CN113929453A - Rare earth-based heat-insulating porous high-entropy ceramic and preparation method thereof - Google Patents
Rare earth-based heat-insulating porous high-entropy ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of rare earth-based heat-insulating porous high-entropy ceramic, which comprises the following steps: s1, synthesizing the rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving at least five rare earth nitrates and a zirconium-containing salt in water, adding citric acid monohydrate, and stirring to dissolve to obtain a clear solution; adding ethylene glycol into the solution, cooling to room temperature after reaction, adding ammonia water to adjust the pH value to 5.0-7.0, and evaporating to dryness to obtain dry gel; sintering the dried gel at high temperature, and performing ball milling to obtain high-entropy ceramic powder; s2, mixing the rare earth high-entropy ceramic powder with an inorganic binder, a reinforcing fiber, a dispersing agent and water, uniformly dispersing, freezing and drying in liquid nitrogen, and calcining at high temperature to obtain the rare earth-based porous high-entropy ceramic. The invention utilizes the rare earth element doping to design the high-entropy material, reduces the phonon mean free path, increases the mass scattering and bond disorder, improves the valence electron coverage space, and simultaneously utilizes the porosification of the material, increases the specific surface area of the material and reduces the thermal conductivity of the material.
Description
Technical Field
The invention belongs to the technical field of porous high-entropy ceramic materials, and particularly relates to a rare earth-based heat-insulating porous high-entropy ceramic and a preparation method thereof.
Background
Thermal Barrier Coatings (TBCs) are widely used in aircraft and industrial gas turbine engines to isolate turbine and combustor engine components from the hot gas stream, as well as to improve the durability and energy efficiency of metal components at high temperatures. The thermal barrier coating skeleton has the following requirements: (1) the thermal stability is high; (2) the heat conductivity coefficient is low; (3) has a coefficient of thermal expansion matched to that of the metal matrix. Yttria Stabilized Zirconia (YSZ) is limited to use below 1200 ℃ due to phase transformation. At higher operating temperatures, new thermal barrier coating materials such as La2Zr2O7LaPO4 and Yb3Al5O12The TBC material has higher thermal stability and lower thermal conductivity and is considered as a potential candidate material, and the thermal stress induced cracking and the improvement of the thermal conductivity are serious problems caused by the growth of crystal grains in the long-term service process of the TBC material at high temperature. Therefore, reducing the grain growth rate is effective for preventing thermal stress cracking and reducing the thermal conductivity of the TBC material. With the increasingly harsh use conditions, the requirement on the thermal insulation performance of the original TBC material is higher, and the thermal conductivity of the material needs to be further reduced.
In recent years, high-entropy ceramics (HECs) have been drawing attention as solid solutions of one-component compounds containing three or more main components at or near equimolar ratios because of their properties such as low thermal conductivity, high hardness, and high environmental resistance. High-entropy ceramics (High-entropy ceramics) generally refer to solid solutions formed by five or more ceramic components, and have become hot spots in the ceramic field in recent years due to unique "High-entropy effect" and superior performance. Entropy is a parameter that characterizes the degree of material disorder in thermodynamics, and its concept was proposed by clausius (t. clausius) in 1854. The lower the entropy, the more stable and ordered the system; the higher the entropy, the more chaotic the system. The research of the high-entropy ceramics can be traced back to 2015 for the first time, and then more and more high-entropy ceramics, including high-entropy oxide ceramics with fluorite structures, perovskite structures and spinel structures and non-oxide high-entropy ceramics such as boride, carbide, nitride, silicide and the like emerge like spring bamboo shoots after rain, and gradually become a research hotspot. One of the core effects of the high-entropy material is slow diffusion, wherein atom movement and effective diffusion of atoms are hindered due to lattice distortion caused by solid solution and multi-element synergistic diffusion, so that when the high-entropy material is used at high temperature, fine grains can be maintained, and slow grain growth speed is expected, and the slow diffusion effect opens up a new window for the design of the TBC material, namely the high-entropy solid solution with fine grains and slow growth speed. However, the existing porous high-entropy ceramics mainly form a porous structure by generating escaping gas through the reaction of raw materials, so that the prepared ceramic material has high thermal conductivity and cannot meet the heat insulation performance under the high-temperature condition.
With the increasingly strict use conditions and the increasingly high requirements on the heat insulation performance of materials, the currently prepared high-entropy ceramics (HECs) cannot meet the requirements, and therefore, how to find a high-entropy ceramic with high temperature resistance and low thermal conductivity becomes a hot point of research.
Disclosure of Invention
The invention aims to provide a rare earth-based heat-insulating porous high-entropy ceramic and a preparation method thereof, wherein the high-entropy ceramic has the characteristics of high temperature resistance, low heat conductivity and the like, and meets the requirement that a heat-insulating material keeps better heat-insulating property in a harsher environment.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a rare earth-based heat insulating porous high-entropy ceramic, comprising the steps of: s1, synthesizing the rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving at least five rare earth nitrates and a zirconium-containing salt in water, adding citric acid monohydrate, mixing and stirring to dissolve the rare earth nitrates and the zirconium-containing salt to obtain a clear solution; adding ethylene glycol into the clear solution, heating, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 5.0-7.0, and evaporating to dryness to obtain dry gel; sintering the xerogel at high temperature, and performing ball milling to obtain high-entropy ceramic powder; s2, preparing the rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: and (4) mixing the rare earth high-entropy ceramic powder prepared in the step (S1) with an inorganic binder, a reinforcing fiber, a dispersing agent and water, uniformly dispersing, freezing and freeze-drying in liquid nitrogen, and calcining the dried material at high temperature to obtain the rare earth-based porous high-entropy ceramic.
According to the present invention, the inorganic binder used in step S2 is an aluminoborosilicate sol, a silica sol, or boron oxide.
According to the invention, the method for preparing the aluminoborosilicate sol comprises the following steps: and dispersing Tetraethoxysilane (TEOS), inorganic salt containing aluminum and boric acid in water, mixing, stirring and reacting to obtain the aluminoborosilicate sol. Preferably, the inorganic salt containing aluminum is one or more of aluminum nitrate nonahydrate, aluminum chloride hexahydrate and aluminum phosphate. Preferably, in the step of synthesizing the aluminoborosilicate sol, the mass ratio of the ethyl orthosilicate to the aluminum nitrate nonahydrate to the boric acid is (25-35): 12-26): 1. Preferably, the mixing and stirring reaction time is 2 to 8 hours, more preferably 3 to 6 hours, and an exemplary time is 4 hours.
According to the invention, the rare earth nitrate is any five or more than five of lanthanum nitrate hexahydrate, gadolinium nitrate hexahydrate, erbium nitrate pentahydrate, yttrium nitrate hexahydrate, ytterbium nitrate pentahydrate, europium nitrate pentahydrate, samarium nitrate hexahydrate, neodymium nitrate hexahydrate, yttrium nitrate hexahydrate and cerium nitrate hexahydrate. Preferably, the zirconium-containing salt is one or more of zirconium nitrate pentahydrate, zirconium chloride and zirconyl nitrate hydrate. Preferably, the molar ratio of the rare earth nitrates is 1: 1;
preferably, the molar ratio of any rare earth nitrate, the zirconium nitrate pentahydrate, the citric acid monohydrate and the ethylene glycol is 1 (n-2 n) to (2 n-3 n) to (4 n-5 n), wherein n is a natural number of more than 5.
According to the invention, the mass ratio of the rare earth high-entropy ceramic powder, the inorganic binder, the reinforcing fiber, the dispersing agent and the water is as follows: (15-25): (3-6): (0-5): (0.8-6): (40-60).
Preferably, the fiber is silica fiber or zirconia fiber, and the diameter of the fiber is 0.07-5.0 μm. Preferably, the mass ratio of the rare earth high-entropy ceramic powder, the aluminoborosilicate sol, the silica or zirconia fiber, the dispersant and the water is as follows: (15-25): (18-30): (0-5): (0.8-6): (40-60).
According to the invention, in the step S1, ethylene glycol is added into the clear solution, and the reaction is carried out for 2-6 hours at the temperature of 60-120 ℃; for example, at 80 ℃ for 2 hours. Preferably, ammonia water is added to adjust the pH value, and then the mixture is evaporated to dryness at 120-180 ℃ to obtain xerogel. For example, it can be evaporated to dryness at 150 ℃ to give a xerogel.
Preferably, in the step S1, the xerogel is sintered at 900 to 1200 ℃ for 5 to 10 hours, and is preferably sintered at a high temperature in a muffle furnace. Preferably, the dried gel is sintered and then is subjected to high-energy ball milling for 6 to 36 hours at the rotating speed of 100 to 600 rpm.
According to the invention, in the step S2, the freeze-dried material is calcined at 900-1200 ℃ for 5-8 hours to obtain the rare earth-based porous high-entropy ceramic.
According to the invention, the dispersant is sodium polyacrylate or polyacrylamide. Preferably, the number average molecular weight of the sodium polyacrylate is 4000 to 6000, more preferably 4500 to 5500, and exemplary is 4000. Preferably, the number average molecular weight of the polyacrylamide is 20000 to 8000000, more preferably 300000 to 7000000, exemplary 200000 or 8000000.
According to another aspect of the invention, the rare earth-based heat-insulating porous high-entropy ceramic is obtained by any one of the preparation methods, and has the following structural general formula: (RE)1RE2RE3RE4RE5…REn)2/δZr2O7Where δ is n, REnIs prepared from rare-earth elements of lanthanum, gadolinium, erbium, yttrium, ytterbium, europium, samarium, neodymium, yttrium,Any five or more different elements of cerium.
For example, the structural formula of the rare earth-based heat-insulating porous high-entropy ceramic is (Y)0.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7；(Y0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7；(Tm0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7；(Y0.2La0.2Gd0.2Nd0.2Yb0.2)2Zr2O7；(Ce0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7。
According to the invention, the thermal conductivity of the rare earth-based heat-insulating porous high-entropy ceramic at 600 ℃ can reach 0.06-0.120W/m.K; for example, it may be 0.06W/mK, 0.08W/mK, 0.09W/mK or 0.120W/mK.
The invention has the beneficial effects that:
the invention adopts at least five rare earth nitrates as raw materials, designs the high-entropy ceramic material by selecting the components of the material, reduces the thermal conductivity of the material and improves the shielding performance by utilizing the doping and high entropy of multiple rare earth elements, thereby preparing the novel zirconic acid rare earth based porous high-entropy ceramic. The invention utilizes rare earth element doping to design a high entropy material, reduces phonon mean free path, increases mass scattering and bond disorder, and improves valence electron coverage space, thereby reducing thermal conductivity. Meanwhile, the invention utilizes the porous material, increases the specific surface area of the material, improves the contact effect of the material and phonons, and reduces the thermal conductivity of the material. Therefore, the rare earth-based heat-insulating porous high-entropy ceramic prepared by the method has the advantages of high temperature resistance, low thermal conductivity and the like.
Drawings
FIG. 1 is (Y) prepared in example 10.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7Scanning electron micrographs of porous high-entropy ceramics.
FIG. 2 shows a high-entropy ceramic (Y) prepared in example 10.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7Local X-ray microanalysis map (EDS).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments. It should be emphasized that the specific embodiments described herein are merely illustrative of the invention, are some, not all, and therefore do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
Preparation of (Y)0.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7Porous high-entropy ceramics:
(1) firstly, synthesizing rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving 0.512g of lanthanum nitrate hexahydrate, 0.536g of gadolinium nitrate hexahydrate, 0.548g of erbium nitrate pentahydrate, 0.455g of yttrium nitrate hexahydrate, 0.533g of ytterbium nitrate pentahydrate and 2.54g of zirconium nitrate pentahydrate in 20ml of water, adding 2.50g of citric acid monohydrate, mixing, stirring and dissolving, adding 1.49g of ethylene glycol until the solution is clear, reacting for 2 hours at 80 ℃, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 6.0, and evaporating to dryness at 150 ℃ to obtain the xerogel. And sintering the xerogel in a muffle furnace at 900 ℃ for 5h, and ball-milling for 36 h at the rotating speed of 220rpm to obtain the high-entropy ceramic powder.
(2) Aluminoborosilicate sol: the reaction mixture was stirred and reacted for 4 hours while dispersing 6.08g of tetraethyl orthosilicate (TEOS), 2.42g of aluminum nitrate nonahydrate and 0.18g of boric acid in 18ml of water.
(3) Preparing rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: the prepared rare earth high-entropy ceramic powder 10g, aluminoborosilicate sol 25.58g, silica fiber 1.2g (diameter is 1 μm) and polyacrylamide 1.2g (number average molecular weight 8000000) dispersing agent are uniformly dispersed in 30ml of water, and after uniform dispersion, the mixture is frozen in liquid nitrogen and then freeze-dried. And (3) heating the dried material to 900 ℃ at the heating rate of 2 ℃/min, and calcining for 5h to obtain the rare earth-based porous high-entropy ceramic.
According to GB/T17911.8-2002, the thermal conductivity of the ceramic material is tested, and the thermal conductivity of the material can reach 0.080W/m.K at 600 ℃. The high temperature resistance of the alloy reaches 1650 ℃ according to GB/T17430-2015 test.
FIG. 1 is (Y) prepared in example 10.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7And (3) a scanning electron microscope image of the porous high-entropy ceramic shows that the microstructure and the porous structure of the prepared porous ceramic can be seen by SEM. FIG. 2 shows a porous high-entropy ceramic (Y) prepared in example 10.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7Local EDS picture, prove to get the high entropy ceramic material.
Example 2
Preparation of (Y)0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7Porous high-entropy ceramics:
(1) firstly, synthesizing rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving 0.512g of lanthanum nitrate hexahydrate, 0.536g of gadolinium nitrate hexahydrate, 0.530g of europium nitrate pentahydrate, 0.455g of yttrium nitrate hexahydrate, 0.533g of ytterbium nitrate pentahydrate and 2.54g of zirconium nitrate pentahydrate in 20ml of water, adding 2.50g of citric acid monohydrate, mixing, stirring and dissolving, adding 1.49g of ethylene glycol until the solution is clear, reacting for 2 hours at 80 ℃, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 6.0, and evaporating to dryness at 150 ℃ to obtain the xerogel. And sintering the xerogel in a muffle furnace at 1000 ℃ for 6h, and then ball-milling at 300rpm for 24 h to obtain the high-entropy ceramic powder.
(2) Aluminoborosilicate sol: the reaction mixture was stirred and reacted for 4 hours while dispersing 3.04g of tetraethyl orthosilicate (TEOS), 1.21g of aluminum nitrate nonahydrate and 0.09g of boric acid in 18ml of water.
(3) Preparing rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: 20g of the prepared rare earth high-entropy ceramic powder, 21.91g of aluminoborosilicate sol, 1.2g of silicon dioxide fiber (the diameter is 700nm) and 2.4g of polyacrylamide dispersant (the number average molecular weight is 8000000) are uniformly dispersed in 30ml of water, and after the uniform dispersion, the mixture is frozen in liquid nitrogen and then is freeze-dried. And (3) raising the temperature of the dried material to 900 ℃ at the heating rate of 2 ℃/min, and calcining for 5h to obtain the rare earth-based porous high-entropy ceramic.
According to GB/T17911.8-2002, the thermal conductivity of the ceramic material is tested, and the thermal conductivity of the material can reach 0.090W/m.K at 600 ℃. The high temperature resistance reaches 1550 ℃ according to GB/T17430-2015 test.
Example 3
Preparation (Tm)0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7Porous high-entropy ceramics:
(1) firstly, synthesizing rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving 0.512g of lanthanum nitrate hexahydrate, 0.536g of gadolinium nitrate hexahydrate, 0.530g of europium nitrate pentahydrate, 0.550g of thulium nitrate hexahydrate, 0.533g of ytterbium nitrate pentahydrate and 2.54g of zirconium nitrate pentahydrate in 20ml of water, adding 2.50g of citric acid monohydrate, mixing, stirring and dissolving, adding 1.49g of ethylene glycol after the solution is clarified, reacting for 2 hours at 80 ℃, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 6.0, and evaporating to dryness at 150 ℃ to obtain the xerogel. And sintering the xerogel in a muffle furnace at 1100 ℃ for 8h, and performing high-energy ball milling at 400rpm for 18h to obtain the high-entropy ceramic powder.
(2) Aluminoborosilicate sol: is prepared by dispersing 3.04g of Tetraethoxysilane (TEOS), 1.21g of aluminum nitrate nonahydrate and 0.09g of boric acid in 18ml of water, mixing and stirring for reaction for 4 hours.
(3) Preparing rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: 30g of the prepared rare earth high-entropy ceramic powder, 21.91g of aluminoborosilicate sol, 1.2g of silicon dioxide fiber (the diameter is 2 mu m), 1.2g of sodium polyacrylate dispersant (the number average molecular weight is 4000), and the rare earth high-entropy ceramic powder, the aluminum borosilicate sol, the silicon dioxide fiber and the sodium polyacrylate dispersant are uniformly dispersed in 30ml of water, are frozen in liquid nitrogen after being uniformly dispersed, and are then frozen and dried. And (3) heating the dried material to 900 ℃ at the heating rate of 2 ℃/min, and calcining for 10h to obtain the rare earth-based porous high-entropy ceramic.
According to GB/T17911.8-2002, the thermal conductivity of the ceramic material is tested, and the thermal conductivity of the material can reach 0.120W/m.K at 600 ℃. The high temperature resistance reaches 1620 ℃ according to GB/T17430-2015 test.
Example 4
Preparation of (Y)0.2La0.2Gd0.2Nd0.2Yb0.2)2Zr2O7Porous high-entropy ceramics:
(1) firstly, synthesizing rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving 0.512g of lanthanum nitrate hexahydrate, 0.536g of gadolinium nitrate hexahydrate, 0.521g of neodymium nitrate pentahydrate, 0.455g of yttrium nitrate hexahydrate, 0.533g of ytterbium nitrate pentahydrate and 2.54g of zirconium nitrate pentahydrate in 20ml of water, adding 2.50g of citric acid monohydrate, mixing, stirring and dissolving, adding 1.49g of ethylene glycol until the solution is clear, reacting for 2 hours at 80 ℃, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 6.0, and evaporating to dryness at 150 ℃ to obtain xerogel. And sintering the dried gel in a muffle furnace at 1000 ℃ for 10h, and ball-milling at 500rpm for 12h to obtain the high-entropy ceramic powder.
(2) Aluminoborosilicate sol: is prepared by dispersing 6.08g of Tetraethoxysilane (TEOS), 2.42g of aluminum nitrate nonahydrate and 0.18g of boric acid in 18ml of water, mixing and stirring for reaction for 4 hours.
(3) Preparing rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: uniformly dispersing 10g of the prepared rare earth high-entropy ceramic powder, 25.58g of aluminoborosilicate sol, 1.6g of silicon dioxide fiber and 2.4g of sodium polyacrylate dispersant (number average molecular weight of 6000) in 30ml of water, freezing in liquid nitrogen after uniform dispersion, and then freeze-drying. And (3) heating the dried material to 1200 ℃ at the heating rate of 2 ℃/min, and calcining for 5h to obtain the rare earth-based porous high-entropy ceramic.
According to GB/T17911.8-2002, the thermal conductivity of the ceramic material is tested, and the thermal conductivity of the material can reach 0.06W/m.K at 600 ℃. The high temperature resistance reaches 1500 ℃ according to GB/T17430-2015 test.
Example 5
Preparation (Ce)0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7Porous high-entropy ceramics:
(1) firstly, synthesizing rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving 0.512g of lanthanum nitrate hexahydrate, 0.536g of gadolinium nitrate hexahydrate, 0.530g of europium nitrate pentahydrate, 0.516g of cerium nitrate hexahydrate, 0.533g of ytterbium nitrate pentahydrate and 2.54g of zirconium nitrate pentahydrate in 20ml of water, adding 2.50g of citric acid monohydrate, mixing, stirring and dissolving, adding 1.49g of ethylene glycol after the solution is clarified, reacting for 2 hours at 80 ℃, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 6.0, and evaporating to dryness at 150 ℃ to obtain the xerogel. And sintering the xerogel in a muffle furnace at 1200 ℃ for 8h, and ball-milling at 500rpm for 12h to obtain the high-entropy ceramic powder.
(2) Aluminoborosilicate sol: is prepared by dispersing 6.08g of Tetraethoxysilane (TEOS), 2.42g of aluminum nitrate nonahydrate and 0.18g of boric acid in 18ml of water, mixing and stirring for reaction for 4 hours.
(3) Preparing rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: uniformly dispersing 10g of the prepared rare earth high-entropy ceramic powder, 25.58g of aluminoborosilicate sol, 6.0g of zirconia fiber (diameter is 2 mu m) and 1.2g of polyacrylamide dispersant (number average molecular weight is 200000) in 30ml of water, freezing in liquid nitrogen after uniform dispersion, and then carrying out freeze drying. And (3) heating the dried material to 1200 ℃ at the heating rate of 2 ℃/min and calcining for 10h to obtain the rare earth-based porous high-entropy ceramic.
According to GB/T17911.8-2002, the thermal conductivity of the ceramic material is tested, and the thermal conductivity of the material can reach 0.090W/m.K at 600 ℃. The high temperature resistance reaches 1600 ℃ according to GB/T17430-2015 test.
The foregoing is only a preferred application of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the technical principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of rare earth-based heat-insulating porous high-entropy ceramic is characterized by comprising the following steps:
s1, synthesizing the rare earth high-entropy ceramic powder by adopting a sol-gel method: dissolving at least five rare earth nitrates and a zirconium-containing salt in water, adding citric acid monohydrate, mixing and stirring to dissolve the rare earth nitrates and the zirconium-containing salt to obtain a clear solution; adding ethylene glycol into the clear solution, heating, cooling to room temperature after the reaction is finished, adding ammonia water to adjust the pH value to 5.0-7.0, and evaporating to dryness to obtain dry gel; sintering the xerogel at high temperature, and performing ball milling to obtain high-entropy ceramic powder;
s2, preparing the rare earth-based heat-insulating porous high-entropy ceramic by adopting an ice template method: and (4) mixing the high-entropy ceramic powder prepared in the step (S1) with an inorganic binder, a reinforcing fiber, a dispersing agent and water, uniformly dispersing, freezing and freeze-drying in liquid nitrogen, and calcining the dried material at high temperature to obtain the rare earth-based porous high-entropy ceramic.
2. The method according to claim 1, wherein the inorganic binder used in step S2 is aluminoborosilicate sol, silica sol, or boron oxide.
3. The method of claim 2, wherein the aluminoborosilicate sol is prepared by a method comprising: and dispersing Tetraethoxysilane (TEOS), inorganic salt containing aluminum and boric acid in water, mixing, stirring and reacting to obtain the aluminoborosilicate sol.
Preferably, the inorganic salt containing aluminum is one or more of aluminum nitrate nonahydrate, aluminum chloride hexahydrate and aluminum phosphate.
In the step of synthesizing the aluminoborosilicate sol, the mass ratio of the ethyl orthosilicate to the aluminum nitrate nonahydrate to the boric acid is (25-35): 12-26): 1.
Preferably, the mixing and stirring reaction time is 2-8 hours, more preferably 3-6 hours, and an exemplary time is 4 hours.
4. The production method according to any one of claims 1 to 3, wherein the rare earth nitrate is any five or more of lanthanum nitrate hexahydrate, gadolinium nitrate hexahydrate, erbium nitrate pentahydrate, yttrium nitrate hexahydrate, ytterbium nitrate pentahydrate, europium nitrate pentahydrate, samarium nitrate hexahydrate, neodymium nitrate hexahydrate, yttrium nitrate hexahydrate, and cerium nitrate hexahydrate.
Preferably, the zirconium-containing salt is one or more of zirconium nitrate pentahydrate, zirconium chloride and zirconyl nitrate hydrate.
Preferably, the molar ratio of the rare earth nitrates is 1: 1;
the molar ratio of any one of the rare earth nitrate, the zirconium nitrate pentahydrate, the citric acid monohydrate and the ethylene glycol is 1 (n-2 n), 2 n-3 n and 4 n-5 n, wherein n is a natural number not less than 5.
5. The preparation method according to any one of claims 2 to 4, wherein the mass ratio of the rare earth high-entropy ceramic powder to the inorganic binder to the reinforcing fiber to the dispersing agent to water is as follows: (15-25): (3-6): (0-5): (0.8-6): (40-60).
Preferably, the fiber is silica fiber or zirconia fiber, and the diameter of the fiber is 0.07-5.0 μm.
Preferably, the mass ratio of the rare earth high-entropy ceramic powder, the aluminoborosilicate sol, the silica or zirconia fiber, the dispersant and the water is as follows: (15-25): (18-30): (0-5): (0.8-6): (40-60).
6. The method according to any one of claims 1 to 5, wherein ethylene glycol is added to the clear solution in step S1, and the reaction is carried out at 60-120 ℃ for 2-6 hours; for example, at 80 ℃ for 2 hours.
Preferably, ammonia water is added to adjust the pH value, and then the mixture is evaporated to dryness at 120-180 ℃ to obtain xerogel. For example, it can be evaporated to dryness at 150 ℃ to give a xerogel.
In the step S1, the dried gel is sintered for 5-10 hours at 900-1200 ℃, and preferably sintered at high temperature by adopting a muffle furnace.
Preferably, the dried gel is sintered and then is subjected to high-energy ball milling for 6 to 36 hours at the rotating speed of 100 to 600 rpm.
7. The preparation method according to any one of claims 1 to 6, wherein in the step S2, the freeze-dried material is calcined at 900-1200 ℃ for 5-8 hours to obtain the rare earth-based porous high-entropy ceramic.
8. The production method according to any one of claims 1 to 7, wherein the dispersant is sodium polyacrylate or polyacrylamide.
Preferably, the number average molecular weight of the sodium polyacrylate is 4000 to 6000, more preferably 4500 to 5500, and exemplary is 4000.
Preferably, the number average molecular weight of the polyacrylamide is 20000 to 8000000, more preferably 300000 to 7000000, exemplary 200000 or 8000000.
9. The rare earth-based heat-insulating porous high-entropy ceramic is obtained by the preparation method of any one of claims 1 to 8, and is characterized by having the following structural general formula: (RE)1RE2RE3RE4RE5…REn)2/δZr2O7Where δ is n, REnIs any five or more than five different elements of rare earth elements of lanthanum, gadolinium, erbium, yttrium, ytterbium, europium, samarium, neodymium, yttrium and cerium.
For example, the structural formula of the rare earth-based heat-insulating porous high-entropy ceramic is (Y)0.2La0.2Gd0.2Er0.2Yb0.2)2Zr2O7；(Y0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7；(Tm0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7；(Y0.2La0.2Gd0.2Nd0.2Yb0.2)2Zr2O7；(Ce0.2La0.2Gd0.2Eu0.2Yb0.2)2Zr2O7。
10. The rare earth-based heat-insulating porous high-entropy ceramic of claim 9, wherein the thermal conductivity of the rare earth-based heat-insulating porous high-entropy ceramic at 600 ℃ can reach 0.06-0.120W/m-K; for example, 0.06W/mK, 0.08W/mK, 0.09W/mK or 0.120W/mK.
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