CN115418730A - Preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fiber - Google Patents
Preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fiber Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000835 fiber Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 42
- 238000009413 insulation Methods 0.000 title claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 53
- 238000009987 spinning Methods 0.000 claims abstract description 49
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 44
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 23
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000001523 electrospinning Methods 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 102220092852 rs754853086 Human genes 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 abstract description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002121 nanofiber Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000009975 flexible effect Effects 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 239000003605 opacifier Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- -1 titanium alkoxide Chemical class 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- 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
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- 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
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C01P2006/32—Thermal properties
Abstract
The invention discloses a preparation method of a silicon dioxide/titanium dioxide infrared heat insulation composite fiber, and belongs to the technical field of silicon dioxide heat insulation fibers. Taking ethyl orthosilicate as a silicon source, using oxalic acid as a catalyst for hydrolysis, and adding a template agent to prepare a spinnable silicon dioxide electrospinning precursor solution; adding a titanium source and a hydrolysis inhibitor thereof into a silicon dioxide electrospinning precursor by taking butyl titanate as the titanium source and acetylacetone as the butyl titanate hydrolysis inhibitor to prepare a composite precursor electrospinning solution; the silicon dioxide/titanium dioxide infrared heat-insulation composite fiber is obtained by utilizing electrostatic spinning equipment for spinning, and then is dried and calcined, is of a micron-sized structure, and has the characteristics of low infrared transmittance, good high-temperature stability, excellent flexibility and the like.
Description
Technical Field
The invention relates to the technical field of silicon dioxide heat insulation fibers, in particular to a preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fibers.
Background
Amorphous SiO 2 The thermal insulation material has a three-dimensional network structure with short-range order and long-range disorder, so that the thermal insulation material is endowed with extremely low intrinsic thermal conductivity, and has wide development prospect in the field of thermal insulation. However, siO 2 The inherent brittleness and lower mechanical strength of the material limits its further use to some extent. Compared with bulk materials, the one-dimensional nano material has room temperature superplasticity and extremely high Young modulus, and can endow the material withGood flexibility. Meanwhile, the sharply increased specific surface area of the nano material greatly enhances the scattering effect in the phonon propagation process, so that the thermal conductivity of the material is obviously reduced. Thus, novel SiO is prepared 2 The nano-fiber is used for heat insulation and solves the problem of the traditional SiO 2 Effective means of applying the defect. According to Stefan-Boltzmann law and Planck's law, near-infrared radiation is the predominant mode of heat transfer between objects at high temperatures, but pure SiO 2 Almost completely transparent to near infrared radiation of 1 to 8 μm. Thus, siO is improved 2 The infrared radiation resistance of the nanofiber membrane is a key link for expanding the application prospect at present.
Chinese patent publication No. CN106431186A discloses a fiber-loaded rutile TiO 2 Composite SiO 2 The invention discloses a preparation method of aerogel, which loads TiO on the surface of hydroxylated fiber by a dipping-pulling method 2 The rutile structure is obtained by high-temperature treatment of sol, and the method has the characteristics of simple operation, low cost, wide application prospect and the like, and the invention not only improves TiO 2 Uneven dispersion, improved mechanical property and thermal insulation property, however, tiO 2 Particles and SiO 2 The combination of (2) occurs only in a macroscopic scale, depends on the interfacial compatibility of the two, and is not beneficial to the exertion of the high-temperature stability of the material.
Chinese patent publication No. CN113957567A discloses a TiO 2 -SiO 2 The invention discloses a method for preparing precursor sol spinning solution and titanium-silicon composite oxide nano-fiber, which comprises the steps of taking titanium alkoxide as a raw material, synthesizing the precursor sol spinning solution of titanium with high spinnability by a sol-gel method, and then adding a certain amount of silicon alkoxide into the spinning solution to obtain stable TiO 2 -SiO 2 The precursor sol spinning solution can be used for obtaining the titanium-silicon composite oxide nano-fiber with good comprehensive performance through electrostatic spinning and heat treatment. The invention has the characteristics of good product flexibility, low production cost and the like, and the prepared composite fiber overcomes the defects of granular TiO 2 Dispersion in the fibers. But in preparation ofIn the process, the process of the reduced pressure concentration of the low carbon alcohol solution of the titanium alkoxide and the water exists, the experimental process is still relatively complex, and the industrial production cost is increased.
The invention discloses a flexible electroluminescent nanofiber based on titanium dioxide/silicon dioxide, which is prepared by taking tetrabutyl titanate, tetraethyl orthosilicate and Er nitrate as main raw materials, preparing a precursor solution, drying and calcining the precursor fiber obtained by electrostatic spinning to obtain the rare earth erbium-doped titanium dioxide/silicon dioxide composite nanofiber. Similarly, in the field of water pollution treatment, chinese patent publication No. CN107626287A discloses an electrospinning preparation method of an aminated nano titanium dioxide/silicon dioxide composite fiber membrane, which also accelerates the hydrolysis of tetraethoxysilane in the spinning process and shortens the spinning window of the precursor solution under the condition that acetic acid is used as a tetrabutyl titanate hydrolysis inhibitor.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of a silicon dioxide/titanium dioxide infrared heat insulation composite fiber, which has the advantages of stable structure, high temperature resistance, good mechanical property, low infrared heat conductivity, simple process and low cost.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a silicon dioxide/titanium dioxide infrared heat insulation composite fiber, which comprises the following steps:
1) Preparing a spinning precursor solution: uniformly mixing Tetraethoxysilane (TEOS) with water, adding a catalyst, and hydrolyzing to obtain a solution A; mixing butyl titanate (TBT), acetylacetone (AcAc) and absolute ethyl alcohol, adding the mixture into a mixed solution of a spinning aid and an organic solvent, and stirring to obtain a solution B; dropwise adding the solution A into the solution B under stirring to prepare a spinning precursor solution;
2) Performing electrostatic spinning on the spinning precursor solution to prepare a precursor fiber film;
3) And drying, calcining and cooling the precursor fiber film to obtain the silicon dioxide/titanium dioxide infrared heat-insulating composite fiber.
Further, in the step 1), tetraethoxysilane (TEOS) and water are mixed according to the mass ratio of 1:1 and mixing.
Further, the mass ratio of the ethyl orthosilicate, the butyl titanate and the acetylacetone in the step 1) is 1: (0.04-0.24): 0.02.
further, the mass ratio of the solution A to the solution B in the step 1) is 1:1.
further, in the step 1), the catalyst is oxalic acid, the spinning aid is polyvinylpyrrolidone (PVP), and the organic solvent is N, N-Dimethylformamide (DMF).
Further, the hydrolysis time of the step 1) is 8-12 h.
Further, the mass ratio of the ethyl orthosilicate and the catalyst in the step 1) is 1: (0.02-0.04).
Further, the electrostatic spinning process parameters in step 2) are as follows: A21G spinning needle is selected, the positive pole of a direct-current high-voltage power supply is connected with the spinning needle, the voltage is 15-18 kV, the negative pole voltage is 2.5kV, the liquid inlet speed is (1-1.5) mL/h, and the spinning distance is 15-20 cm.
Further, the heating rate of the drying process in the step 3) is less than 10 ℃/min, and the drying time is 5-8 h.
Further, in the step 3), the temperature rise rate in the calcining process is less than 5 ℃/min, the calcining temperature is 600-900 ℃, and the temperature is kept for 1-2 h.
The invention discloses the following technical effects:
1. the invention takes the butyl titanate as the titanium source and obtains the rutile type titanium dioxide with strong refractive index by heat treatment. The in-situ composite silicon dioxide/titanium dioxide fiber is prepared by co-precursor electrostatic spinning, the crosslinking of two oxides on a molecular scale is realized, the damage of the traditional opacifier particles to the continuity of the fiber is overcome, the mechanical property of the composite fiber is effectively improved, the heat insulation effect of a pure silicon dioxide heat insulation material in a high-temperature environment is improved, and an important reference significance is provided for developing a high-efficiency flexible heat insulation film at a high temperature.
2. The invention abandons the scheme of adding acetic acid to generate complex compound in the prior art on solving the problem of butyl titanate hydrolysis, and proposes that acetylacetone is directly adopted as hydrolysis inhibitor, thereby avoiding the damage of acidic environment to the stability of the silica gel system, effectively reducing irrelevant variables influencing the spinning effect, prolonging the spinning window time to more than 10 days, and effectively simplifying the preparation process.
3. The diameter of the silicon dioxide/titanium dioxide composite fiber prepared by the invention is 1-2 μm, the fiber film meets the requirement of practical application, the final thermal decomposition temperature is 530 ℃, the mass loss in the whole process is 80%, and the TiO content is 2 The phase transition temperature is 803 ℃. The thermal conductivity coefficient at normal temperature is 0.046W/(m.K), the thermal conductivity coefficient at 500 ℃ is 0.0899W/(m.K), and the heat insulation performance at high temperature is obviously superior to that of common SiO under the high temperature environment 2 A fibrous membrane.
4. The method has the advantages of simple process, low cost and easy control of preparation conditions, has more obvious industrialization potential compared with the existing preparation method of the composite fiber, and the prepared silicon dioxide/titanium dioxide composite fiber has excellent infrared shielding performance and can be widely applied to the field of high-temperature heat insulation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a photograph of a silica/titania infrared thermal insulation composite fiber according to example 1 of the present invention, wherein (a) is a photograph of macro morphology of a calcined sample, and (b) is a photograph showing flexibility of the sample;
FIG. 2 is a scanning electron micrograph of a silica/titania infrared thermal insulation composite fiber according to example 1 of the present invention;
FIG. 3 is a thermogravimetric-differential thermogram of a silica/titania infrared thermal insulation composite fiber decomposition process in example 2 of the present invention;
FIG. 4 is a graph of the infrared transmittance of the silica/titania infrared thermal insulation composite fibers of examples 1 to 3 of the present invention;
FIG. 5 is a Fourier infrared spectrum of a silica/titania infrared thermal insulation composite fiber according to example 2 of the present invention;
FIG. 6 is a tensile stress-strain curve of a silica/titania infrared thermal insulation composite fiber according to example 3 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated or intervening value in a stated range, and every other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The embodiment of the invention provides a preparation method of a silicon dioxide/titanium dioxide infrared heat insulation composite fiber, which comprises the following steps:
1) Preparing a spinning precursor solution: uniformly mixing Tetraethoxysilane (TEOS) with water (preferably deionized water), adding a catalyst, and hydrolyzing to obtain a solution A; mixing butyl titanate (TBT), acetylacetone (AcAc) and absolute ethyl alcohol, adding the mixture into a mixed solution of a spinning aid and an organic solvent, and stirring to obtain a solution B; dropwise adding the solution A into the solution B under stirring to prepare a spinning precursor solution;
2) Carrying out electrostatic spinning on the spinning precursor solution to prepare a precursor fiber film;
3) And drying, calcining and cooling the precursor fiber film (preferably, cooling the precursor fiber film to room temperature along with a furnace) to obtain the silica/titanium dioxide infrared heat-insulating composite fiber.
In the embodiment of the invention, step 1) of Tetraethoxysilane (TEOS) and water are mixed according to the mass ratio of 1:1 and mixing.
In the embodiment of the invention, the mass ratio of the ethyl orthosilicate, the butyl titanate and the acetylacetone in the step 1) is 1: (0.04-0.24): 0.02.
in the embodiment of the invention, the mass ratio of the solution A to the solution B in the step 1) is 1:1.
in the embodiment of the invention, the catalyst in the step 1) is oxalic acid, the spinning aid is polyvinylpyrrolidone (PVP), the organic solvent is N, N-Dimethylformamide (DMF), acetylacetone is used as a hydrolysis inhibitor to prevent butyl titanate from being hydrolyzed into TiO (OH) 2 Gels, precursors lose spinnability. The acetylacetone hydrolysis inhibitor maintains the near-neutral environment of the spinning solution, and the window time of the spinning of the precursor solution can be up toFor more than 10 days.
In the embodiment of the invention, the hydrolysis time of the step 1) is 8-12 h.
In the embodiment of the invention, the mass ratio of the ethyl orthosilicate and the catalyst in the step 1) is 1: (0.02-0.04).
In the embodiment of the invention, in the mixing process of butyl titanate (TBT), acetylacetone (AcAc) and absolute ethyl alcohol, acetylacetone and butyl titanate are sequentially added into the absolute ethyl alcohol drop by drop, and the mass fraction of the spinning aid in the precursor solution is 25-31%.
In the embodiment of the present invention, the electrostatic spinning process parameters in step 2) are as follows: A21G spinning needle is selected, the positive pole of a direct-current high-voltage power supply is connected with the spinning needle, the voltage is 15-18 kV, the negative pole voltage is 2.5kV, the liquid inlet speed is (1-1.5) mL/h, and the spinning distance is 15-20 cm. The environmental humidity in the electrostatic spinning process is kept at 25 percent, the needle head blockage caused by too fast solvent volatilization can be prevented, and the continuity of the fiber is improved. And collecting the precursor fiber film obtained by electrostatic spinning by using an aluminum foil, and fixing the precursor fiber film on a roller collector at the rotating speed of 20-40 r/min.
In the embodiment of the invention, the heating rate of the drying process in the step 3) is less than 10 ℃/min, the drying time is 5-8 h, and the fiber stress concentration and the macroscopic integrity damage caused by too fast early-stage drying are prevented.
In the embodiment of the invention, the temperature rise rate in the calcining process in the step 3) is less than 5 ℃/min, the calcining temperature is 600-900 ℃, and the temperature is kept for 1-2 h.
In the embodiment of the present invention, room temperature means 25 ± 2 ℃.
The method takes tetraethoxysilane as a silicon source, oxalic acid as a catalyst for hydrolysis, and a template agent is added to prepare a spinnable silicon dioxide electrospinning precursor solution; adding a titanium source and a hydrolysis inhibitor thereof into a silicon dioxide electrospinning precursor by taking butyl titanate as the titanium source and acetylacetone as the butyl titanate hydrolysis inhibitor to prepare a composite precursor electrospinning solution; the method has the advantages that the electrostatic spinning equipment is utilized for spinning, then the silicon dioxide/titanium dioxide infrared heat insulation composite fiber is obtained through drying and calcining, the prepared silicon dioxide/titanium dioxide infrared heat insulation composite fiber is of a micron-sized structure and has the characteristics of low infrared transmittance, good high-temperature stability, excellent flexibility and the like, the preparation process is simple, the light screening agent is endowed with a better dispersion effect through in-situ doping, the mechanical property of the fiber is optimized, the operation of the whole process is simple, and the potential of large-scale industrial production is realized.
Example 1
A preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fiber comprises the following steps:
1) 5g of tetraethoxysilane and deionized water with equal mass are uniformly mixed, 0.1g of oxalic acid is added as a catalyst, and the mixture is magnetically stirred for 12 hours to obtain a solution A. Sequentially adding acetylacetone, absolute ethyl alcohol and butyl titanate into a mixed solution of a spinning assistant (polyvinylpyrrolidone) and an organic solvent (N, N-dimethylformamide), magnetically stirring for 6 hours at room temperature, and recording as a solution B, wherein the polyvinylpyrrolidone: n, N-dimethylformamide: acetylacetone: anhydrous ethanol: butyl titanate =5g:5g:0.1g:1.5g:0.8g. And dropwise adding the solution A into the solution B to obtain spinning precursor solution.
2) Carrying out electrostatic spinning on the spinning precursor solution, wherein the spinning parameters are as follows: at room temperature, the anode voltage is 15kV, the cathode voltage is 2.5kV, the distance between a stainless steel needle and a receiver is 18cm, the flow rate of a precursor liquid is 1mL/h, a precursor fiber membrane obtained by electrostatic spinning is collected by an aluminum foil and fixed on a roller collector at the rotating speed of 30r/min;
3) Drying the precursor fiber membrane prepared by electrospinning in the step 2) at 50 ℃ for 8h, placing the dried precursor fiber membrane in an intelligent temperature-controlled box type resistance furnace, heating to 900 ℃ at the speed of 1 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace.
Example 2
A preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fiber comprises the following steps:
1) 5g of tetraethoxysilane and deionized water with equal mass are uniformly mixed, 0.15g of oxalic acid is added as a catalyst, and the mixture is magnetically stirred for 8 hours to obtain a solution A. Sequentially adding acetylacetone, absolute ethyl alcohol and butyl titanate into a mixed solution of a spinning assistant (polyvinylpyrrolidone) and an organic solvent (N, N-dimethylformamide), magnetically stirring for 4 hours at room temperature, and recording as a solution B, wherein the polyvinylpyrrolidone: n, N-dimethylformamide: acetylacetone: anhydrous ethanol: butyl titanate =5g:5g:0.15g:1.5g:1.2g. And dropwise adding the solution A into the solution B to obtain a spinning precursor solution.
2) Carrying out electrostatic spinning on the spinning precursor solution, wherein the spinning parameters are as follows: at room temperature, the voltage of an anode is 15kV, the voltage of a cathode is 2.5kV, a stainless steel needle is 21G, the distance between the needle and a receiver is 15cm, the flow rate of a precursor liquid is 1.2mL/h, a precursor fiber film obtained by electrostatic spinning is collected by an aluminum foil and fixed on a roller collector at the rotating speed of 30r/min;
3) Drying the precursor fiber membrane prepared by electrospinning in the step 2) at 50 ℃ for 6h, placing the dried precursor fiber membrane in an intelligent temperature-controlled box type resistance furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 1h, and cooling to room temperature along with the furnace.
Example 3
A preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fiber comprises the following steps:
1) Uniformly mixing 20g of tetraethoxysilane with deionized water with equal mass, adding 0.4g of oxalic acid serving as a catalyst, and magnetically stirring for 12 hours to obtain a solution A. Sequentially adding acetylacetone, absolute ethyl alcohol and butyl titanate into a mixed solution of a spinning assistant (polyvinylpyrrolidone) and an organic solvent (N, N-dimethylformamide), magnetically stirring for 4 hours at room temperature, and recording as a solution B, wherein the polyvinylpyrrolidone: n, N-dimethylformamide: acetylacetone: anhydrous ethanol: butyl titanate =20g:20g:0.4g:6g:6.4g. And dropwise adding the solution A into the solution B to obtain spinning precursor solution.
2) Carrying out electrostatic spinning on the spinning precursor solution, wherein the spinning parameters are as follows: at room temperature, the voltage of an anode is 15kV, the voltage of a cathode is 2.5kV, a stainless steel needle of 21G is used, the distance between the needle and a receiver is 20cm, the flow rate of a precursor liquid is 1.5mL/h, a precursor fiber film obtained by electrostatic spinning is collected by an aluminum foil and fixed on a roller collector at the rotating speed of 30r/min;
3) Drying the precursor fiber membrane prepared by electrospinning in the step 2) at 60 ℃ for 5h, placing the dried precursor fiber membrane in an intelligent temperature-controlled box type resistance furnace, heating to 900 ℃ at the speed of 2 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace.
FIG. 1 is a photograph of the silica/titania infrared thermal insulation composite fiber according to example 1 of the present invention (where (a) is a macro morphology photograph of the calcined sample, and (b) is a flexible property display result of the sample), and it can be seen from FIG. 1 that: the fiber is white in macroscopical view, can keep a complete membrane structure and has good flexibility.
FIG. 2 is a scanning electron micrograph of the silica/titania infrared thermal insulation composite fiber according to example 1 of the present invention, and it can be seen from FIG. 2 that: the fiber has good appearance in microcosmic aspect, uniform diameter, good continuity, smooth surface and no adhesion.
FIG. 3 is a thermogravimetric-differential thermogram of the decomposition process of the silica/titania infrared thermal insulation composite fiber in example 2 of the present invention, and it can be seen from FIG. 3 that: the final thermal decomposition temperature of the precursor fiber organic matter is 530 ℃, and the fiber sample quality is stable after the temperature is exceeded, so that a pure inorganic compound is obtained.
FIG. 4 is a graph of the infrared transmittance of the silica/titania infrared thermal insulation composite fibers of examples 1 to 3 of the present invention, as can be seen from FIG. 4: doped TiO 2 2 After the opacifier, the fiber obtains higher infrared shielding capability, the infrared transmittance can reach 50% at the lowest, meanwhile, the calcination temperature and the opacifier content influence the infrared shielding effect of the fiber, and example 3 shows better infrared shielding capability than examples 1 and 2.
FIG. 5 is a Fourier infrared spectrum of the silica/titania infrared thermal insulation composite fiber of example 2 of the present invention, and it can be seen from FIG. 5 that: the product is 1000-1250 cm -1 The strong absorption broad peak existing in the range and 798cm -1 The nearby absorption peaks belong to the antisymmetric and symmetric stretching vibration peaks of Si-O-Si respectively, and the product is at 427cm -1 TiO with rutile structure nearby 2 The characteristic vibration band of the medium Ti-O bond evidences that TiO is present at this temperature 2 A crystalline phase transition has occurred. The product is at 950cm -1 A distinct absorption peak appears, which is the stretching vibration peak of Ti-OH and Ti-O-Si bonds, and indicates the SiO in the composite fiber 2 And TiO 2 Has generated a keyAnd (4) performing combined action.
FIG. 6 is a tensile stress-strain curve of the silica/titania infrared thermal insulation composite fiber in example 3 of the present invention, and it can be seen from FIG. 6 that: the fiber can still maintain certain strength after being calcined, and the tensile strength reaches 3.09MPa, because the amorphous silicon dioxide micro-nano fiber used as the matrix has good mechanical property.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of silicon dioxide/titanium dioxide infrared heat insulation composite fiber is characterized by comprising the following steps:
1) Preparing a spinning precursor solution: uniformly mixing ethyl orthosilicate and water, adding a catalyst, and hydrolyzing to obtain a solution A; mixing butyl titanate, acetylacetone and absolute ethyl alcohol, adding the mixture into a mixed solution of a spinning aid and an organic solvent, and stirring to obtain a solution B; dropwise adding the solution A into the solution B under stirring to prepare a spinning precursor solution;
2) Carrying out electrostatic spinning on the spinning precursor solution to prepare a precursor fiber film;
3) And drying, calcining and cooling the precursor fiber film to obtain the silicon dioxide/titanium dioxide infrared heat-insulating composite fiber.
2. The preparation method according to claim 1, wherein the weight ratio of the ethyl orthosilicate in the step 1) to the water is 1:1 and mixing.
3. The preparation method according to claim 1, wherein the mass ratio of the ethyl orthosilicate, the butyl titanate and the acetylacetone in the step 1) is 1: (0.04-0.24): 0.02.
4. the preparation method according to claim 1, wherein the mass ratio of the solution A to the solution B in the step 1) is 1:1.
5. the preparation method according to claim 1, wherein the catalyst in step 1) is oxalic acid, the spinning aid is polyvinylpyrrolidone, and the organic solvent is N, N-dimethylformamide.
6. The preparation method according to claim 1, wherein the hydrolysis time in step 1) is 8-12 h.
7. The preparation method according to claim 1, wherein the mass ratio of the ethyl orthosilicate to the catalyst in the step 1) is 1: (0.02-0.04).
8. The method according to claim 1, wherein the parameters of the electrospinning process in the step 2) are as follows: A21G spinning needle is selected, the positive pole of a direct-current high-voltage power supply is connected with the spinning needle, the voltage is 15-18 kV, the negative pole voltage is 2.5kV, the liquid inlet speed is (1-1.5) mL/h, and the spinning distance is 15-20 cm.
9. The preparation method according to claim 1, wherein the temperature rise rate in the drying process in the step 3) is less than 10 ℃/min, and the drying time is 5-8 h.
10. The preparation method of claim 1, wherein the temperature rise rate in the calcination process in the step 3) is less than 5 ℃/min, the calcination temperature is 600-900 ℃, and the temperature is kept for 1-2 h.
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