Preparation method and application of high-temperature and high-strength Janus structure zirconium oxide-titanium oxide fiber membrane

Abstract

The invention discloses a preparation method and application of a high-temperature and high-strength Janus structure zirconium oxide-titania fiber membrane, belonging to the field of inorganic non-metallic ceramic fiber materials. The preparation method provided by the invention adopts zirconium and titanium precursors of the same organic system to prepare a spinning solution, and uses a shoulder-to-shoulder electrostatic spinning technology to prepare a zirconium oxide-titania precursor fiber membrane with a Janus structure by controlling the injection speed, flow rate ratio and spinning parameters, and then the precursor fiber membrane is subjected to segmented heat treatment to obtain a high-temperature and high-strength Janus structure zirconium oxide-titania fiber membrane; the method is simple to operate and has a stable process; the fibers in the obtained fiber membrane have a uniform Janus structure, are resistant to high temperatures, have a stable structure and good mechanical properties, and can be used as a high-temperature thermal insulation material.

Description

Technical Field

[0001] The invention belongs to the field of inorganic non-metallic ceramic fiber materials, and specifically relates to a preparation method and application of a high-temperature and high-strength Janus structure zirconium oxide-titanium oxide fiber membrane. Background Art

[0002] With the continuous development of aerospace, aviation, and high-temperature insulation, the development of ultra-high temperature insulation materials that can meet the requirements of long-term use in ultra-high temperature environments is currently a hot topic. From the basic physical process of heat transfer, heat transfer is mainly carried out in three ways: thermal radiation, thermal conduction, and thermal convection. At medium and low temperatures, thermal conduction and thermal convection are the main ways of heat transfer of materials. At high temperatures, the proportion of thermal radiation in the total heat transfer increases, and suppressing thermal radiation improves the thermal insulation performance of the material more significantly. Studies have found that the infrared reflection ability of metals and inorganic powders can effectively reduce the heat loss caused by thermal radiation and achieve the effect of thermal insulation.

[0003] Zirconia fiber not only inherits the inherent characteristics of zirconium oxide itself, such as high melting point (2715℃), low thermal conductivity, strong resistance to high-temperature oxidation, strong infrared reflection and scattering capabilities, but also has the characteristics of good flexibility of fiber materials, which makes zirconium oxide fiber have better temperature resistance, heat insulation and energy saving effects than other oxide fibers.

[0004] Titanium dioxide (TiO2) is a typical broadband absorption semiconductor material with the advantages of high melting point (1850℃), extremely high refractive index, moderate bandgap, good chemical stability, abundant reserves, and environmental friendliness. Among them, rutile TiO2 has a refractive index of 2.72, which is an inorganic oxide with an extremely high refractive index and is often used as a near-infrared reflective material.

[0005] The Chinese patent document with publication number CN109876763A discloses a method for preparing a zirconium dioxide / titanium dioxide composite adsorption material, which uses a centrifugal spinning process and high-temperature heat treatment to obtain high-quality titanium dioxide-zirconium oxide composite fibers. The fiber material increases the contact area with the degradation product and has a better photocatalytic effect. However, this method only uses one spinning solution to obtain a two-phase mixed fiber and the application field is the catalytic field. If a two-dimensional or even three-dimensional structure with a larger specific surface area, good mechanical properties and easy recycling can be prepared, it is of great practical significance to further expand its application form.

[0006] The Chinese paper "Preparation and Performance Research of Lightweight Zirconia-Based Fiber Insulation Materials" (Dong Jianhong. Preparation and Performance Research of Lightweight Zirconia-Based Fiber Insulation Materials [D]. Jinan: Shandong University, 2022.) discloses a method for preparing zirconium oxide-titanium oxide composite fiber membranes using zirconium and titanium precursors of different systems as raw materials using a side-by-side spinning method, which effectively combines low thermal conductivity and high strength zirconium oxide with titanium oxide with strong infrared reflection ability, achieving a comprehensive improvement in the thermal insulation performance of the fiber membrane. However, further research has found that its mechanical properties can be further improved after treatment at high temperatures. Therefore, considering the important nature of the insulation material to maintain a stable form during long-term use to extend its service life and the problem that the fiber membrane needs to have sufficient strength to withstand the mechanical external forces during transportation, installation, and application, it is of great practical significance to further improve the mechanical properties of the fiber membrane at high temperatures. Summary of the invention

[0007] The first object of the present invention is to provide a method for preparing a high-temperature and high-strength Janus structure zirconium oxide-titania fiber membrane. By selecting two organic polymer precursors of the same system, polyacetylacetonate zirconium and polyacetylacetonate titanium, as raw materials for preparing the Janus structure zirconium oxide-titania fiber membrane, the tensile properties of the fiber membrane can be significantly improved. The second object of the present invention is to provide an application of the fiber membrane prepared by the above method in high-temperature thermal insulation materials.

[0008] In order to achieve this object, the present invention adopts the following technical solutions:

[0009] In one aspect, the present invention provides a method for preparing a high-temperature and high-strength Janus structure zirconium oxide-titanium oxide fiber membrane, comprising the following steps:

[0010] (1) dissolving poly(zirconium acetylacetonate), hydrated inorganic yttrium salt stabilizer, deionized water, and organic polymer spinning aid in methanol, heating and stirring, to prepare poly(zirconium acetylacetonate) spinning solution;

[0011] (2) dissolving titanium polyacetylacetonate, an organic polymer spinning aid and deionized water in ethanol, heating and stirring, to prepare titanium polyacetylacetonate spinning solution;

[0012] (3) The poly(acetylacetonate) zirconium spinning solution and the poly(acetylacetonate) titanium spinning solution are spun by the side-by-side electrospinning technology to obtain a zirconium oxide-titania precursor fiber membrane. The zirconium oxide-titania precursor fiber membrane is heat treated to obtain a high-temperature and high-strength Janus structured zirconium oxide-titania fiber membrane.

[0013] In the step (1), the hydrated inorganic yttrium salt stabilizer is one of yttrium nitrate hexahydrate, yttrium chloride hexahydrate or yttrium sulfate octahydrate; the organic polymer spinning aid is one of polyethylene oxide, polyvinyl pyrrolidone or polyvinyl alcohol. The hydrated inorganic yttrium salt stabilizer is added as a crystal phase stabilizer to stabilize the zirconium oxide crystal form. The addition of the organic polymer spinning aid is used to regulate the spinnability of the precursor sol and to achieve the optimal ratio of the zirconium source, solvent and organic polymer spinning aid to meet the different requirements of the fiber.

[0014] In the step (1), the mass ratio of polyacetylacetonate zirconium, hydrated inorganic yttrium salt stabilizer, organic polymer spinning aid, deionized water and methanol is 1:0.1-0.3:0.007-0.02:0.05-0.1:1.5-4.5.

[0015] In step (2), the organic polymer spinning aid is one of polyethylene oxide, polyvinyl pyrrolidone or polyvinyl alcohol. The addition of the organic polymer spinning aid is used to adjust the spinnability of the precursor sol and to achieve the optimal ratio of titanium source, solvent and organic polymer spinning aid to meet different fiber requirements.

[0016] In the step (2), the mass ratio of titanium polyacetylacetonate, organic polymer spinning aid, deionized water and ethanol is 1:0.008-0.04:0.1-0.15:2-4.

[0017] In the step (3), the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution are spun by the side-by-side electrospinning technology to obtain the zirconium oxide-titanium oxide precursor fiber membrane. The steps are as follows: the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution are added into two identical syringes respectively, and the two syringes are respectively connected to two parallel electrospinning needles of the side-by-side electrospinning needle, wherein the inner diameter of the needle is 0.25-0.4 mm and the outer diameter is 0.55-0.7 mm, and the syringes are fixed on the propulsion pump, and the injection flow rate of the polyacetylacetonate zirconium spinning solution is set. The electrospinning speed is 0.5-1.5 mL / h, the flow rate ratio of the zirconium polyacetylacetonate spinning solution to the titanium polyacetylacetonate spinning solution is 1:1-2, the propulsion pump is turned on to make the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution converge at the needle head, the spinning voltage is controlled to be 5-20 kV, the spinning solution is stretched into filaments and wound on a metal drum, the distance between the shoulder-to-shoulder electrospinning needle head and the drum is 15-30 cm, the drum speed is 60-200 r / min, the ambient temperature is 20-35 ° C, and the relative humidity of the air is 30%-55%, and a zirconium oxide-titanium oxide precursor fiber membrane is prepared.

[0018] The spinning parameters in the electrospinning process are related to the quality of the fiber, which is manifested in the mechanical properties of the fiber membrane. When the spinning voltage is too high, short fibers are ejected from the spinning needle in a jet-like manner during the electrospinning process, and the resulting precursor fibers are short in length, too thin in diameter, and have poor strength; when the spinning distance is too small, the solvent does not evaporate completely, the fibers are flat and stick together; when the humidity is too high and the temperature is too low during the spinning process, the solvent does not evaporate completely and water condenses on the fiber surface, a slight droplet enrichment appears at the spinning needle, and the resulting fibers stick together.

[0019] In the step (3), the heat treatment is carried out in an air atmosphere, and the heat treatment procedure is: heating from room temperature to 450°C at a heating rate of 0.5-1°C / min, then heating to 1000°C-1200°C at a heating rate of 2-4°C / min, and keeping the temperature for 60-200 minutes.

[0020] The reason for the segmented heat treatment process is that before 450°C, the decomposition reaction of the organic components in the precursor fiber (residual organic solvents and ligands) mainly occurs. As the heat treatment temperature increases, the organic matter in the precursor fiber undergoes a violent oxidative decomposition reaction, which will quickly produce a large amount of CO2, H2O and other gases to destroy the fiber matrix, forming defects such as pores and cracks that endanger the fiber quality, and may even directly lead to fiber pulverization. Controlling a smaller heating rate is beneficial to reducing the intensity of the reaction and protecting the fiber matrix. After 450°C, rapid heating is carried out while ensuring that the organic matter is completely removed, which can effectively increase the phase transition temperature of titanium oxide from anatase phase to rutile phase, reduce the influence of volume change caused by phase transition on fiber strength, and make the fiber membrane have excellent mechanical properties.

[0021] On the other hand, the present invention provides an application of a high-temperature and high-strength Janus structure zirconia-titania fiber membrane prepared by the above method, and the high-temperature and high-strength Janus structure zirconia-titania fiber membrane is applied to high-temperature thermal insulation materials.

[0022] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0023] 1. The technical scheme of the present invention adopts two organic polymer precursors of the same system, namely polyacetylacetonate zirconium and polyacetylacetonate titanium, to respectively prepare spinning solutions and perform side-by-side spinning to prepare zirconium oxide-titania precursor fiber membranes. The decomposition temperature of the acetylacetonate ligand group is relatively low and the organic ligand groups in the zirconium and titanium polymers are decomposed at the same temperature, which can reduce the heat treatment temperature and prevent the organic ligand groups in the fiber from undergoing multiple violent oxidative decomposition reactions during the heat treatment of the fiber membrane, thereby preventing a large amount of CO2, H2O and other gases from destroying the fiber matrix and forming defects such as pores and cracks that endanger the fiber quality, thereby avoiding fiber pulverization and protecting the fiber morphology. Compared with the fiber membranes prepared by conventional organic polymer precursors of different systems, the strength of the fiber membranes is improved, so that the fiber membranes have excellent mechanical properties.

[0024] 2. The technical scheme of the present invention prepares spinning solutions of two different substances, zirconium and titanium, respectively, and adopts shoulder-to-shoulder spinning to prepare high-temperature and high-strength Janus structure zirconium oxide-titanium oxide fiber membranes. On the one hand, zirconium oxide and titanium oxide are assembled on a single fiber, so that the fiber has the characteristics of high melting point and thermal insulation performance of zirconium oxide fiber, good mechanical properties, and strong near-infrared reflection ability of titanium oxide, and can be widely used in the field of high-temperature thermal insulation. On the other hand, the fiber membrane has the characteristics of high porosity, large specific surface area, and easy recycling, which further expands its application range.

[0025] 3. The high-temperature and high-strength Janus structure zirconia-titania fiber membrane prepared by the technical solution of the present invention has a tensile strength of up to 0.85MPa and has excellent high temperature softness and tensile properties.

[0026] 4. The technical solution of the present invention controls the heating rate during the heat treatment process in sections, thereby reducing the severity of the decomposition of organic matter during the calcination of the precursor fiber, allowing relatively mild analysis and transformation of the organic matter, reducing the formation of defects, and obtaining high-quality, high-strength fibers; on the other hand, rapid heating while ensuring the complete removal of organic matter can effectively increase the phase transition temperature of titanium oxide from anatase phase to rutile phase, reduce the influence of volume change caused by phase change on fiber strength, and make the fiber membrane have excellent mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The X-ray diffraction (XRD) pattern of the high-temperature and high-strength Janus structure zirconia-titania fiber membrane obtained in Example 1;

[0028] Figure 2 This is a scanning electron microscope (SEM) photograph of the high-temperature and high-strength Janus structure zirconia-titania fiber membrane obtained in Example 1. DETAILED DESCRIPTION

[0029] The present invention will be further described below with reference to the embodiments and drawings, but is not limited thereto. Example 1

[0030] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0031] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0032] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0033] (4) The zirconium oxide-titania precursor fiber membrane is placed on a support plate, and the support plate is placed in a muffle furnace. The temperature is increased from room temperature to 450°C at a heating rate of 0.8°C / min, and then increased to 1100°C at a heating rate of 3°C / min, and kept at this temperature for 120 minutes to obtain a high-temperature and high-strength Janus structured zirconium oxide-titania fiber membrane.

[0034] The XRD spectrum of the high-temperature and high-strength Janus structure zirconium oxide-titanium oxide fiber membrane prepared in this embodiment is as follows: Figure 1 As shown in Figure 2, the XRD spectrum results show that the fiber is a zirconium oxide-titanium oxide composite fiber; the SEM image is shown in Figure 2 Figure 2 As shown, it can be seen that the fibers in the fiber membrane are Janus structures, and zirconium oxide and titanium oxide are assembled on a single fiber, so that the fiber has the characteristics of high melting point and thermal insulation performance of zirconium oxide fiber, good mechanical properties, and strong near-infrared reflection ability of titanium oxide, and can be widely used in the field of high-temperature thermal insulation. Example 2

[0035] (1) poly(zirconium acetylacetonate), yttrium chloride hexahydrate, polyvinyl alcohol, deionized water, and methanol were mixed in a mass ratio of 1:0.1:0.007:0.1:1.5, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0036] (2) mixing titanium polyacetylacetonate, polyvinyl pyrrolidone, deionized water and ethanol in a mass ratio of 1:0.008:0.15:2, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0037] (3) Add the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.25 mm, and the outer diameter to be 0.55 mm, and fix the two syringes on different propulsion pumps respectively, the polyacetylacetonate zirconium spinning solution push injection flow rate is 1.5 mL / h, the polyacetylacetonate titanium spinning solution push injection flow rate is 3 mL / h, the spinning voltage is 5 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 30 cm, the roller speed is 60 r / min, the ambient temperature is 20 ° C, the relative humidity of the air is 30%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0038] (4) The zirconia-titania precursor fiber membrane is placed on a sintering plate, and the sintering plate is placed in a muffle furnace. The temperature is increased from room temperature to 450°C at a heating rate of 0.5°C / min, and then increased to 1000°C at a heating rate of 4°C / min, and kept at this temperature for 60 minutes to obtain a high-temperature and high-strength Janus structure zirconia-titania fiber membrane. Example 3

[0039] (1) poly(zirconium acetylacetonate), yttrium sulfate octahydrate, polyvinyl pyrrolidone, deionized water, and methanol were mixed in a mass ratio of 1:0.3:0.02:0.05:4.5, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0040] (2) mixing titanium polyacetylacetonate, polyvinyl alcohol, deionized water and ethanol in a mass ratio of 1:0.04:0.1:4, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0041] (3) Add the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.4 mm and the outer diameter to be 0.7 mm, and fix the two syringes on different propulsion pumps respectively, the polyacetylacetonate zirconium spinning solution push injection flow rate is 0.5 mL / h, the polyacetylacetonate titanium spinning solution push injection flow rate is 0.5 mL / h, the spinning voltage is 20 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 16 cm, the roller speed is 200 r / min, the ambient temperature is 35 ° C, the relative humidity of the air is 55%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0042] (4) The zirconia-titania precursor fiber membrane is placed on a sintering plate, and the sintering plate is placed in a muffle furnace. The temperature is increased from room temperature to 450°C at a heating rate of 1°C / min, and then increased to 1200°C at a heating rate of 2°C / min, and kept at this temperature for 200 minutes to obtain a high-temperature and high-strength Janus structure zirconia-titania fiber membrane. Example 4

[0043] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyvinyl pyrrolidone, deionized water, and methanol were mixed in a mass ratio of 1:0.3:0.015:0.1:2, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0044] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.03:0.1:2, and stirring at 35° C. for 3 hours to prepare titanium polyacetylacetonate spinning solution;

[0045] (3) Add the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the polyacetylacetonate zirconium spinning solution push injection flow rate is 0.8 mL / h, the polyacetylacetonate titanium spinning solution push injection flow rate is 1 mL / h, the spinning voltage is 12 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 110 r / min, the ambient temperature is 30 ° C, the relative humidity of the air is 35%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0046] (4) The zirconia-titania precursor fiber membrane is placed on a sintering plate, and the sintering plate is placed in a muffle furnace. The temperature is increased from room temperature to 450°C at a heating rate of 0.6°C / min, and then increased to 1200°C at a heating rate of 3°C / min, and kept at this temperature for 180 min to obtain a high-temperature and high-strength Janus structure zirconia-titania fiber membrane. Comparative Example 1

[0047] Compared with Example 1, this example selects polyzirconium oxyacetate as the zirconium source for side-by-side spinning.

[0048] (1) polyzirconium oxyacetate, yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a polyzirconium acetylacetonate spinning solution;

[0049] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0050] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0051] (4) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 1100°C at a heating rate of 3°C / min, and keep the temperature for 120 min to obtain a zirconium oxide-titania fiber membrane.

[0052] Compared with Example 1, the tensile strength of the fiber membrane obtained by selecting polyzirconium acetate as the zirconium source for side-by-side spinning is lower than that of the side-by-side spinning with the same system spinning solution, indicating that spinning with the same system spinning solution can indeed improve the strength of the fiber membrane. Comparative Example 2

[0053] Compared with Example 1, in this example, two spinning solutions are mixed before spinning to carry out single needle spinning.

[0054] (1) Zirconium polyacetylacetonate, yttrium nitrate hexahydrate, polyethylene oxide, deionized water and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40°C for 3 h to prepare zirconium polyacetylacetonate spinning solution; titanium polyacetylacetonate, polyethylene oxide, deionized water and ethanol were mixed in a mass ratio of 1:0.02:0.12:3, and stirred at 35°C for 3 h to prepare titanium polyacetylacetonate spinning solution; finally, the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution were mixed, and stirred at 40°C for 1 h to prepare zirconium polyacetylacetonate-titanium polyacetylacetonate mixed spinning solution.

[0055] (2) The mixed spinning solution was added into a 20 ml syringe, which was connected to an electrospinning needle with an inner diameter of 0.35 mm and an outer diameter of 0.65 mm. The syringe was fixed on a propulsion pump, and the spinning solution injection flow rate was set to 2.5 mL / h. The spinning voltage was 9 kV, and a metal roller was used as a receiving device. The distance between the shoulder-to-shoulder electrospinning needle and the roller was 20 cm. The roller speed was 120 r / min, the ambient temperature was 25 °C, and the relative humidity of the air was 45%. Zirconia-titania precursor fiber membrane was obtained by electrospinning.

[0056] (3) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 1100°C at a heating rate of 3°C / min, and keep the temperature for 120 min to obtain a zirconium oxide-titania fiber membrane.

[0057] Compared with Example 1, the two spinning solutions are mixed before spinning and single-needle spinning is carried out. The mechanical properties of the obtained fiber membrane are worse than those of the fiber membrane obtained by side-by-side spinning. The fibers in which zirconium oxide and titanium oxide are uniformly mixed are greatly affected by titanium oxide. Even after high-temperature treatment, the fiber membrane cannot maintain excellent mechanical properties even in the presence of zirconium oxide with excellent mechanical properties. Comparative Example 3

[0058] Compared with Example 1, the heat treatment procedure of this embodiment does not perform staged temperature increase.

[0059] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0060] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0061] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0062] (4) The zirconium oxide-titania precursor fiber membrane is placed on a sintering plate, the sintering plate is placed in a muffle furnace, the temperature is increased from room temperature to 1100°C at a heating rate of 3°C / min, and the temperature is kept at this temperature for 120 min to obtain the zirconium oxide-titania fiber membrane.

[0063] Compared with Example 1, the zirconium oxide-titania precursor fiber membrane was not subjected to a staged temperature increase procedure, and the fiber experienced a violent oxidation reaction during the decomposition of organic matter, and the resulting fiber membrane had poor flexibility and low strength. Comparative Example 4

[0064] Compared with Example 1, the amount of the organic polymer spinning aid in the spinning solution is reduced in this example.

[0065] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.003:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0066] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0067] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0068] (4) The zirconium oxide-titania precursor fiber membrane is placed on a sintering plate, and the sintering plate is placed in a muffle furnace. The temperature is increased from room temperature to 450°C at a heating rate of 0.8°C / min, and then increased to 1100°C at a heating rate of 3°C / min, and kept at this temperature for 120 minutes to obtain a high zirconium oxide-titania fiber membrane.

[0069] Compared with Example 1, the amount of the organic polymer spinning aid in the spinning solution is reduced, the fiber formation in the electrospinning process is difficult, and the spinning solution is ejected from the spinning needle in the form of short fibers or fine droplets. Comparative Example 5

[0070] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0071] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0072] (3) Add the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the polyacetylacetonate zirconium spinning solution push injection flow rate is 1 mL / h, the polyacetylacetonate titanium spinning solution push injection flow rate is 3 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0073] (4) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 1100°C at a heating rate of 3°C / min, and keep the temperature for 120 min to obtain a zirconium oxide-titania fiber membrane.

[0074] Compared with Example 1, the flow rate ratio of the two spinning solutions was increased, droplets gathered at the spinning needle during the electrospinning process, and the fiber membrane after heat treatment had poor flexibility. Titanium oxide fiber accounted for a large proportion, and zirconium oxide was insufficient to support the structure, resulting in poor fiber strength. Comparative Example 6

[0075] Compared with Example 1, the present embodiment increases the spinning distance and the spinning voltage.

[0076] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0077] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0078] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 22 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 35 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0079] (4) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 1100°C at a heating rate of 3°C / min, and keep the temperature for 120 min to obtain a zirconium oxide-titania fiber membrane.

[0080] Compared with Example 1, the spinning spacing and the spinning voltage are increased. During the electrospinning process, short fibers are ejected from the spinning needle in a jet-like shape. The resulting precursor fibers are shorter in length, too thin in diameter, and have poor strength. Comparative Example 7

[0081] Compared with Example 1, spinning in this example is carried out under high humidity.

[0082] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0083] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0084] (3) Add the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the polyacetylacetonate zirconium spinning solution push injection flow rate is 1 mL / h, the polyacetylacetonate titanium spinning solution push injection flow rate is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 60%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0085] (4) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 1100°C at a heating rate of 3°C / min, and keep the temperature for 120 min to obtain a zirconium oxide-titania fiber membrane.

[0086] Compared with Example 1, spinning was carried out under high humidity, and slight droplet enrichment appeared at the spinning needle during the spinning process, and the obtained fibers were sticky. Comparative Example 8

[0087] Compared with Example 1, the heat treatment temperature in this example is lower.

[0088] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0089] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0090] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0091] (4) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 900°C at a heating rate of 3°C / min, and keep the temperature for 120 minutes to obtain a zirconium oxide-titania fiber membrane.

[0092] Compared with Example 1, the heat treatment temperature is lowered, and the crystal phase of titanium oxide in the prepared fiber membrane is anatase phase, and the near-infrared reflectivity is low. Comparative Example 9

[0093] Compared with Example 1, the heat treatment temperature in this example is higher.

[0094] (1) poly(zirconium acetylacetonate), yttrium nitrate hexahydrate, polyethylene oxide, deionized water, and methanol were mixed in a mass ratio of 1:0.2:0.01:0.07:3, and stirred at 40° C. for 3 h to prepare a poly(zirconium acetylacetonate) spinning solution;

[0095] (2) mixing titanium polyacetylacetonate, polyethylene oxide, deionized water, and ethanol in a mass ratio of 1:0.02:0.12:3, and stirring at 35° C. for 3 h to prepare titanium polyacetylacetonate spinning solution;

[0096] (3) Add the zirconium polyacetylacetonate spinning solution and the titanium polyacetylacetonate spinning solution into two 20 ml syringes respectively, connect the two syringes to the two parallel electrospinning needles of the shoulder-to-shoulder electrospinning needles respectively, select the inner diameter of the two needles to be 0.35 mm and the outer diameter to be 0.65 mm, and fix the two syringes on different propulsion pumps respectively, the injection flow rate of the zirconium polyacetylacetonate spinning solution is 1 mL / h, the injection flow rate of the titanium polyacetylacetonate spinning solution is 1.5 mL / h, the spinning voltage is 9 kV, a metal roller is used as a receiving device, the distance between the shoulder-to-shoulder electrospinning needle mouth and the roller is 20 cm, the roller speed is 120 r / min, the ambient temperature is 25 ° C, the relative humidity of the air is 45%, and the zirconium oxide-titanium oxide precursor fiber membrane is obtained by electrospinning;

[0097] (4) Place the zirconium oxide-titania precursor fiber membrane on a sintering plate, place the sintering plate in a muffle furnace, and heat the temperature from room temperature to 450°C at a heating rate of 0.8°C / min, then heat the temperature to 1300°C at a heating rate of 3°C / min, and keep the temperature for 120 minutes to obtain a zirconium oxide-titania fiber membrane.

[0098] Compared with Example 1, the heat treatment temperature is increased. If the treatment temperature is too high, the fiber grains will grow larger, and the prepared fiber membrane will have poor flexibility and low strength.

[0099] Test Example 1

[0100] The fiber membrane obtained in Example 1 was subjected to phase testing, and the measured XRD spectrum was as follows: Figure 1 As shown. Figure 1 It can be seen that at 30.24°, 35.29°, 50.25°, 50.77°, 59.32°, and 60.24°, there are diffraction peaks corresponding to the standard PDF card of tetragonal zirconia (JCPDS 79-1770), indicating that the phase constituting the fiber membrane is tetragonal zirconia with good mechanical properties. In addition, at 27.45° and 54.32°, there are diffraction peaks corresponding to rutile titanium oxide (JCPDS 21-1276), indicating that titanium oxide is successfully transformed from anatase phase to rutile phase, which provides a strong guarantee for the high infrared reflection performance of the fiber membrane.

[0101] Test Example 2

[0102] The fiber membrane obtained in Example 1 was subjected to microscopic morphology testing, and the SEM image obtained was as follows: Figure 2 As shown in the figure, a clear Janus structure can be seen, indicating that the low thermal conductivity and high strength zirconium oxide and the strong infrared reflective titanium oxide are effectively combined to provide structural support.

[0103] Test Example 3

[0104] The tensile strength of the fiber membrane was analyzed using the LLY-06 electronic fiber strength tester. The specific parameters were: sample size 20 mm × 5 mm, chuck spacing 10 mm, tensile rate 1 mm min -1 Each sample was subjected to 10 tensile tests and the average value was taken. The specific experimental results are shown in Table 1.

[0105]

[0106] From the data comparison, it can be seen that the high-temperature and high-strength Janus structure zirconia-titania fiber membranes prepared in Examples 1-4 still have excellent tensile properties after high-temperature treatment.

[0107] Compared with Comparative Example 1, Examples 1-4 all use zirconium and titanium spinning solutions of the acetylacetone system, and the fiber membranes prepared have higher strength than those prepared with spinning solutions of different systems. This is because the decomposition temperature of the acetylacetone ligand group is lower and the organic ligand groups in the zirconium and titanium polymers are decomposed at the same temperature, which prevents the organic ligand groups in the fibers from undergoing multiple violent oxidative decomposition reactions during the heat treatment of the precursor fiber membrane, generating a large amount of CO2, H2O and other gases that destroy the fiber matrix and form defects such as pores and cracks that endanger the fiber quality, thereby avoiding fiber pulverization, protecting the fiber morphology, improving the strength of the fiber membrane, and giving the fiber membrane excellent mechanical properties.

[0108] In Comparative Example 2, two spinning solutions were mixed before spinning and single needle spinning was performed. The mechanical properties of the obtained fiber membrane were poorer than those of the fiber membrane obtained by side-by-side spinning in Examples 1-4. This is because the fiber with uniform zirconium oxide and titanium oxide mixed phases was greatly affected by titanium oxide. Even after high-temperature treatment, zirconium oxide with excellent mechanical properties did not maintain excellent mechanical properties for the fiber membrane. In contrast, the use of side-by-side needles for electrospinning to prepare Janus structure fiber membranes can not only effectively separate zirconium oxide spinning solution from titanium oxide spinning solution to avoid the formation of a single phase as the heat treatment temperature increases, but also allow a single fiber to have both zirconium oxide and titanium oxide, thereby allowing the fiber membrane to have excellent mechanical properties.

[0109] In the heat treatment procedure of Comparative Example 3, the temperature was not raised in stages. In the early calcination stage, the organic matter in the precursor fiber underwent a violent oxidation reaction during the decomposition process. The organic matter was rapidly analyzed and transformed, which easily formed defects, and the resulting fiber was of poor quality and low strength.

[0110] Comparative Examples 4-7 mainly reflect the influence of spinning parameters on the strength of fiber membranes. Comparative Example 4 reduces the amount of organic polymer spinning aids, and the fiber formation during the electrospinning process is difficult, and the spinning solution is in the form of short fibers or fine droplets ejected from the spinning needle; Comparative Example 5 increases the flow rate ratio of the two spinning solutions, and droplets gather at the spinning needle during the electrospinning process, and the fiber membrane after heat treatment has poor flexibility. Titanium oxide fibers account for a large proportion, and zirconium oxide is not enough to support the structure, resulting in poor fiber strength; Comparative Example 6 increases the spinning spacing and the spinning voltage, and short fibers are ejected from the spinning needle in a jet-like state during the electrospinning process. The resulting precursor fibers are short in length, too thin in diameter, and poor in strength; Comparative Example 7 is spun under high humidity, and slight droplet enrichment occurs at the spinning needle during the spinning process, and the resulting fibers are adhered. The above-mentioned obtained fiber membrane can be directly judged by observation only, and no tensile test is performed.

[0111] Comparative Examples 8 and 9 mainly reflect the effect of heat treatment temperature on the fiber membrane. Comparative Example 8 lowers the heat treatment temperature, and the crystal phase of titanium oxide in the prepared fiber membrane is anatase phase, the near-infrared reflectivity is low, and titanium oxide does not undergo a transformation from anatase phase to rutile phase. The fiber membrane has good flexibility, and the stress is too small to be detected during the test; Comparative Example 9 increases the heat treatment temperature, and the treatment temperature is too high, the fiber grains grow significantly, the prepared fiber membrane is sintered, the strength is low, and the tensile test cannot be performed.

Claims

1. A method for preparing a high-temperature and high-strength Janus structure zirconium oxide-titanium oxide fiber membrane, characterized in that: The following steps are involved: (1) dissolving poly(zirconium acetylacetonate), hydrated inorganic yttrium salt stabilizer, deionized water, and organic polymer spinning aid in methanol, heating and stirring, to prepare poly(zirconium acetylacetonate) spinning solution; (2) dissolving titanium polyacetylacetonate, an organic polymer spinning aid and deionized water in ethanol, heating and stirring, to prepare titanium polyacetylacetonate spinning solution; (3) The poly(acetylacetonate) zirconium oxide spinning solution and the poly(acetylacetonate) titanium oxide spinning solution were spun at a relative humidity of 30% to 55% by side-by-side electrospinning technology. The injection flow rate of the poly(acetylacetonate) zirconium oxide spinning solution was set to 0.5 to 1.5 mL / h. The flow rate ratio of the poly(acetylacetonate) zirconium oxide spinning solution to the poly(acetylacetonate) titanium oxide spinning solution was 1:1 to 2. Zirconia-titania precursor fiber membrane was obtained. The zirconium oxide-titania precursor fiber membrane was heat treated in an air atmosphere. The heat treatment procedure was as follows: heating from room temperature to 450°C at a heating rate of 0.5 to 1°C / min, then heating to 1000°C to 1200°C at a heating rate of 2 to 4°C / min, and keeping the temperature for 60 to 200 min. Thus, a high-temperature and high-strength Janus structured zirconium oxide-titania fiber membrane was obtained.

2. The preparation method according to claim 1, characterized in that: In the step (1), the hydrated inorganic yttrium salt stabilizer is one of yttrium nitrate hexahydrate, yttrium chloride hexahydrate or yttrium sulfate octahydrate; and the organic polymer spinning aid is one of polyethylene oxide, polyvinyl pyrrolidone or polyvinyl alcohol.

3. The preparation method according to claim 1, characterized in that: In the step (1), the mass ratio of polyacetylacetonate zirconium, hydrated inorganic yttrium salt stabilizer, organic polymer spinning aid, deionized water and methanol is 1:0.1-0.3:0.007-0.02:0.05-0.1:1.5-4.

5.

4. The preparation method according to claim 1, characterized in that: In the step (2), the organic polymer spinning aid is one of polyethylene oxide, polyvinyl pyrrolidone or polyvinyl alcohol.

5. The preparation method according to claim 1, characterized in that: In the step (2), the mass ratio of titanium polyacetylacetonate, organic polymer spinning aid, deionized water and ethanol is 1:0.008-0.04:0.1-0.15:2-4.

6. The preparation method according to claim 1, characterized in that: In the step (3), the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution are spun by the side-by-side electrospinning technology to obtain a zirconium oxide-titanium oxide precursor fiber membrane, and the steps are as follows: the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution are added to two identical syringes respectively, and the two syringes are connected to two parallel electrospinning needles of the side-by-side electrospinning needles respectively, wherein the inner diameter of the needle is 0.25-0.4 mm and the outer diameter is 0.5 5~0.7mm, and fix the syringe on the propulsion pump, turn on the propulsion pump, make the polyacetylacetonate zirconium spinning solution and the polyacetylacetonate titanium spinning solution converge at the needle, control the spinning voltage to 5~20kV, stretch the spinning solution into filaments, and wind them on the metal roller, the distance between the shoulder-to-shoulder electrospinning needle and the roller is 16~30cm, the roller speed is 60~200r / min, the ambient temperature is 20~35℃, and the zirconium oxide-titanium oxide precursor fiber membrane is prepared.

7. An application of a high-temperature and high-strength Janus structured zirconia-titania fiber membrane prepared by the method according to any one of claims 1 to 6, characterized in that: The high-temperature and high-strength Janus structure zirconia-titania fiber membrane is applied to high-temperature thermal insulation materials.

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