CN-122013598-A - Flexible ceramic nanofiber paper and folding and shaping method and application thereof

CN122013598ACN 122013598 ACN122013598 ACN 122013598ACN-122013598-A

Abstract

The invention belongs to the technical field of ceramic nanofiber paper manufacture, and in particular relates to flexible ceramic nanofiber paper, and a folding and shaping method and application thereof, wherein the flexible ceramic nanofiber paper comprises the steps of synthesizing a linear inorganic molecular chain with long-short lateral groups, preparing a fiber spinning solution, and spinning the fiber spinning solution to form a precursor; the method comprises the steps of softening a precursor through infrared heating, folding and shaping, calcining to obtain ceramic nanofiber paper, carrying out coordination modification and copolymerization on a metal alkoxide monomer by a long/short inert ligand on a linear inorganic molecular chain with long-short side groups, carrying out chain extension to obtain the linear inorganic molecular chain with long-short side groups, carrying out ultrasonic vibration in the folding and shaping process, and then cooling. Compared with the prior art, the invention solves the problems that the ceramic nanofiber paper with the existing three-dimensional structure has poor performance and the structure is difficult to maintain. According to the scheme, through the cooperative improvement of the precursor structure and the process, the ceramic nanofiber paper has excellent flexibility and structural stability, and the integrity and stability of the three-dimensional structure are improved.

Inventors

DING BIN
WU FAN
LIU CHENG
HUANG JIA
Fang Songchun
TIAN SHIJIN
SHAO JINGYI
WANG HAOXUAN
YU JIANYONG

Assignees

东华大学

Dates

Publication Date: 20260512
Application Date: 20260325

Claims (10)

1. The folding and shaping method of the flexible ceramic nanofiber paper is characterized by comprising the following steps of: firstly, synthesizing a linear inorganic molecular chain with long-short side groups, preparing a fiber spinning solution, spinning the fiber spinning solution into a precursor, sequentially carrying out infrared heating softening and folding shaping on the precursor, and finally calcining to obtain ceramic nanofiber paper; the linear inorganic molecular chain with long-short side groups is synthesized by respectively carrying out coordination modification on metal alkoxide monomers by long inert ligands and short inert ligands, mixing and carrying out copolymerization reaction, and chain extension to obtain the linear inorganic molecular chain with long-short side groups; In the process of folding and shaping, ultrasonic vibration is applied to the molded precursor to relax and rearrange the fibers along the crease direction, and then the fibers are cooled to be lower than the glass transition temperature to fix the fiber bonding points.
2. The method of claim 1, wherein the metal alkoxide monomer is selected from the group consisting of one or more of a titanium source, a zirconium source, an aluminum source, an indium source, a tin source, a hafnium source, a gallium source, a tantalum source, and a niobium source, and wherein: The titanium source is selected from one or more of titanium tetramethoxide, titanium tetraethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide and titanium isobutanol; The zirconium source is selected from one or more of zirconium tetramethoxide, zirconium tetraethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium isobutanol; the aluminum source is selected from one or more of trimethoxy aluminum, triethanol aluminum, tri-n-propoxy aluminum, isopropyl aluminum, n-butyl aluminum and sec-butyl aluminum; the indium source is selected from one or more of indium isopropoxide, triethoxy indium and tert-butyl alcohol indium; The tin source is selected from one or more of tetramethanolate tin, tetraethanolate tin, n-propanol tin, isopropanol tin, n-butanol tin, isobutanol tin and tert-butanol tin; the hafnium source is selected from one or more of hafnium tetramethoxide, hafnium tetraethoxide, hafnium n-propoxide, hafnium isopropoxide, hafnium n-butoxide, hafnium isobutanol and hafnium tert-butoxide; the gallium source is selected from one or more of triethoxy gallium, isopropanol gallium, n-butanol gallium and tert-butanol gallium; the tantalum source is selected from one or two of tantalum isopropoxide and tantalum n-butoxide; The niobium source is selected from one or two of niobium isopropoxide and niobium n-butoxide; the short inert ligand is one or a combination of more of acetic acid, oxalic acid, ethylenediamine and acetylacetone; The long inert ligand is one or more of citric acid, aminotriacetic acid, ammonium citrate, stearic acid, oleic acid and caproic acid.
3. The method for folding and shaping the flexible ceramic nanofiber paper according to claim 1, wherein a catalyst is added in the copolymerization reaction process; The catalyst is selected from one or more of boron trifluoride, aluminum trichloride, boron tribromide, boron triiodide, tin tetrachloride, silicon tetrachloride and titanium tetrachloride.
4. The method for folding and shaping the flexible ceramic nanofiber paper according to claim 1, wherein a chain extender is added in the chain extending process; The chain extender is selected from one or more of diisopropyl bis (ethyl acetoacetate) titanate, zirconium bis (diethyl citrate) dipropionate, titanium diisopropoxy diacetylacetonate, titanium dichloride, zirconium dichloride and hafnium dichloride.
5. The method for folding and shaping the flexible ceramic nanofiber paper according to claim 1, wherein the infrared heating and softening are performed by using mid-infrared light as an irradiation source, and the wavelength range is 0.75-1000 μm.
6. The method for folding and shaping the flexible ceramic nanofiber paper according to claim 1, wherein the ultrasonic vibration frequency is 40-80 kHz.
7. The method for folding and shaping the flexible ceramic nanofiber paper according to claim 1, wherein the temperature of cooling is-5-15 ℃.
8. The method for folding and shaping the flexible ceramic nanofiber paper according to claim 1, wherein the calcination temperature is 400-1500 ℃ and the calcination time is 10-60 min.
9. A flexible ceramic nanofiber paper, characterized in that the flexible ceramic nanofiber paper is obtained by a folding and shaping method of the ceramic nanofiber paper according to any one of claims 1-9; The cross section shape of the ceramic nanofiber paper comprises a flat plate structure, a corrugated structure and a corrugated structure.
10. Use of the flexible ceramic nanofiber paper of claim 9 in a fire-resistant insulation mat, solid electrolyte, flexible electrode or membrane support layer, flexible substrate or functional layer, catalytic and filtration support, and flame retardant noise reduction insulation layer.

Description

Flexible ceramic nanofiber paper and folding and shaping method and application thereof Technical Field The invention belongs to the technical field of ceramic nanofiber paper manufacturing, and particularly relates to flexible ceramic nanofiber paper, and a folding and shaping method and application thereof. Background The ceramic fiber paper has the intrinsic characteristics of high temperature resistance, corrosion resistance, good chemical stability and the like of ceramic materials, and also has flexibility and workability endowed by a fiber structure, and has important application value in the fields of high-temperature heat insulation, catalytic carriers, gas filtration and the like. However, the conventional ceramic fiber paper is mainly a two-dimensional sheet, and is difficult to match with the space configuration requirement of a complex service environment. Therefore, the ceramic fiber paper is prepared into a three-dimensional structure product from a simple plane material, and has extremely important significance for solving the application difficulty of the ceramic material in a complex scene. The prior art is to fold the calcined ceramic fiber paper by means of die pressing, mechanical folding or bonding assembly, and then to form the ceramic fiber product with three-dimensional configuration such as corrugated, ripple or honeycomb by drying, solidifying or high-temperature sintering. For example, in patent cn202510867554.X, solid amine is coated on ceramic fiber paper, then dried and cured, and then corrugated roll pressing and shaping are performed to prepare the ceramic fiber corrugated paper containing the solid amine. However, the conventional ceramic fiber paper is mainly prepared by a wet forming process, and the connection between the short fibers mainly depends on an adhesive or simple physical entanglement, so that the fiber paper has loose structure and poor mechanical strength. Meanwhile, because the sliding space among the fibers is locked by high-temperature sintering, when the folding deformation is carried out, the ceramic fibers at the crease are extremely easy to generate brittle fracture, so that the strength of the product is greatly reduced. The patent CN202510314915.8 is a technology of carrying out epoxy resin impregnation, drying, corrugating and sintering on fiber paper. However, the forming process is often completed under the static state that the fiber movement is limited, and residual internal stress is extremely easy to introduce. Meanwhile, the organic components relied on by the method are thermally decomposed in the high-temperature calcination stage, so that the corrugated configuration is extremely easy to distort, the structure is collapsed and even the whole structure is unstable, and the three-dimensional structure of the corrugated configuration is difficult to maintain. In addition, the ceramic fiber paper prepared by the method mainly comprises micron-sized short fibers, the diameter is large, the length-diameter ratio is low, the pore diameter of the formed fiber network is large, the specific surface area is low, the uniformity is poor, and the problems of poor mechanical properties, weak heat insulation capability and the like of the fiber paper and products thereof are difficult to meet the requirement of high performance. Therefore, the development of ceramic fiber paper based on continuous nanofibers and products thereof is a key direction for breaking through the prior performance bottleneck and expanding the prior scene application. Therefore, development of a preparation method of flexible ceramic nanofiber paper capable of realizing three-dimensional structure forming is needed to obtain flexible ceramic nanofiber paper product with complete structure and excellent performance, so as to meet urgent demands of application fields such as high-temperature heat insulation, efficient catalysis and gas filtration. Disclosure of Invention The invention aims to solve at least one of the problems, and provides flexible ceramic nanofiber paper, a folding and shaping method and application thereof, so as to solve the problems of poor performance and difficult maintenance of the three-dimensional structure of the ceramic nanofiber paper in the prior art. According to the scheme, through the cooperative improvement of the precursor structure and the process, the ceramic nanofiber paper has excellent flexibility and structural stability, and the integrity and stability of the three-dimensional structure are improved. The aim of the invention is achieved by the following technical scheme: The invention discloses a method for folding and shaping flexible ceramic nanofiber paper in a first aspect, which comprises the following steps: firstly, synthesizing a linear inorganic molecular chain with long-short side groups, preparing a fiber spinning solution, spinning the fiber spinning solution into a precursor, sequentially carrying out infrared heating softeni