CN-122013449-A - Particle-based flexible high-temperature-resistant ceramic nanofiber membrane and preparation method thereof

CN122013449ACN 122013449 ACN122013449 ACN 122013449ACN-122013449-A

Abstract

The invention discloses a particle-based flexible high-temperature-resistant ceramic nanofiber membrane and a preparation method thereof, wherein the preparation method comprises the steps of adding ceramic nanoparticles and a dispersing agent into a water/ethanol mixed solution, stirring and dispersing for a period of time, adding an alkaline regulator, then adding a semi-gel silica sol, continuously stirring and mixing uniformly to obtain a mixed solution, utilizing a hot air assisted electrostatic spinning technology to enable the surface of a spinning jet to be rapidly solidified, keeping certain fluidity in the jet to enable the spinning jet to continuously stretch and refine to obtain a precursor fiber membrane, carrying out ultrafast Joule heat treatment on the obtained precursor fiber membrane, and then transferring the precursor fiber membrane into a muffle furnace for calcination to finally obtain the flexible high-temperature-resistant ceramic nanofiber membrane, so that the problems of poor metal salt solubility, unstable solution, less spinnable raw materials, high crystallization and sintering temperature in the preparation process of the ceramic nanofiber membrane are solved, and the problems of easy brittle fracture, low temperature resistance and the like of the traditional ceramic nanofiber membrane are solved.

Inventors

SHAN HAORU
ZHANG HANWEN
FU QIUXIA
ZHANG MENGJIAO
ZHANG YINUO
Tang Jiawang

Assignees

南通大学

Dates

Publication Date: 20260512
Application Date: 20251229

Claims (9)

1. The preparation method of the particle-based flexible high-temperature-resistant ceramic nanofiber membrane is characterized by comprising the following steps of: Step 1), adding one or more ceramic nano particles and a dispersant matched with the ceramic nano particles into a mixed solution of ethanol and water, stirring and dispersing for 1-6 hours, and then adding an alkaline regulator; Step 2), adding one or more silicon sources and catalysts into the mixed solution of ethanol and water, regulating and controlling the pH value of the silica sol to be in a semi-gel state, and then placing the silica sol in an ice water bath for preservation; Step 3), mixing the semi-gel silica sol obtained in the step 2) with the dispersion liquid obtained in the step 1), and continuously stirring for 5-12 hours to uniformly mix the semi-gel silica sol and the dispersion liquid to prepare spinnable precursor solution; Step 4), carrying out hot air flow assisted electrostatic spinning on the precursor spinning solution in the step 3), promoting the surface of the spinning jet flow to be quickly gel and solidified, and keeping certain fluidity in the jet flow to enable the jet flow to be continuously drawn and thinned, so as to prepare the precursor fiber membrane; And 5) firstly carrying out ultra-fast joule heat treatment on the precursor fiber film obtained in the step 4), then transferring the precursor fiber film into a muffle furnace for continuous calcination, and finally obtaining the flexible high-temperature-resistant ceramic nanofiber film.
2. The method for preparing a particle-based flexible refractory ceramic nanofiber membrane according to claim 1, wherein in the step 1), the ceramic nano particles are aluminum oxide, titanium oxide, vanadium oxide, germanium oxide, niobium pentoxide, hafnium oxide, zinc oxide, bismuth oxide, cobalt oxide, molybdenum oxide, tin oxide, tantalum oxide, zirconium oxide, tungsten oxide, nickel oxide, magnesium oxide, iron oxide, copper oxide, chromium oxide, yttrium oxide, lutetium oxide, terbium oxide, indium oxide, holmium trioxide, scandium trioxide, samarium trioxide, praseodymium oxide, neodymium trioxide, lanthanum trioxide, gadolinium trioxide, gallium trioxide, dysprosium trioxide, cerium dioxide, zirconium carbide, tungsten carbide, vanadium carbide, titanium carbide, tantalum carbide, silicon carbide, niobium carbide, molybdenum carbide, manganese carbide, hafnium carbide, chromium carbide, boron carbide, aluminum carbide, boron nitride, hafnium carbide niobium nitride, vanadium nitride, yttrium nitride, tantalum nitride, zirconium nitride, titanium nitride, silicon nitride, magnesium nitride, chromium nitride, aluminum nitride, ditungsten pentaboride, chromium diboride, vanadium diboride, nickel diboride, molybdenum diboride, manganese diboride, magnesium diboride, chromium diboride, tungsten diboride, vanadium diboride, silicon hexaboride, hafnium diboride, calcium hexaboride, zirconium diboride, titanium diboride, lanthanum hexaboride, titanium tin carbide, titanium aluminum carbide, niobium aluminum carbide, vanadium aluminum carbide, titanium silicon carbide, molybdenum disulfide, tungsten disulfide, titanium dihydride, zirconium dihydride, hafnium dihydride, tungsten silicide, tantalum disilicide, zirconium disilicide, molybdenum disilicide, titanium disilicide, hafnium disilicide; The average particle size of the nano particles is 20-200 nm; the ratio of the ceramic nano particles to the dispersing agent is 100g (1-15 g), and the ratio of the mixed solution of the ceramic nano particles and ethanol and water is 10g (5-30 mL); The dispersing agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, dodecyl benzene sulfonic acid, dodecyl ammonium sulfate, dodecyl phosphate, sodium stearate, sodium lauryl sulfate, cetyltrimethylammonium bromide, benzalkonium chloride, dioctadecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, octadecyl trimethyl ammonium chloride, cetyl pyridine bromide, sodium dodecyl aminopropionate, dodecyl dimethyl betaine, sodium lauroyl sarcosinate and sorbitan monolaurate; the alkaline regulator is one or more of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate.
3. The preparation method of the particle-based flexible high-temperature-resistant ceramic nanofiber membrane according to claim 1, wherein in the step 2), zirconium salt is any one or more of zirconium acetate, zirconium n-propoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconium basic carbonate, zirconium nitrate pentahydrate and zirconium oxychloride octahydrate, the complexing agent is any one or more of ethylenediamine tetraacetic acid, acetylacetone, acetic acid, citric acid, tartaric acid and diethanolamine, the ratio of the zirconium salt to a solvent is 5g (5-50) mL, and the molar ratio of the zirconium salt to the complexing agent is 1:1-1:10.
4. The method for preparing the particle-based flexible high-temperature-resistant ceramic nanofiber membrane according to claim 1, wherein in the step 2), the silicon source is any one or more of tetramethyl silicate, tetraethyl silicate, vinyl trimethoxy silane, vinyl triethoxy silane, methyl triethoxy silane, 3-chloropropyl trichlorosilane, 3-chloropropyl triethoxy silane, gamma-mercaptopropyl trimethoxy silane, gamma-aminopropyl methyldiethoxy silane and gamma-aminopropyl triethoxy silane; The catalyst is any one or more of hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, oxalic acid, formic acid and propionic acid; The ratio of the silicon source to the mixed solution of ethanol and water is 10g (5-60) mL, and the ratio of ethanol to water is (0-60) mL.
5. The method for preparing the particle-based flexible high-temperature-resistant ceramic nanofiber membrane according to claim 1, wherein in the step 3), the ratio of the semi-gel silica sol to the dispersion liquid is (1-20) g/100 mL, and the dynamic viscosity of the precursor solution is 1-30 Pa.s.
6. The method for preparing the particle-based flexible high-temperature-resistant ceramic nanofiber membrane according to claim 1, wherein in the step 4), the technological parameters of hot air flow assisted electrostatic spinning are that the pressure of an assisted air flow is 0.02-0.7 MPa, the air flow is 5-100L/min, the air flow temperature is 30-80 ℃, the ambient temperature is 20-40 ℃, the ambient relative humidity is 20-60%, the voltage is 15-60 kV, the distance between a receiving device and a spinneret is 20-50 cm, and the filling speed is 0.1-10 mL/h; In the step 5), the process parameters of the Joule heat treatment are that the voltage is 15-30V, the current is 50-250A, and the heating time is 100 ms-1 min.
7. The method for preparing the particle-based flexible high-temperature-resistant ceramic nanofiber membrane according to claim 1, wherein the temperature rise rate of the muffle furnace is 0.5-10 ℃ per minute, the highest calcination temperature is 900-1700 ℃, and the temperature is kept at the highest temperature for 10-180 minutes.
8. The particle-based flexible high-temperature-resistant ceramic nanofiber membrane prepared by the method according to any one of claims 1 to 7, wherein the average diameter of fibers in the particle-based flexible high-temperature-resistant ceramic nanofiber membrane is 100-1000 nm, the average grain size in the fibers is 5-60 nm, the softness of the fiber membrane is 30-150 mN, and brittle fracture does not occur after 10000 times of repeated bending and doubling of the fiber membrane.
9. The particle-based flexible high temperature resistant ceramic nanofiber membrane of claim 8, wherein the particle-based flexible high temperature resistant ceramic nanofiber membrane has a long-term temperature resistance of up to 1100 ℃ or more.

Description

Particle-based flexible high-temperature-resistant ceramic nanofiber membrane and preparation method thereof Technical Field The application belongs to the technical field of ceramic nanofiber material preparation, and particularly relates to a preparation method of a particle-based flexible high-temperature-resistant ceramic nanofiber membrane. Background Ceramic fibers are widely used in the fields of aerospace, national defense and military industry, nuclear energy, petrochemical industry, metallurgy and the like due to excellent temperature resistance, thermal stability, thermal shock resistance, mechanical vibration resistance, low thermal conductivity and chemical corrosion resistance. The diameter of the existing ceramic fiber is generally in the order of micrometers, and the fiber is generally hard and brittle, is difficult to weave and form efficiently, and limits the improvement of application performance and the expansion of functionality. When the diameter of the ceramic fiber is further reduced to the nanometer order, the bending deformability and the high-temperature heat insulation performance of the ceramic fiber can be obviously improved. The electrostatic spinning technology has the characteristics of simple equipment, wide spinnable raw material range, strong controllability of fiber structure, easiness in integration with other technologies and the like, and becomes one of the effective means for preparing ceramic nanofibers at present. At present, more than 50 ceramic oxide nanofiber membranes have been prepared by utilizing an electrostatic spinning technology and have excellent application performance. The existing ceramic nanofiber mainly uses inorganic or organic metal salt as a raw material in the preparation process, and is limited by the solubility and easy hydrolyzability of the metal salt, and the occupation ratio of the metal salt in the fiber is generally not high. In addition, it is common to add a polymeric spin aid to the precursor solution to enhance spinnability of the spinning solution. However, the introduction of the polymeric spin aid results in a lower ceramic component content in the precursor fiber film, which in turn results in an extremely low yield of inorganic fibers. In addition, a large amount of high molecular polymers in the precursor fiber are oxidized and cracked in the annealing process, so that the ceramic nanofiber structure is unstable, single fiber defects are large, the fiber is easy to brittle fracture, and flexible ceramic nanofiber is difficult to obtain. Disclosure of Invention The invention aims to provide a particle-based flexible high-temperature-resistant ceramic nanofiber membrane and a preparation method thereof, which solve the problems of poor metal salt solubility, unstable solution, less spinnable raw materials and high crystallization sintering temperature in the preparation process of the traditional ceramic nanofiber membrane, and the bottleneck problems of easy brittle failure, low temperature resistance and the like of the traditional ceramic nanofiber membrane. The present invention prepares a dispersion from one or more ceramic nanoparticles as a raw material, and imparts excellent spinnability to the dispersion by incorporating a semi-colloidal silica sol into the dispersion. Meanwhile, as the high molecular polymer is not introduced into the precursor solution, the damage to the complete skeleton structure of the single fiber due to destabilization and decomposition of a large amount of organic components in the calcination process is avoided, and the flexible ceramic nanofiber membrane is finally obtained. Firstly, the semi-gel silica sol is added into a dispersion liquid containing one or more ceramic nano particles, and the viscoelasticity and spinnability of the mixed solution are effectively improved through the incomplete network molecular chain structure in the semi-gel silica sol. In the subsequent electrostatic spinning process, a hot air flow assisted spinning method is adopted to promote the surface of the spinning jet flow to be quickly solidified by gel, and the jet flow still maintains certain fluidity to enable the spinning jet flow to be continuously drawn and thinned, so that the precursor fiber film is prepared. Finally, the precursor fiber film is subjected to ultrafast joule heat treatment to realize instantaneous high-temperature reaction of the precursor fiber, so that formation and preliminary crystallization of a main crystalline phase are instantaneously completed, rapid growth of crystal grains is effectively inhibited, and coarsening of the crystal grains in a slow temperature rising process is avoided. And then transferring the fiber into a muffle furnace to be continuously calcined according to a traditional temperature programming mode, repairing defects such as lattice distortion, microcracks, pores and the like in the ceramic fiber in a slow temperature programming process, gently removing resi