in the temperature range of 1400 ℃, and the high-temperature phase stability is also good after the treatment at 1400 ℃ (the treatment time is more than 300 h); thermal conductivity at 1000 ℃ is more than SrZrO3The thermal conductivity of (a) is reduced by more than 15% and has a longer service life, which is not further listed here.
In addition, in other embodiments, an atmospheric plasma spraying process may be first used to prepare the NiCoCrAlY metal bonding layer on the surface of the base material, and then the suspension plasma spraying process is used to prepare the low thermal conductivity thermal barrier coating with the vertical crack structure on the surface of the NiCoCrAlY metal bonding layer by using the method of embodiment 1.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (10)
1. A low thermal conductivity thermal barrier coating having a vertical crack structure, wherein the chemical formula of the low thermal conductivity thermal barrier coating is Srx(Zr0.9A0.05B0.05)O1.95+xA and B are respectively one of lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium and yttrium, A and B are different, and x is more than or equal to 0.8 and less than or equal to 1.0.
2. The low thermal conductivity thermal barrier coating having a vertical crack structure as claimed in claim 1, wherein the low thermal conductivity thermal barrier coating material has a chemical formula of Sr1.0(Zr0.9 La0.05B0.05)O2.95B is neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium or yttrium;
alternatively, the chemical formula of the low-thermal-conductivity thermal barrier coating material is Sr0.9(Zr0.9Nd0.05B0.05)O2.85B is samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium or yttrium;
alternatively, the chemical formula of the low-thermal-conductivity thermal barrier coating material is Sr0.8(Zr0.9Sm0.05B0.05)O2.75And B is europium, gadolinium, dysprosium, erbium, ytterbium, lutetium or yttrium.
3. The low thermal conductivity thermal barrier coating having a vertical crack structure as claimed in claim 1, wherein the low thermal conductivity thermal barrier coating material has a chemical formula of Sr1.0(Zr0.9 Yb0.05Y0.05)O2.95。
4. A preparation method of a low-thermal-conductivity thermal barrier coating with a vertical crack structure is characterized by comprising the following steps:
step A: sr (NO)3)2Powder of Zr (NO)3)2Powder, A (NO)3)3Powder and B (NO)3)3Sequentially adding the powder into water, and uniformly stirring to obtain a mixed nitrate solution; dropping ammonium oxalate (NH) into the mixed nitrate solution and ammonia water simultaneously4)2C2O4In solution; after titration is completed and aging is carried out for 3-6 hours, after the upper layer liquid is clarified, washing precipitates obtained by reaction with water and alcohol in sequence, washing to be neutral and centrifuging to obtain powder slurry;
and B: mixing the powder slurry with a dispersant solution, placing the mixture into a container, adding deionized water and grinding beads, and carrying out ball milling to obtain a precursor suspension;
and C: spraying the precursor suspension onto a base material by adopting a suspension plasma spraying process to prepare the low-thermal-conductivity thermal barrier coating with the vertical crack structure;
the chemical formula of the low-thermal-conductivity thermal barrier coating is Srx(Zr0.9A0.05B0.05)O1.95+xA and B are respectively one of lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium and yttrium, A and B are different, and x is more than or equal to 0.8 and less than or equal to 1.0.
5. The method for preparing a low thermal conductivity thermal barrier coating having a vertical crack structure as claimed in claim 4, wherein in step A, Sr is mixed in nitrate solution2+The concentration of (A) is 0.1-0.3 mol/L; ammonium oxalate (NH)4)2C2O4Ammonium oxalate (NH) in solution4)2C2O4The concentration of (A) is 0.2-0.4 mol/L, NH in ammonia water325-28 wt.%; mixed nitrate solution and ammonium oxalate (NH)4)2C2O4The volume ratio of the solution is 1: 3-5; and during the dripping, the pH value of the reaction system is kept in a range of 9-12.
6. The method for preparing a low thermal conductivity thermal barrier coating with a vertical crack structure as claimed in claim 4, wherein in step B, the mass fraction of the powder slurry in the precursor suspension is 5-20 wt.%, and the mass of the dispersant in the precursor suspension is 0.5-2% of the mass of the powder slurry; the dispersant solution is ammonium polyacrylate aqueous solution, and the mass fraction of ammonium polyacrylate in the ammonium polyacrylate aqueous solution is 50 wt.%.
7. The preparation method of the low-thermal-conductivity thermal barrier coating with the vertical crack structure is characterized in that in the step B, the ball milling time is 1.5-3 h; in the precursor suspension, the median particle diameter of the powder slurry particles is less than or equal to 1.2 μm.
8. The method for preparing a low thermal conductivity thermal barrier coating having a vertical crack structure as claimed in claim 4, wherein in step C, the precursor suspension is fed into the atomizing nozzle through an axial liquid feeding device; the liquid feeding speed of the precursor suspension is 24-40 mL/min, and the atomizing air flow rate of the atomizing nozzle is 12-20L/min.
9. The method for preparing a low thermal conductivity thermal barrier coating having a vertical crack structure as claimed in claim 4, wherein in step C, the parameters of the suspension plasma spraying process are as follows: the total flow rate of the gas is 240-300L/min, and in the gas, the volume fraction of argon is 75-77%, the volume fraction of hydrogen is 12-13%, and the volume fraction of nitrogen is 11-12%; the current is 200-220A, and the power is 85-90 kW; the transverse moving speed of the spray gun is 700-800 mm/s, and the longitudinal step length of the spray gun is 1-2 mm/step; the spraying distance is 50-100 mm, and the preheating temperature of the matrix material is 200-450 ℃; the thickness of the prepared low-thermal-conductivity thermal barrier coating with the vertical crack structure is within the range of 100-300 mu m.
10. The method for preparing a low thermal conductivity thermal barrier coating with a vertical crack structure as claimed in claim 4, wherein in step C, an NiCoCrAlY metal bonding layer is prepared on the surface of the base material by using an atmospheric plasma spraying process, and then a low thermal conductivity thermal barrier coating with a vertical crack structure is prepared on the surface of the NiCoCrAlY metal bonding layer by using a suspension plasma spraying process.
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