CN115286809A - Flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof - Google Patents

Flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof Download PDF

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CN115286809A
CN115286809A CN202210959854.7A CN202210959854A CN115286809A CN 115286809 A CN115286809 A CN 115286809A CN 202210959854 A CN202210959854 A CN 202210959854A CN 115286809 A CN115286809 A CN 115286809A
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rare earth
zirconium
acetylacetone
polymer
trichloride
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许杰
位明月
冯晓颖
王恒昌
杨润伍
高峰
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Northwestern Polytechnical University
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Abstract

The invention provides a zirconium-rare earth ion acetylacetone polymer and preparation thereof, a flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof, and relates to the technical field of ceramic fibers. The zirconium-rare earth acetylacetone polymer is a one-dimensional chain structure, has higher spinnability, and does not need to add excessive spinning auxiliary agent when being used for preparing the rare earth zirconate high-entropy ceramic fiber membrane, so that the flexibility of the fiber membrane is lost during subsequent calcination. In addition, the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu, and the delayed diffusion effect brought by the high entropy effect enables the fiber crystal grains to be smaller, so that the flexibility of the fiber membrane is improved.

Description

Flexible rare earth zirconate high-entropy ceramic fiber film and preparation and application thereof
Technical Field
The invention relates to the technical field of ceramic fibers, in particular to a zirconium-rare earth ion acetylacetone polymer and preparation thereof, a flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof.
Background
The rare earth zirconate is a novel rare earth composite oxide material, mainly has two crystal phases of pyrochlore and fluorite according to the difference of rare earth ions, and the pyrochlore structure and the fluorite structure belong to a cubic phase structure. At one atmosphere, the crystal structure of a single rare earth zirconate is predominantly related to the ratio of its cationic radii when r (A) 3+ )/r(Zr 4+ ) = 1.46-1.78, the pyrochlore structure is stable, when r (A) 3+ )/r(Zr 4+ ) When the molecular weight is less than 1.46, the fluorite structure is relatively stable. Each basic A of pyrochlore structure and fluorite structure of rare earth zirconate crystal 2 Zr 2 O 7 In addition, the rare earth zirconate material has no phase change generation point, has better toughness, can still keep stable structure at 2000 ℃, has high radiation thermal impedance, and is a new generation of high-temperature heat insulation candidate material. A. The 2 Zr 2 O 7 The high-entropy ceramics are rare earth composite oxides with pyrochlore or fluorite phase structures, have the advantages of higher melting point, lower lattice thermal conductivity, high mechanical property, high thermal stability and the like due to larger lattice distortion in the high-entropy ceramics, and have larger application potential in aerospace heat-insulating candidate materials.
The ceramic fiber has the advantages of low density, high strength, high temperature resistance, good oxidation resistance and mechanical shock resistance and the like, and is a key high-temperature heat insulation material required in the thermal protection fields of aerospace vehicles, nuclear power generation, chemical metallurgy and the like. At present, in a thermal protection system of an aerospace vehicle, aluminum silicate fibers, quartz fibers or mullite fibers with high thermal stability are mostly selected as fiber matrixes for ceramic fiber rigid heat insulation tiles. Research on rare earth zirconate flexible ceramic fiber membranes has mainly focused on single rare earth zirconate materials, such as lanthanum zirconate, gadolinium zirconate, yttrium zirconate, and the like. For the rare earth zirconate high-entropy ceramic fiber, a spinning solution is prepared by directly adding a large amount of spinning auxiliaries into inorganic salt of rare earth elements, and as organic matters escape in the calcining stage, the fiber surface has more defects and fiber flexibility is lost.
Disclosure of Invention
The invention aims to provide a zirconium-rare earth ion acetylacetone polymer and preparation thereof, a flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a zirconium-rare earth acetylacetone polymer, which comprises zirconium polyacetylacetonate with a one-dimensional chain structure and rare earth polyacetylacetone elements with a one-dimensional chain structure; the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu.
Preferably, the molar ratio of zirconium to rare earth elements in the zirconium-rare earth acetylacetone polymer is 1.
The invention provides a preparation method of the zirconium-rare earth acetylacetone polymer in the scheme, which comprises the following steps:
dissolving a hydrate of rare earth trichloride and a hydrate of zirconium oxychloride into an alcohol solvent to obtain a dissolved solution; the rare earth trichloride is any 5 of lanthanum trichloride, neodymium trichloride, samarium trichloride, europium trichloride, gadolinium trichloride, dysprosium trichloride, yttrium trichloride, holmium trichloride, erbium trichloride, ytterbium trichloride and lutetium trichloride;
mixing the dissolved solution with acetylacetone and triethylamine, carrying out hydrolysis and polycondensation, and after the solution is clarified, drying under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
and (3) soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride into acetone, performing solid-liquid separation, and drying the obtained supernatant under reduced pressure to obtain the zirconium-rare earth acetylacetone polymer.
Preferably, the molar ratio of the hydrate of the rare earth trichloride to the hydrate of zirconium oxychloride is 1.
Preferably, the molar ratio of the zirconium oxychloride hydrate to the acetylacetone is 1: (1.8-3.2); the molar ratio of the zirconium oxychloride hydrate to the triethylamine is 1: (4.3-6.5).
The invention provides a preparation method of a flexible rare earth zirconate high-entropy ceramic fiber film, which comprises the following steps:
mixing a zirconium-rare earth acetylacetone polymer, an alcohol solvent and a spinning auxiliary agent to obtain a spinning solution; the zirconium-rare earth acetylacetone polymer is the zirconium-rare earth acetylacetone polymer in the scheme or the zirconium-rare earth acetylacetone polymer prepared by the preparation method in the scheme; the mass ratio of the zirconium-rare earth acetylacetone polymer to the alcohol solvent is (50-150): (200-300); the mass ratio of the alcohol solvent to the spinning auxiliary agent is (200-300): (1-10);
and (3) carrying out electrostatic spinning on the spinning solution, and drying and calcining the obtained rare earth zirconate high-entropy ceramic precursor fiber film in sequence to obtain the flexible rare earth zirconate high-entropy ceramic fiber film.
Preferably, the ambient humidity of the electrostatic spinning is 15-40%, and the temperature is 20-35 ℃; the voltage of the electrostatic spinning is 9-24 kV, the distance between the spinning needle and the receiving shaft is 10-30 cm, and the propelling speed of the propelling pump is 0.5-2 mL/h.
Preferably, the calcining temperature is 600-1200 ℃, and the holding time is 2-5 h.
The invention provides a flexible rare earth zirconate high-entropy ceramic fiber film prepared by the preparation method in the scheme, which comprises A 2 Zr 2 O 7 The A is any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu.
The invention provides application of the flexible rare earth zirconate high-entropy ceramic fiber film in the scheme in high-temperature-resistant heat-insulating ceramic.
The invention provides a zirconium-rare earth acetylacetone polymer, which comprises zirconium polyacetylacetonate with a one-dimensional chain structure and rare earth polyacetylacetonate with a one-dimensional chain structure; the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu. The zirconium-rare earth acetylacetone polymer is a one-dimensional chain structure, has higher spinnability, and does not need to add excessive spinning auxiliary agent when being used for preparing the rare earth zirconate high-entropy ceramic fiber membrane, so that the flexibility of the fiber membrane is lost during subsequent calcination. In addition, the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu, and the delayed diffusion effect brought by the high entropy effect enables the fiber crystal grains to be smaller, so that the flexibility of the fiber membrane is improved.
The rare earth zirconate high-entropy ceramic fiber membrane prepared by the invention A 2 B 2 O 7 In the high-entropy component, various phonon scattering mechanisms are introduced, and different rare earth elements exist in the high-entropy ceramic crystal lattice, so that phonon scattering centers are increased, and the low thermal conductivity is shown.
Drawings
FIG. 1 shows A prepared in example 1 2 Zr 2 O 7 XRD pattern of the high entropy ceramic fiber membrane;
FIG. 2 shows A prepared in example 1 (a) and example 2 (b) 2 Zr 2 O 7 SEM pictures of the high-entropy ceramic fiber membrane;
FIG. 3 shows A prepared in example 1 2 Zr 2 O 7 TEM pictures of high-entropy ceramic fiber membranes;
FIG. 4 shows A prepared in example 1 2 Zr 2 O 7 Optical photographs of high entropy ceramic fiber membranes.
Detailed Description
The invention provides a zirconium-rare earth acetylacetone polymer, which comprises zirconium polyacetylacetonate with a one-dimensional chain structure and rare earth polyacetylacetone elements with a one-dimensional chain structure; the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu.
In the present invention, the molar ratio of zirconium to rare earth element in the zirconium-rare earth acetylacetone polymer is preferably 1. In the present invention, each of the rare earth elements is preferably in an equimolar ratio. The zirconium-rare earth acetylacetone polymer is of a one-dimensional chain structure, has high spinnability, and does not need to be added with excessive spinning auxiliary agent when being used for preparing the rare earth zirconate high-entropy ceramic fiber membrane, so that the flexibility of the fiber membrane is lost during subsequent calcination. In addition, the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu, and the delayed diffusion effect brought by the high entropy effect enables the fiber crystal grains to be smaller, so that the flexibility of the fiber membrane is improved.
The invention provides a preparation method of the zirconium-rare earth acetylacetone polymer in the scheme, which comprises the following steps:
dissolving a hydrate of rare earth trichloride and a hydrate of zirconium oxychloride into an alcohol solvent to obtain a dissolved solution; the rare earth trichloride is any 5 of lanthanum trichloride, neodymium trichloride, samarium trichloride, europium trichloride, gadolinium trichloride, dysprosium trichloride, yttrium trichloride, holmium trichloride, erbium trichloride, ytterbium trichloride and lutetium trichloride;
mixing the dissolved solution with acetylacetone and triethylamine to perform hydrolysis and polycondensation, and after the solution is clarified, drying the solution under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
and soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride into acetone, performing solid-liquid separation, and drying the obtained supernatant under reduced pressure to obtain the zirconium-rare earth acetylacetone polymer.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention dissolves the hydrate of rare earth trichloride and the hydrate of zirconium oxychloride in the alcohol solvent to obtain the dissolved solution.
In the present invention, the hydrate of the rare earth trichloride is preferably a hexahydrate rare earth trichloride; in the invention, the rare earth trichloride is any 5 of lanthanum trichloride, neodymium trichloride, samarium trichloride, europium trichloride, gadolinium trichloride, dysprosium trichloride, yttrium trichloride, holmium trichloride, erbium trichloride, ytterbium trichloride and lutetium trichloride, and each rare earth trichloride is preferably in an equal molar ratio.
In the present invention, the hydrate of zirconium oxychloride is preferably zirconium oxychloride octahydrate. In the present invention, the alcohol solvent is preferably methanol or ethanol. In the present invention, the ratio of the amounts of zirconium oxychloride and alcoholic solvent used is preferably 1mol:1500 to 2500g. The method has no special requirement on the dissolving process, and can completely dissolve the hydrate of the rare earth trichloride and the hydrate of the zirconium oxychloride.
After the solution is obtained, the solution is mixed with acetylacetone and triethylamine to carry out hydrolysis and polycondensation, and after the solution is clarified, the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride is obtained after decompression and drying.
In the present invention, the molar ratio of the zirconium oxychloride hydrate to the acetylacetone is preferably 1: (1.8 to 3.2), more preferably 1: (2-2.5); the molar ratio of the zirconium oxychloride hydrate to triethylamine is preferably 1: (4.3 to 6.5), more preferably 1: (4.7-5.0).
In the present invention, the mixing is preferably performed under stirring, and the mixing time is preferably 4 to 8 hours, more preferably 5 to 6 hours. In the mixing process, triethylamine is used as a hydrolysis catalyst to firstly promote the hydrolysis of the hydrate of the rare earth trichloride and the hydrate of the zirconium oxychloride, and the hydrolysis equation is as follows: zrOCl 2 ·8H 2 O+Hacac+2TEA→Zr(OH) 3 acac+2TEA·HCl↓+6H 2 O；RECl 3 ·6H 2 O+Hacac+3TEA→RE(OH) 2 acac+3TEA·HCl↓+3H 2 O, wherein Hacac is acetylacetone, and TEA is triethylamine; zirconium acetylacetonate Zr (OH) then formed 3 acac and acetylacetone rare earth elements RE (OH) 2 The acac generates the polyacetylacetonatozirconium and the polyacetylacetonathearareearth element (nRE (OH) with a one-dimensional chain structure through polycondensation reaction 2 acac→[RE(OH) 2 acac] n ，nZr(OH) 2 acac→[Zr(OH) 2 acac] n )。
After the solution is clarified, the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride is obtained by decompression drying. In the present invention, the temperature of the reduced pressure drying is preferably 30 to 50 ℃.
After obtaining the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride, the invention soaks the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride into acetone, and after solid-liquid separation, the obtained supernatant is decompressed and dried to obtain the zirconium-rare earth acetylacetone polymer.
In the present invention, the ratio of the amounts of zirconium oxychloride and acetone is preferably 1mol: 3000-6000 mL, more preferably 1mol:4000mL. In the present invention, the soaking time is preferably 24 to 120 hours, and more preferably 72 to 100 hours. Triethylamine hydrochloride is insoluble in acetone, and zirconium polyacetylacetonate and rare earth elements polyacetylacetone are soluble in acetone. The solid-liquid separation mode is not particularly required in the invention, and any solid-liquid separation mode well known in the field can be adopted, such as filtration. In the present invention, the temperature of the reduced pressure drying is preferably 30 to 50 ℃.
The invention provides a preparation method of a flexible rare earth zirconate high-entropy ceramic fiber film, which comprises the following steps:
mixing a zirconium-rare earth acetylacetone polymer, an alcohol solvent and a spinning auxiliary agent to obtain a spinning solution; the zirconium-rare earth acetylacetone polymer is the zirconium-rare earth acetylacetone polymer in the scheme or the zirconium-rare earth acetylacetone polymer prepared by the preparation method in the scheme; the mass ratio of the zirconium-rare earth acetylacetone polymer to the alcohol solvent is (50-150): (200-300); the mass ratio of the alcohol solvent to the spinning auxiliary agent is (200-300): (1-10);
and (3) carrying out electrostatic spinning on the spinning solution, and drying and calcining the obtained rare earth zirconate high-entropy ceramic precursor fiber film in sequence to obtain the flexible rare earth zirconate high-entropy ceramic fiber film.
The invention mixes zirconium-rare earth acetylacetone polymer, alcohol solvent and spinning auxiliary agent to obtain spinning solution.
In the present invention, the alcohol solvent is preferably methanol or ethanol, more preferably methanol; the spinning aid is preferably polyvinylpyrrolidone, polyethylene oxide or polyvinyl alcohol, more preferably polyvinylpyrrolidone.
In the invention, the mass ratio of the zirconium-rare earth acetylacetone polymer to the alcohol solvent is (50-150): (200 to 300), preferably (80 to 120): (200-300); the mass ratio of the alcohol solvent to the spinning auxiliary agent is (200-300): (1-10), preferably (200-300): (4-8). The zirconium-rare earth acetylacetone polymer is of a one-dimensional chain structure, has high spinnability, and does not need to be added with excessive spinning auxiliary agent when being used for preparing the rare earth zirconate high-entropy ceramic fiber membrane, so that the flexibility of the fiber membrane is lost during subsequent calcination.
The invention has no special requirements on the mixing process of the zirconium-rare earth acetylacetone polymer, the alcohol solvent and the spinning auxiliary agent, and can adopt the mixing process well known in the field. In the mixing process, the alcohol solvent dissolves the zirconium-rare earth acetylacetone polymer and the spinning auxiliary agent.
After the spinning solution is obtained, the spinning solution is subjected to electrostatic spinning, and the obtained rare earth zirconate high-entropy ceramic precursor fiber film is sequentially dried and calcined to obtain the flexible rare earth zirconate high-entropy ceramic fiber film.
In the present invention, the ambient humidity of the electrospinning is preferably 15 to 40%, more preferably 20 to 30%; the temperature is preferably 20-35 ℃; the voltage of the electrostatic spinning is preferably 9-24 kV, and more preferably 14-2024 kV; the distance between the spinning needle head and the receiving shaft is preferably 10-30 cm, and more preferably 15-25 cm; the propulsion speed of the propulsion pump is preferably 0.5 to 2mL/h, more preferably 1 to 1.5mL/h.
In the present invention, the drying temperature is preferably 40 to 150 ℃, more preferably 80 to 120 ℃; the calcination temperature is preferably 600 to 1200 ℃, more preferably 700 to 1100 ℃, and even more preferably 800 to 1000 ℃, and the holding time is preferably 2 to 5 hours, and more preferably 3 to 4 hours. In the present invention, the rate of temperature rise to the calcination temperature is preferably 1 to 5 ℃/min, more preferably 1 ℃/min before 300 ℃, and 5 ℃ after 300 ℃And/min. In the calcining process, the spinning auxiliary agent is removed by carbonization and decomposition, the acetylacetone is also carbonized and decomposed, and the crystallization is carried out to generate A along with the temperature rise 2 Zr 2 O 7 And (4) phase(s).
The invention provides a flexible rare earth zirconate high-entropy ceramic fiber membrane prepared by the preparation method in the scheme, which comprises A 2 Zr 2 O 7 The fiber, wherein A is any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu; the rare earth elements in the A are preferably in an equimolar ratio. A is described 2 Zr 2 O 7 The average diameter of the fiber is preferably 278 to 529nm, the tensile strength of the flexible rare earth zirconate high-entropy ceramic fiber membrane is preferably 0.66 to 2.85MPa, and the room-temperature thermal conductivity is preferably 0.0337 to 0.042W/(m.K).
The rare earth zirconate high-entropy ceramic fiber membrane prepared by the invention A 2 B 2 O 7 In the high-entropy component, various phonon scattering mechanisms are introduced, and different rare earth elements exist in the high-entropy ceramic crystal lattice, so that phonon scattering centers are increased, and the low thermal conductivity is shown. The delayed diffusion effect brought by the high entropy effect enables the fiber crystal grains to be smaller, and the flexibility of the fiber is improved. In addition, the spinning solution prepared from the zirconium-rare earth acetylacetone polymer has higher spinnability, and is also beneficial to improving the flexibility of the fiber membrane.
The invention provides application of the flexible rare earth zirconate high-entropy ceramic fiber film in the scheme in high-temperature-resistant heat-insulating ceramic.
The zirconium-rare earth ion acetylacetone polymer and the preparation thereof, the flexible rare earth zirconate high-entropy ceramic fiber membrane and the preparation and application thereof provided by the invention are described in detail by referring to the following examples, but they should not be construed as limiting the scope of the invention.
Example 1 (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7
(1) Dissolving 70.67g of lanthanum chloride hexahydrate, 71.74g of neodymium chloride hexahydrate, 72.92g of samarium chloride hexahydrate, 73.28g of europium chloride hexahydrate, 74.34g of gadolinium chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate in 2000g of anhydrous methanol, sequentially adding 200g of acetylacetone and 480g of triethylamine (the molar ratio of the zirconium oxychloride octahydrate to the acetylacetone to the triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
(3) And (3) soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 72 hours, and then filtering out the triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-rare earth acetylacetone polymer, wherein the solution is clear and transparent and is light purple.
(4) And (4) carrying out reduced pressure drying on the acetone solution containing the zirconium-rare earth acetylacetone polymer obtained in the step (3) at the temperature of 40 ℃ to obtain the zirconium-rare earth acetylacetone polymer.
(5) Dissolving 10g of the zirconium-rare earth acetylacetone polymer obtained in the step (4) in 20g of anhydrous methanol, adding 0.5g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) Performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain a rare earth zirconate high-entropy ceramic precursor fiber film, wherein the electrostatic spinning voltage is 18kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from a needle to a receiving shaft is 15cm;
(7) Drying the rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (6) in an oven at the temperature of 80 ℃ for 2 hours;
(8) Calcining the dried rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (7) in air atmosphere at the heating rate of 1 ℃/min before 300 ℃, at the temperature of 5 ℃/min after 300 ℃, at the calcining temperature of 800 ℃ and for 2h to obtain the (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 High entropy ceramic fiber membrane.
The high-entropy ceramic fiber membrane prepared in the embodiment has a fluorite phase structure, the average diameter of the fiber is 357nm, the grain size of the fiber is 21.8nm, the tensile strength is 2.1MPa, and the room-temperature thermal conductivity is 0.0355W/(m.K). The fiber has compact diameter and good flexibility.
Example 2 (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Zr 2 O 7
(1) Dissolving 70.67g of lanthanum chloride hexahydrate, 71.74g of neodymium chloride hexahydrate, 72.92g of samarium chloride hexahydrate, 74.34g of gadolinium chloride hexahydrate, 75.70g of ytterbium chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate in 2000g of anhydrous methanol, sequentially adding 200g of acetylacetone and 480g of triethylamine (the molar ratio of the zirconium oxychloride octahydrate to the acetylacetone to the triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
(3) Soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 72 hours, and then filtering out triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-rare earth acetylacetone polymer, wherein the solution is clear and transparent and is light purple;
(4) And (4) carrying out reduced pressure drying on the acetone solution containing the zirconium-rare earth acetylacetone polymer obtained in the step (3) at the temperature of 40 ℃ to obtain the zirconium-rare earth acetylacetone polymer.
(5) Dissolving 10g of the zirconium-rare earth acetylacetone polymer obtained in the step (4) in 20g of anhydrous methanol, adding 1.5g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) And (3) performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain the rare earth zirconate high-entropy ceramic precursor fiber film, wherein the electrostatic spinning voltage is 15kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from a needle to a receiving shaft is 15cm.
(7) And (4) drying the rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (6) in an oven at the temperature of 80 ℃ for 2 hours.
(8) And (4) calcining the dried high-entropy ceramic precursor fiber film of the rare earth zirconate obtained in the step (7) in an air atmosphere, wherein the heating rate is 1 ℃/min before 300 ℃, the heating rate is 5 ℃/min after 300 ℃, the calcining temperature is 1000 ℃, and the heat preservation time is 2h. To obtain (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Zr 2 O 7 High entropy ceramic fiber membrane.
The high-entropy ceramic fiber membrane prepared by the embodiment has a fluorite phase structure, the average diameter of the fiber is 508nm, the grain size of the fiber is 26.7nm, the tensile strength is 0.75MPa, and the room-temperature thermal conductivity is 0.042W/(m.K). The fiber has compact diameter and good flexibility.
Example 3 (La) 0.2 Nd 0.2 Y 0.2 Er 0.2 Yb 0.2 ) 2 Zr 2 O 7
(1) Dissolving 70.67g of lanthanum chloride hexahydrate, 71.74g of neodymium chloride hexahydrate, 60.67g of yttrium chloride hexahydrate, 76.34g of erbium chloride hexahydrate, 75.70g of ytterbium chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate in 2000g of anhydrous methanol, sequentially adding 200g of acetylacetone and 500g of triethylamine (the molar ratio of the zirconium oxychloride octahydrate to the acetylacetone to the triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
(3) Soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 48 hours, and then filtering out triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-rare earth acetylacetone polymer, wherein the solution is clear and transparent and is light pink;
(4) Carrying out reduced pressure drying on the acetone solution containing the zirconium-rare earth acetylacetone polymer obtained in the step (3) at 40 ℃ to obtain a zirconium-rare earth acetylacetone polymer;
(5) Taking 10g of the zirconium-rare earth acetylacetone polymer obtained in the step (4), dissolving the zirconium-rare earth acetylacetone polymer in 20g of anhydrous methanol, adding 1g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) Performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain a rare earth zirconate high-entropy ceramic precursor fiber film, wherein the electrostatic spinning voltage is 21kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from a needle to a receiving shaft is 15cm;
(7) Drying the rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (6) in an oven at the temperature of 80 ℃ for 2 hours;
(8) And (4) calcining the dried high-entropy ceramic precursor fiber film of the rare earth zirconate obtained in the step (7) in an air atmosphere, wherein the heating rate is 1 ℃/min before 300 ℃, the heating rate is 5 ℃/min after 300 ℃, the calcining temperature is 800 ℃, and the heat preservation time is 2h. To obtain (La) 0.2 Nd 0.2 Y 0.2 Er 0.2 Yb 0.2 ) 2 Zr 2 O 7 High entropy ceramic fiber membrane.
The high-entropy ceramic fiber membrane prepared in the embodiment has a fluorite phase structure, the average diameter of the fiber is 427nm, the grain size of the fiber is 20.7nm, the tensile strength is 1.23MPa, and the room-temperature thermal conductivity is 0.034W/(m.K). The fiber has compact diameter and good flexibility.
Example 4 (Dy) 0.2 Y 0.2 Ho 0.2 Er 0.2 Yb 0.2 ) 2 Zr 2 O 7
(1) Dissolving 70.67g of dysprosium chloride hexahydrate, 60.67g of yttrium chloride hexahydrate, 75.88g of holmium chloride hexahydrate, 76.34g of erbium chloride hexahydrate, 75.70g of ytterbium chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate in 2000g of anhydrous methanol, adding 280g of acetylacetone and 480g of triethylamine (the molar ratio of the zirconium oxychloride octahydrate to the acetylacetone to the triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
(3) Soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 72 hours, and then filtering out triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-rare earth acetylacetone polymer, wherein the solution is clear and transparent and is bright yellow;
(4) Carrying out reduced pressure drying on the acetone solution containing the zirconium-rare earth acetylacetone polymer obtained in the step (3) at 40 ℃ to obtain a zirconium-rare earth acetylacetone polymer;
(5) Dissolving 10g of the zirconium-rare earth acetylacetone polymer obtained in the step (4) in 20g of anhydrous methanol, adding 0.5g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) Performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain a rare earth zirconate high-entropy ceramic precursor fiber film, wherein the electrostatic spinning voltage is 18kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from a needle to a receiving shaft is 25cm;
(7) And (5) drying the rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (6) in an oven at the temperature of 80 ℃ for 2 hours.
(8) And (3) calcining the dried high-entropy ceramic precursor fiber film of the rare earth zirconate obtained in the step (7) in an air atmosphere, wherein the heating rate is 1 ℃/min before 300 ℃, the heating rate is 5 ℃/min after 300 ℃, the calcining temperature is 600 ℃, and the heat preservation time is 2h. To obtain (Dy) 0.2 Y 0.2 Ho 0.2 Er 0.2 Yb 0.2 ) 2 Zr 2 O 7 High entropy ceramic fiber membrane.
The high-entropy ceramic fiber membrane prepared by the embodiment has a fluorite phase structure, the average diameter of the fiber is 274nm, the grain size of the fiber is 19.6nm, the tensile strength is 0.85MPa, and the room-temperature thermal conductivity is 0.0337W/(m.K). The fiber has compact diameter and good flexibility.
Example 5 (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7
(1) Dissolving 70.67g of lanthanum chloride hexahydrate, 71.74g of neodymium chloride hexahydrate, 72.92g of samarium chloride hexahydrate, 73.28g of europium chloride hexahydrate, 74.34g of gadolinium chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate in 2000g of anhydrous methanol, sequentially adding 200g of acetylacetone and 480g of triethylamine (the molar ratio of the zirconium oxychloride octahydrate to the acetylacetone to the triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
(3) Soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 72 hours, and then filtering out triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-rare earth acetylacetone polymer, wherein the solution is clear and transparent and is light purple;
(4) Carrying out reduced pressure drying on the acetone solution containing the zirconium-rare earth acetylacetone polymer obtained in the step (3) at 40 ℃ to obtain a zirconium-rare earth acetylacetone polymer;
(5) Dissolving 10g of the zirconium-rare earth acetylacetone polymer obtained in the step (4) in 20g of anhydrous methanol, adding 0.5g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) Performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain a rare earth zirconate high-entropy ceramic precursor fiber film, wherein the electrostatic spinning voltage is 24kV, the electrostatic spinning humidity is 30%, the propelling speed is 2mL/h, and the distance from a needle to a receiving shaft is 25cm;
(7) Drying the rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (6) in an oven at the temperature of 80 ℃ for 2 hours;
(8) And (3) calcining the dried high-entropy ceramic precursor fiber film of the rare earth zirconate obtained in the step (7) in an air atmosphere, wherein the heating rate is 1 ℃/min before 300 ℃, the heating rate is 5 ℃/min after 300 ℃, the calcining temperature is 1200 ℃, and the heat preservation time is 2h. To obtain (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 High entropy ceramic fiber membranes.
The high-entropy ceramic fiber membrane prepared by the embodiment has a fluorite phase structure, the average diameter of the fiber is 460nm, the grain size of the fiber is 76.2nm, the tensile strength is 0.66MPa, and the room-temperature thermal conductivity is 0.041W/(m.K). The fiber has compact diameter and good flexibility.
Example 6 (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7
(1) Dissolving 70.67g of lanthanum chloride hexahydrate, 71.74g of neodymium chloride hexahydrate, 72.92g of samarium chloride hexahydrate, 73.28g of europium chloride hexahydrate, 74.34g of gadolinium chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate in 2000g of anhydrous methanol, sequentially adding 200g of acetylacetone and 480g of triethylamine (the molar ratio of the zirconium oxychloride octahydrate to the acetylacetone to the triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
(3) Soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 72 hours, and then filtering out triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-rare earth acetylacetone polymer, wherein the solution is clear and transparent and is light purple;
(4) Carrying out reduced pressure drying on the acetone solution containing the zirconium-rare earth acetylacetone polymer obtained in the step (3) at 40 ℃ to obtain a zirconium-rare earth acetylacetone polymer;
(5) Taking 10g of the zirconium-rare earth acetylacetone polymer obtained in the step (4), dissolving the zirconium-rare earth acetylacetone polymer in 20g of anhydrous methanol, adding 0.5g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) Performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain a rare earth zirconate high-entropy ceramic precursor fiber film, wherein the electrostatic spinning voltage is 18kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from a needle to a receiving shaft is 15cm;
(7) Drying the rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (6) in an oven at the temperature of 80 ℃ for 2 hours;
(8) Calcining the dried rare earth zirconate high-entropy ceramic precursor fiber film obtained in the step (7) in an air atmosphere, wherein the heating rate is 2The temperature is 800 ℃ per min, the calcining temperature is 800 ℃, and the heat preservation time is 5h. To obtain (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 High entropy ceramic fiber membrane.
The high-entropy ceramic fiber membrane prepared in the embodiment has a fluorite phase structure, the average diameter of the fiber is 529nm, the grain size of the fiber is 108.7nm, the tensile strength is 0.72MPa, and the room-temperature thermal conductivity is 0.039W/(m.K). The fiber has compact diameter and good flexibility.
Comparative example 1 (La) 2 Zr 2 O 7 )
(1) 353.36g of lanthanum chloride hexahydrate and 322.25g of zirconium oxychloride octahydrate are dissolved in 2000g of anhydrous methanol, 200g of acetylacetone and 480g of triethylamine (molar ratio of zirconium oxychloride octahydrate: acetylacetone: triethylamine is 1;
(2) Drying the solution obtained in the step (1) at 40 ℃ under reduced pressure to obtain a zirconium-lanthanum acetylacetone polymer containing triethylamine hydrochloride;
(3) And (3) soaking the zirconium-lanthanum acetylacetone polymer containing triethylamine hydrochloride obtained in the step (2) in 4000mL of acetone for 72h, and then filtering out the triethylamine hydrochloride precipitate to obtain an acetone solution containing the zirconium-lanthanum acetylacetone polymer, wherein the solution is clear and transparent and is light purple.
(4) And (4) drying the acetone solution containing the zirconium-lanthanum acetylacetone polymer obtained in the step (3) at 40 ℃ under reduced pressure to obtain the zirconium-lanthanum acetylacetone polymer.
(5) Taking 10g of the zirconium-lanthanum acetylacetone polymer obtained in the step (4), dissolving the zirconium-lanthanum acetylacetone polymer in 20g of anhydrous methanol, adding 0.5g of polyvinylpyrrolidone (PVP), magnetically stirring for 1h until the PVP is completely dissolved, and continuously stirring for 5h to obtain a transparent and clear spinning solution;
(6) Performing electrostatic spinning on the spinning solution obtained in the step (5) to obtain a precursor fiber membrane, wherein the electrostatic spinning voltage is 18kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from a needle to a receiving shaft is 15cm;
(7) Drying the precursor fiber film obtained in the step (6) in an oven at 80 ℃ for 2h;
(8) Calcining the dried precursor fiber film obtained in the step (7) in an air atmosphere, wherein the heating rate is 1 ℃/min before 300 ℃, the heating rate is 5 ℃/min after 300 ℃, the calcining temperature is 800 ℃, and the heat preservation time is 2h to obtain La 2 Zr 2 O 7 High entropy ceramic fiber membranes.
The lanthanum zirconate ceramic fiber film prepared by the comparative example has a fluorite phase structure, the average diameter of the fiber is 545nm, the grain size of the fiber is 127.3nm, the tensile strength is 0.35MPa, and the room-temperature thermal conductivity is 0.0474W/(m.K). The fiber diameter is compact, but the fiber flexibility is poor, and the calcined fiber film is not a monolithic ceramic fiber film but a fiber film fragment.
Comparative example 2 (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Zr 2 O 7
(1) Dissolving 7.067g of lanthanum chloride hexahydrate, 7.174g of neodymium chloride hexahydrate, 7.292g of samarium chloride hexahydrate, 7.434g of gadolinium chloride hexahydrate, 7.570g of ytterbium chloride hexahydrate and 32.225g of zirconium oxychloride octahydrate in a mixed solution of 150mL of absolute ethyl alcohol and 250mL of deionized water, adding 600mLN and N-dimethylformamide after complete dissolution, and stirring until the solution is clear and transparent;
(2) Slowly adding 75g of polyvinylpyrrolidone (PVP) into the solution obtained in the step (1), and stirring until the solution is clear and transparent to obtain a spinning precursor solution;
(3) And (3) performing electrostatic spinning on the spinning solution obtained in the step (2) to obtain a precursor fiber membrane, wherein the electrostatic spinning voltage is 20kV, the electrostatic spinning humidity is 30%, the propelling speed is 1mL/h, and the distance from the needle to the receiving shaft is 15cm.
(4) And (4) drying the precursor fiber film obtained in the step (3) in an oven at 80 ℃ for 2h.
(5) And (4) calcining the dried precursor fiber film obtained in the step (4) in an air atmosphere, wherein the heating rate is 2 ℃/min, the calcining temperature is 800 ℃, and the heat preservation time is 2h. To obtain (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Zr 2 O 7 High entropy ceramic fibers.
The high-entropy ceramic fiber prepared in comparative example 2 is of a fluorite phase structure, the average diameter of the fiber is 273nm, the high-entropy ceramic fiber obtained by calcining is not a ceramic fiber film but a powdery high-entropy ceramic fiber, the mechanical property is poor, the tensile strength cannot be measured, and the room-temperature thermal conductivity is 0.22W/(m.K).
To further illustrate the invention provided with A 2 Zr 2 O 7 Correlation of high entropy ceramic fiber membranes to A provided in examples 1-2 2 Zr 2 O 7 The high-entropy ceramic fiber membrane was subjected to the relevant tests, as shown in FIGS. 1 to 4.
FIG. 1 shows A prepared in example 1 2 Zr 2 O 7 XRD pattern of high entropy ceramic fiber membrane. As can be seen from fig. 1, it has a single-phase fluorite structure and no second-phase impurity phase.
FIG. 2 shows A prepared in example 1 (a) and example 2 (b) 2 Zr 2 O 7 SEM pictures of high entropy ceramic fiber membranes. From FIG. 2, the diameter distribution of the fiber membrane is uniform, and the diameter is below 500 nm.
FIG. 3 shows A prepared in example 1 2 Zr 2 O 7 TEM pictures of high entropy ceramic fiber membranes. As can be seen from fig. 3, all of them have a single-phase fluorite structure and are excellent in crystallinity.
FIG. 4 shows A prepared in example 1 2 Zr 2 O 7 Optical photographs of high entropy ceramic fiber membranes. The A produced can be seen from FIG. 4 2 Zr 2 O 7 The high-entropy ceramic fiber membrane has good flexibility.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. A zirconium-rare earth acetylacetone polymer is characterized by comprising zirconium polyacetylacetonate with a one-dimensional chain structure and rare earth polyacetylacetone with a one-dimensional chain structure; the rare earth elements in the zirconium-rare earth acetylacetone polymer are any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu.
2. The zirconium-rare earth ionic acetylacetone polymer of claim 1, wherein a molar ratio of zirconium to rare earth elements in the zirconium-rare earth acetylacetone polymer is 1.
3. A process for preparing a zirconium-rare earth acetylacetone polymer of claim 1 or 2, comprising the steps of:
dissolving a hydrate of rare earth trichloride and a hydrate of zirconium oxychloride into an alcohol solvent to obtain a dissolved solution; the rare earth trichloride is any 5 of lanthanum trichloride, neodymium trichloride, samarium trichloride, europium trichloride, gadolinium trichloride, dysprosium trichloride, yttrium trichloride, holmium trichloride, erbium trichloride, ytterbium trichloride and lutetium trichloride;
mixing the dissolved solution with acetylacetone and triethylamine, carrying out hydrolysis and polycondensation, and after the solution is clarified, drying under reduced pressure to obtain a zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride;
and soaking the zirconium-rare earth acetylacetone polymer containing triethylamine hydrochloride into acetone, performing solid-liquid separation, and drying the obtained supernatant under reduced pressure to obtain the zirconium-rare earth acetylacetone polymer.
4. The production method according to claim 3, wherein the molar ratio of the hydrate of the rare earth trichloride to the hydrate of zirconium oxychloride is 1.
5. The method according to claim 3, wherein the molar ratio of the hydrated zirconium oxychloride to the acetylacetone is 1: (1.8-3.2); the molar ratio of the zirconium oxychloride hydrate to the triethylamine is 1: (4.3-6.5).
6. A preparation method of a flexible rare earth zirconate high-entropy ceramic fiber film is characterized by comprising the following steps:
mixing a zirconium-rare earth acetylacetone polymer, an alcohol solvent and a spinning auxiliary agent to obtain a spinning solution; the zirconium-rare earth acetylacetone polymer is the zirconium-rare earth acetylacetone polymer of claim 1 or 2 or the zirconium-rare earth acetylacetone polymer prepared by the preparation method of any one of claims 3 to 5; the mass ratio of the zirconium-rare earth acetylacetone polymer to the alcohol solvent is (50-150): (200-300); the mass ratio of the alcohol solvent to the spinning auxiliary agent is (200-300): (1-10);
and (3) carrying out electrostatic spinning on the spinning solution, and drying and calcining the obtained rare earth zirconate high-entropy ceramic precursor fiber film in sequence to obtain the flexible rare earth zirconate high-entropy ceramic fiber film.
7. The preparation method according to claim 6, wherein the ambient humidity of the electrostatic spinning is 15-40% and the temperature is 20-35 ℃; the voltage of the electrostatic spinning is 9-24 kV, the distance between the spinning needle and the receiving shaft is 10-30 cm, and the propelling speed of the propelling pump is 0.5-2 mL/h.
8. The preparation method of claim 6, wherein the calcining temperature is 600-1200 ℃ and the holding time is 2-5 h.
9. A flexible rare earth zirconate high-entropy ceramic fiber membrane prepared by the preparation method of any one of claims 6 to 8, which comprises A 2 Zr 2 O 7 The A is any 5 of La, nd, sm, eu, gd, dy, Y, ho, er, yb and Lu.
10. Use of the flexible rare earth zirconate high-entropy ceramic fiber film of claim 9 in high temperature resistant thermal insulation ceramics.
CN202210959854.7A 2022-08-11 2022-08-11 Flexible rare earth zirconate high-entropy ceramic fiber membrane and preparation and application thereof Pending CN115286809A (en)

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CN110982524A (en) * 2019-11-20 2020-04-10 太原理工大学 Rare earth doped lanthanum zirconate up-conversion luminescence fiber and preparation method and application thereof
CN111187424A (en) * 2020-02-14 2020-05-22 山东大学 Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, and preparation method and application thereof
CN113135755A (en) * 2021-04-14 2021-07-20 厦门稀土材料研究所 Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof

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CN110982524A (en) * 2019-11-20 2020-04-10 太原理工大学 Rare earth doped lanthanum zirconate up-conversion luminescence fiber and preparation method and application thereof
CN111187424A (en) * 2020-02-14 2020-05-22 山东大学 Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, and preparation method and application thereof
CN113135755A (en) * 2021-04-14 2021-07-20 厦门稀土材料研究所 Flexible cerium acid rare earth high-entropy nanofiber ceramic membrane and preparation method and application thereof

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