CN113502599B - Flexible Y 2 Mo 3 O12/Al 2 O 3 High-temperature heat-insulation nanofiber membrane and preparation method thereof - Google Patents
Flexible Y 2 Mo 3 O12/Al 2 O 3 High-temperature heat-insulation nanofiber membrane and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a flexible Y 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following steps of: firstly, preparing a precursor solution by yttrium salt, molybdenum salt, a catalyst, polyaluminium chloride and a solvent; then, preparing the precursor solution into a precursor nanofiber membrane by adopting an electrostatic spinning technology; and finally, calcining the precursor fiber film in an inert atmosphere, and then performing low-temperature thermal oxidation treatment in an air atmosphere. The method provided by the invention effectively overcomes the defects of high infrared permeability and high-temperature thermal conductivity of the existing ceramic fiber material, remarkably improves the reflection and absorption capacity of the ceramic fiber material to infrared radiation, and the finally prepared nanofiber membrane has the advantages of good flexibility, low gas-solid thermal conductivity, low infrared permeability, good high-temperature heat insulation property, good high-temperature stability and the like.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to a flexible Y 2 Mo 3 O 12 /Al 2 O 3 A high-temperature heat-insulating nanofiber membrane and a preparation method thereof.
Background
The ceramic fiber has the advantages of good high temperature resistance, oxidation resistance and mechanical vibration resistance of the ceramic material and the advantages of large length-diameter ratio, good continuity and low volume density of the fiber material, and is an irreplaceable key thermal protection material in a plurality of high-temperature heat insulation fields. The diameter of the traditional ceramic fiber is generally in the micron order, the pore size between the fibers is large, the brittleness is large, the thermal conductivity is high, and the application of the traditional ceramic fiber in the field of practical heat insulation is greatly limited. When the diameter of the micron ceramic fiber is thinned to nanometer order of magnitude, the specific surface area of the fiber material can be obviously increased, the pore size among the fibers is reduced, and the heat insulation performance is further improved.
According to Planck's law, radiation heat transfer is mainly used in a high-temperature state, and the infrared transmittance of the currently prepared ceramic nanofiber material in near-infrared and mid-infrared bands is high, so that the ceramic nanofiber material has high thermal conductivity and poor heat insulation performance under the high-temperature condition. Therefore, the reduction of the infrared transmittance of the ceramic nanofibers is an effective way to improve the high-temperature heat insulation performance of the ceramic nanofibers. At present, researchers mainly reduce the infrared transmittance of materials by constructing a high-reflectivity coating on the surface of ceramic fibers, for example, the method of constructing TiO on the surface of mullite fibers by using a solvothermal method is reported in Thin Solid Films 520 (2012), 2651-2655 2 Coating, Ceramics International 43 (2017) 14183- 2 Coating, Ceramics International 46 (2020) 3400- 2 And (4) coating. Although the method improves the reflection capability of the material to infrared radiation to a certain extent, the lap joints of the ceramic fibers are adhered together by the coating, so that the solid heat conduction among the fibers is increased, and the heat insulation performance of the ceramic fiber material cannot be effectively improved. In addition, because the coating and the ceramic fiber matrix lack effective bonding force, the coating is easy to fall off and has unstable structure, and the long-term service performance of the coating in practical application is limited.
Disclosure of Invention
The invention aims to provide a flexible Y 2 Mo 3 O 12 /Al 2 O 3 The high-temperature heat-insulation nanofiber membrane and the preparation method thereof solve the defects of high infrared permeability and high-temperature heat conductivity of the conventional ceramic fiber material, remarkably improve the reflection and absorption capacity of the ceramic fiber material on infrared radiation, and prepare the high-temperature heat-insulation nanofiber membrane with low gas-solid heat conductivity and infrared transmissionCeramic nanofiber thermal insulation materials with low properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
flexible Y 2 Mo 3 O 12 /Al 2 O 3 The high-temperature heat-insulation nanofiber membrane is characterized in that the preparation raw materials comprise yttrium salt, molybdenum salt, a catalyst, polyaluminium chloride and a solvent.
Above flexible Y 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following steps:
(1) preparing a precursor solution, wherein the precursor solution comprises yttrium salt, molybdenum salt, a catalyst, polyaluminium chloride and a solvent;
(2) preparing precursor nano-fibers from the precursor solution by adopting an electrostatic spinning technology;
(3) calcining precursor fiber in inert atmosphere, and then performing low-temperature thermal oxidation treatment in air atmosphere to obtain flexible Y 2 Mo 3 O 12 /Al 2 O 3 A nanofiber membrane.
As a preferred technical scheme:
a flexible Y as described above 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following steps of (1) preparing a precursor solution: adding yttrium salt, molybdenum salt and a catalyst into a solvent, stirring for 30-90 min, then adding polyaluminium chloride, stirring and mixing for 30-120 min, and obtaining a precursor solution.
A flexible Y as described above 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following steps of (1) enabling the molar ratio of yttrium salt to molybdenum salt in the precursor solution to be 1: 1.5; the molar ratio of the yttrium salt to the catalyst is 1: 0.01-0.05; the molar ratio of yttrium salt to polyaluminum chloride is 1: 0.3-1; the ratio of the total mass of the yttrium salt, the molybdenum salt and the polyaluminum chloride to the solvent is 10g: 10-75 mL; the dynamic viscosity of the precursor solution is 0.3-15 Pa s, and the conductivity is 0.3-76 mS/m.
A flexible Y as described above 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following steps of (1) preparing a yttrium salt, namely one of yttrium nitrate hexahydrate, yttrium chloride hexahydrate or yttrium sulfate octahydrate;
the molybdenum salt is one of ammonium molybdate, molybdenum acetylacetonate or phosphomolybdate hydrate;
the catalyst is one of hydrochloric acid, nitric acid, acetic acid or oxalic acid;
the solvent is one or more of water, methanol, ethanol, ethylene glycol, glycerol, N-propanol, isopropanol, benzyl alcohol, N-dimethylformamide or dimethyl sulfoxide.
A flexible Y as described above 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following process parameters of electrostatic spinning in the step (2): under the conditions that the spinning environment temperature is 10-55 ℃ and the relative humidity is 10-70%, the precursor solution is filled at the flow rate of 0.1-20 mL/h, a spinning nozzle is connected to a high-voltage power supply of 0-65 kV for spinning, and the distance between a receiving device and the spinning nozzle is 5-45 cm; the receiving device is a metal roller or a flat plate.
A flexible Y as described above 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following calcining process parameters in the step (3): under an inert atmosphere, gradually increasing the temperature from room temperature to 500-950 ℃, wherein the temperature increasing speed is 0.5-10 ℃/min, and the temperature is kept for 30-600 min at the highest calcining temperature, and the inert atmosphere is nitrogen, helium or argon; then, low-temperature thermal oxidation treatment is carried out for 60-360 min at the temperature of 200-360 ℃ in the air atmosphere.
Flexibility Y as described above 2 Mo 3 O 12 /Al 2 O 3 High temperature thermal insulating nanofiber membrane, flexible Y 2 Mo 3 O 12 /Al 2 O 3 Y in the fibrous Membrane 2 Mo 3 O 12 With Al 2 O 3 The phases are uniformly dispersed in the fiber matrix so that Y is 2 Mo 3 O 12 /Al 2 O 3 The nano-fiber has low gas-solid heat conductivity, high infrared shielding performance and flexibility 2 Mo 3 O 12 /Al 2 O 3 The average infrared reflectivity of the nanofiber membrane in a near infrared band is more than or equal to 92.5%, and the thermal conductivity coefficient of the nanofiber membrane in the temperature range of 100-1200 ℃ is 0.025-0.124W/(m.K).
Flexibility Y as described above 2 Mo 3 O 12 /Al 2 O 3 High temperature thermal insulating nanofiber membrane, flexible Y 2 Mo 3 O 12 /Al 2 O 3 The average fiber diameter of the nanofiber membrane is 20-580 nm, the relative standard deviation is 0.1-9%, the average internal crystal grain size is 5-40 nm, and the flexibility Y is 2 Mo 3 O 12 /Al 2 O 3 The softness of the nanofiber membrane is 10-100 mN. The fiber diameter is small, and the flexibility of the single fiber is good; the smaller the relative deviation value is, the better the distribution uniformity of the fiber diameter is; the smaller the average grain size, the higher the mechanical properties of the single fibers, and the better the flexibility of the fiber film.
The invention principle is as follows:
in the first step of the invention, yttrium salt, molybdenum salt and catalyst are added into solvent and stirred uniformly, free yttrium ions and molybdenum ions are released from yttrium salt and molybdenum salt under the stirring action, metal ions are prevented from being hydrolyzed rapidly to generate metal hydroxide precipitate under the action of catalyst, and meanwhile, partial metal hydroxides are subjected to condensation reaction slowly, thereby forming metal hydroxide colloidal particles and micelles. Then, adding polyaluminium chloride into the solution, uniformly stirring, carrying out hydrolytic polycondensation reaction on the polyaluminium chloride under the action of a catalyst to gradually form an Al-O-Al long-chain structure, gradually entangling chains to form a polymerization ring chain body, and adsorbing yttrium hydroxide and molybdenum hydroxide colloidal particles onto the polymerization ring chain body through electrostatic attraction and the bridging action of hydroxyl groups, so that the viscosity of the precursor solution is increased, the viscoelasticity is increased, and the spinnability is enhanced. And then, preparing the precursor solution into precursor fibers with better continuity by adopting an electrostatic spinning technology. Finally, the precursor fiber film is firstly calcined in inert atmosphere, and the colloidal particles of yttrium hydroxide and molybdenum hydroxide are decomposed under the action of calcination to gradually form Y 2 Mo 3 O 12 Eutectic phase, polymeric cyclic chain cracked to form Al under calcination 2 O 3 . Meanwhile, because the ionic radiuses of the aluminum ions are closer to those of the yttrium ions and the molybdenum ions, the aluminum ions in the polymerization ring chain body can replace Y ions in the calcining process 2 Mo 3 O 12 Yttrium ion or molybdenum ion in eutectic phase, thereby effectively suppressing Y 2 Mo 3 O 12 /Al 2 O 3 The too fast growth of crystal grains and the sliding of crystal boundary prepare the flexible Y with small average crystal grain size and less single fiber defects 2 Mo 3 O 12 /Al 2 O 3 And (3) nano fibers.
Has the advantages that:
(1) flexible Y of the invention 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane utilizes the adsorption effect of a polymeric ring chain body formed by polyaluminium chloride on yttrium hydroxide and molybdenum hydroxide colloidal particles to increase the viscosity, increase the viscoelasticity and enhance the spinnability of a precursor solution, and then obtains a precursor fiber with good fiber continuity through an electrostatic spinning technology.
(2) At present, flexible Y is not available at home and abroad 2 Mo 3 O 12 /Al 2 O 3 Report of nanofiber preparation, a Flexible Y of the invention 2 Mo 3 O 12 /Al 2 O 3 Preparation method of high-temperature heat-insulation nanofiber membrane and prepared Y 2 Mo 3 O 12 /Al 2 O 3 The nanofiber has good flexibility, few single fiber defects, simple preparation process and easy industrialization, and can provide reference for the preparation of flexible ceramic fiber materials.
(3) Flexible Y of the invention 2 Mo 3 O 12 /Al 2 O 3 The high-temperature heat-insulation nanofiber membrane has the characteristics of low gas-solid heat conductivity and low infrared permeability, and solves the defects of high infrared permeability and high-temperature heat conductivity of the conventional ceramic fiber material.
The specific implementation mode is as follows:
the invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Flexible Y 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following specific steps:
(1) sequentially dissolving yttrium nitrate hexahydrate, molybdenum ammonium molybdate and catalyst hydrochloric acid in mixed solvent water/N, N-dimethylformamide, stirring for 35min, then adding polyaluminum chloride, stirring for 85min, and uniformly mixing, wherein the molar ratio of yttrium salt, molybdenum salt, catalyst and polyaluminum chloride in the solution is 1:1.5:0.03:0.45, the ratio of the total mass of yttrium salt, molybdenum salt and polyaluminum chloride to the solvent is 10g:40mL, the volume ratio of water to N, N-dimethylformamide is 1:1, and uniformly mixing to prepare uniform stable precursor solution with dynamic viscosity of 5.9 Pa.s and conductivity of 53.6 mS/m;
(2) preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 23 ℃, the relative humidity is 52%, the perfusion speed is 2mL/h, the voltage is 44kV, the distance between the receiving device and the spinning nozzle is 25cm, and the receiving device is a metal roller;
(3) calcining the precursor fiber film in a nitrogen atmosphere, gradually increasing the temperature from room temperature to 750 ℃, increasing the temperature at a speed of 5 ℃/min, and keeping the temperature at the highest calcining temperature for 360 min; then carrying out low-temperature thermal oxidation treatment on the fiber membrane for 180min at 300 ℃ in air atmosphere to finally obtain flexible Y 2 Mo 3 O 12 /Al 2 O 3 A nanofiber membrane.
For the flexible Y prepared above 2 Mo 3 O 12 /Al 2 O 3 The performance of the nanofiber membrane is tested, and the flexibility Y is measured according to the national standard GB/T18319-2019 & lt method for testing the light and heat storage performance of textiles 2 Mo 3 O 12 /Al 2 O 3 The average infrared reflectivity of the nanofiber membrane in the near-infrared and mid-infrared bands is 92.8%. Y is measured according to GB/T5990- 2 Mo 3 O 12 /Al 2 O 3 The nanofiber membrane has a thermal conductivity coefficient of 0.027-0.123W/(mK) within a temperature range of 100-1200 ℃. Flexible Y 2 Mo 3 O 12 /Al 2 O 3 The average diameter of the nano-fiber is 350nm, the relative standard deviation of the diameter is 2.6% (measured by reference to national standard GB/T34520.2-2017 part 2 of continuous silicon carbide fiber measuring method: single fiber diameter), the average grain size inside the fiber is 32nm (measured according to GB/T23413- 2 Mo 3 O 12 /Al 2 O 3 The softness of the nanofiber membrane was 57mN (measured according to the national standard GB/T8942-2016 paper softness measurement).
Example 2
Flexible Y 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following specific steps:
(1) dissolving yttrium salt hexahydrate yttrium chloride, molybdenum salt ammonium molybdate and catalyst oxalic acid in a mixed solvent of water/ethylene glycol in sequence, stirring for 60min, then adding polyaluminum chloride, stirring for 80min, and uniformly mixing, wherein the molar ratio of yttrium salt, molybdenum salt, catalyst and polyaluminum chloride in the solution is 1:1.5:0.04:0.75, the ratio of the total mass of yttrium salt, molybdenum salt and polyaluminum chloride to the mixed solvent is 10g:55mL, the volume ratio of water to ethylene glycol is 1:2, and uniformly mixing to prepare a uniform stable precursor solution with dynamic viscosity of 7.8 Pa.s and conductivity of 32.7 mS/m;
(2) preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 30 ℃, the relative humidity is 55%, the perfusion speed is 1.5mL/h, the voltage is 46kV, the distance between the receiving device and a spinning nozzle is 21cm, and the receiving device is a metal flat plate;
(3) calcining the precursor fiber film in a nitrogen atmosphere, gradually increasing the temperature from room temperature to 850 ℃, increasing the temperature at a speed of 5 ℃/min, and keeping the temperature at the highest calcining temperature for 300 min; then, the fiber film is subjected to low-temperature thermal oxidation treatment for 120min at 320 ℃ in air atmosphere, and finally, the flexible Y is prepared 2 Mo 3 O 12 /Al 2 O 3 A nanofiber membrane.
The same test method as in example 1 was used for the performance measurement, and the flexibility Y was 2 Mo 3 O 12 /Al 2 O 3 The average infrared reflectivity of the nanofiber membrane in near-infrared and mid-infrared bands is 93.5%, and the heat conductivity coefficient within the range of 100-1200 ℃ is 0.026-0.119W/(m.K). Y is 2 Mo 3 O 12 /Al 2 O 3 The average diameter of the nanofibers was 410nm, the relative standard deviation of the diameters was 3.4%, and the Y inside the fibers 2 Mo 3 O 12 /Al 2 O 3 Average grain size of 18nm, flexibility Y 2 Mo 3 O 12 /Al 2 O 3 The softness of the nanofiber membrane was 23 mN.
Example 3
Flexible Y 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following specific steps:
(1) dissolving yttrium salt octahydrate yttrium sulfate, molybdenum salt ammonium molybdate and catalyst nitric acid in a solvent N, N-dimethylformamide in sequence, stirring for 75min, then adding polyaluminium chloride, stirring for 100min, and uniformly mixing, wherein the molar ratio of yttrium salt, molybdenum salt, catalyst and polyaluminium chloride in the solution is 1:1.5:0.035:0.8, the ratio of the total mass of yttrium salt, molybdenum salt and polyaluminium chloride to the solvent is 10g:35mL, and uniformly mixing to prepare a uniform stable precursor solution with dynamic viscosity of 9.6 Pa.s and conductivity of 39.7 mS/m;
(2) preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 25 ℃, the relative humidity is 44%, the perfusion speed is 1mL/h, the voltage is 42kV, the distance between a receiving device and a spinning nozzle is 26cm, and the receiving device is a metal roller;
(3) calcining the precursor fiber film in a nitrogen atmosphere, gradually increasing the temperature from room temperature to 900 ℃, increasing the temperature at a speed of 5 ℃/min, and keeping the temperature at the highest calcining temperature for 240 min; then, the fiber film is subjected to low-temperature thermal oxidation treatment for 300min at 280 ℃ in air atmosphere, and finally the flexible Y is prepared 2 Mo 3 O 12 /Al 2 O 3 A nanofiber membrane.
The same test method as in example 1 was used for the performance measurement, and the flexibility Y was 2 Mo 3 O 12 /Al 2 O 3 The average infrared reflectivity of the nanofiber membrane in near-infrared and mid-infrared bands is 94.2%, and the thermal conductivity coefficient in the range of 100-1200 ℃ is 0.027-0.114W/(m.K). Y is 2 Mo 3 O 12 /Al 2 O 3 The average diameter of the nanofibers was 370nm, the relative standard deviation of the diameters was 2.5%, and the Y inside the fibers 2 Mo 3 O 12 /Al 2 O 3 Average grain size of 34nm, flexibility Y 2 Mo 3 O 12 /Al 2 O 3 The softness of the nanofiber membrane was 73 mN.
Example 4
Flexible Y 2 Mo 3 O 12 /Al 2 O 3 The preparation method of the high-temperature heat-insulation nanofiber membrane comprises the following specific steps:
(1) dissolving yttrium nitrate hexahydrate, molybdenum acetylacetonate and catalyst hydrochloric acid of yttrium salt in turn in a mixed solvent of benzyl alcohol/N, N-dimethylformamide, stirring for 50min, then adding polyaluminium chloride, stirring for 90min, and uniformly mixing, wherein the molar ratio of the yttrium salt, the molybdenum salt, the catalyst and the polyaluminium chloride in the solution is 1:1.5:0.025:0.9, the ratio of the total mass of the yttrium salt, the molybdenum salt and the polyaluminium chloride to the mixed solvent is 10g:40mL, the volume ratio of the benzyl alcohol to the N, N-dimethylformamide is 1:4, and uniformly mixing is carried out to prepare a uniform stable precursor solution with the dynamic viscosity of 5.6 Pa.s and the conductivity of 47.2 mS/m;
(2) preparing the precursor solution into precursor nanofiber by adopting an electrostatic spinning technology, wherein the process parameters of electrostatic spinning are as follows: the environment temperature is 25 ℃, the relative humidity is 53%, the perfusion speed is 1.5mL/h, the voltage is 52kV, the distance between a receiving device and a spinneret is 18cm, and the receiving device is a metal roller;
(3) calcining the precursor fiber film in a nitrogen atmosphere, gradually increasing the temperature from room temperature to 800 ℃, increasing the temperature at a speed of 2 ℃/min, and keeping the temperature at the highest calcining temperature for 60 min; then, the fiber membrane is subjected to low-temperature thermal oxidation treatment for 120min at 350 ℃ in air atmosphere, and finally the flexible Y is prepared 2 Mo 3 O 12 /Al 2 O 3 A nanofiber membrane.
The same test method as in example 1 was used for the performance measurement, and the flexibility Y 2 Mo 3 O 12 /Al 2 O 3 The average infrared reflectivity of the nanofiber membrane in near-infrared and mid-infrared bands is 93.8%, and the thermal conductivity coefficient of the nanofiber membrane in the range of 100-1200 ℃ is 0.027-0.116W/(mK). Flexible Y 2 Mo 3 O 12 /Al 2 O 3 The average diameter of the nanofibers was 280nm, the relative standard deviation of the diameters was 2.4%, and the Y inside the fibers 2 Mo 3 O 12 /Al 2 O 3 Average grain size of 22nm, flexibility Y 2 Mo 3 O 12 /Al 2 O 3 The softness of the nanofiber membrane was 46 mN.
Claims (5)
1. Flexible Y 2 Mo 3 O 12 /Al 2 O 3 High temperature thermal-insulated nanofiber membrane, its characterized in that: the preparation method comprises the following steps:
(1) adding yttrium salt, molybdenum salt and a catalyst into a solvent, stirring for 30-90 min, then adding polyaluminium chloride, stirring and mixing for 30-120 min, and obtaining a precursor solution;
the molar ratio of yttrium salt to molybdenum salt in the precursor solution is 1:1.5, the molar ratio of yttrium salt to catalyst is 1: 0.01-0.05, the molar ratio of yttrium salt to polyaluminum chloride is 1: 0.3-1, and the ratio of the total mass of yttrium salt, molybdenum salt and polyaluminum chloride to the solvent is 10g: 10-75 mL;
the yttrium salt is one of yttrium nitrate hexahydrate, yttrium chloride hexahydrate or yttrium sulfate octahydrate;
the molybdenum salt is one of ammonium molybdate, molybdenum acetylacetonate or phosphomolybdate hydrate;
the catalyst is one of hydrochloric acid, nitric acid, acetic acid or oxalic acid;
the solvent is one or more of water, methanol, ethanol, ethylene glycol, glycerol, N-propanol, isopropanol, benzyl alcohol, N-dimethylformamide and dimethyl sulfoxide;
(2) preparing the precursor solution into precursor nanofibers by adopting an electrostatic spinning technology;
(3) calcining precursor nano-fiber in inert atmosphere, and then performing low-temperature thermal oxidation treatment in air atmosphere to obtain flexible Y 2 Mo 3 O 12 /Al 2 O 3 A nanofiber membrane;
the calcination process parameters are as follows: under an inert atmosphere, gradually increasing the temperature from room temperature to 500-950 ℃, wherein the temperature increasing speed is 0.5-10 ℃/min, and the temperature is kept for 30-600 min at the highest calcining temperature, and the inert atmosphere is nitrogen, helium or argon; then, low-temperature thermal oxidation treatment is carried out for 60-360 min at the temperature of 200-360 ℃ in the air atmosphere.
2. Flexible Y according to claim 1 2 Mo 3 O 12 /Al 2 O 3 High temperature thermal-insulated nanofiber membrane, its characterized in that: the dynamic viscosity of the precursor solution in the step (1) is 0.3-15 Pa.s, and the conductivity is 0.3-76 mS/m.
3. Flexible Y according to claim 1 2 Mo 3 O 12 /Al 2 O 3 The high-temperature heat-insulation nanofiber membrane is characterized in that the electrostatic spinning in the step (2) has the following technological parameters: under the conditions that the temperature of a spinning environment is 10-55 ℃ and the relative humidity is 10-70%, the precursor solution is poured at the flow speed of 0.1-20 mL/h, a spinning nozzle is connected to a high-voltage power supply of 0-65 kV for spinning, and the distance between a receiving device and the spinning nozzle is 5-45 cm; the receiving device is a metal roller or a flat plate.
4. Flexible Y according to claim 1 2 Mo 3 O 12 /Al 2 O 3 The high-temperature heat-insulating nanofiber membrane is characterized in that the flexible Y 2 Mo 3 O 12 /Al 2 O 3 The average infrared reflectivity of the high-temperature heat-insulating nanofiber membrane in near-infrared and mid-infrared bands is more than or equal to 92.5%, and the thermal conductivity coefficient within the range of 100-1200 ℃ is 0.025-0.124W/(m.K).
5. Flexible Y according to claim 1 2 Mo 3 O 12 /Al 2 O 3 The high-temperature heat-insulating nanofiber membrane is characterized in that the flexible Y 2 Mo 3 O 12 /Al 2 O 3 The average fiber diameter of the high-temperature heat-insulation nanofiber membrane is 20-580 nm, the relative standard deviation is 0.1-9%, the average internal crystal grain size is 5-40 nm, and the flexibility Y is 2 Mo 3 O 12 /Al 2 O 3 The softness of the nanofiber membrane is 10-100 mN.
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