CN113463268A - Preparation method of light thin flexible lanthanum manganate nanofiber heat insulation film - Google Patents
Preparation method of light thin flexible lanthanum manganate nanofiber heat insulation film Download PDFInfo
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- lanthanum
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- lanthanum manganate
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 98
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000009413 insulation Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 239000012528 membrane Substances 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 150000002696 manganese Chemical class 0.000 claims abstract description 28
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000010041 electrostatic spinning Methods 0.000 claims description 23
- 238000009987 spinning Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 6
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 5
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 claims description 4
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- YRKCZRMEPGLHRN-UHFFFAOYSA-K lanthanum(3+);triacetate;hydrate Chemical compound O.[La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O YRKCZRMEPGLHRN-UHFFFAOYSA-K 0.000 claims description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 14
- 239000012774 insulation material Substances 0.000 abstract description 8
- 238000001523 electrospinning Methods 0.000 abstract description 4
- 229920001410 Microfiber Polymers 0.000 abstract description 3
- 239000003658 microfiber Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 abstract 2
- 239000007822 coupling agent Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 8
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 6
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 6
- 230000010412 perfusion Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- -1 lanthanum ions Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
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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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- 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
-
- 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
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—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 by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
本发明涉及一种轻质薄型柔性锰酸镧纳米纤维隔热膜的制备方法，先将锰盐和镧盐依次加入到溶剂中，搅拌后调整溶液pH，随后加入胶溶剂继续搅拌后加入硅烷偶联剂搅拌混合均匀，获得均一、稳定的前驱体溶液；然后采用静电纺丝技术将前驱体溶液制备成前驱体纳米纤维膜；最后将前驱体纳米纤维膜在空气气氛中煅烧，得到轻质薄型柔性锰酸镧纳米纤维隔热膜。本发明方法有效制备出体积密度低、厚度小、高温隔热性好的陶瓷纳米纤维膜，有效解决了当前陶瓷微米纤维膜普遍存在的厚重、高温隔热性能差等不足，可满足狭窄空间隔热领域对陶瓷纤维隔热材料的应用需求，表现出良好的实用价值和广泛的应用前景。The invention relates to a method for preparing a light-weight and thin flexible lanthanum manganate nanofiber thermal insulation film. First, manganese salt and lanthanum salt are added to a solvent in sequence, the pH of the solution is adjusted after stirring, and then a peptizer is added to continue stirring, and then a silane coupling agent is added. The coupling agent is stirred and mixed evenly to obtain a uniform and stable precursor solution; then the precursor solution is prepared into a precursor nanofiber membrane by electrospinning technology; finally, the precursor nanofiber membrane is calcined in an air atmosphere to obtain a lightweight and thin film Flexible Lanthanum Manganate Nanofiber Insulation Film. The method of the invention effectively prepares the ceramic nanofiber membrane with low bulk density, small thickness and good high temperature heat insulation, effectively solves the common shortcomings of the current ceramic microfiber membrane, such as thickness and poor high temperature heat insulation performance, and can meet the requirements of narrow space separation The application demand of ceramic fiber insulation materials in the thermal field shows good practical value and wide application prospects.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to a preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film.
Background
The ceramic fiber material has the structural advantages of both ceramic and fiber materials, shows excellent high temperature resistance, thermal shock resistance, thermal and chemical stability and the like, and has great application value in the fields of metallurgy, national defense, military industry, aerospace and the like. The traditional ceramic fiber is generally a micron ceramic fiber material, when the ceramic fiber is processed into a ceramic fiber felt through a needling or spunlace process, due to the thick diameter of a single fiber, the material has the defects of large inter-fiber pore diameter, low fiber felt porosity, poor high-temperature heat insulation property and the like, and the performance requirements of narrow space fields (such as electronic components, new energy automobile batteries, fire-fighting clothing, fire shoes, sleeping bag fireproof linings and the like) on heat insulation materials are difficult to meet. When the diameter of the micron ceramic fiber is further refined into the nano fiber, the aperture between the fibers can be obviously reduced, and the porosity of the material can be improved, so that the gas-solid coupling thermal conductivity of the material can be effectively reduced. Meanwhile, the ceramic material with high infrared reflection characteristic is adopted as the fiber substrate, which is beneficial to further reducing the high-temperature heat radiation of the ceramic fiber material, thereby being beneficial to ensuring that the ceramic nanofiber material has excellent high-temperature heat insulation performance under the conditions of low volume density and small thickness.
Lanthanum manganate is of great interest due to its excellent infrared reflection performance, good high temperature resistance, low thermal conductivity, low toxicity and other characteristics, and when it is processed into nanofiber, it can simultaneously reduce gas heat conduction, solid heat conduction and radiation heat conduction of the material, and is expected to prepare high-efficiency ceramic nanofiber thermal insulation material with both low gas-solid heat conduction and high infrared shielding performance. The preparation method of the ceramic nanofiber material mainly comprises a hydrothermal synthesis method, a sol-gel method, a spinning method, a solid-liquid gas phase method, an electrostatic spinning method and the like, wherein the electrostatic spinning method has the advantages of simple manufacturing device, wide range of spinnable raw materials, good adjustability of fiber structure and the like, and is one of the main technologies for preparing the ceramic nanofiber material at present.
Materials Letters 62(2008)470-472, ACS Applied Materials & Interfaces 2(2010) 2689-2693, ACSR-Advances in Complex Science Research 39(2015)1838-1841, and ACSR-Advances in Complex Science Research 35(2015)957-963 all use manganese acetate tetrahydrate and lanthanum acetate hydrate as metal sources, polyvinyl alcohol as a polymer template, and the lanthanum manganate nanofiber is prepared by an electrostatic spinning technology and a high-temperature calcination method.
Bulletin of the Chinese Ceramic Society 27(2008)64-66, Journal of Japan University of Science and Technology (Natural Science Edition)25(2011)31-34, Journal of electronic Chemistry 727(2014) 21-26, Materials Science in Semiconductor Processing 41(2016) 364-.
Rare Metal Materials and Engineering 38(2009)1000-1002 reports that manganese nitrate and lanthanum nitrate are used as Metal sources, polyvinyl butyral is used as a high molecular polymer template, and lanthanum manganate nanofibers are obtained by utilizing an electrostatic spinning technology and a high-temperature calcination method; journal of Nanoparticle Research 20(2018)65 reports that lanthanum manganate/tin oxide composite nanofibers are prepared using an electrospinning technique and a high-temperature calcination method.
Blending lanthanum manganate particles with polyvinyl alcohol and electrospinning followed by high temperature calcination to remove the polymer template was reported in American Journal of Nanoscience and Nanotechnology 1(2013)65-69, New York Science Journal 6(2013) 101-.
Although the above documents utilize the electrospinning technology to prepare the lanthanum manganate nanofiber material, the content of inorganic components in the precursor solution is low due to the addition of a large amount of high molecular polymers in the precursor solution, so that the yield of calcined lanthanum manganate fibers is low, and the lanthanum manganate fibers are mainly formed by particle accumulation. In addition, the high molecular polymer in the precursor fiber is decomposed stably in the calcining process, so that the fiber continuity is poor, the single fiber defects are more, the obtained lanthanum manganate nanofiber membrane is generally brittle, the vibration resistance is poor in practical application, and the lanthanum manganate nanofiber membrane is not easy to machine and form. Therefore, how to develop a lanthanum manganate nanofiber membrane with good flexibility, excellent mechanical properties, low volume density, high yield and simple preparation process is a technical bottleneck to be solved in the current high-temperature narrow space heat insulation field.
Disclosure of Invention
The invention aims to provide a preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film, which solves the defects of thick diameter, large aperture between fibers, low porosity, poor high-temperature heat insulation property and the like of the existing ceramic micro fibers, and the prepared light thin flexible lanthanum manganate nanofiber heat insulation film has the advantages of small fiber diameter, small aperture, good flexibility and small volume density, so that the application requirement of the high-temperature narrow space heat insulation field on heat insulation materials can be met.
In order to achieve the purpose, the invention adopts the following technical scheme that the preparation method of the light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following steps:
step 1: sequentially adding manganese salt and lanthanum salt into a solvent, stirring for 10-30 min, adjusting the pH value of the solution to 9-12, then adding a peptizing agent, continuously stirring for 10-90 min, and finally adding a silane coupling agent, stirring and mixing for 10-60 min to obtain a precursor solution;
wherein the molar ratio of the manganese salt to the lanthanum salt is 1: 1; the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g: 10-75 mL; the molar ratio of the manganese salt to the peptizing agent is 1: 0.01-0.06; the molar ratio of the manganese salt to the silane coupling agent is 1: 0.05-0.2.
Step 2: preparing a precursor nanofiber membrane from the precursor solution by adopting an electrostatic spinning technology;
and step 3: and calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane.
As a preferred technical scheme:
according to the preparation method of the light thin flexible lanthanum manganate nanofiber heat insulation film, in the step 1, the manganese salt is one of manganese acetate tetrahydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate or manganese sulfate monohydrate;
the lanthanum salt is one of lanthanum nitrate hexahydrate, lanthanum chloride hexahydrate, lanthanum acetate hydrate or lanthanum sulfate;
the solvent is one of water, methanol, ethanol, glycol or N, N-dimethylformamide;
the peptizing agent is one of hydrochloric acid, nitric acid, perchloric acid or acetic acid;
the silane coupling agent is one of methyltrichlorosilane, methyltriethoxysilane, 3-chloropropyltrichlorosilane, 3-chloropropyltriethoxysilane, (3-mercaptopropyl) triethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane or vinyltrimethoxysilane.
According to the preparation method of the light thin flexible lanthanum manganate nanofiber heat insulation film, the electrostatic spinning process parameters in the step 2 are as follows: under the conditions that the spinning environment temperature is 10-55 ℃ and the relative humidity is 10-75%, the precursor solution is filled at the flow rate of 0.1-10 mL/h, a spinning nozzle is connected to a high-voltage power supply of 10-65 kV for spinning, and the distance between a receiving device and the spinning nozzle is 5-40 cm; the receiving device is a metal roller or a metal flat plate.
According to the preparation method of the light thin flexible lanthanum manganate nanofiber heat insulation film, the calcination process parameters in the step 3 are as follows: gradually increasing the temperature from the room temperature to 400-1000 ℃, wherein the temperature increasing speed is 0.5-10 ℃/min, and the temperature is kept for 0-720 min at the highest calcining temperature; further, the calcination temperature is kept at the highest calcination temperature for 60-600 min.
The light thin flexible lanthanum manganate prepared by the method provided by the inventionCompared with the traditional ceramic micron fiber heat insulation material, the flexible lanthanum manganate nanofiber heat insulation film has the characteristics of small fiber diameter, small aperture, good flexibility, small volume density and the like, so that the thickness and the weight are remarkably reduced under the condition that the heat insulation effect of the ceramic micron fiber is achieved, and the application requirement of the high-temperature narrow space heat insulation field on the heat insulation material can be met. The volume density of the flexible lanthanum manganate nanofiber heat insulation film is 50-120 kg/m3The thermal conductivity coefficient at normal temperature is 0.023-0.027W/(mK), and the thermal conductivity coefficient at 1100 ℃ is 0.1-0.12W/(mK).
According to the light thin flexible lanthanum manganate nanofiber heat insulation film, the average fiber diameter of the flexible lanthanum manganate nanofiber film is 30-600 nm, the relative standard deviation is 0.1-5%, the size of internal crystal grains is 2-40 nm, the tensile strength of the lanthanum manganate nanofiber film is 5-12 MPa, and the softness of the fiber film is 10-80 mN.
The invention principle is as follows:
the method comprises the first step of sequentially adding manganese salt and lanthanum salt into a solvent, rapidly releasing manganese ions and lanthanum ions from the manganese salt and the lanthanum salt through ionization, adjusting the pH value of the solution to 9-12 after stirring for 10-30 min, generating manganese hydroxide colloidal particles and lanthanum hydroxide colloidal particles through the combined action of the manganese ions, the lanthanum ions and hydroxyl ions, and rapidly coagulating the manganese hydroxide colloidal particles and the lanthanum hydroxide colloidal particles at the bottom of the solution. And then, adding a peptizing agent into the solution, and continuously stirring for 10-90 min, wherein the peptizing agent is adsorbed on the surfaces of the manganese hydroxide colloidal particles and the lanthanum hydroxide colloidal particles to form an electric double layer structure, so that electrostatic repulsion is generated among the colloidal particles and the peptizing agent is dispersed in the solution. Meanwhile, the colloidal particles of manganese hydroxide and lanthanum hydroxide are mainly composed of chain molecular chains. On the basis, a silane coupling agent is added and stirred for 10-60 min to be uniformly mixed, the silane coupling agent is hydrolyzed and polymerized under the action of a peptizing agent to form a reticular molecular chain structure, and the reticular molecular chain structure is mutually bonded with the manganese hydroxide and lanthanum hydroxide micelles through electrostatic interaction and hydrogen bond interaction to form a chain-type and reticular molecular chain structure which is mutually and alternately entangled, so that the uniformity and the stability of the precursor solution are remarkably improved. The invention effectively improves the spinnability of the precursor solution without adding high molecular polymer as the spinning aid. And then, preparing the precursor solution into a precursor nanofiber membrane by adopting an electrostatic spinning technology. And finally, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane.
Has the advantages that:
(1) under the condition that no high molecular polymer is added as a spinning aid, the chain molecular chains of manganese hydroxide colloidal particles and lanthanum hydroxide colloidal particles and the reticular molecular chains of hydrolytic polymerization of a silane coupling agent are interlaced and intertwined, so that the spinnability of a precursor solution is effectively improved, and the influence of unstable decomposition of the polymer on the stability of a fiber structure in the subsequent calcining process is avoided;
(2) according to the preparation method of the light thin flexible lanthanum manganate nanofiber heat insulation film, provided by the invention, the ceramic material with high infrared reflectivity is directly prepared into the flexible ceramic nanofiber material by using an electrostatic spinning method, the infrared transmission performance of the material is effectively reduced on the premise of keeping the low gas-solid thermal conductivity of the ceramic nanofiber material, and reference can be provided for the design of a high-efficiency ceramic nanofiber heat insulation material.
(3) The light thin flexible lanthanum manganate nanofiber heat insulation film obtained by the method provided by the invention has the excellent characteristics of small fiber diameter, small inter-fiber pore size, good flexibility, low volume density and the like, effectively solves the defects of thick diameter, large inter-fiber pore size, low porosity, poor high-temperature heat insulation and the like commonly existing in ceramic microfiber, and can meet the application requirements of the high-temperature narrow space heat insulation field on heat insulation materials.
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
A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following specific steps:
step 1, sequentially adding manganese acetate tetrahydrate and lanthanum nitrate hexahydrate into solvent water, stirring for 15min, adjusting the pH value of the solution to 10, then adding a peptizing agent hydrochloric acid, continuously stirring for 60min, finally adding a silane coupling agent 3-chloropropyltrichlorosilane, stirring for 40min, and uniformly mixing to obtain a uniform and stable precursor solution. Wherein the molar ratio of the manganese salt, the lanthanum salt, the peptizing agent and the silane coupling agent in the precursor solution is 1:1:0.04:0.14, and the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g:40 mL;
and 2, spinning the precursor solution into a precursor fiber membrane by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 24 ℃, the relative humidity is 52%, the perfusion speed is 1mL/h, the voltage is 43kV, the distance between a receiving device and a spinneret is 26cm, and the receiving device is a metal roller;
and 3, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane, wherein the calcining parameters are as follows: the temperature is gradually increased from room temperature to 600 ℃, the temperature increasing speed is 2 ℃/min, and the temperature is kept for 120min at the highest calcining temperature, so that the flexible lanthanum manganate nanofiber membrane is obtained.
The prepared flexible lanthanum manganate nanofiber membrane is subjected to performance test, and the volume density of the flexible lanthanum manganate nanofiber heat insulation membrane is 80kg/m3(according to the national standard GB/T17911-. According to GB/T5990-. The average diameter of the lanthanum manganate nanofiber is 340nm, the relative standard deviation of the diameters is 2.8% (measured by reference to national standard GB/T34520.2-2017 part 2 of continuous silicon carbide fiber testing method: single fiber diameter), the grain size of lanthanum manganate inside the fiber is 30nm (measured by GB/T23413-Measured) and a softness of 63mN (measured according to national standard GB/T8942-2016 paper softness measurement).
Example 2
A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following specific steps:
step 1, sequentially adding manganese nitrate tetrahydrate and lanthanum nitrate hexahydrate into a mixed solvent ethanol/N, N-dimethylformamide, stirring for 30min, adjusting the pH of the solution to 9.5, then adding a peptizing agent nitric acid, continuously stirring for 30min, finally adding a silane coupling agent (3-mercaptopropyl) triethoxysilane, stirring for 50min, and uniformly mixing to obtain a uniform and stable precursor solution. Wherein the molar ratio of the manganese salt, the lanthanum salt, the peptizing agent and the silane coupling agent in the precursor solution is 1:1:0.03:0.16, the ratio of the total mass of the manganese salt and the lanthanum salt to the mixed solvent is 10g:40mL, and the volume ratio of the ethanol to the N, N-dimethylformamide is 1: 1;
and 2, spinning the precursor solution into a precursor fiber membrane by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 27 ℃, the relative humidity is 41%, the perfusion speed is 2mL/h, the voltage is 54kV, the distance between a receiving device and a spinning nozzle is 28cm, and the receiving device is a metal roller;
and 3, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane, wherein the calcining parameters are as follows: the temperature is gradually increased from room temperature to 700 ℃, the temperature increasing speed is 1 ℃/min, and the temperature is kept for 60min at the highest calcining temperature, so that the flexible lanthanum manganate nanofiber membrane is obtained.
The flexible lanthanum manganate nanofiber heat-insulating film had a bulk density of 90kg/m as measured by the same method as in example 13The thermal conductivity at room temperature was 0.024W/(mK), and the thermal conductivity at 1100 ℃ was 0.118W/(mK). The average diameter of the lanthanum manganate nanofiber is 420nm, the relative standard deviation of the diameters is 3.5%, the grain size of lanthanum manganate inside the fiber is 26nm, the tensile strength of a lanthanum manganate nanofiber membrane is 7MPa, and the softness is 39 mN.
Example 3
A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following specific steps:
step 1, sequentially adding manganese chloride tetrahydrate and lanthanum nitrate hexahydrate into a mixed solvent methanol/N, N-dimethylformamide, stirring for 10min, adjusting the pH value of the solution to 11, then adding a peptizing agent perchloric acid, continuously stirring for 40min, finally adding a silane coupling agent gamma-aminopropyl methyl diethoxy silane, stirring for 30min, and uniformly mixing to obtain a uniform and stable precursor solution. Wherein the molar ratio of the manganese salt, the lanthanum salt, the peptizing agent and the silane coupling agent in the precursor solution is 1:1:0.03:0.15, and the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g:50 mL;
and 2, spinning the precursor solution into a precursor fiber membrane by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 24 ℃, the relative humidity is 52%, the perfusion speed is 1mL/h, the voltage is 43kV, the distance between the receiving device and the spinneret is 26cm, and the receiving device is a metal flat plate;
and 3, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane, wherein the calcining parameters are as follows: the temperature is gradually increased to 650 ℃ from the room temperature, the temperature rising speed is 2.5 ℃/min, and the temperature is kept for 360min at the highest calcining temperature, so that the flexible lanthanum manganate nanofiber membrane is obtained.
The flexible lanthanum manganate nanofiber heat-insulating film had a bulk density of 100kg/m as measured by the same method as in example 13The thermal conductivity at room temperature was 0.026W/(m.K), and the thermal conductivity at 1100 ℃ was 0.118W/(m.K). The average diameter of the lanthanum manganate nanofiber is 370nm, the relative standard deviation of the diameters is 2.3%, the grain size of lanthanum manganate inside the fiber is 35nm, the tensile strength of a lanthanum manganate nanofiber membrane is 10MPa, and the softness is 76 mN.
Example 4
A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following specific steps:
step 1, sequentially adding manganese sulfate monohydrate, manganese nitrate hexahydrate and lanthanum nitrate hexahydrate into a solvent N, N-dimethylformamide, stirring for 10min, adjusting the pH value of the solution to 11, then adding a peptizing agent acetic acid, continuously stirring for 45min, finally adding a silane coupling agent gamma-aminopropyltriethoxysilane, stirring for 30min, and uniformly mixing to obtain a uniform and stable precursor solution. Wherein the molar ratio of the manganese salt, the lanthanum salt, the peptizing agent and the silane coupling agent in the precursor solution is 1:1:0.025:0.12, and the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g:55 mL;
and 2, spinning the precursor solution into a precursor fiber membrane by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 28 ℃, the relative humidity is 45%, the perfusion speed is 5mL/h, the voltage is 60kV, the distance between a receiving device and a spinning nozzle is 23cm, and the receiving device is a metal roller;
and 3, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane, wherein the calcining parameters are as follows: the temperature is gradually increased to 800 ℃ from the room temperature, the temperature increasing speed is 5 ℃/min, and the temperature is kept for 540min at the highest calcining temperature, so that the flexible lanthanum manganate nanofiber membrane is obtained.
The volume density of the flexible lanthanum manganate nanofiber heat-insulating film was 80kg/m, as measured by the same method as in example 13The thermal conductivity at room temperature was 0.024W/(mK), and the thermal conductivity at 1100 ℃ was 0.115W/(mK). The average diameter of the lanthanum manganate nanofiber is 320nm, the relative standard deviation of the diameters is 2.4%, the grain size of lanthanum manganate inside the fiber is 29nm, the tensile strength of a lanthanum manganate nanofiber membrane is 11.6MPa, and the softness is 66 mN.
Example 5
A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following specific steps:
step 1, sequentially adding manganese acetate tetrahydrate and lanthanum chloride hexahydrate into a mixed solvent methanol/N, N-dimethylformamide, stirring for 20min, adjusting the pH value of the solution to 12, then adding a peptizing agent perchloric acid, continuously stirring for 20min, finally adding a silane coupling agent gamma-aminopropyltriethoxysilane, stirring for 40min, and uniformly mixing to obtain a uniform and stable precursor solution. Wherein the molar ratio of the manganese salt, the lanthanum salt, the peptizing agent and the silane coupling agent in the precursor solution is 1:1:0.035:0.15, the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g:30mL, and the volume ratio of the methanol to the N, N-dimethylformamide is 2: 1;
and 2, spinning the precursor solution into a precursor fiber membrane by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 22 ℃, the relative humidity is 35%, the perfusion speed is 3mL/h, the voltage is 40kV, the distance between a receiving device and a spinning nozzle is 21cm, and the receiving device is a metal roller;
and 3, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane, wherein the calcining parameters are as follows: the temperature is gradually increased to 650 ℃ from the room temperature, the temperature increasing speed is 1 ℃/min, and the temperature is kept for 240min at the highest calcining temperature, so that the flexible lanthanum manganate nanofiber membrane is obtained.
The volume density of the flexible lanthanum manganate nanofiber heat-insulating film was 78kg/m, as measured by the same method as in example 13The thermal conductivity at room temperature was 0.025W/(mK), and the thermal conductivity at 1100 ℃ was 0.116W/(mK). The average diameter of the lanthanum manganate nanofiber is 370nm, the relative standard deviation of the diameters is 3.9%, the grain size of lanthanum manganate inside the fiber is 37nm, the tensile strength of a lanthanum manganate nanofiber membrane is 7.5MPa, and the softness is 59 mN.
Example 6
A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film comprises the following specific steps:
step 1, sequentially adding manganese nitrate tetrahydrate and lanthanum chloride hexahydrate into solvent water, stirring for 30min, adjusting the pH value of the solution to 11, then adding a peptizing agent hydrochloric acid, continuously stirring for 30min, finally adding a silane coupling agent vinyl trimethoxy silane, stirring for 50min, and uniformly mixing to obtain a uniform and stable precursor solution. Wherein the molar ratio of the manganese salt, the lanthanum salt, the peptizing agent and the silane coupling agent in the precursor solution is 1:1:0.026:0.13, and the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g:45 mL;
and 2, spinning the precursor solution into a precursor fiber membrane by adopting an electrostatic spinning technology, wherein the electrostatic spinning process parameters are as follows: the environment temperature is 31 ℃, the relative humidity is 47%, the perfusion speed is 2mL/h, the voltage is 45kV, the distance between a receiving device and a spinning nozzle is 20cm, and the receiving device is a metal roller;
and 3, calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane, wherein the calcining parameters are as follows: the temperature is gradually increased from room temperature to 700 ℃, the temperature increasing speed is 2 ℃/min, and the temperature is kept for 270min at the highest calcining temperature, so that the flexible lanthanum manganate nanofiber membrane is obtained.
The volume density of the flexible lanthanum manganate nanofiber heat-insulating film was 86kg/m, as measured by the same method as in example 13The thermal conductivity at room temperature was 0.026W/(m.K), and the thermal conductivity at 1100 ℃ was 0.118W/(m.K). The average diameter of the lanthanum manganate nanofiber is 410nm, the relative standard deviation of the diameters is 3.7%, the grain size of lanthanum manganate inside the fiber is 35nm, the tensile strength of a lanthanum manganate nanofiber membrane is 8.5MPa, and the softness is 60 mN.
Examples 7 to 11
The preparation steps of examples 7 to 11 are the same as example 1, wherein the parameters of the precursor solution, the electrostatic spinning and calcining parameters, and the performance parameters of the flexible lanthanum manganate fiber membrane are shown in table 1. (note: stirring time 1 is the stirring time after the manganese salt and the lanthanum salt are added into the solvent, stirring time 2 is the stirring time after the peptizing agent is added, and stirring time 3 is the stirring time after the silane coupling agent is added)
TABLE 1
Claims (7)
1. A preparation method of a light thin flexible lanthanum manganate nanofiber heat insulation film is characterized by comprising the following steps:
step 1: sequentially adding manganese salt and lanthanum salt into a solvent, stirring for 10-30 min, adjusting the pH value of the solution to 9-12, then adding a peptizing agent, continuously stirring for 10-90 min, and finally adding a silane coupling agent, stirring and mixing for 10-60 min to obtain a precursor solution;
step 2: preparing a precursor nanofiber membrane from the precursor solution by adopting electrostatic spinning;
and step 3: and calcining the precursor nanofiber membrane in an air atmosphere to obtain the light thin flexible lanthanum manganate nanofiber heat insulation membrane.
2. The method for preparing the light-weight thin flexible lanthanum manganate nanofiber thermal insulation film as in claim 1, wherein in step 1, the manganese salt is one of manganese acetate tetrahydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate or manganese sulfate monohydrate;
the lanthanum salt is one of lanthanum nitrate hexahydrate, lanthanum chloride hexahydrate, lanthanum acetate hydrate or lanthanum sulfate;
the solvent is one of water, methanol, ethanol, glycol or N, N-dimethylformamide;
the peptizing agent is one of hydrochloric acid, nitric acid, perchloric acid or acetic acid;
the silane coupling agent is one of methyltrichlorosilane, methyltriethoxysilane, 3-chloropropyltrichlorosilane, 3-chloropropyltriethoxysilane, (3-mercaptopropyl) triethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltriethoxysilane or vinyltrimethoxysilane.
3. The method for preparing the light thin flexible lanthanum manganate nanofiber thermal insulation film as in claim 1, wherein in step 1, the molar ratio of manganese salt to lanthanum salt is 1: 1; the ratio of the total mass of the manganese salt and the lanthanum salt to the solvent is 10g: 10-75 mL; the molar ratio of the manganese salt to the peptizing agent is 1: 0.01-0.06; the molar ratio of the manganese salt to the silane coupling agent is 1: 0.05-0.2.
4. The preparation method of the light thin flexible lanthanum manganate nanofiber thermal insulation film as claimed in claim 1, wherein the electrostatic spinning process parameters in step 2 are as follows: under the conditions that the spinning environment temperature is 10-55 ℃ and the relative humidity is 10-75%, the precursor solution is filled at the flow rate of 0.1-10 mL/h, a spinning nozzle is connected to a high-voltage power supply of 10-65 kV for spinning, and the distance between a receiving device and the spinning nozzle is 5-40 cm; the receiving device is a metal roller or a metal flat plate.
5. The method for preparing the light thin flexible lanthanum manganate nanofiber thermal insulation film as claimed in claim 1, wherein the calcination process parameters in step 3 are as follows: gradually increasing the temperature from the room temperature to 400-1000 ℃, wherein the temperature increasing speed is 0.5-10 ℃/min, and the temperature is kept for 0-720 min at the highest calcining temperature.
6. The light thin flexible lanthanum manganate nanofiber thermal insulation film prepared by the method of any one of claims 1 to 5, wherein the volume density of the light thin flexible lanthanum manganate nanofiber thermal insulation film is 50-120 kg/m3The thermal conductivity coefficient at normal temperature is 0.023-0.027W/(mK), and the thermal conductivity coefficient at 1100 ℃ is 0.1-0.12W/(mK).
7. The light thin flexible lanthanum manganate nanofiber thermal insulation film as claimed in claim 6, wherein the average fiber diameter of the light thin flexible lanthanum manganate nanofiber thermal insulation film is 30-600 nm, the relative standard deviation is 0.1-5%, the internal crystal grain size is 2-40 nm, the tensile strength of the lanthanum manganate nanofiber film is 5-12 MPa, and the softness of the fiber film is 10-80 mN.
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