CN114920559A - High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof - Google Patents
High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of materials for aerospace engines, and discloses a high-entropy oxide powder material for a thermal barrier coating, and a preparation method and application thereof 2 The fluorite structure of (A) is taken as a matrix, and a coprecipitation method is adopted to carry out reaction on CeO 2 At least two metal elements are introduced into the fluorite structure to obtain a high-entropy oxide powder material with a disordered fluorite structure; the metal elements include rare earth elements and transition group metal elements; the rare earth element is one or two of La and Pr; the transition metal element is one or two of Zr and Y. The invention uses coprecipitation method to synthesize micron-level high-entropy oxide powder material, and combines brushing method with vacuum melting methodThe preparation of the thermal barrier coating is completed, the high-entropy oxide powder material prepared by the invention overcomes the defects of the traditional YSZ material of the thermal barrier coating, can still maintain phase stability near 1500 ℃, and widens the thermal barrier coating material system to the high-entropy ceramic field.
Description
Technical Field
The invention relates to the technical field of materials for aerospace engines, in particular to a high-entropy oxide powder material for a thermal barrier coating, and a preparation method and application thereof.
Background
The Thermal Barrier Coating (TBC) is a thermal protection technology which adopts a ceramic material with high temperature resistance and low thermal conductivity to be compounded with metal in a coating mode so as to reduce the surface temperature of the metal in a high-temperature environment. The thermal barrier coating is mainly applied to hot end parts of an aircraft engine, and comprises high-pressure turbine guide vanes, turbine rotor blades, a combustion chamber and the like. High temperature protective coatings (thermal barrier coatings), high temperature structural materials, and high temperature cooling techniques have all contributed to three major problems in advanced turbine engines.
The hot end part of the aero-engine mainly comprises a metal material, and the metal material is difficult to resist in a working environment of about 1300 ℃, so that the mechanical property is seriously reduced, and the working safety of the engine is influenced. However, the cost for developing the ultra-high temperature resistant alloy material far exceeds the cost for developing a thermal barrier coating, so that the ceramic material thermal barrier coating with better high-temperature performance is prepared on the hot end component of the aircraft engine, and the method is a main method for solving the high-temperature protection problem.
To this end, those skilled in the art have proposed using MCrAlY (M ═ Ni, Co, Fe, Ni + Co) high temperature oxidation resistant alloy as a bond coat, Y 2 O 3 Stabilized ZrO 2 Ceramic (YSZ) thermal barrier coating. ZrO (ZrO) 2 Has excellent performances of high melting point, low thermal conductivity, high thermal expansion coefficient and the like, and is a preferred material of a thermal barrier coating ceramic layer. But pure ZrO 2 The phase stability is poor, the thermal shock resistance is not good, and the phase is not suitable for being directly used as a thermal barrier coating, and the common solution in the prior art is that ZrO is used as a heat barrier coating 2 Adding a stabilizer. The rare earth element is used as ZrO by those skilled in the art 2 When the temperature of the thermal barrier coating prepared by the stabilizing agent is higher than 1250 ℃ for a long time, the YSZ thermal barrier coating can generate phase change to generate cracks in the coating, and further cause the coating to fail.
Besides failure of the coating caused by phase change, the YSZ thermal barrier coating is easy to sinter and densify in the using process, so that the strain capacity of the coating is reducedThe limit is lowered and the heat insulating performance is lowered. When the surface temperature of the thermal barrier coating of the turbine blade exceeds 1200 ℃, sand dust and the like attached to the surface will melt. The main components of the deposits are CaO, MgO, and Al 2 O 3 ，SiO 2 Known as CMAS. The melted CMAS enters the coating and reacts with Y 2 O 3 A reaction occurs which causes the stabilizer to fail, further causing the YSZ coating to fail.
In order to solve the technical problems, the invention provides a high-entropy oxide powder material for a thermal barrier coating, and a preparation method and application thereof.
Disclosure of Invention
In order to solve the problems of poor thermal stability, limited use temperature, serious grain growth at high temperature, easy phase change, CMAS corrosion phenomena and the like of the conventional aluminum-based thermal barrier coating, the invention provides a high-entropy oxide powder material for the thermal barrier coating, and a preparation method and application thereof.
The invention designs a new high-entropy oxide ceramic material suitable for a heat-insulating coating of a hot-end component of an aeroengine according to the service requirement of a thermal barrier coating, completes the synthesis of micron-sized powder of the new material by using a coprecipitation method, and provides a technology combining a coating method with a vacuum melting method to complete the preparation of the thermal barrier coating. The new material makes up the defects of the traditional YSZ material of the thermal barrier coating, can still maintain phase stability near 1500 ℃, and widens the material system of the thermal barrier coating to the field of high-entropy ceramics.
The invention relates to a high-entropy oxide powder material for a thermal barrier coating, a preparation method and application thereof, which are realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of high-entropy oxide powder material for thermal barrier coating, which comprises the following steps:
by coprecipitation with CeO 2 With fluorite structure as matrix in CeO 2 At least two metal elements are introduced into the fluorite structure to obtain a high-entropy oxide powder material with a disordered fluorite structure;
the metal elements include rare earth elements and transition group metal elements; the rare earth element comprises one or two of La and Pr; the components of the transition group metal elements are one or two of Zr and Y.
Further, the components of the rare earth elements are La and Pr.
Further, the components of the transition group metal element are Zr and Y.
Further, each of the metal elements is introduced in an equimolar amount, and the introduced amount is allowed to fluctuate by 10% above and below the equimolar ratio.
Further, the preparation method of the high-entropy oxide powder material for the thermal barrier coating specifically comprises the following steps:
step 1, uniformly dispersing each metal element source in a water solvent to obtain a mixed solution containing multiple metal cations, then stirring the obtained mixed solution at 70-90 ℃, and adjusting the pH of a solution system to be 4-5 in the whole stirring treatment process by using citric acid to prevent the metal cations from being hydrolyzed in advance to obtain a mixture A;
step 2, adding a precipitator into the mixture A, and completely precipitating all metal cations in the mixture A through stirring treatment; and in the whole stirring treatment process, the pH value of the solution system is kept at 7-8, and the solution system is dried and ground until the particle size of the powder is less than or equal to 0.0385mm to obtain a mixture B;
and 3, sintering the mixture B at the temperature of 1000-1500 ℃ for 1-5 h, and performing ball milling to obtain the high-entropy ceramic powder material.
Further, the ratio of the total molar amount of the metal elements to the amount of the water solvent is 0.8-1.2 mol: 1L.
Further, in the step 2, the stirring time of the stirring treatment is 6-10 h.
The second purpose of the invention is to provide a high-entropy ceramic powder material prepared by the preparation method.
The third purpose of the invention is to provide the application of the high-entropy ceramic powder material in preparing thermal barrier coatings.
Further, a thermal barrier coating is made by:
step A, performing wet ball milling treatment on the high-entropy ceramic powder material, and drying to obtain ball-milled high-entropy ceramic powder;
and step B, uniformly mixing the ball-milled high-entropy ceramic powder with a binder and an aqueous solvent to prepare mixed slurry, uniformly coating the mixed slurry on a base material, freeze-drying, and vacuum-melting for 5-10 s to obtain the thermal barrier coating.
Further, the binder is polyoxyethylene-8-octylphenyl ether.
Furthermore, in the mixed slurry, the volume concentration of the high-entropy ceramic powder is 10-35%.
Furthermore, the mass ratio of the adhesive to the high-entropy ceramic powder after ball milling is 0.08-0.12: 1.
Further, the processing solvent of the wet ball milling treatment is absolute ethyl alcohol, the ball-to-material ratio is 8-12: 1, and the ball milling time is 1-3 hours.
Compared with the prior art, the invention has the following beneficial effects:
the invention designs a new high-entropy oxide ceramic material suitable for a heat insulation coating of a hot end component of an aero-engine according to the service requirement of a thermal barrier coating, completes the synthesis of micron-sized powder of the new material by using a coprecipitation method, and provides a technology combining a coating method with a vacuum melting method to complete the preparation of the thermal barrier coating. The new material makes up the defects of the traditional YSZ material of the thermal barrier coating, can still keep phase stability near 1500 ℃, and widens the thermal barrier coating material system to the high-entropy ceramic field.
The invention provides a new oxide high-entropy ceramic powder and a preparation method of a coating thereof, in CeO 2 A large amount of rare earth elements and other transition group metal elements are introduced into the fluorite structure, and the design and preparation of the high-entropy oxide with the disordered fluorite structure are completed. The existence of a large amount of metal atoms with larger mass leads to the doped CeO 2 A large number of defects are generated in the disordered fluorite structure, the mean free path of phonon propagation in the disordered fluorite structure is reduced, phonon scattering is increased, and the thermal conductivity of the high-entropy oxide material is greatly reduced. The high-entropy oxide has high thermal stability in high-temperature environmentThe material has very low thermal conductivity, and can maintain stable phase structure and no obvious grain growth phenomenon in high temperature environment.
The invention selects rare earth elements La, Ce and Pr, transition metal elements Zr and Y and the like as the components of the high-entropy oxide, and when the elements are independently used as the oxides, the high-entropy oxide has excellent performances of high thermal stability, good oxidation resistance, corrosion resistance, creep resistance, slow grain growth and the like. And when the engine blade material is Al 2 O 3 When the composite material is used as a thermal barrier coating on the surface of the composite material, the high-entropy oxide synthesized by the invention is mixed with Al 2 O 3 Matched thermal expansion coefficients (all of which are 3-4 multiplied by 10) -6 /K)。
The coprecipitation method is used when the high-entropy oxide powder material is synthesized, the oxide synthesized by the method has the characteristics of uniform element distribution, small and uniform powder particle size and the like, and the method has low requirements on equipment and is simple. The synthesized micron-sized oxide high-entropy ceramic powder can be directly prepared into slurry, and the subsequent coating preparation is completed by a brushing method and the like; in addition, after the powder material with uniform particle size distribution is granulated, the additive manufacturing method such as plasma spraying can be used for completing the preparation of high-quality compact coating.
The coating method combines the preparation technology of the composite coating by vacuum melting, and provides a thought for preparing the coating by preparing slurry from powder. The brushing method is simple to operate, the thickness of the coating can be controlled, and the adhesive is added when the slurry is prepared, so that weak bonding is generated between the brushing layer and the substrate. Vacuum melting causes mutual diffusion between the coating layer and the substrate, so that weak bonding is changed into strong bonding, and the preparation of a high-quality thermal barrier coating with excellent performance is completed.
Drawings
FIG. 1 is a schematic structural view of a high-entropy oxide ceramic powder according to example 1 of the present invention;
FIG. 2 is a photograph of an object of the high-entropy oxide prepared by the present invention, wherein FIG. 2(a) is a photograph of an object of the high-entropy oxide of example 1; FIG. 2(b) is a photomicrograph of the high entropy oxide of example 2; FIG. 2(c) is a photomicrograph of the high entropy oxide of example 3; FIG. 2(d) is a photomicrograph of the high entropy oxide of example 4;
FIG. 3 is an X-ray diffraction pattern of a high-entropy oxide prepared by the present invention, wherein FIG. 3(a) is an X-ray diffraction pattern of a high-entropy oxide of example 1; FIG. 3(b) is an X-ray diffraction pattern of the high entropy oxide of example 2; FIG. 3(c) is an X-ray diffraction pattern of the high entropy oxide of example 3; FIG. 3(d) is an X-ray diffraction pattern of the high entropy oxide of example 4;
FIG. 4 is an elemental energy spectrum distribution (EDS) plot of a high entropy oxide powder prepared in accordance with the present invention;
FIG. 5 is a photograph of transmission electron diffraction pattern of the high-entropy oxide powder prepared in accordance with the present invention;
FIG. 6 shows a high-entropy oxide coating prepared by the present invention and using SiC composite material as matrix.
Detailed Description
As described in the background, YSZ thermal barrier coatings not only fail due to phase transformation, but they are susceptible to densification by sintering during use, resulting in reduced strain tolerance and reduced thermal insulation properties of the coating.
Based on the research of YSZ coating, the inventors found that besides the traditional YSZ material, rare earth zirconate material (REZ) with fluorite structure or pyrochlore structure has more vacancies inside, the unit cell structure is more complex, and the large mass of rare earth atoms can greatly increase phonon scattering, which results in the reduction of phonon mean free path, and the thermal conductivity of the material is reduced. REZ has the advantages of low thermal conductivity, good high temperature stability, sintering resistance, etc., but compared to YSZ, REZ has a lower thermal expansion coefficient and fracture toughness, which limits the wide application of REZ.
In order to solve the problem, the invention provides a high-entropy oxide powder material for a thermal barrier coating, a preparation method and application thereof, and the technical scheme in the embodiment of the invention will be clearly and completely described below by combining the drawings in the embodiment of the invention.
Example 1
The embodiment provides a high-entropy oxide powder material for a thermal barrier coating, which has the composition of (La, Ce, Pr, Zr) O; the preparation method of the high-entropy oxide powder material of the embodiment is as follows:
step 1, uniformly dispersing various metal element sources, namely an La source, a Ce source, a Pr source and a Zr source in an equimolar ratio in a water solvent (deionized water) to prepare a homogeneous mixed solution with the concentration of 1M, then adding an acid solution into the prepared homogeneous mixed solution, and stirring at the temperature of 80 ℃ to uniformly mix the homogeneous mixed solution to obtain a mixture A;
it should be noted that specific types of the La source, the Ce source, the Pr source, and the Zr source are not limited in this embodiment as long as the corresponding metal elements can be provided. In this embodiment, the nitrate hydrate of each element may be optionally used as a raw material, i.e., La (NO) 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 O、ZrO(NO 3 ) 2 ·xH 2 Adding O as raw material.
The embodiment does not limit the specific manner of dispersing the metal in the water solvent, as long as the raw material corresponding to each metal element can be uniformly dissolved in the deionized water. In this embodiment, a magnetic stirring manner may be optionally adopted for dispersing, and in this embodiment, the stirring speed is 400rpm, and the stirring temperature is room temperature.
In the present embodiment, the specific acid solution component for adjusting the pH is not limited as long as the metal cations in the solution can be prevented from being hydrolyzed in advance. In the embodiment, citric acid is used as the acid solution, the citric acid can adjust the pH value to be 4-5, so that the metal cations are prevented from being hydrolyzed in advance, impurities introduced into the solution by the citric acid can be removed in the subsequent washing, drying and sintering processes, and the purity of subsequent products cannot be influenced.
Step 2, adding a precipitator into the mixture A, and completely precipitating all metal cations in the mixture A through stirring treatment; and in the whole stirring treatment process, the pH value of the solution system is kept at 7-8, the solution system is ground until the particle size of the powder is less than or equal to 0.0385mm after drying, and the mixture B is obtained after surface impurities are washed away and drying;
in this embodiment, the specific heating and stirring manner in step 2 is not limited, as long as the solution can be heated and stirred at the same time, so as to ensure that the precipitation reaction is fully performed. In this embodiment, a magnetic stirring water bath using dimethylsilicone oil as a medium may be optionally used for heating and stirring.
The present example does not limit the specific components of the precipitant, so long as all the metal cations in the mixture a can be completely precipitated. According to the embodiment, an ammonia water solution with the concentration of 15% is optionally adopted as a precipitator, so that all metal cations in the compound A are completely precipitated, and meanwhile, the pH value of the solution can be adjusted to be kept between 7 and 8. Specifically, in the embodiment, the mixture a is stirred at a constant temperature of 80 ℃ for 8 hours, and in the first 4 hours, an ammonia water solution with a concentration of 15% is dripped to completely precipitate all metal cations in the compound a, and meanwhile, the pH of the solution is adjusted to be 7-8, and the stirring speed is set to be 400 rpm; and after 4 hours, the viscosity of the mixture obviously rises, the rotating speed is adjusted to 550rpm, an ammonia water solution with the concentration of 15% is not dripped any more, and the pH value of the mixture can still be kept between 7 and 8. In this embodiment, an ammonia solution with a concentration of 15% is used for adjustment, the introduced impurity ions are all water-soluble, and deionized water is subsequently used for washing the precipitate.
In this embodiment, if other compounds are used as the precipitating agent and the pH adjusting agent, the detergent for subsequently cleaning the precipitate can be selected according to the kind of the compound.
In this example, in step 2, a washing treatment is further performed after the polishing treatment, but the specific manner of the washing treatment is not limited in this example as long as the water-soluble NH attached to the surface of the product can be removed 4+ And NO 3- And (5) removing. This example can be optionally washed 3-5 times by flowing deionized water to remove the water-soluble NH attached to the surface 4+ And NO 3- After washing, the mixture is treated at the temperature of 120 ℃ for 12h to remove the water solvent on the surface, and then the mixture is dried to obtain a mixture B.
In this example, the specific drying method of the drying treatment in step 2 is not limited as long as the solvent in the product can be removed. In this example, the product of each stage may be optionally dried in a hot air dryer at 120 ℃ for 12 hours.
This example does not limit the specific manner of milling in step 2, as long as the milled powder can pass through a sieve having an aperture of 0.0385 mm. In the embodiment, the grinding time is 2h by using a disc grinder.
And 3, sintering the mixture B at 1400 ℃ for 2h, and performing ball milling to obtain the micron-level high-entropy ceramic powder material.
It should be noted that, in this embodiment, the specific temperature increase rate in step 3 is not limited, as long as the mixture B can be ensured to be increased to 1400 ℃ at a stable temperature increase rate. In this embodiment, optionally
Heating to 1400 ℃ at a heating rate of less than or equal to 10 ℃/min and then sintering.
The specific ball milling method in step 3 is not limited in this embodiment, as long as the powder can be sufficiently dispersed and the particle size of the obtained powder is uniformly distributed in the range of 0.1 to 1 μm. In this embodiment, a wet ball milling method may be optionally used for ball milling, and the ball milling aid for ball milling in this embodiment is absolute ethanol, and the ball-to-material ratio is 10:1, the mass ratio of the absolute ethyl alcohol to the powder is 1: 1, ball milling time is 2 h.
In the embodiment, nitrates of each element are used as raw materials, a hydroxide precipitate precursor is prepared by adopting a coprecipitation method, and the obtained hydroxide precipitate precursor is sintered for thermal decomposition, so that high-entropy oxide powder is obtained.
Example 2
The embodiment provides a high-entropy oxide powder material for a thermal barrier coating, which has the composition of (La, Ce, Y, Zr) O; and the preparation method of the high-entropy oxide powder material of the embodiment is different from that of the embodiment 1 only in that:
in this example, the raw material of nitrate hydrate of each element, i.e., La (NO) 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Y(NO 3 ) 3 ·6H 2 O、ZrO(NO 3 ) 2 ·xH 2 Adding O as raw material.
Example 3
The embodiment provides a high-entropy oxide powder material for a thermal barrier coating, which has the composition of (La, Ce, Y, Pr, Zr) O; and the preparation method of the high-entropy oxide powder material of the embodiment is different from that of the embodiment 1 only in that:
in this example, the raw material of nitrate hydrate of each element, i.e., La (NO) 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 O、Y(NO 3 ) 3 ·6H 2 O、ZrO(NO 3 ) 2 ·xH 2 O is added as raw material.
Example 4
The embodiment provides a high-entropy oxide powder material for a thermal barrier coating, which has the composition of (La, Ce, Y, Zr) O; and the preparation method of the high-entropy oxide powder material of the embodiment is different from that of the embodiment 2 only in that:
in this example, the sintering temperature in step 3 was 1200 ℃.
Example 5
The present embodiment provides a thermal barrier coating, and a method for preparing the thermal barrier coating of the present embodiment is as follows:
step A, carrying out wet ball milling treatment on the high-entropy ceramic powder material prepared in any one of the embodiments 1 to 4, and drying to obtain ball-milled high-entropy ceramic powder;
in the step a of this embodiment, the specific conditions of the wet ball milling process are not limited, and the ball milling process is performed until the particle size is 0.1 to 1 μm. In this embodiment, a planetary high-energy ball milling device is optionally used for wet ball milling, and the ball milling assistant in this embodiment is absolute ethyl alcohol, the ball-to-material ratio is 10:1, the planetary ball milling parameter is standby for 15min after 45min forward and reverse rotation, the rotation speed is 400rpm/min, and the ball milling time is 24 h.
In this embodiment, the specific manner of drying is not limited in step a, as long as the auxiliary used in the ball milling and the absolute ethyl alcohol can be removed. In the embodiment, the drying treatment can be realized by optionally adopting freeze drying at the temperature of lower than-40 ℃ for 24 h.
Step B, uniformly mixing the ball-milled high-entropy ceramic powder with a binder and a water solvent to prepare mixed slurry, wherein the volume fraction of the high-entropy ceramic powder in the mixed slurry is 10-35%; and then, uniformly coating the mixed slurry on a base material, freeze-drying, and vacuum-melting for 5-10 s to obtain the thermal barrier coating.
It should be noted that, in this embodiment, the specific type of the binder is not limited, and the high-entropy ceramic powder after ball milling and the water solvent can be prepared into a uniform mixed slurry. In this embodiment, in order to increase the powder viscosity and the binder can be decomposed in the subsequent vacuum melting, triton X-100, i.e., polyoxyethylene-8-octylphenyl ether, is optionally used as the binder. In the present embodiment, the amount of the binder added is 0.5% to 1% by mass of the oxide high-entropy ceramic powder.
The present embodiment is not limited to a specific coating manner as long as the mixed slurry can be uniformly coated on the surface of the base material. In the embodiment, the coating is preferably performed by brushing, and the thickness of the coating obtained by brushing and drying in one time in the embodiment is 10 to 100 μm.
The present embodiment does not limit the specific vacuum condition as long as a vacuum environment can be provided. In this embodiment, a vacuum arc melting device is optionally used for vacuum melting, and the vacuum degree in the melting chamber in the melting process of this embodiment is 10 -4 Pa, surface area for melting is 100mm 2 And the smelting time is 5-10 s.
In this embodiment, the high-entropy oxide powder prepared by the present invention is coated on a substrate after being prepared into slurry, so as to prepare a weakly-bonded high-entropy oxide coating, and then a vacuum melting technology is combined to further realize strong bonding between the coating and the substrate.
Example 6
The present embodiment provides a high-entropy oxide powder material for thermal barrier coating, which has a composition of (La, Ce, Y) O; and the preparation method of the high-entropy oxide powder material of the present example is different from that of example 1 only in that:
in this example, the nitrate hydrate of each element was used as a raw material, i.e., La (NO) 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Y(NO 3 ) 3 ·6H 2 Adding O as raw material.
Example 7
The present embodiment provides a high-entropy oxide powder material for thermal barrier coating, which has a composition of (Pr, Ce, Zr) O; and the preparation method of the high-entropy oxide powder material of the present example is different from that of example 1 only in that:
in this example, each element nitrate hydrate was used as a raw material, i.e., Pr (NO) 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、ZrO(NO 3 ) 2 ·xH 2 O is added as raw material.
Experimental part
(I) structural testing
The present invention is exemplified by the high entropy oxide ceramic powder prepared in example 1, and the structure test is performed, and the test result is shown in fig. 1.
As can be seen from fig. 1: in the high-entropy oxide crystal structure of the defect fluorite structure synthesized by the invention, all cations are randomly positioned at a 4a lattice point, and oxygen vacancies are formed due to the introduction of the + 3-valent rare earth element, so that the disorder degree of a system and phonon scattering are increased, and the material has the characteristic of low thermal conductivity.
(II) photograph of powder
The invention takes the high-entropy oxide ceramic powder prepared in examples 1-4 as an example, and the obtained product real objects are respectively photographed, and the results are shown in FIG. 2, wherein FIG. 2(a) is a real object photograph of the high-entropy oxide in example 1; FIG. 2(b) is a photomicrograph of the high entropy oxide of example 2; FIG. 2(c) is a photomicrograph of the high entropy oxide of example 3; FIG. 2(d) is a photomicrograph of the high entropy oxide of example 4.
As can be seen from fig. 2: the high-entropy oxide powders synthesized in the present invention have different macroscopic morphologies, the colors of the powders are different due to the difference of the kinds of rare earth elements, examples 1 and 3 containing Pr element are dark curry, and examples 2 and 4 containing no Pr element are off-white.
(III) X-ray diffraction test
Taking the high-entropy oxide ceramic powders prepared in examples 1 to 4 as examples, the obtained product real objects are respectively subjected to X-ray diffraction tests, and the results are shown in FIG. 3, wherein FIG. 3(a) is an X-ray diffraction spectrum of the high-entropy oxide in example 1; FIG. 3(b) is an X-ray diffraction pattern of the high entropy oxide of example 2; FIG. 3(c) is an X-ray diffraction pattern of the high entropy oxide of example 3; FIG. 3(d) is the X-ray diffraction pattern of the high entropy oxide of example 4.
(IV) elemental Spectroscopy testing
The invention takes the high entropy oxide ceramic powder prepared in example 1 as an example, and element energy spectrum (EDS) test is carried out on the high entropy oxide ceramic powder, and the test result is shown in FIG. 4.
As can be seen from fig. 4: the high-entropy oxide ceramic powder prepared by the invention has uniform distribution of each element, does not have element segregation, and can be further proved to successfully synthesize the high-entropy oxide which has a single product phase and uniform components and takes disordered fluorite as a structure by being matched with the result of figure 3.
(V) Transmission Electron diffraction test
The invention takes the high-entropy oxide ceramic powder prepared in example 1 as an example, and the transmission electron diffraction test is carried out on the high-entropy oxide ceramic powder, and the test result is shown in fig. 5.
As can be seen from fig. 5: the crystal structure of the high-entropy oxide ceramic powder prepared by the invention is FCC, and the lattice constant is
With CeO having fluorite structure 2 The lattice constants of the materials are different due to La 3+ 、Y 3+ And Zr 4+ With Ce 4+ The ions have different ionic radii, and during the formation of the high-entropy oxide, the solid solution phenomenon of the metal cations causes the metal cations to have lattice distortion, which is represented by the change of the lattice constant marked in fig. 5.
(VI) preparation of the coating
In this example, the SiC composite material is used as a base material, and the coating effect is shown in fig. 6 by coating the SiC composite material by the method of example 5, wherein the left side is the uncoated SiC/SiC composite material, the middle is the sample coated with the high-entropy oxide, and the right side is the sample coated with the high-entropy oxide after vacuum melting.
As can be seen from fig. 6: the weakly-bonded high-entropy oxide prepared by the coating method is uniform in thickness, and after vacuum melting, the weak bonding is changed into strong bonding, so that the coating can still maintain certain integrity.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. 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.
Claims (10)
1. A preparation method of a high-entropy oxide powder material for a thermal barrier coating is characterized by comprising the following steps:
by coprecipitation with CeO 2 With fluorite structure as matrix in CeO 2 At least two metal elements are introduced into the fluorite structure to obtain a high-entropy oxide powder material with a disordered fluorite structure;
the metal elements include rare earth elements and transition group metal elements; the rare earth element is one or two of La and Pr; the transition metal element is one or two of Zr and Y.
2. The method according to claim 1, wherein each of said metal elements is introduced in an equimolar amount, and the introduced amount is allowed to fluctuate by 10% from the equimolar ratio.
3. The preparation method according to claim 1, characterized by comprising the following steps:
step 1, uniformly dispersing each metal element source in a water solvent to obtain a mixed solution containing multiple metal cations, then stirring the obtained mixed solution at the temperature of 70-90 ℃, and keeping the pH of a solution system at 4-5 in the whole stirring treatment process to obtain a mixture A;
step 2, adding a precipitator into the mixture A, and completely precipitating all metal cations in the mixture A through stirring treatment; in the whole stirring treatment process, the pH value of the solution system is kept at 7-8, and the solution system is dried and ground until the particle size of the powder is less than or equal to 0.0385mm to obtain a mixture B;
and 3, sintering the mixture B at the temperature of 1000-1500 ℃ for 1-5 h, and performing ball milling to obtain the micron-level high-entropy ceramic powder material.
4. The method according to claim 3, wherein the ratio of the total molar amount of the metal element to the amount of the water solvent is 0.8 to 1.2mol: 1L.
5. The preparation method according to claim 3, wherein in the step 2, the stirring time of the stirring treatment is 6 to 10 hours.
6. A high-entropy ceramic powder material produced by the production method according to any one of claims 1 to 5.
7. Use of the high-entropy ceramic powder material as claimed in claim 6 for producing thermal barrier coatings.
8. The use of claim 7, wherein the thermal barrier coating is made by:
step A, performing wet ball milling treatment on the high-entropy ceramic powder material until the particle size of the powder is 0.1-1 mu m, and drying to obtain ball-milled high-entropy ceramic powder;
and step B, uniformly mixing the ball-milled high-entropy ceramic powder with a binder and an aqueous solvent to prepare mixed slurry, uniformly coating the mixed slurry on a base material, freeze-drying, and vacuum-melting for 5-10 s to obtain the thermal barrier coating.
9. The use according to claim 7, wherein the binder is polyoxyethylene-8-octylphenyl ether.
10. The use according to claim 7, wherein the volume concentration of the high-entropy ceramic powder in the mixed slurry is 10-35%;
the mass ratio of the adhesive to the ball-milled high-entropy ceramic powder is 0.08-0.12: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368134A (en) * | 2022-08-29 | 2022-11-22 | 中国科学院兰州化学物理研究所 | High-entropy oxide ceramic material resisting molten salt corrosion and preparation method thereof |
| CN116375470A (en) * | 2023-03-31 | 2023-07-04 | 太原理工大学 | Preparation method of fluorite type high-entropy ceramic |
Citations (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900639A (en) * | 1986-06-25 | 1990-02-13 | 501 Glyco-Metall-Werke Daelen | Cladding of bearing metal and process for production thereof |
| US5560993A (en) * | 1994-02-16 | 1996-10-01 | Mitsubishi Jukogyo Kabushiki Kaisha | Oxide-coated silicon carbide material and method of manufacturing same |
| CN1891633A (en) * | 2005-07-01 | 2007-01-10 | 中南大学 | Method for preparing nano antimony-doped tin dioxide powder |
| CN101037224A (en) * | 2007-02-15 | 2007-09-19 | 苏州大学 | Preparation process of antimony doped stannum oxide nano-crystal |
| CN101597022A (en) * | 2009-07-15 | 2009-12-09 | 河北理工大学 | A kind of preparation method of antimony doped stannic oxide nano powder |
| CN101830731A (en) * | 2010-06-09 | 2010-09-15 | 哈尔滨工业大学（威海） | Method for preparing carbon material surface ceramic coat |
| CN102617147A (en) * | 2012-04-17 | 2012-08-01 | 江苏科技大学 | Perovskite structure aluminate-based mixing conductive ceramics and preparation method thereof |
| CN102732902A (en) * | 2011-04-15 | 2012-10-17 | 洪若瑜 | Preparation method of conductive metal oxide nanorod |
| CN105887117A (en) * | 2014-12-26 | 2016-08-24 | 苏州纳康纳米材料有限公司 | Preparation method for tin oxide one-dimensional nano material |
| CN107266128A (en) * | 2017-07-13 | 2017-10-20 | 北京理工大学 | A kind of silicate Environmental Barrier Coatings on Si-based Ceramics and preparation method thereof |
| US20180086672A1 (en) * | 2016-09-27 | 2018-03-29 | Skyworks Solutions, Inc. | Enhanced fracture toughness thermal barrier coating material |
| CN108998716A (en) * | 2018-07-26 | 2018-12-14 | 江苏理工学院 | A kind of preparation method of electric arc deposited powder cored filament material and its high entropy alloy coating |
| CN110273077A (en) * | 2019-07-12 | 2019-09-24 | 长沙理工大学 | A kind of preparation method of large scale infusibility high-entropy alloy |
| CN110776310A (en) * | 2019-11-06 | 2020-02-11 | 常州大学 | Method for preparing perovskite type composite oxide high-entropy ceramic powder by coprecipitation of ion compensation mixture |
| CN110845237A (en) * | 2019-11-28 | 2020-02-28 | 太原理工大学 | High-entropy ceramic powder, preparation method thereof and high-entropy ceramic block |
| US10604454B1 (en) * | 2016-06-16 | 2020-03-31 | United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration | Advanced high temperature environmental barrier coating for SiC/SiC ceramic matrix composites |
| CN111097429A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
| CN111235511A (en) * | 2020-03-15 | 2020-06-05 | 河北工业大学 | Preparation method of multi-element ceramic composite coating |
| CN111254379A (en) * | 2020-03-15 | 2020-06-09 | 河北工业大学 | Preparation method of high-entropy ceramic coating |
| CN111302781A (en) * | 2020-02-27 | 2020-06-19 | 中钢集团南京新材料研究院有限公司 | Preparation method of Fe-Ti-Ni-Co-Mn high-entropy oxide ceramic material |
| CN111349800A (en) * | 2020-03-25 | 2020-06-30 | 石家庄铁道大学 | Preparation method of high-entropy alloy duplex process |
| CA3106049A1 (en) * | 2018-10-09 | 2020-07-09 | Oerlikon Metco (Us) Inc. | High-entropy oxides for thermal barrier coating (tbc) top coats |
| CN113023776A (en) * | 2021-03-10 | 2021-06-25 | 上海交通大学 | Fluorite-structured high-entropy oxide powder for thermal barrier coating and preparation method thereof |
| CN113248255A (en) * | 2021-03-08 | 2021-08-13 | 东南大学 | High-temperature heat-insulation fluorite type intermediate entropy oxide and preparation method thereof |
| CN113683430A (en) * | 2021-10-12 | 2021-11-23 | 西北工业大学 | Oxide high-entropy ceramic with defect fluorite structure and preparation method of anti-ablation coating thereof |
| CN113772723A (en) * | 2021-09-23 | 2021-12-10 | 中国地质大学（武汉） | CMAS corrosion-resistant multi-component high-entropy pyrochlore structure thermal barrier coating material and preparation method and application thereof |
| US20220134316A1 (en) * | 2020-11-03 | 2022-05-05 | National Technology & Engineering Solutions Of Sandia, Llc | Synthesis of high surface area, high entropy oxides |
| CN114516657A (en) * | 2021-12-27 | 2022-05-20 | 上海交通大学 | High-entropy oxide ceramic nanocrystalline and preparation method and application thereof |
-
2022
- 2022-06-07 CN CN202210632009.9A patent/CN114920559A/en active Pending
Patent Citations (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900639A (en) * | 1986-06-25 | 1990-02-13 | 501 Glyco-Metall-Werke Daelen | Cladding of bearing metal and process for production thereof |
| US5560993A (en) * | 1994-02-16 | 1996-10-01 | Mitsubishi Jukogyo Kabushiki Kaisha | Oxide-coated silicon carbide material and method of manufacturing same |
| CN1891633A (en) * | 2005-07-01 | 2007-01-10 | 中南大学 | Method for preparing nano antimony-doped tin dioxide powder |
| CN101037224A (en) * | 2007-02-15 | 2007-09-19 | 苏州大学 | Preparation process of antimony doped stannum oxide nano-crystal |
| CN101597022A (en) * | 2009-07-15 | 2009-12-09 | 河北理工大学 | A kind of preparation method of antimony doped stannic oxide nano powder |
| CN101830731A (en) * | 2010-06-09 | 2010-09-15 | 哈尔滨工业大学（威海） | Method for preparing carbon material surface ceramic coat |
| CN102732902A (en) * | 2011-04-15 | 2012-10-17 | 洪若瑜 | Preparation method of conductive metal oxide nanorod |
| CN102617147A (en) * | 2012-04-17 | 2012-08-01 | 江苏科技大学 | Perovskite structure aluminate-based mixing conductive ceramics and preparation method thereof |
| CN105887117A (en) * | 2014-12-26 | 2016-08-24 | 苏州纳康纳米材料有限公司 | Preparation method for tin oxide one-dimensional nano material |
| US10604454B1 (en) * | 2016-06-16 | 2020-03-31 | United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration | Advanced high temperature environmental barrier coating for SiC/SiC ceramic matrix composites |
| US20180086672A1 (en) * | 2016-09-27 | 2018-03-29 | Skyworks Solutions, Inc. | Enhanced fracture toughness thermal barrier coating material |
| CN107266128A (en) * | 2017-07-13 | 2017-10-20 | 北京理工大学 | A kind of silicate Environmental Barrier Coatings on Si-based Ceramics and preparation method thereof |
| CN108998716A (en) * | 2018-07-26 | 2018-12-14 | 江苏理工学院 | A kind of preparation method of electric arc deposited powder cored filament material and its high entropy alloy coating |
| CA3106049A1 (en) * | 2018-10-09 | 2020-07-09 | Oerlikon Metco (Us) Inc. | High-entropy oxides for thermal barrier coating (tbc) top coats |
| US20210347699A1 (en) * | 2018-10-09 | 2021-11-11 | Oerlikon Metco (Us) Inc. | High-entropy oxides for thermal barrier coating (tbc) top coats |
| CN112839915A (en) * | 2018-10-09 | 2021-05-25 | 欧瑞康美科（美国）公司 | High entropy oxide for Thermal Barrier Coating (TBC) topcoats |
| CN111097429A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
| CN110273077A (en) * | 2019-07-12 | 2019-09-24 | 长沙理工大学 | A kind of preparation method of large scale infusibility high-entropy alloy |
| CN110776310A (en) * | 2019-11-06 | 2020-02-11 | 常州大学 | Method for preparing perovskite type composite oxide high-entropy ceramic powder by coprecipitation of ion compensation mixture |
| CN110845237A (en) * | 2019-11-28 | 2020-02-28 | 太原理工大学 | High-entropy ceramic powder, preparation method thereof and high-entropy ceramic block |
| CN111302781A (en) * | 2020-02-27 | 2020-06-19 | 中钢集团南京新材料研究院有限公司 | Preparation method of Fe-Ti-Ni-Co-Mn high-entropy oxide ceramic material |
| CN111254379A (en) * | 2020-03-15 | 2020-06-09 | 河北工业大学 | Preparation method of high-entropy ceramic coating |
| CN111235511A (en) * | 2020-03-15 | 2020-06-05 | 河北工业大学 | Preparation method of multi-element ceramic composite coating |
| CN111349800A (en) * | 2020-03-25 | 2020-06-30 | 石家庄铁道大学 | Preparation method of high-entropy alloy duplex process |
| US20220134316A1 (en) * | 2020-11-03 | 2022-05-05 | National Technology & Engineering Solutions Of Sandia, Llc | Synthesis of high surface area, high entropy oxides |
| CN113248255A (en) * | 2021-03-08 | 2021-08-13 | 东南大学 | High-temperature heat-insulation fluorite type intermediate entropy oxide and preparation method thereof |
| CN113023776A (en) * | 2021-03-10 | 2021-06-25 | 上海交通大学 | Fluorite-structured high-entropy oxide powder for thermal barrier coating and preparation method thereof |
| CN113772723A (en) * | 2021-09-23 | 2021-12-10 | 中国地质大学（武汉） | CMAS corrosion-resistant multi-component high-entropy pyrochlore structure thermal barrier coating material and preparation method and application thereof |
| CN113683430A (en) * | 2021-10-12 | 2021-11-23 | 西北工业大学 | Oxide high-entropy ceramic with defect fluorite structure and preparation method of anti-ablation coating thereof |
| CN114516657A (en) * | 2021-12-27 | 2022-05-20 | 上海交通大学 | High-entropy oxide ceramic nanocrystalline and preparation method and application thereof |
Non-Patent Citations (7)
| Title |
|---|
| DONG Y等: "high-entropy environmental barrier coating for the ceramic matrix composites", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| DONG Y等: "high-entropy environmental barrier coating for the ceramic matrix composites", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》, vol. 37, no. 7, 31 July 2019 (2019-07-31), pages 2574 - 2579 * |
| 刘喜明 等: "氩弧熔覆Ni35B-SiC层的强化机制", 《金属热处理学报》 * |
| 刘喜明 等: "氩弧熔覆Ni35B-SiC层的强化机制", 《金属热处理学报》, vol. 20, no. 4, 31 December 1999 (1999-12-31), pages 41 - 45 * |
| 张丰年等: "高熵陶瓷(Zr1/7Hf1/7Ce1/7Y2/7La2/7)O2-δ的制备及烧结行为", 《无机材料学报》 * |
| 张丰年等: "高熵陶瓷(Zr1/7Hf1/7Ce1/7Y2/7La2/7)O2-δ的制备及烧结行为", 《无机材料学报》, vol. 36, no. 4, 30 April 2021 (2021-04-30), pages 372 - 378 * |
| 彭迎慧;徐旺生;: "配合-均相沉淀法制备纳米掺锑氧化锡", 无机盐工业, no. 03, pages 30 - 31 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368134A (en) * | 2022-08-29 | 2022-11-22 | 中国科学院兰州化学物理研究所 | High-entropy oxide ceramic material resisting molten salt corrosion and preparation method thereof |
| CN116375470A (en) * | 2023-03-31 | 2023-07-04 | 太原理工大学 | Preparation method of fluorite type high-entropy ceramic |
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