A method for preparing zirconia ceramic nanofibers

Abstract

This invention provides a method for preparing zirconia ceramic nanofibers, comprising the following steps: (1) preparation of precursor solution: preparing an aqueous solution containing a silicon source compound and a zirconium source compound; (2) preparation of zirconia ceramic fiber precursor solution; (3) preparation of hybrid zirconia ceramic nanofibers; (4) preparation of zirconia ceramic nanofibers; wherein, the zirconium source compound in step (1) is an organic zirconium source compound. The zirconia ceramic nanofibers provided by this invention have good spinnability and continuous and uniform fibers; while the multiphase structure gives them good mechanical properties, and at the same time coordinates the balance between thermal conductivity and stable structure at high temperature, making them less prone to brittle fracture, highly processable, and reusable.

Description

Technical Field

[0001] This invention belongs to the field of zirconia ceramic preparation, and specifically relates to a method for preparing zirconia ceramic nanofibers. Background Technology

[0002] Ceramic materials, as an emerging type of material, refer to a class of inorganic non-metallic materials made from natural or synthetic compounds through shaping and high-temperature sintering. They are widely used in the materials field due to their unique high aspect ratio and circular or elliptical cross-sectional shape. However, the brittle nature of ceramic materials limits their application in complex stress, large strain, and high vibration environments.

[0003] Ceramic matrix composites refer to composites in which a second phase is added to the ceramic matrix to improve the intrinsic brittleness of ceramic materials. Fibers are often the best choice for the second phase, as fiberization is an effective means of imparting flexibility and elasticity to brittle ceramic materials. Fiber-reinforced ceramic matrix composites can combine the advantages of both materials, particularly significantly improving the toughness of the composite while also enhancing its thermodynamic and mechanical properties. Ceramic fibers can be broadly classified into oxide fibers and non-oxide fibers based on their chemical composition. Oxide fibers typically possess high mechanical strength, low thermal conductivity, good electrical insulation, and chemical stability, and remain stable in an oxygen atmosphere. Common oxide fibers include silica fibers, alumina fibers, zirconium oxide fibers, titanium dioxide fibers, and zinc oxide fibers. Among these, zirconium oxide is a crucial structural and functional material with excellent physicochemical properties, particularly valuable for its thermal insulation performance in aerospace, metallurgy, and energy industries. However, despite significant achievements in zirconium oxide fiber development in my country, its mechanical properties still do not meet expectations, making it difficult to withstand the stresses of processing and assembly.

[0004] In the existing technology, there is a considerable amount of research on oxide ceramic fibers. Invention patent CN 113668139 A discloses a method for preparing flexible, high-temperature resistant SiO2 ceramic nanofiber membranes. The SiO2 ceramic nanofiber membranes are prepared by sol-gel electrospinning and can be used at 800–1200℃ without changing the fiber morphology and structure. They also have a low thermal conductivity, making them suitable for high-temperature applications, especially in high-temperature and humid environments. However, the prepared fiber membranes may have relatively poor deformation properties, and the tensile strength still has room for improvement. Furthermore, the processability and reusability of the material are not ideal.

[0005] Therefore, there is an urgent need to invent a zirconia ceramic nanofiber that can achieve a balance between lower thermal conductivity and higher mechanical properties, while also improving its flexibility and thermal stability, so that it can be better applied in the field of thermal protection materials. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing zirconia ceramic nanofibers. The zirconia ceramic nanofibers prepared by this invention are continuous and uniform, and have stable high-temperature performance. In addition, the zirconia ceramic nanofibers prepared by this invention have good mechanical properties, especially being less prone to brittle fracture, with strong processability and reusability.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] This invention provides a method for preparing zirconia ceramic nanofibers, comprising the following steps:

[0009] (1) Preparation of precursor solution: Prepare an aqueous solution containing silicon source compound and zirconium source compound, add complexing agent, mix evenly, and stir at room temperature for 2-4 hours to obtain precursor solution;

[0010] (2) Preparation of zirconia ceramic fiber precursor solution: The spinning aid and the precursor solution in step (1) are mixed evenly at 50-70°C and stirred at room temperature for 0.5-2 hours to obtain zirconia ceramic fiber precursor solution;

[0011] (3) Preparation of hybrid zirconia ceramic nanofibers: The zirconia ceramic fiber precursor solution in step (2) is spun into hybrid zirconia ceramic nanofibers by electrospinning process.

[0012] (4) Preparation of zirconia ceramic nanofibers: The hybrid zirconia ceramic nanofibers in step (3) are dried under vacuum, and then sintering aids are added. The zirconia ceramic nanofibers are obtained by sintering using a high-temperature calcination process.

[0013] The zirconium source compound mentioned in step (1) is an organozirconium source compound.

[0014] Preferably, in step (1), the silicon source compound is silica sol and / or vinyltrimethylsilane, and the zirconium source compound is butyl zirconate and / or zirconium n-butoxide.

[0015] More preferably, the zirconium source compound in step (1) is a mixed zirconium source compound of butyl zirconate and zirconium n-butoxide.

[0016] More preferably, the mass ratio of the butyl zirconate to the zirconium n-butoxide is (0.5-1):1.

[0017] Preferably, the mass ratio of silicon source compound to zirconium source compound in step (1) is 1:(1-3).

[0018] More preferably, the mass ratio of silicon source compound to zirconium source compound in step (1) is 1:1.5.

[0019] This invention improves the ductility of ceramic nanofibers to a certain extent by introducing an amorphous Si-O-Si phase. There is a good synergistic effect between the amorphous and crystalline phase structures, which increases and coordinates the strength and toughness of the ceramic fibers. At the same time, by effectively avoiding uncontrolled crystal growth, the high-temperature resistance of the ceramic fibers is stabilized.

[0020] Preferably, in step (1), the mass ratio of zirconium source compound to complexing agent is 1:(3-4).

[0021] More preferably, in step (1), the mass ratio of the zirconium source compound to the complexing agent is 1:3.5.

[0022] More preferably, the complexing agent is acetic acid. This invention controls the spinnability of the precursor solution by varying the amount of acetic acid added, thus avoiding gelation of the precursor solution within a preferred range, i.e., the precursor solution becoming a white solid and losing its spinnability. A possible reason is that organozirconium source compounds are readily hydrolyzed under aqueous conditions, leading to gelation of the precursor solution. The addition of the complexing agent acetic acid allows the organozirconium source compound to form a stable bridging coordination structure. Simultaneously, the steric hindrance effect of acetic acid itself hinders the three-dimensional development of Zr, reducing the degree of condensation reaction and further forming chain-like polymer molecules with a lower degree of polymerization rather than network polymer molecules.

[0023] Preferably, the amount of spinning aid added in step (2) is 6 to 12 wt% of the precursor solution in step (1).

[0024] Preferably, the spinning aid in step (2) comprises the following raw materials: solute, solvent and catalyst; the solvent is anhydrous ethanol and the catalyst is oxalic acid.

[0025] Preferably, the mass ratio of the solute, solvent and catalyst is 1:(8-15):(1-1.5).

[0026] Preferably, the spinning aid in step (2) is a spinning aid containing solute A and solute B, and the mass ratio of solute A to solute B is 1:(2-5).

[0027] Preferably, solute A is polyvinylpyrrolidone with a molecular weight of 400,000 to 600,000; and solute B is polyvinylpyrrolidone with a molecular weight of 1,000,000 to 1,800,000.

[0028] In existing technologies, polymer solutes in spinning auxiliaries play a crucial role in imparting spinnability to the precursor solution, particularly in the bonding force between fibers. However, when the polymer is inappropriate, the inorganic component content is too low, resulting in low fiber yield and poor continuity after high-temperature calcination. This invention uses a mixture of solutes A and B with different properties. The resulting linear molecular structure allows the spinning auxiliaries to achieve good spinnability without requiring excessive polymer addition. In particular, the reaction of carbonyl oxygen with hydroxyl groups in the system to form hydrogen bonds facilitates jet formation during electrospinning, avoiding the impact of improper polymer addition on fiber flexibility during high-temperature calcination. Simultaneously, it imparts high viscosity and conductivity to the zirconia ceramic fiber precursor solution, allowing for appropriate stretching during electrospinning. This results in smaller diameter ceramic nanofibers with larger bending radii, increasing the continuity and uniformity of the nanofiber structure.

[0029] Preferably, the steps further include step (5) surface treatment of zirconia ceramic nanofibers.

[0030] More preferably, the surface treatment steps for the zirconia ceramic nanofibers are as follows:

[0031] Potassium persulfate and an equimolar amount of dopamine hydrochloride were dissolved in an equimolar buffer solution to obtain a buffer solution mixture. The zirconia ceramic nanofibers from step (4) were immersed in the equimolar buffer solution mixture for 2-4 hours, and then immersed in a 50% by mass nano-titanium carbide colloidal solution. After ultrasonic dispersion for 30-60 minutes, the immersion and ultrasonic steps were repeated 5-15 times to obtain surface-treated zirconia ceramic nanofibers.

[0032] More preferably, the surface treatment steps for the zirconium oxide ceramic nanofibers are as follows:

[0033] Dissolve 0.5–1.2 mol of potassium persulfate and an equimolar amount of dopamine hydrochloride in an equimolar buffer solution to obtain a buffer solution mixture. Immerse the zirconia ceramic nanofibers from step (4) in the equimolar buffer solution mixture for 2–4 h, and then immerse them in a 50% by mass nano-titanium carbide colloidal solution. After ultrasonic dispersion for 30–60 min, repeat the immersion and ultrasonic steps 5–15 times to obtain surface-treated zirconia ceramic nanofibers.

[0034] Preferably, the buffer solution is a neutral dibasic sodium phosphate / citric acid buffer solution.

[0035] The applicant has surface-treated zirconia ceramic nanofibers and loaded them with -OH and -NH2 active groups. These groups combine with the negative ions of the nanosheets through hydrogen bonds, jointly driving the nanosheets to coat the zirconia ceramic nanofibers and forming a complete and uniform coating layer. This results in zirconia ceramic nanofibers having a better aspect ratio, and the fiber continuity and toughness are further improved.

[0036] Preferably, the conditions for the electrospinning process in step (3) are: ambient humidity of 30-40%, ambient temperature of 15-25℃, spinning rate of 1-2 mL / hr, spinning distance of 15-20 cm, and spinning voltage of 15-20 kV.

[0037] Preferably, the vacuum drying conditions in step (4) are 60°C for 6 hours.

[0038] Preferably, the sintering aid in step (4) is chromium oxide.

[0039] More preferably, the amount of chromium oxide added is 0.4% to 1% of the mass of the hybrid zirconia ceramic nanofibers. This invention, by adding a certain amount of chromium oxide as a sintering aid, has found that it inhibits the volume expansion caused by the phase transformation of zirconia, which is beneficial to the stress-induced phase transformation toughening and microcrack fracture toughening of zirconia in ceramic nanofibers, thereby increasing its fracture toughness.

[0040] Preferably, the conditions for the high-temperature calcination process in step (4) are as follows: heating to 600°C at a rate of 0.5–2°C / min in an inert atmosphere and holding at that temperature for 1–3 hours. Finally, heating to 800–1200°C at a rate of 1–10°C / min and holding at that temperature for 0.5–2 hours, and then cooling to room temperature in the furnace.

[0041] More preferably, the high-temperature calcination process in step (4) involves heating to 600°C at a rate of 1°C / min in an argon atmosphere and holding for 2 hours. Finally, it is heated to 1000°C at a rate of 5°C / min and held for 1 hour, then cooled to room temperature in the furnace. Under this preferred calcination process, the slow heating ensures the complete removal of residual organic components from the gel fibers after vacuum drying, while maintaining the internal structure of the fibers, avoiding defects such as pores, stabilizing mechanical properties, ensuring the continuity of the formed fibers, fully utilizing the reinforcing and toughening effect of the fibers on the ceramic matrix, and making the mechanical properties of the prepared zirconia ceramic nanofibers more stable.

[0042] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0043] (1) The method for preparing zirconia ceramic nanofibers provided by the present invention uses a mixed zirconium source compound in butyl zirconate and zirconium n-butoxide as the zirconium source compound in the precursor solution. Acetic acid is added as a complexing agent and the dosage is adjusted to make the organic zirconium source compound form a stable bridging coordination structure, which solves the problem that it is easily hydrolyzed under aqueous conditions, leading to gelation of the precursor solution. At the same time, it hinders the three-dimensional development of Zr, reduces the degree of condensation reaction, and further forms a chain polymer molecule with a lower degree of polymerization.

[0044] (2) The zirconium oxide ceramic nanofibers prepared by the present invention are obtained by using solute A and solute B with different properties in combination. The linear molecular structure obtained allows the spinning aid to have good spinnability without adding too much polymer, avoiding the influence of improper polymer addition on fiber flexibility and fiber yield. The obtained nanofibers have good flexibility and have a continuous and uniform structure.

[0045] (3) The method for preparing zirconia ceramic nanofibers provided by the present invention involves surface treatment of zirconia ceramic nanofibers, loading -OH and -NH2 active groups, and combining them with the negative ions of nanosheets through hydrogen bonds, thereby driving the nanosheets to coat the zirconia ceramic nanofibers and forming a complete and uniform coating layer. This results in zirconia ceramic nanofibers having a better aspect ratio, and the fiber continuity and toughness are further improved. Detailed Implementation

[0046] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0047] Unless otherwise specified, the chemicals involved in the specific embodiments of this invention can be readily obtained from commercially available sources: polyvinylpyrrolidone with a molecular weight of 500,000 and polyvinylpyrrolidone with a molecular weight of 1,500,000 were purchased from Aladdin Reagent Co., Ltd., and nano-titanium carbide was purchased from Suzhou Beike Nanotechnology Co., Ltd.

[0048] Implementation methods for some steps in Examples 1-3:

[0049] The conditions for electrospinning in step (3) are: ambient humidity of 35%, ambient temperature of 22℃, spinning rate of 1.5mL / hr, spinning distance of 18cm, and spinning voltage of 20kV.

[0050] In step (4), the vacuum drying conditions are 60℃ for 6 hours;

[0051] The conditions for the high-temperature calcination process in step (4) are: heating to 600°C at a rate of 1°C / min in an argon atmosphere and holding for 2 hours, heating to 1000°C at a rate of 5°C / min and holding for 1 hour, and then cooling to room temperature in the furnace.

[0052] The surface treatment steps for the zirconia ceramic nanofibers in step (5) are as follows:

[0053] 1 mol of potassium persulfate and 1 mol of dopamine hydrochloride were dissolved in 1 mol of sodium dibasic phosphate / citric acid buffer solution (pH=7) to obtain a buffer solution mixture. The zirconia ceramic nanofibers in step (4) were soaked in the buffer solution mixture of equal mass for 3 h, and then soaked in a nano-titanium carbide colloidal solution with a mass ratio of 50%. After ultrasonic dispersion for 50 min, the soaking and ultrasonic steps were repeated 10 times to obtain surface-treated zirconia ceramic nanofibers.

[0054] In the following embodiments:

[0055] Solute A is polyvinylpyrrolidone with a molecular weight of 500,000; solute B is polyvinylpyrrolidone with a molecular weight of 1,500,000.

[0056] Example 1

[0057] A method for preparing zirconia ceramic nanofibers includes the following steps:

[0058] (1) Preparation of precursor solution: Prepare an aqueous solution containing vinyltrimethylsilane and zirconium source compound, add acetic acid, mix well, and stir at room temperature for 3 h to obtain precursor solution;

[0059] The mass ratio of vinyltrimethylsilane, zirconium source compound, and acetic acid is 0.33:1:3.5.

[0060] The zirconium source compound was obtained by mixing butyl zirconate and zirconium n-butoxide in a mass ratio of 0.7:1.

[0061] (2) Preparation of zirconia ceramic fiber precursor solution: The spinning aid and the precursor solution in step (1) were mixed evenly at 60°C and stirred at room temperature for 1 hour to obtain zirconia ceramic fiber precursor solution.

[0062] The amount of spinning aid added is 10 wt% of the precursor solution in step (1);

[0063] In this process, solute A, solute B, anhydrous ethanol and oxalic acid are mixed in a mass ratio of 1:3.5:45:4.5 and stirred at room temperature for 2 hours to obtain a spinning aid.

[0064] (3) Preparation of hybrid zirconia ceramic nanofibers: The zirconia ceramic fiber precursor solution in step (2) is spun into hybrid zirconia ceramic nanofibers by electrospinning process.

[0065] (4) Preparation of zirconia ceramic nanofibers: The hybrid zirconia ceramic nanofibers in step (3) are dried under vacuum, then chromium oxide is added, and sintered using a high-temperature calcination process to obtain zirconia ceramic nanofibers.

[0066] The amount of chromium oxide added is 0.7% of the mass of the hybrid zirconia ceramic nanofibers;

[0067] (5) Surface treatment of zirconia ceramic nanofibers.

[0068] Example 2

[0069] A method for preparing zirconia ceramic nanofibers includes the following steps:

[0070] (1) Preparation of precursor solution: Prepare an aqueous solution containing vinyltrimethylsilane and zirconium source compound, add acetic acid, mix well, and stir at room temperature for 3 h to obtain precursor solution;

[0071] The mass ratio of vinyltrimethylsilane, zirconium source compound, and acetic acid is 0.33:1:3.

[0072] The zirconium source compound was obtained by mixing butyl zirconate and zirconium n-butoxide in a mass ratio of 0.7:1.

[0073] (2) Preparation of zirconia ceramic fiber precursor solution: The spinning aid and the precursor solution in step (1) were mixed evenly at 60°C and stirred at room temperature for 1 hour to obtain zirconia ceramic fiber precursor solution.

[0074] The amount of spinning aid added is 12 wt% of the precursor solution in step (1);

[0075] In this process, solute A, solute B, anhydrous ethanol and oxalic acid are mixed in a mass ratio of 1:3.5:45:4.5 and stirred at room temperature for 2 hours to obtain a spinning aid.

[0076] (3) The preparation of hybrid zirconia ceramic nanofibers is the same as in Example 1;

[0077] (4) The preparation of zirconia ceramic nanofibers is the same as in Example 1;

[0078] (5) Surface treatment of zirconia ceramic nanofibers.

[0079] Example 3

[0080] A method for preparing zirconia ceramic nanofibers includes the following steps:

[0081] (1) Preparation of precursor solution: Prepare an aqueous solution containing vinyltrimethylsilane and zirconium source compound, add acetic acid, mix well, and stir at room temperature for 3 h to obtain precursor solution;

[0082] The mass ratio of vinyltrimethylsilane, zirconium source compound, and acetic acid is 0.33:1:4.

[0083] The zirconium source compound was obtained by mixing butyl zirconate and zirconium n-butoxide in a mass ratio of 0.7:1.

[0084] (2) Preparation of zirconia ceramic fiber precursor solution: The spinning aid and the precursor solution in step (1) were mixed evenly at 60°C and stirred at room temperature for 1 hour to obtain zirconia ceramic fiber precursor solution.

[0085] The amount of spinning aid added is 6 wt% of the precursor solution in step (1);

[0086] In this process, solute A, solute B, anhydrous ethanol and oxalic acid are mixed in a mass ratio of 1:3.5:45:4.5 and stirred at room temperature for 2 hours to obtain a spinning aid.

[0087] (3) The preparation of hybrid zirconia ceramic nanofibers is the same as in Example 1;

[0088] (4) The preparation of zirconia ceramic nanofibers is the same as in Example 1;

[0089] (5) Surface treatment of zirconia ceramic nanofibers.

[0090] Example 4

[0091] A method for preparing zirconia ceramic nanofibers includes the following steps:

[0092] (1) The preparation of the precursor solution is the same as in Example 1;

[0093] (2) The preparation of the zirconia ceramic fiber precursor solution was the same as in Example 1;

[0094] (3) The preparation of hybrid zirconia ceramic nanofibers is the same as in Example 1;

[0095] (4) The preparation of zirconia ceramic nanofibers is the same as in Example 1, except that the amount of chromium oxide added is 1.5% of the mass of the hybrid zirconia ceramic nanofibers;

[0096] (5) The surface treatment of zirconia ceramic nanofibers is the same as in Example 1.

[0097] Example 5

[0098] A method for preparing zirconia ceramic nanofibers includes the following steps:

[0099] (1) The preparation of the precursor solution is the same as in Example 1;

[0100] (2) The preparation of the zirconia ceramic fiber precursor solution was the same as in Example 1;

[0101] (3) The preparation of hybrid zirconia ceramic nanofibers is the same as in Example 1;

[0102] (4) The preparation of zirconia ceramic nanofibers is the same as in Example 1, except that the high-temperature calcination process in step (4) is to heat to 600°C at a rate of 1°C / min in an argon atmosphere and hold for 2 hours. Finally, it is heated to 1200°C at a rate of 10°C / min and held for 1 hour, and then cooled to room temperature in the furnace.

[0103] (5) The surface treatment of zirconia ceramic nanofibers is the same as in Example 1.

[0104] Example 6

[0105] A method for preparing zirconia ceramic nanofibers includes the following steps:

[0106] (1) The preparation of the precursor solution is the same as in Example 1;

[0107] (2) The preparation of the zirconia ceramic fiber precursor solution was the same as in Example 1;

[0108] (3) The preparation of hybrid zirconia ceramic nanofibers is the same as in Example 1;

[0109] (4) The preparation of zirconia ceramic nanofibers is the same as in Example 1.

[0110] Performance testing:

[0111] The above-mentioned zirconia ceramic nanofibers were subjected to the following performance tests, and the test results are shown in Table 1.

[0112] (1) Tensile strength and fracture toughness test: The mechanical properties of zirconia ceramic nanofibers were tested using a DMA1 dynamic thermomechanical analyzer (METTLERTOLEDO, Switzerland): The samples were clamped in a fixture at 20°C and then tested.

[0113] (2) Thermal conductivity test: The test was conducted using a Hot Disk instrument according to the transient planar source method of ISO 220072:2015.

[0114] Table 1

[0115]

[0116] As shown in Table 1 above, the zirconia ceramic nanofibers prepared in Examples 1-3 are excellent thermal insulation materials. The precursor solution exhibits high spinnability, a continuous and uniform fiber structure, stable high-temperature performance, and good mechanical properties, particularly resistance to brittle fracture, strong processability, and reusability. In contrast to Examples 1-3, Example 4 suffers from improper chromium oxide addition, affecting the structural compactness of the zirconia ceramic nanofibers. Increased porosity causes stress concentration points in the pore structure when the zirconia ceramic fibers are subjected to stress, reducing fracture toughness. In Example 5, improper high-temperature calcination conditions result in a surface structure with numerous voids and roughness, exhibiting a granular aggregate structure, thus affecting mechanical properties. In Example 6, the zirconia ceramic nanofibers prepared without surface treatment show decreased mechanical properties, indicating that the present invention can compensate for the structural defects of zirconia ceramic nanofibers, resulting in excellent overall mechanical properties.

[0117] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing zirconia ceramic nanofibers, characterized in that, Includes the following steps: (1) Preparation of precursor solution: Prepare an aqueous solution containing silicon source compound and zirconium source compound, add complexing agent, mix evenly, and stir at room temperature for 2-4 hours to obtain precursor solution; (2) Preparation of zirconia ceramic fiber precursor solution: The spinning aid and the precursor solution in step (1) are mixed evenly at 50-70°C and stirred at room temperature for 0.5-2 hours to obtain the zirconia ceramic fiber precursor solution; the spinning aid contains the following raw materials: solute, solvent and catalyst; the amount of the spinning aid added is 6-12 wt% of the precursor solution, and the mass ratio of the solute, solvent and catalyst is 1:(8-15):(1-1.5); the solvent is anhydrous ethanol, and the catalyst is oxalic acid; the solute is solute A and solute B, and the mass ratio of solute A and solute B is 1:(2-5); the solute A is polyvinylpyrrolidone with a molecular weight of 400,000-600,000; the solute B is polyvinylpyrrolidone with a molecular weight of 1,000,000-1,800,000. (3) Preparation of hybrid zirconia ceramic nanofibers: The zirconia ceramic fiber precursor solution in step (2) is spun into hybrid zirconia ceramic nanofibers by electrospinning. (4) Preparation of zirconia ceramic nanofibers: The hybrid zirconia ceramic nanofibers in step (3) are dried under vacuum, and then sintering aids are added. The zirconia ceramic nanofibers are obtained by sintering using a high-temperature calcination process. The zirconium source compound mentioned in step (1) is an organozirconium source compound.

2. The method for preparing zirconia ceramic nanofibers according to claim 1, characterized in that, In step (1), the silicon source compound is silica sol and / or vinyltrimethylsilane, and the zirconium source compound is butyl zirconate.

3. The method for preparing zirconia ceramic nanofibers according to claim 1, characterized in that, In step (1), the mass ratio of silicon source compound to zirconium source compound is 1:(1-3).

4. The method for preparing zirconia ceramic nanofibers according to claim 1, characterized in that, In step (1), the mass ratio of zirconium source compound to complexing agent is 1:(3-4).

5. The method for preparing zirconia ceramic nanofibers according to claim 1, characterized in that, It also includes step (5), which is the surface treatment of zirconia ceramic nanofibers.

6. The method for preparing zirconia ceramic nanofibers according to claim 1, characterized in that, The conditions for electrospinning in step (3) are: ambient humidity of 30-40%, ambient temperature of 15-25℃, spinning rate of 1-2 mL / hr, spinning distance of 15-20 cm, and spinning voltage of 15-20 kV.

7. The method for preparing zirconia ceramic nanofibers according to claim 1, characterized in that, The conditions for the high-temperature calcination process in step (4) are as follows: heating to 600°C at a rate of 0.5–2°C / min in an argon inert atmosphere and holding for 1–3 hours, then heating to 1000°C at a rate of 1–10°C / min and holding for 0.5–2 hours, and then cooling to room temperature in the furnace.

Images