CN112062566A - Cerate composite material and preparation method and application thereof - Google Patents

Cerate composite material and preparation method and application thereof Download PDF

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CN112062566A
CN112062566A CN201910429426.1A CN201910429426A CN112062566A CN 112062566 A CN112062566 A CN 112062566A CN 201910429426 A CN201910429426 A CN 201910429426A CN 112062566 A CN112062566 A CN 112062566A
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cerate
rare earth
composite material
earth elements
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王一光
王乾坤
任科
廉玉龙
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Beijing Institute of Technology BIT
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Abstract

The invention provides a cerate composite material and a preparation method and application thereof, wherein the composition of the cerate composite material is A2Ce2O7Wherein A is selected from at least three rare earth elements, and the mass ratio of any two rare earth elements in the at least three rare earth elements is X, 2/7 is less than or equal to X is less than or equal to 7/2. The cerate composite material not only has good phase stability, but also has extremely low ultralow thermal conductivity and extremely strong sintering resistance, and is suitable for being used and popularized as a new-generation thermal barrier coating.

Description

Cerate composite material and preparation method and application thereof
Technical Field
The invention relates to a coating material, in particular to a cerate composite material and a preparation method and application thereof, belonging to the technical field of materials.
Background
In advanced aeroengines, the thermal barrier coating technology is classified as three key technologies of high-performance aeroengine high-pressure turbine blade manufacturing technology which is combined with high-temperature structural materials and efficient blade cooling technology. At present, the temperature resistance level cannot meet the increasing requirements of the development of the aero-engine by only developing the high-temperature alloy, and compared with two modes of improving the cooling technology and the heat resistance level of the high-temperature alloy, the thermal barrier coating technology is the most obvious and effective technical measure for improving the heat resistance of the turbine blade, has good economical efficiency and small risk, is simple and feasible, and is also the key technology for the preferential development of aeronautical developed countries such as America and Europe and China.
The thermal barrier coating ceramic thermal insulation layer material successfully applied to the aeroengine and the ground gas turbine at present is zirconia (YSZ) stabilized by 6-8% of yttria. However, when YSZ is in service for a long time in an environment with the temperature higher than 1200 ℃, sintering is easy to occur, the thermal conductivity is reduced due to the growth of crystal grains, and therefore the cracking failure of the coating is caused due to the change of phase change volume; in addition, the higher oxygen conductivity of YSZ leads to TGO (thermally grown oxide between the coating and the substrate) formation, further exacerbating failure of the coating.
Disclosure of Invention
The invention provides a cerate composite material, a preparation method and application thereof, and the cerate composite material has good phase stability, extremely low ultralow thermal conductivity, extremely high sintering resistance and extremely high thermal expansion coefficient, and is suitable for being used and popularized as a new-generation thermal barrier coating.
The invention provides a cerate composite material, which comprises the following components A2Ce2O7，
Wherein A is selected from at least three rare earth elements, and the mass ratio of any two rare earth elements in the at least three rare earth elements is X, 2/7 is less than or equal to X, and is less than or equal to 7/2.
The cerate composite material as described above, wherein the rare earth element is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Er, Y.
The cerate composite material as described above, wherein the ratio X of the amounts of the substances of the arbitrary two rare earth elements is 1.
The invention also provides a preparation method of any one of the above-mentioned cerate composite materials, which comprises the following steps:
1) mixing a cerium salt solution and at least three rare earth salt solutions to obtain a mixed solution;
2) mixing the mixed solution with alkali liquor, stirring, filtering, and collecting a filter cake;
3) sequentially carrying out freeze drying treatment and calcining treatment on the filter cake to obtain the cerate composite material;
wherein in the salt solution of at least three rare earth elements, the mass ratio of any two rare earth elements is X, X is not less than 2/7 and not more than 7/2;
the molar ratio of the cerium element in the cerium element salt solution to the sum of the at least three rare earth elements in the at least three rare earth element salt solution is (1-2): (1-2).
The preparation method of the cerate composite material comprises the steps of mixing the cerium nitrate with water, and stirring to obtain the salt solution of the cerium element.
The preparation method of the cerate composite material comprises the steps of mixing nitrates of at least three rare earth elements with water respectively, and stirring to obtain salt solutions of the at least three rare earth elements.
The preparation method as described above, wherein the alkali solution is ammonia water.
The method for producing a cerate composite material as described above, wherein in the step 2), the pH of the reaction solution in which the mixed solution is mixed with the aqueous ammonia is maintained at > 9.
The preparation method of the cerate composite material comprises the steps of calcining at the temperature of 1000-1800 ℃ for 2-48h, and calcining at the temperature of 1800 ℃.
The invention also provides an application of any one of the above-mentioned cerate composite materials in a thermal barrier coating.
The implementation of the invention at least comprises the following advantages:
1. the cerate composite material is a rare earth cerate material with a single stable phase, does not generate phase change and sintering at the high temperature of 1700 ℃, and has extremely high thermal stability;
2. the thermal conductivity of the cerate composite material in 1273-1573K is 0.6-1.8W/(mk), so that the cerate composite material has extremely low thermal conductivity and is not easy to generate a heat conduction phenomenon;
3. the cerate composite material has extremely high thermal expansion coefficient which is as high as 14.5 to 10 at 298-1573K-6K-1Close to the thermal expansion coefficient of the nickel-based high-temperature alloy for the engine;
4. the preparation method of the cerate composite material is simple to operate, easy to control, free of assistance of large instruments and beneficial to forming the cerate composite material with a single crystal structure;
5. the cerate composite material can be used as a thermal barrier coating, is not easy to corrode or crack even if being in a high-temperature water-oxygen environment for a long time, and can effectively protect an inner layer material, so that the cerate composite material is suitable for being widely popularized in the application field of the thermal barrier coating.
Drawings
FIG. 1 is an XRD pattern of a cerate composite of example 1 of the present invention;
fig. 2 is an SEM image of a bulk of the cerate composite of example 1 of the present invention;
FIG. 3 is a graph of the coefficient of thermal expansion of the bulk of the cerate composite of example 1 of the present invention;
FIG. 4 is an XRD pattern of the cerate composite of example 2 of the present invention;
FIG. 5 is an XRD pattern of the cerate composite of example 3 of the present invention;
fig. 6 is an XRD pattern of the cerate composite of example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a cerate composite material, which comprises the following components A2Ce2O7，
Wherein A is selected from at least three rare earth elements, and the mass ratio of any two rare earth elements in the at least three rare earth elements is X, 2/7 is less than or equal to X, and is less than or equal to 7/2.
Specifically, a is at least three metal elements among the rare earth elements, and the valence of each metal element is + 3.
Preferably, the amount of each rare earth element substance to a may be made the same. That is, the ratio X of the amounts of the two arbitrary rare earth elements is 1.
Further, the rare earth element is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Er and Y.
That is, a in the cerate composite of the present invention may be selected from at least three of the above elements.
Further, the molar ratio of the cerium element to the sum of the above at least three rare earth elements is (1-2): (1-2), preferably 1: 1.
The inventors of the present application found that the cerate composite material of the present invention having the above composition is a compound having a pyrochlore structure or a fluorite structure with defects with good phase stability, which type of structure can maintain structural stability at a melting point so that no phase transition occurs. In addition, the cerate composite material is doped with at least three rare earth elements, so that the crystal structure is more complex, and the relative mass is larger, so that phonon scattering can be enhanced, and the thermal conductivity is reduced.
In addition, the anti-sintering performance of the cerate composite material is remarkably improved, and the thermal expansion coefficient is even close to that of a high-temperature nickel-based alloy, so that the cerate composite material has obvious advantages in the field of high-temperature novel thermal barrier coating materials.
The preparation method of the cerate composite material comprises the following steps:
s101: and mixing the salt solution of the cerium element and the salt solution of at least three rare earth elements to obtain a mixed solution.
In the present invention, the salt solution of cerium means an aqueous solution of a compound containing cerium and having a readily volatile anion, and the anion may be, for example, acetate, nitrate, or carbonate.
Specifically, the invention selects an aqueous solution of cerium nitrate as a salt solution of cerium element. In the preparation of the aqueous solution of cerium nitrate, the aqueous solution of cerium nitrate may be obtained by mixing cerium nitrate with water and stirring to dissolve the cerium nitrate. Generally, the concentration of the aqueous solution of cerium nitrate is 0.1-2.0mol/L, and the amount of water is reduced as much as possible on the premise of ensuring the dissolution of the cerium nitrate, so as to avoid the difficulty in removing water in the subsequent drying treatment.
The salt solution of at least three rare earth elements refers to an aqueous solution of a compound in which at least three different rare earth elements are respectively used as cations and anions are volatile, and for example, the anions can be acetate, nitrate or carbonate.
Further, the rare earth element is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Er and Y.
Specifically, the invention selects the aqueous solution of the rare earth nitrate as the salt solution of the rare earth element, and the purity of the rare earth nitrate is not lower than 99.99%. In the preparation of the aqueous solution of each rare earth nitrate, the rare earth nitrate may be mixed with water and stirred to dissolve the rare earth nitrate, thereby obtaining the aqueous solution of the rare earth nitrate. Generally, the concentration of the nitrate aqueous solution of the rare earth is 0.1-0.5mol/L, and the using amount of water is reduced as much as possible on the premise of ensuring the dissolution of the nitrate of the rare earth, so as to avoid the difficulty in removing water in the subsequent drying treatment.
When preparing the mixed solution, respectively preparing the aqueous solution of each rare earth nitrate, mixing the aqueous solution of each rare earth nitrate with the aqueous solution of cerium nitrate, stirring, and filtering to remove insoluble impurities to obtain the mixed solution.
In addition, when salt solutions of at least three rare earth elements are prepared separately, the ratio of the amounts of substances of any two rare earth elements is X and 2/7 is not less than X not more than 7/2;
in preparing the salt solution of cerium element, the molar ratio of cerium element to the sum of at least three rare earth elements in the salt solution of at least three rare earth elements is (1-2): (1-2), preferably 1: 1.
S102: and mixing the mixed solution with alkali liquor, stirring, filtering and collecting a filter cake.
And mixing the mixed solution with alkali liquor, stirring to enable metal cations in the mixed solution to react with the alkali liquor to generate precipitates, then washing and filtering the precipitates, and collecting filter cakes.
Wherein, can put into aquatic with the sediment, stir into the turbid liquid and wash the sediment to utilize centrifugal mode or suction filtration mode to carry out the washing of sediment and filter, guarantee the impurity minimizing of sediment.
S103: and sequentially carrying out freeze drying treatment and calcining treatment on the filter cake to obtain the cerate composite material.
Subjecting the cake to freeze-drying treatment for removing water therefrom and calcination treatment for removing residual impurities therein (e.g., nitrate ions introduced from cerium salt and rare earth element salt) and making metal atoms orderly arranged to have a composition A of a defective fluorite structure or a pyrochlore structure2Ce2O7The cerate composite of (1).
Specifically, the temperature of the freeze drying treatment is-50 to-30 ℃, and the time of the freeze drying treatment is 24 to 48 hours; the temperature of the calcination treatment is 1000-1800 ℃, and the time of the calcination treatment is 2-48 h. Wherein the calcination treatment may be performed in a muffle furnace.
Further, in S102, ammonia water is preferable as the alkali solution for precipitating the metal ions. If a strong alkaline solution is selected as the alkali solution for precipitating the metal ions, impurities are introduced to reduce the purity of the final cerate composite material.
Specifically, the mixed solution was slowly dropped into ammonia water under stirring to gradually precipitate metal ions in the mixed solution.
In order to ensure the maximum precipitation, in the process of adding the mixed solution into the ammonia water, the pH value of the reaction solution needs to be continuously tested and is ensured to be greater than 9, and once the pH value is lower than 9, the ammonia water needs to be added into the reaction solution in time.
Composition A obtained by the above preparation method2Ce2O7The cerate composite material is represented by powder properties, and can be directly sprayed on the surface of a metal to be protected by a plasma method, so that the metal is isolated from external heat, the temperature of the surface of the metal is reduced, and the metal is prevented from being oxidized and corroded at high temperature.
Hereinafter, the cerate composite material and the method for preparing the same according to the present invention will be described in more detail with reference to specific examples.
Example 1
The composition of the cerate composite material of the present example was (La)aSmaDyaTbaYba)2Ce2O7Wherein a is 1/5.
The cerate composite of the present example was prepared as follows:
1. preparation of the Mixed solution
Respectively using La (NO) with the purity of 99.99%3)3·6H2O、Sm(NO3)3·6H2O、Dy(NO3)3·6H2O、Tb(NO3)3·6H2O、Yb(NO3)3·6H2Mixing each salt with water and stirring until the salts are dissolved to obtain five salt solutions with the concentration of 0.1mol/L, and mixing the five salt solutions to obtain a mixture of rare earth salt solutions;
with the purity of 99.99 percent of Ce (NO)3)3·6H2Mixing O as cerium salt with water and stirring until the salt is dissolved to obtain cerium salt solution with the concentration of 0.1 mol/L;
wherein, La (NO)3)3·6H2O、Sm(NO3)3·6H2O、Tb(NO3)3·6H2O、Dy(NO3)3·6H2O、Yb(NO3)3·6H2O、Ce(NO3)3·6H2The molar ratio of O is 0.2: 0.2: 0.2: 0.2: 0.2: 1;
and mixing the mixture of the rare earth salt solution and the cerium salt solution, magnetically stirring for 1h, and filtering to remove insoluble impurities to obtain a transparent mixed solution.
2. Formation and collection of precipitate
Slowly dripping the mixed solution into ammonia water, stirring, and keeping the pH value of the reaction solution to be more than 9 in the process of dripping the mixed solution, thereby ensuring that metal ions can completely and uniformly form precipitates;
after the dropwise addition, the precipitate and water are mixed for a plurality of times by a high-speed centrifugation method for washing and separation, and the lower-layer precipitate is collected.
3. Preparation of cerate composite material
The precipitate was subjected to freeze-drying and calcination in this order to obtain a cerate composite powder of the present example.
Wherein the temperature of the freeze drying treatment is-49 ℃ and the time is 24 h; the temperature of the calcination treatment is 1500 ℃, and the time is 3 h.
The powder of the cerate composite material of the present embodiment was subjected to X-ray diffraction. Fig. 1 is an XRD spectrum of the cerate composite material of example 1 of the present invention, and as can be seen from comparison of fig. 1 with a standard PDF card of a single-phase rare earth cerate (lanthanum zirconate), the composition of the cerate composite material prepared in this example is a2Ce2O7And is of fluorite structure.
In addition, in order to facilitate evaluation of the sintering resistance and the thermal conductivity of the cerate composite powder of the present example, the above-mentioned cerate composite powder was subjected to the following post-treatment so that the prepared cerate composite powder became a dense bulk of the cerate composite.
The post-treatment step comprises:
1. ball-milling the cerate composite material powder with the fluorite structure phase for 24 hours by using a high-purity zirconia grinding ball to obtain slurry, wherein a ball-milling medium is deionized water, and the rotating speed is 150 r/min; freeze-drying the obtained slurry at-49 ℃ for 24h, adding PVA (polyvinyl alcohol) for granulation and sieving to obtain fine and uniform-particle-size-distribution cerate composite material powder;
2. molding the cerate composite material powder at 4MPa for 60s, and then carrying out cold isostatic pressing at 200MPa for 10min to obtain a ceramic biscuit;
3. slowly heating the ceramic biscuit to 600 ℃ in a low-temperature furnace, preserving heat for 4 hours, slowly cooling to 200 ℃, and naturally cooling to room temperature, thereby removing PVA in the ceramic biscuit; subsequently, the reactant is pressureless sintered for 5h at 1800 ℃ to obtain the fluorite structured cerate composite material block.
Fig. 2 is an SEM image of a bulk of the cerate composite of example 1 of the present invention. As shown in fig. 2, the pore size of the cerate composite material of the present embodiment is still larger after sintering at 1800 ℃ for 5 hours, which illustrates that the pore size of the cerate composite material of the present embodiment does not shrink or even disappear after sintering at high temperature, and thus the cerate composite material of the present invention has good sintering resistance. And because the air in the pore diameter is not beneficial to heat conduction, the heat conduction performance of the cerate composite material is further reduced.
Fig. 3 is a graph of the coefficient of thermal expansion of the bulk of the cerate composite of example 1 of the present invention. As shown in fig. 3, the coefficient of thermal expansion of the cerate composite material of the present embodiment is as high as 13.272 × 10-6K-1(ambient temperature-1400 ℃ C.)
Example 2
The composition of the cerate composite material of the present example was (Eu)aSmaDyaTbaLua)2Ce2O7Wherein a is 1/5.
The cerate composite of the present example was prepared as follows:
1. preparation of the Mixed solution
Respectively using Eu (NO) with purity of 99.99%3)3·6H2O、Sm(NO3)3·6H2O、Dy(NO3)3·6H2O、Tb(NO3)3·6H2O、Lu(NO3)3·6H2Mixing each salt with water and stirring until the salts are dissolved to obtain five salt solutions with the concentration of 0.1mol/L, and mixing the five salt solutions to obtain a mixture of rare earth salt solutions;
with the purity of 99.99 percent of Ce (NO)3)3·6H2Mixing O as cerium salt with water and stirring until the salt is dissolved to obtain cerium salt solution with the concentration of 0.1 mol/L;
wherein Eu (NO)3)3·6H2O、Sm(NO3)3·6H2O、Tb(NO3)3·6H2O、Dy(NO3)3·6H2O、Lu(NO3)3·6H2O、Ce(NO3)3·6H2The molar ratio of O is 0.2: 0.2: 0.2: 0.2: 0.2: 1;
and mixing the mixture of the rare earth salt solution and the cerium salt solution, magnetically stirring for 1h, and filtering to remove insoluble impurities to obtain a transparent mixed solution.
2. Formation and collection of precipitate
Slowly dripping the mixed solution into ammonia water, stirring, and keeping the pH value of the reaction solution to be more than 9 in the process of dripping the mixed solution, thereby ensuring that metal ions can completely and uniformly form precipitates;
after the dropwise addition, the precipitate and water are mixed for a plurality of times by a high-speed centrifugation method for washing and separation, and the lower-layer precipitate is collected.
3. Preparation of cerate composite material
The precipitate was subjected to freeze-drying and calcination in this order to obtain a cerate composite powder of the present example.
Wherein the temperature of the freeze drying treatment is-40 ℃, and the time is 24 h; the temperature of the calcination treatment is 1500 ℃, and the time is 3 h.
The powder of the cerate composite material of the present embodiment was subjected toAnd (4) carrying out X-ray diffraction. Fig. 4 is an XRD spectrum of the cerate composite material of example 2 of the present invention, and as can be seen from comparison of fig. 4 with a standard PDF card of a single-phase rare earth cerate (lanthanum cerate), the composition of the cerate composite material prepared in this example is a2Ce2O7And is of fluorite structure.
Example 3
The composition of the cerate composite material of the embodiment is (Sm)aDyaTba)2Ce2O7Wherein a is 1/3.
The cerate composite of the present example was prepared as follows:
1. preparation of the Mixed solution
Respectively with a purity of Sm (NO)3)3·6H2O、Dy(NO3)3·6H2O、Tb(NO3)3·6H2Mixing each salt with water and stirring until the salts are dissolved to obtain three salt solutions with the concentration of 0.1mol/L, and mixing the three salt solutions to obtain a mixture of rare earth salt solutions;
with the purity of 99.99 percent of Ce (NO)3)3·6H2Mixing O as cerium salt with water and stirring until the salt is dissolved to obtain cerium salt solution with the concentration of 0.1 mol/L;
wherein Sm (NO)3)3·6H2O、Tb(NO3)3·6H2O、Dy(NO3)3·6H2O、Ce(NO3)3·6H2The molar ratio of O is 1/3: 1/3: 1/3: 1
And mixing the mixture of the rare earth salt solution and the cerium salt solution, magnetically stirring for 1h, and filtering to remove insoluble impurities to obtain a transparent mixed solution.
2. Formation and collection of precipitate
Slowly dripping the mixed solution into ammonia water, stirring, and keeping the pH value of the reaction solution to be more than 9 in the process of dripping the mixed solution, thereby ensuring that metal ions can completely and uniformly form precipitates;
after the dropwise addition, the precipitate and water are mixed for a plurality of times by a high-speed centrifugation method for washing and separation, and the lower-layer precipitate is collected.
3. Preparation of cerate composite material
The precipitate was subjected to freeze-drying and calcination in this order to obtain a cerate composite powder of the present example.
Wherein the temperature of the freeze drying treatment is-35 ℃ and the time is 6 h; the temperature of the calcination treatment is 1500 ℃, and the time is 3 h.
The powder of the cerate composite material of the present embodiment was subjected to X-ray diffraction. Fig. 5 is an XRD pattern of the cerate composite of example 3 of the present invention. As can be seen from comparison of the standard PDF card of the single-phase rare earth cerate (lanthanum cerate) in fig. 5, the composition of the cerate composite material prepared in this embodiment is a2Ce2O7And is of fluorite structure.
Example 4
The composition of the cerate composite material of the embodiment is (Sm)aEuaDyaTba)2Ce2O7Wherein a is 1/4.
The cerate composite of the present example was prepared as follows:
1. preparation of the Mixed solution
Respectively using Eu (NO) with purity of 99.99%3)3·6H2O、Sm(NO3)3·6H2O、Dy(NO3)3·6H2O、Tb(NO3)3·6H2O is used as rare earth element salt, each salt is mixed with water and stirred until the salt is dissolved, four salt solutions with the concentration of 0.1mol/L are obtained, and the four salt solutions are mixed to obtain a mixture of rare earth salt solutions;
with the purity of 99.99 percent of Ce (NO)3)3·6H2Mixing O as cerium salt with water and stirring until the salt is dissolved to obtain cerium salt solution with the concentration of 0.1 mol/L;
wherein Eu (NO)3)3·6H2O、Sm(NO3)3·6H2O、Tb(NO3)3·6H2O、Dy(NO3)3·6H2O、Ce(NO3)3·6H2The molar ratio of O is 1/4: 1/4: 1/4: 1/4: 1;
and mixing the mixture of the rare earth salt solution and the cerium salt solution, magnetically stirring for 1h, and filtering to remove insoluble impurities to obtain a transparent mixed solution.
2. Formation and collection of precipitate
Slowly dripping the mixed solution into ammonia water, stirring, and keeping the pH value of the reaction solution to be more than 9 in the process of dripping the mixed solution, thereby ensuring that metal ions can completely and uniformly form precipitates;
after the dropwise addition, the precipitate and water are mixed for a plurality of times by a high-speed centrifugation method for washing and separation, and the lower-layer precipitate is collected.
3. Preparation of cerate composite material
The precipitate was subjected to freeze-drying and calcination in this order to obtain a cerate composite powder of the present example.
Wherein the temperature of the freeze drying treatment is-50 ℃ and the time is 3 h; the temperature of the calcination treatment is 1500 ℃, and the time is 3 h.
The powder of the cerate composite material of the present embodiment was subjected to X-ray diffraction. Fig. 6 is an XRD spectrum of the cerate composite material of example 4 of the present invention, and as can be seen from comparison of fig. 6 with a standard PDF card of a single-phase rare earth cerate (lanthanum cerate), the composition of the cerate composite material prepared in this example is a2Ce2O7And is of fluorite structure.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A cerate composite material is characterized in that the composition of the cerate composite material is A2Ce2O7，
Wherein A is selected from at least three rare earth elements, and the mass ratio of any two rare earth elements in the at least three rare earth elements is X, 2/7 is less than or equal to X, and is less than or equal to 7/2.
2. The cerate composite of claim 1, wherein the rare earth element is selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Er, Y.
3. The cerate composite material of claim 2, wherein the ratio X of the amounts of the substances of any two rare earth elements is 1.
4. A method of preparing a cerate composite material as claimed in any one of claims 1 to 3, comprising the steps of:
1) mixing a cerium salt solution and at least three rare earth salt solutions to obtain a mixed solution;
2) mixing the mixed solution with alkali liquor, stirring, filtering, and collecting a filter cake;
3) sequentially carrying out freeze drying treatment and calcining treatment on the filter cake to obtain the cerate composite material;
wherein in the salt solution of at least three rare earth elements, the mass ratio of any two rare earth elements is X, X is not less than 2/7 and not more than 7/2;
the molar ratio of the cerium element in the cerium element salt solution to the sum of the rare earth elements in the at least three rare earth element salt solutions is (1-2): (1-2).
5. The method according to claim 4, wherein the cerium nitrate is mixed with water and stirred to obtain a salt solution of the cerium element.
6. The method according to claim 4, wherein the nitrate salts of at least three rare earth elements are mixed with water and stirred to obtain the salt solution of at least three rare earth elements.
7. The method of claim 4, wherein the alkali solution is ammonia.
8. The method for producing the cerate composite material according to claim 7, wherein in the step 2), the reaction liquid in which the mixed solution is mixed with the aqueous ammonia is maintained at a pH > 9.
9. The method as claimed in claim 4, wherein the calcination treatment is carried out at a temperature of 1000-1800 ℃ for a period of 2-48 h.
10. Use of a cerate composite as claimed in any of claims 1 to 3 in a thermal barrier coating.
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