CN116143506A - Oxide nanofiber sponge and preparation method thereof - Google Patents
Oxide nanofiber sponge and preparation method thereof Download PDFInfo
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- CN116143506A CN116143506A CN202310164319.7A CN202310164319A CN116143506A CN 116143506 A CN116143506 A CN 116143506A CN 202310164319 A CN202310164319 A CN 202310164319A CN 116143506 A CN116143506 A CN 116143506A
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 85
- 238000009987 spinning Methods 0.000 claims abstract description 74
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 230000005686 electrostatic field Effects 0.000 claims abstract description 21
- 230000009471 action Effects 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000005422 blasting Methods 0.000 claims abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000010041 electrostatic spinning Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
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- 230000005684 electric field Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6224—Fibres based on silica
- C04B35/62245—Fibres based on silica rich in aluminium oxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention provides a preparation method of an oxide nanofiber sponge body, which comprises the following steps: (1) Adding a high molecular polymer, metal aluminum salt and an organosilicon source into a solvent, and uniformly mixing to obtain a precursor solution; (2) Injecting the precursor solution into a spinning needle, spinning the precursor solution under the action of an electrostatic field and an airflow field, and collecting by a collecting device to obtain a nanofiber sponge precursor; (3) And sequentially carrying out heating blasting treatment and high-temperature calcination treatment on the nanofiber sponge precursor to obtain the oxide nanofiber sponge. The preparation method is simple, the oxide nanofiber sponge body with the three-dimensional structure can be prepared through one-step spinning, and the prepared oxide nanofiber sponge body has excellent heat insulation performance, high-temperature heat stability and good rebound performance.
Description
Technical Field
The invention relates to the technical field of oxide nanofibers, in particular to an oxide nanofiber sponge and a preparation method thereof.
Background
Conventional oxide ceramics severely limit their use under dynamic, impact, etc., conditions due to inherent rigidity and brittleness; the oxide nanofiber has wide application prospects in extreme environments by virtue of the advantages of good flexibility, low heat conductivity, stable chemical properties and the like, and particularly has a three-dimensional structure formed by nanofibers, so that the flexibility of the oxide nanofiber assembly at high temperature is realized, and the application of the oxide nanofiber assembly to flexible devices and heat insulation protection is a challenging problem.
In the prior art, aiming at the construction of the three-dimensional oxide nanofiber component, the oxide nanofiber component with heat insulation and elasticity is mainly prepared at home and abroad by firstly manufacturing flexible amorphous one-dimensional fibers and then performing post-treatment, for example, adopting a method of stacking the fibers, adding a cross-linking agent and then freeze-drying. The preparation process of the preparation method is complex, and the oxide nanofiber is limited by the preparation method and has poor thermal performance and rebound resilience. Accordingly, in view of the above-described problems, there is a need for an oxide nanofiber sponge that exhibits excellent thermal and elastic properties.
Disclosure of Invention
The embodiment of the invention provides an oxide nanofiber sponge body and a preparation method thereof, wherein the preparation method is simple, the oxide nanofiber sponge body with a three-dimensional structure can be prepared through one-step spinning, and the prepared oxide nanofiber sponge body has excellent heat insulation performance, high-temperature heat stability and good rebound performance.
In a first aspect, a method for preparing an oxide nanofiber sponge, the method comprising the steps of:
(1) Adding a high molecular polymer, metal aluminum salt and an organosilicon source into a solvent, and uniformly mixing to obtain a precursor solution;
(2) Injecting the precursor solution into a spinning needle, spinning the precursor solution under the action of an electrostatic field and an airflow field, and collecting by a collecting device to obtain a nanofiber sponge precursor;
(3) And sequentially carrying out heating blasting treatment and high-temperature calcination treatment on the nanofiber sponge precursor to obtain the oxide nanofiber sponge.
Preferably, the high molecular polymer is at least one of polyvinylpyrrolidone or polyethylene oxide;
the metal aluminum salt is at least one of aluminum chloride, aluminum nitrate, aluminum isopropoxide or aluminum sec-butoxide;
the organic silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, silicone resin and polymethyl siloxane;
the solvent is at least one of isopropanol, methanol, ethanol, N-dimethylformamide or deionized water.
Preferably, the mass percentage of the metal aluminum salt in the precursor solution is 10-30%, and the mass percentage of the organic silicon source is 0.1-5%;
the viscosity of the precursor solution is 0.1-50 Pa.s.
Preferably, in the step (2), the liquid supply speed of the precursor solution is 0.5-5 mL/h, and the distance between the spinning needle and the collecting device is 20-50 cm.
Preferably, in the step (2), the voltage of the electrostatic field is 1-20 kV, and the flow rate of the airflow field is 10-40 m/s.
Preferably, in the step (2), the temperature of the spinning is 25 to 40 ℃ and the humidity of the spinning is 50 to 60%.
Preferably, in the step (3), the heating and blasting treatment is to raise the temperature to 150-300 ℃ at a heating rate of 1-10 ℃/min in an air atmosphere, and keep the temperature for 0-3 h.
Preferably, in step (3), the high temperature calcination includes a first stage calcination and a second stage calcination.
Preferably, in the step (3), the temperature of the first-stage calcination is 400-700 ℃, the temperature rising rate is 0.1-5 ℃/min, and the heat preservation time is 0-2 h;
the temperature of the second stage calcination is 1000-1600 ℃, the temperature rising rate is 2-10 ℃/min, and the heat preservation time is 0.1-2 h.
In a second aspect, the present invention provides an oxide nanofiber sponge prepared by the method of any one of the first aspects.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, the precursor solution containing the high molecular polymer, the metal aluminum salt and the organic silicon source is spun under the action of a composite field, the oxide nanofiber formed in the spinning process can be uniformly constructed into a stable three-dimensional space structure through physical and chemical bonding under the combined action of an electrostatic field and an airflow field, and finally, the oxide nanofiber sponge with excellent performance can be directly obtained after heating and calcining treatment without complex post-treatment process;
(2) The preparation method has the advantages of low cost, simple process and short flow, and the oxide nanofiber prepared by the method has excellent heat insulation performance and rebound performance and has excellent high-temperature heat stability performance at 1600 ℃.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram showing the structure of a physical structure of an oxide nanofiber sponge according to an embodiment of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of an oxide nanofiber sponge provided in example 1 of the present invention; wherein the scale is 2 μm;
FIG. 3 is a Scanning Electron Microscope (SEM) image of an oxide nanofiber sponge provided in example 1 of the present invention after being treated at 1600℃for 10 minutes; wherein the scale is 1 μm;
FIG. 4 is a stress-strain plot of a longitudinal compressive recovery strain of 60% for an oxide nanofiber sponge according to example 1 of the present invention;
FIG. 5 is a Scanning Electron Microscope (SEM) image of an oxide nanofiber sponge provided in example 2 of the present invention; wherein the scale is 2 μm;
fig. 6 is a schematic structural diagram of a spinning device used for the oxide nanofiber sponge.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The preparation method of the oxide nanofiber mainly comprises electrostatic spinning and air flow spinning, however, the preparation method is limited by a fiber collection method, and a nanofiber structure prepared by the electrostatic spinning and the air flow spinning is a dense nanofiber membrane formed by random stacking, so that a fluffy three-dimensional structure is difficult to form. In the prior art, in order to prepare the nanofiber sponge body with a three-dimensional structure, the preparation method is complex and difficult to produce in large scale, wherein the nanofiber sponge body is firstly prepared by preparing a flexible amorphous two-dimensional fiber membrane and then carrying out post-treatment processes such as crosslinking, crushing, ultrasonic freeze drying and the like; in addition, in the process of preparing the oxide nanofiber with the three-dimensional structure in the prior art, the force, heat performance and rebound performance of the three-dimensional structure are difficult to ensure. Accordingly, based on the above-mentioned problems, the present invention provides a method for preparing an oxide nanofiber sponge, comprising the steps of:
(1) Adding a high molecular polymer, metal aluminum salt and an organosilicon source into a solvent, and uniformly mixing to obtain a precursor solution;
(2) Injecting the precursor solution into a spinning needle, spinning the precursor solution under the action of an electrostatic field and an airflow field, and collecting by a collecting device to obtain a nanofiber sponge precursor;
(3) And sequentially carrying out heating blasting treatment and high-temperature calcination treatment on the nanofiber sponge precursor to obtain the oxide nanofiber sponge.
According to the invention, the precursor solution containing the high molecular polymer, the metal aluminum salt and the organic silicon source is spun under the action of the composite field, so that oxide nanofibers with uniform size can be formed in the spinning process, and the oxide nanofibers can be uniformly constructed into a stable three-dimensional space structure through physical connection and chemical bonding under the combined action of an electrostatic field and an airflow field, and finally, the oxide nanofiber sponge with excellent performance can be directly obtained after heating and calcining treatment.
The preparation method is simple, no complex post-treatment process is needed, and the stable nanofiber sponge precursor with the three-dimensional space structure can be prepared and obtained only through the selection and the proportioning of raw material components in the spinning precursor solution and the comprehensive control of the electrostatic field, the airflow field, the liquid supply speed, the receiving distance and other conditions in the spinning process.
According to some preferred embodiments, in step (1), the high molecular polymer is at least one of polyvinylpyrrolidone or polyethylene oxide;
the metal aluminum salt is at least one of aluminum chloride, aluminum nitrate, aluminum isopropoxide or aluminum sec-butoxide;
the organic silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, silicone resin and polymethyl siloxane;
the solvent is at least one of isopropanol, methanol, ethanol, N-dimethylformamide or deionized water.
In the present invention, at least one kind is a mixture obtained by mixing any one or any plurality of kinds in any ratio.
According to some preferred embodiments, in step (1), the mass percentage of the metal aluminum salt in the precursor solution is 10-30% (e.g., may be 10wt%, 15wt%, 20wt%, 25wt%, or 30 wt%), and the mass percentage of the organosilicon source is 0.1-5% (e.g., may be 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, or 5 wt%);
the viscosity of the precursor solution is 0.1 to 50pa·s (for example, may be 0.1pa·s, 1pa·s, 5pa·s, 10pa·s, 20pa·s, 30pa·s, 40pa·s, or 50pa·s).
In the invention, by controlling the raw material composition and the proportion of the precursor solution in the above range, the precursor solution has better matching with the spinning process in the invention, and is beneficial to ensuring the heat insulation and temperature resistance and rebound performance of the prepared oxide nanofiber sponge. If the mass ratio of the metal aluminum salt in the precursor solution is too low, the preparation of the oxide nanofiber sponge with excellent high temperature resistance is not facilitated, and the proper increase of the mass ratio of the metal aluminum salt is beneficial to improving the high temperature resistance and the heat insulation performance of the oxide nanofiber sponge, but if the mass ratio of the metal aluminum salt is too high, the fiber brittleness of the oxide nanofiber is larger, the flexibility is worse, and the rebound resilience of the oxide nanofiber sponge is further poorer. If the mass ratio of the organic silicon source in the precursor solution is too low, the rebound resilience of the oxide nanofiber sponge is poor, but when the mass ratio of the organic silicon source is too high, the preparation of the oxide nanofiber sponge with excellent heat insulation performance and high temperature resistance is unfavorable.
Meanwhile, in the invention, the addition amount of the high molecular polymer mainly influences the viscosity of the precursor spinning solution, and the spinnability of the spinning solution can be improved by controlling the viscosity of the precursor spinning solution, so that the oxide nanofiber with controllable size can be further obtained. The average diameter of the oxide nanofiber prepared by the method is controllable between 100 and 999nm, and the oxide nanofiber has good flexibility and uniformity.
According to some preferred embodiments, in step (2), the liquid supply speed of the precursor solution is 0.5 to 5mL/h (for example, may be 0.5mL/h, 1mL/h, 2mL/h, 3mL/h, 4mL/h or 5 mL/h), and the distance between the spinning needle and the collecting device is 20 to 50cm (for example, may be 20cm, 30cm, 40cm or 50 cm).
According to some preferred embodiments, in step (2), the temperature of the spinning is 25-40 ℃ (e.g. may be 25 ℃, 28 ℃, 30 ℃, 35 ℃, 38 ℃ or 40 ℃), and the humidity of the spinning is 50-60% (e.g. may be 50%, 52%, 55%, 58% or 60%).
In the invention, before spinning, a precursor solution is injected into a spinning needle through a liquid supply system and is uniformly pushed out, meanwhile, an electric field and air flow are applied to a liquid outlet position of the spinning needle, liquid drops at the spinning needle are split into small liquid drops containing favorable nano colloidal particles under the combined action of a high-voltage electric field and high-speed air flow, and the small liquid drops are stretched, split and volatilized under the synergistic action of the electric field force and the high-speed air flow to form nano precursor fibers which are randomly distributed, and the precursor of the nanofiber elastic sponge can be obtained after the nano precursor fibers are collected by a collecting device.
In the spinning process, electrostatic auxiliary-air spinning is adopted, namely air spinning is adopted as the main material in the spinning process, and electrostatic spinning is adopted as the auxiliary material, so that compared with the traditional single air spinning process and the traditional single electrostatic spinning process, under the action of a composite field, the spinning solution is subjected to the double effects of air flow shearing force and electrostatic traction force, the solvent is quickly volatilized, the spinning solution has better filigenicity, and the fibers which are preliminarily formed in the air have the same electric charge and are mutually exclusive, so that the fibers are easily separated and cannot adhere to the bundled yarns, the surfaces of the fibers are smooth, the structure is more uniform, and the quality control is more stable. In addition, due to the existence of the composite field, the movement track of the fiber is more complex, and the fiber collides and is entangled in the collecting process, so that the sponge form with the 3D structure with the three-dimensional structure is finally formed.
In the invention, through the cooperative coordination of various parameters in the spinning process, the nanofiber formed by spinning constructs a stable three-dimensional space structure in a physical connection and chemical bonding mode, and the heat insulation and heat resistance and the better rebound performance of the prepared oxide nanofiber sponge can be ensured. The conditions of liquid supply speed, distance of a collecting device, spinning temperature and humidity, applied electrostatic field voltage, airflow field flow speed and the like are mutually influenced in the spinning process, and when a certain parameter is not in the range, the nanofiber sponge with stable three-dimensional structure performance, excellent heat insulation performance, excellent temperature resistance performance and excellent rebound resilience performance is not beneficial to obtaining.
According to some preferred embodiments, in step (2), the voltage of the electrostatic field is 1-20 kV (e.g., may be 1kV, 5kV, 8kV, 15kV, 18kV or 20 kV), and the flow rate of the air flow field is 10-40 m/s (e.g., may be 10m/s, 15m/s, 20m/s, 25m/s, 30m/s, 35m/s or 40 m/s). The electrostatic auxiliary-air flow spinning is mainly realized by regulating and controlling the voltage of an electrostatic field and the flow velocity of an air flow field, when the electrostatic field plays a main role in the spinning process and the air flow is an auxiliary role, namely when the voltage of the electrostatic field is higher than the range, the filament floating phenomenon occurs in the spinning process, and the three-dimensional space structure with stable performance is not favorable for the construction of the nanofiber; however, when the flow rate of the air flow field is higher than the above range, it is unfavorable to form uniform and continuous nano-sized fiber filaments, and is unfavorable to be collected by the collecting device, thereby adversely affecting the performance of the oxide nanofiber.
The invention utilizes the principle of electrostatic spinning and air flow spinning to prepare nano fibers, and applies a composite field in the spinning process, so that the spinning solution forms an oxide nano fiber sponge body with a stable three-dimensional structure under the combined action of an electrostatic field and an air flow field. In some preferred embodiments of the present invention, as shown in fig. 6, the spinning device platform used in the present invention comprises a liquid supply device, a spinning nozzle device, a high-voltage direct current power supply, an air compression device and a collecting device; the liquid supply device is connected with the rear end of the spinning nozzle device through a liquid conveying pipe and is used for controlling the outflow speed of the spinning liquid; the front end of the spinning nozzle device is connected with a high-voltage direct-current power supply and an air compression device through a circuit and a gas pipeline; the fibers formed from the spinning nozzle device are distributed into a collecting device below the fibers, and finally a sponge precursor with a three-dimensional structure is formed. The collecting device in the present invention is preferably a cage-shaped collecting device.
According to some preferred embodiments, in step (3), the heat blasting treatment is to heat up to 150 to 300 ℃ (e.g., may be 150 ℃, 180 ℃, 200 ℃, 250 ℃, 280 ℃ or 300 ℃) in an air atmosphere at a heating rate of 1 to 10 ℃/min (e.g., may be 1 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min or 10 ℃/min), and to keep the temperature for 0 to 3 hours (e.g., may be 0 hours, 1 hours, 2 hours or 3 hours).
In the invention, after the nanofiber sponge precursor is collected, the nanofiber sponge precursor is firstly placed in an air atmosphere and heated from room temperature (25-28 ℃) to 150-300 ℃ at a speed of 1-10 ℃/min for heating and blasting treatment, the air is continuously blasted in the heating process, the room temperature (25-28 ℃) is reserved after the temperature is kept for 0-3 hours, the nanofiber is solidified at low temperature through the heating and blasting treatment, the adhesion between the fibers in the nanofiber sponge precursor is prevented, and the three-dimensional space structure of the nanofiber sponge precursor is further ensured.
According to some preferred embodiments, in step (3), the high temperature calcination comprises a first stage calcination and a second stage calcination.
According to some preferred embodiments, in step (3), the first stage calcination is at a temperature of 400-700 ℃ (e.g., may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, or 700 ℃), at a ramp rate of 0.1-5 ℃/min (e.g., may be 0.1 ℃/min, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, or 5 ℃/min), and a soak time of 0-2 hours (e.g., may be 0 hours, 1 hours, 1.5 hours, or 2 hours);
the temperature of the second stage calcination is 1000-1600 ℃ (for example, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃ or 1600 ℃), the temperature rising rate is 2-10 ℃/min (for example, 2 ℃/min, 5 ℃/min, 7 ℃/min, 8 ℃/min or 10 ℃/min), and the heat preservation time is 0.1-2 h (for example, 0.1h, 1h, 1.5h or 2 h).
And (3) calcining the dried nanofiber sponge precursor at a high temperature, removing organic matters in the sintering process, and converting the nanofibers in the nanofiber sponge precursor into corresponding oxide nanofiber ceramics, thereby obtaining the oxide nanofiber sponge. In the invention, the staged high-temperature calcination treatment is preferably adopted, and the high-temperature calcination temperature, the temperature rising rate and the like of each stage are controlled, so that the method is beneficial to more complete decomposition of organic matters in the nanofiber sponge precursor, and is beneficial to forming the oxide nanofiber sponge body with smooth fiber surface, controllable fiber size and excellent performance.
The preparation method provided by the invention can be used for large-scale and large-scale preparation molding of the nanofiber three-dimensional component, and has the advantages of low preparation cost, simple process and short flow without the method, thus having good industrial application prospect.
The invention also provides an oxide nanofiber sponge body, which is prepared by adopting the preparation method provided by the invention.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a detailed description of an oxide nanofiber sponge and a preparation method thereof will be given below by way of several examples.
Example 1:
(1) Adding a high molecular polymer (polyvinylpyrrolidone), a metal aluminum salt (aluminum sec-butoxide) and an organosilicon source (ethyl orthosilicate) into a solvent (isopropyl alcohol and N, N-dimethylformamide), stirring at 25 ℃ for 6 hours at a rotating speed of 400r/min, and uniformly mixing to obtain a precursor solution with the viscosity of 5 Pa.s; wherein, the mass percentage of the metal aluminum salt is 20 percent, and the mass percentage of the organic silicon source is 1 percent;
(2) Injecting 20mL of precursor solution into a spinning needle through a liquid supply system, controlling the ambient temperature to 25 ℃, the humidity to 50%, the liquid supply speed to 3mL/h, spinning the precursor solution under the action of an electrostatic field (electrostatic voltage 12 kV) and an airflow field (airflow velocity is 15 m/s), orienting the spinning solution under the action of high-speed airflow and static electricity to form randomly arranged fibers, and collecting the fibers by a cage-shaped collecting device to obtain a nanofiber sponge precursor; the distance between the spinning needle head and the collecting device is 30cm;
(3) The nanofiber sponge precursor is placed in an air atmosphere for heating and blasting treatment, the temperature is raised to 200 ℃ at the temperature rising speed of 5 ℃/min, the temperature is kept for 1h, and the temperature is naturally lowered to the room temperature (25 ℃); and then carrying out high-temperature calcination treatment, firstly placing the material in a muffle furnace, raising the temperature from room temperature (25 ℃) to 600 ℃ at a heating rate of 2 ℃/min under the air atmosphere, preserving the temperature at the temperature for 30min, raising the temperature from 600 ℃ to 1300 ℃ at a heating rate of 5 ℃/min, preserving the temperature at the temperature for 1h, and naturally cooling to the room temperature to obtain the oxide nanofiber sponge.
Example 2:
(1) Adding a high molecular polymer (polyvinylpyrrolidone), a metal aluminum salt (aluminum isopropoxide) and an organosilicon source (polymethyl siloxane) into a solvent (ethanol and N, N-dimethylformamide), stirring at a rotating speed of 400r/min for 10 hours at 25 ℃ and uniformly mixing to obtain a precursor solution with a viscosity of 2 Pa.s; wherein, the mass percentage of the metal aluminum salt is 25 percent, and the mass percentage of the organic silicon source is 0.5 percent;
(2) Injecting 20mL of precursor solution into a spinning needle through a liquid supply system, controlling the ambient temperature to be 30 ℃, the humidity to be 50%, the liquid supply speed to be 2mL/h, spinning the precursor solution under the action of an electrostatic field (electrostatic voltage 10 kV) and an airflow field (airflow velocity is 18 m/s), orienting the spinning solution under the action of high-speed airflow and static electricity to form randomly arranged fibers, and collecting the fibers by a cage-shaped collecting device to obtain a nanofiber sponge precursor; the distance between the spinning needle head and the collecting device is 35cm;
(3) The nanofiber sponge precursor is placed in an air atmosphere for heating and blasting treatment, the temperature is increased to 180 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 1h, and the temperature is naturally reduced to the room temperature (25 ℃); and then carrying out high-temperature calcination treatment, firstly placing the material in a muffle furnace, raising the temperature from room temperature (25 ℃) to 700 ℃ at a heating rate of 2 ℃/min under the air atmosphere, preserving heat at the temperature for 20min, raising the temperature from 700 ℃ to 1350 ℃ at a heating rate of 10 ℃/min, preserving heat at the temperature for 1h, and naturally cooling to the room temperature to obtain the oxide nanofiber sponge.
Example 3:
(1) Adding a high molecular polymer (polyethylene oxide), a metal aluminum salt (aluminum sec-butoxide) and an organosilicon source (ethyl orthosilicate) into a solvent (isopropyl alcohol and N, N-dimethylformamide), stirring at a rotating speed of 400r/min for 6 hours at 25 ℃ and uniformly mixing to obtain a precursor solution with the viscosity of 2 Pa.s; wherein, the mass percentage of the metal aluminum salt is 20 percent, and the mass percentage of the organic silicon source is 1 percent;
(2) Injecting 20mL of precursor solution into a spinning needle through a liquid supply system, controlling the ambient temperature to 25 ℃, the humidity to 60%, the liquid supply speed to 2mL/h, spinning the precursor solution under the action of an electrostatic field (electrostatic voltage 10 kV) and an airflow field (airflow velocity is 16 m/s), orienting the spinning solution under the action of high-speed airflow and static electricity to form randomly arranged fibers, and collecting the fibers by a cage-shaped collecting device to obtain a nanofiber sponge precursor; the distance between the spinning needle head and the collecting device is 35cm;
(3) The nanofiber sponge precursor is placed in an air atmosphere for heating and blasting treatment, the temperature is raised to 200 ℃ at the temperature rising speed of 5 ℃/min, the temperature is kept for 1h, and the temperature is naturally lowered to the room temperature (25 ℃); and then carrying out high-temperature calcination treatment, firstly placing the material in a muffle furnace, raising the temperature from room temperature (25 ℃) to 650 ℃ at a heating rate of 1 ℃/min under an air atmosphere, preserving heat at the temperature for 1h, raising the temperature from 650 ℃ to 1400 ℃ at a heating rate of 8 ℃/min, preserving heat at the temperature for 1h, and naturally cooling to the room temperature to obtain the oxide nanofiber sponge.
Performance tests were performed on the oxide nanofiber sponges (hereinafter referred to as samples) prepared in examples 1 to 3; thermal insulation performance test: measuring the back temperature of the sample by heating the face temperature of the sample to 1000 ℃; thermal conductivity testing: measuring the thermal conductivity of each sample at room temperature (25 ℃) by a steady-state thermal conductivity tester; rebound performance: the sample was tested for rebound performance at a loading rate of 2mm/min using a MTS CMT6103 universal tester with a 50-N load cell.
As can be seen from fig. 3 and 4, the oxide nanofiber sponge prepared in examples 1 to 3 of the present invention has good flexibility and elasticity, the oxide nanofiber sponge almost completely recovers after being subjected to 60% compressive strain, the maximum stress is 0.022MPa, and after 300 times of strain is 50% cyclic compression, the plastic deformation of the sample is <20%, and the sample has excellent rebound performance; the oxide nanofiber sponge body in the embodiment of the invention has the thermal conductivity of 0.03W/m.K at room temperature and excellent heat insulation performance and temperature resistance, the back temperature of the oxide nanofiber sponge body with the thickness of 10mm is only 250 ℃ after being placed in a 1000 ℃ surface temperature environment for stabilization, and the structure of a scanning electron microscope image observed after the oxide nanofiber sponge body is treated for 10min at 1600 ℃ is basically unchanged.
Example 4:
example 4 is substantially the same as example 1 except that: in the step (1), the mass content of the metal aluminum salt is 35%.
In this example, the nanofiber precursor was calcined to obtain a nanofiber sponge, but after a period of 1300 ℃ incubation, the grains of the oxide nanofiber became large, the fiber surface became rough, and the elasticity became poor. This is because the metal aluminum salt in the precursor solution is relatively large, the aluminum content in the final oxide becomes high, the amorphous phase is reduced, the alumina grains grow up after high temperature treatment, the fiber toughness gradually decreases, and the temperature resistance of the oxide nanofiber sponge is reduced.
Example 5:
example 5 is substantially the same as example 1 except that: in step (1), the mass content of the organosilicon source is 6%.
In this example, the nanofiber precursor was calcined to give a nanofiber sponge, but after a period of 1300 ℃ incubation, the oxide nanofiber crystallites became larger, volume contracted, and elasticity decreased. At this time, the silicon source in the formula occupies a relatively large area, the aluminum content in the final oxide becomes small, the silicon oxide content is increased, and the temperature resistance of the nanofiber is reduced.
Example 6:
example 6 is substantially the same as example 1 except that: in the step (2), the voltage of the electrostatic field is 30kV, and the flow rate of the airflow field is 15m/s.
In this example, the fibers were spun and the sponge-like fiber was not collected in the collection device, the precursor fibers were dispersed in an unordered manner, and the collected fibers were inelastic after heat treatment.
Example 7:
example 7 is substantially the same as example 1 except that: in the step (2), the voltage of the electrostatic field is 12kV, and the flow rate of the airflow field is 50m/s.
In this example, the precursor spinning solution does not have sufficient time to volatilize due to the too high flow rate of the gas stream, and no fiber can be formed to find a liquid spot in the collection device.
Comparative example 1:
comparative example 1 is substantially the same as example 1 except that: in the step (1), the precursor solution is obtained by mixing only a high molecular polymer (polyvinylpyrrolidone), a metal aluminum salt (aluminum sec-butoxide) and a solvent (isopropyl alcohol and N, N-dimethylformamide); wherein the mass content of the metal aluminum salt is 20%, and the viscosity of the precursor solution is 5 Pa.s.
Oxide nanofiber sponges were prepared in this comparative example, with nanofiber diameters of about 500nm, but with poor mechanical properties. Because the formula does not contain a silicon source, the nanofiber is a pure alumina fiber, the alumina undergoes phase change and crystal grains grow up after high temperature heat treatment, and the surface of the fiber is rough and brittle.
Comparative example 2:
comparative example 2 is substantially the same as example 1 except that: in the step (1), the precursor solution is obtained by mixing only a high molecular polymer (polyvinylpyrrolidone), an organosilicon source (ethyl orthosilicate) and a solvent (isopropanol and N, N-dimethylformamide); wherein the mass content of the organic silicon source is 1%, and the viscosity of the precursor solution is 2 Pa.s.
In the comparative example, the oxide nanofiber sponge is prepared, and because of the silicon source only, after the fiber precursor is subjected to high-temperature treatment at the temperature exceeding 1000 ℃, the silicon oxide fiber has obvious volume shrinkage and fusion adhesion, the precursor structure is shrunk into a relatively compact porous block material, and the structure is hardened without rebound performance.
Comparative example 3:
comparative example 3 is substantially the same as example 1 except that: in the step (2), 20mL of precursor solution is injected into a spinning needle through a liquid supply system, the ambient temperature is controlled to be 25 ℃, the humidity is controlled to be 50%, the liquid supply speed is controlled to be 4mL/h, the precursor solution is spun under the action of an airflow field (the airflow velocity is 15 m/s), and a cage-shaped collecting device is used for collecting the precursor solution to obtain a nanofiber sponge precursor; the distance between the spinning needle head and the collecting device is 30mm;
the fibrous membrane material prepared by adopting the process in the comparative example cannot be prepared into an oxide nanofiber sponge with a three-dimensional structure.
Comparative example 4:
comparative example 4 is substantially the same as example 1 except that: in the step (2), 20mL of precursor solution is injected into a spinning needle through a liquid supply system, the ambient temperature is controlled to be 25 ℃, the humidity is controlled to be 50%, the liquid supply speed is 3mL/h, the precursor solution is spun under the action of an electrostatic field (electrostatic voltage is 12 kV), and a cage-shaped collecting device is used for collecting the precursor solution to obtain a nanofiber sponge precursor; the distance between the spinning needle head and the collecting device is 30mm;
the fibrous membrane material prepared by adopting the process in the comparative example cannot be prepared into an oxide nanofiber sponge with a three-dimensional structure.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing an oxide nanofiber sponge, which is characterized by comprising the following steps:
(1) Adding a high molecular polymer, metal aluminum salt and an organosilicon source into a solvent, and uniformly mixing to obtain a precursor solution;
(2) Injecting the precursor solution into a spinning needle, spinning the precursor solution under the action of an electrostatic field and an airflow field, and collecting by a collecting device to obtain a nanofiber sponge precursor;
(3) And sequentially carrying out heating blasting treatment and high-temperature calcination treatment on the nanofiber sponge precursor to obtain the oxide nanofiber sponge.
2. The method of claim 1, wherein in step (1):
the high molecular polymer is at least one of polyvinylpyrrolidone or polyethylene oxide;
the metal aluminum salt is at least one of aluminum chloride, aluminum nitrate, aluminum isopropoxide or aluminum sec-butoxide;
the organic silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, silicone resin and polymethyl siloxane;
the solvent is at least one of isopropanol, methanol, ethanol, N-dimethylformamide or deionized water.
3. The method of claim 1, wherein in step (1):
the mass percentage of the metal aluminum salt in the precursor solution is 10-30%, and the mass percentage of the organic silicon source is 0.1-5%;
the viscosity of the precursor solution is 0.1-50 Pa.s.
4. The method of claim 1, wherein in step (2):
the liquid supply speed of the precursor solution is 0.5-5 mL/h, and the distance between the spinning needle head and the collecting device is 20-50 cm.
5. The method of claim 1, wherein in step (2):
the voltage of the electrostatic field is 1-20 kV, and the flow speed of the airflow field is 10-40 m/s.
6. The method of claim 1, wherein in step (2):
the temperature of the spinning is 25-40 ℃, and the humidity of the spinning is 50-60%.
7. The method of claim 1, wherein in step (3):
the heating and blasting treatment is to heat up to 150-300 ℃ at a heating rate of 1-10 ℃/min in an air atmosphere, and preserving heat for 0-3 h.
8. The method of claim 1, wherein in step (3):
the high temperature calcination includes a first stage calcination and a second stage calcination.
9. The method of claim 8, wherein in step (3):
the calcining temperature in the first stage is 400-700 ℃, the heating rate is 0.1-5 ℃/min, and the heat preservation time is 0-2 h;
the temperature of the second stage calcination is 1000-1600 ℃, the temperature rising rate is 2-10 ℃/min, and the heat preservation time is 0.1-2 h.
10. An oxide nanofiber sponge prepared by the method of any one of claims 1 to 9.
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