CN115491791B - Preparation method of silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber - Google Patents
Preparation method of silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber Download PDFInfo
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- CN115491791B CN115491791B CN202211200748.7A CN202211200748A CN115491791B CN 115491791 B CN115491791 B CN 115491791B CN 202211200748 A CN202211200748 A CN 202211200748A CN 115491791 B CN115491791 B CN 115491791B
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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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
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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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
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Abstract
The invention discloses a preparation method of a silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber, and belongs to the technical field of silicon dioxide heat insulation fibers. According to the invention, ethyl orthosilicate is used as a silicon source, ethanol is used as a solvent, and oxalic acid is used as a catalyst to prepare ethyl orthosilicate hydrolysate; preparing cesium tungsten bronze by using tungsten powder as a tungsten source and cesium chloride as a cesium source and adopting a sol-gel method; preparing the two into spinning precursors according to a proportion, and finally obtaining the composite fiber by electrostatic spinning and subsequent heat treatment. The method has simple process, the obtained fiber diameter is in a micrometer scale, and the fiber has good flexibility and thermal stability, so that the average near infrared absorbance is improved to 1.5, and the near infrared light can be effectively shielded; the tensile strength reaches 2.25MPa, and has higher application value and industrial production potential.
Description
Technical Field
The invention relates to the technical field of silicon dioxide heat-insulating fibers, in particular to a preparation method of a silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber.
Background
The silicon dioxide micro-nano fiber has stable property, low heat conductivity coefficient and flexibilityGood and the like, and is highly valued in the field of heat insulation. It has been pointed out that SiO 2 Near infrared light (wavelength 780-2500 nm) is almost completely transmitted as a main heat source in solar radiation, which causes energy to be concentrated inside the material, and the temperature is sharply increased. Thus, siO is improved 2 The ability of micro-nanofiber membranes to shield near infrared radiation is an important topic of current insulation research. Traditional infrared opacifier TiO 2 Composite SiO 2 Although the micro-nano fiber has a certain effect on shielding solar heat energy, the traditional shading material has a short plate in the aspect of blocking high-energy short-wave infrared rays.
The invention discloses a preparation method of fibrous cesium tungsten bronze nano powder, which is characterized in that ammonium paratungstate, thiourea, a pH value regulator, a reducing agent, a cesium source and water are mixed and subjected to hydrothermal reduction reaction to obtain the high-length-diameter-ratio cesium tungsten bronze nano powder with the length of 3-10 mu m and the diameter of 25-70 nm, and the preparation method has the advantages of simple synthesis method, good near infrared shielding performance and the like, and the fibrous near infrared shielding performance of the high-length-diameter-ratio cesium tungsten bronze nano powder is improved by 9% -15% compared with that of one-dimensional nanometer short rod-shaped cesium tungsten bronze nano powder. However, the powdery cesium tungsten bronze fiber is difficult to exert the application value, and still needs to be deeply explored in engineering.
The Chinese patent with publication number of CN110067038A discloses a preparation method of nano intelligent fiber for heat storage, which takes polyvinyl butyral doped with cesium tungsten bronze as a shell layer, n-octadecane as a core layer, and prepares core-shell structure nano intelligent fiber with cesium tungsten bronze loaded on the shell layer by a coaxial electrostatic spinning method. However, parameters of the core-shell structure prepared by coaxial electrospinning are difficult to control, the process stability is insufficient, and large-scale production cannot be realized in the industrial field.
Disclosure of Invention
The invention aims to overcome the short plates existing in the technology and provide a preparation method of silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber which has stable structure, excellent mechanical property and certain industrial potential.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a preparation method of a silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber, which comprises the following steps:
1) Preparing an electrostatic spinning precursor: uniformly mixing ethyl orthosilicate with absolute ethyl alcohol, adding oxalic acid, and hydrolyzing to prepare ethyl orthosilicate hydrolysate; adding tungsten (W) powder into hydrogen peroxide (H) 2 O 2 ) Filtering after stirring, heating the filtrate in water bath to obtain a pale yellow solution, adding CsCl powder into the pale yellow solution, and stirring to obtain sol A; uniformly mixing the sol A with the tetraethoxysilane hydrolysate, and adding an organic branched salt into the mixed solution to adjust the conductivity of the spinning precursor solution so as to obtain an electrospinning precursor solution;
2) Controlling the environment temperature to be room temperature, and carrying out electrostatic spinning by utilizing the electrospinning precursor solution to obtain a hybrid fiber membrane;
3) And drying the hybrid fiber membrane, and performing heat treatment to obtain the silicon dioxide/cesium tungsten bronze near infrared shielding composite fiber.
Further, in the step 1), the mass ratio of the tetraethoxysilane, the absolute ethyl alcohol and the oxalic acid is 1:0.5: (0.05-0.1), and the hydrolysis time is 10-12 h.
Further, the mass ratio of the tungsten powder to the tetraethoxysilane in the step 1) is 1:50.
further, after the tungsten powder is added in the step 1), the stirring time is 3-5 h.
Further, the water bath temperature in the step 1) is 80-95 ℃ and the heating time is 4.5-5.5 h.
Further, step 1) ensures that the atomic coefficient ratio n (Cs): n (W) =0.3 to 0.5 after CsCl powder is added.
Further, the organic branched salt in the step 1) is tetrabutylammonium chloride, and the addition amount is 2-5 wt% (the addition amount is calculated by the mass of the mixed solution).
Further, the electrostatic spinning parameters in the step 2) are as follows: the common needle head of 21G is adopted, the distance between the receiver and the needle head is 15-20 cm, the liquid inlet rate is 1-1.5 mL/h, the positive pressure of the power supply is 15-18 kV, the negative pressure is 2.5kV, and the rotating speed of the collecting roller is 20-40 r/min.
Further, the drying temperature in the step 3) is 50-60 ℃ and the drying time is 5-8 h.
Further, the heating rate of the heat treatment in the step 3) is less than 5 ℃/min, the final temperature is 600-800 ℃, and the heat preservation time is 1-2 h.
The invention discloses the following technical effects:
1. the invention adopts the novel near-infrared opacifier cesium tungsten bronze to be in situ compounded with the silicon dioxide fiber, the uniformity of the dispersion of cesium tungsten bronze particles in the silicon dioxide is effectively ensured, and the mechanical property of the fiber is improved by the in situ doped composite structure. The cesium tungsten bronze has the advantages that the material can shield energy in near infrared rays due to small polaron effect and plasma resonance effect of solar heat, the comprehensive heat insulation efficiency of the material is improved, and an important direction is opened for engineering application of silicon dioxide fibers in the infrared heat insulation field.
2. According to the invention, the spinnability of the spinning precursor liquid is regulated and controlled by utilizing hydrolysis of the tetraethoxysilane, so that the use of traditional organic solvents such as DMF is avoided, and the method has certain environmental friendliness. The regulating effect of tetrabutylammonium chloride on the conductivity is also of great significance to the spinning performance of the precursor, and the film forming property of the mixed precursor solution is improved.
3. The silicon dioxide/cesium tungsten bronze composite fiber prepared by the invention has a good three-position network structure, and the components of the cesium tungsten bronze after calcination are Cs 0.33 WO 3 The near infrared shielding performance of the composite material is effectively improved after doping, the average near infrared absorbance of the material reaches 1.5, the tensile strength is 2.25MPa, and the composite material has good high-temperature stability.
4. The preparation process of the invention is relatively simple, and the cesium tungsten bronze nanomaterial synthesized by adopting the sol-gel method has lower production cost compared with the traditional synthesis method. The hybrid precursor solution with spinnability is successfully prepared, and the obtained composite fiber film has excellent near infrared heat insulation performance and can be widely applied to the field of outdoor solar 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 that are 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 other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction curve of the near infrared shielding composite fiber of examples 1-3 of the present invention (tables of the a, b, c scale represent examples 1, 2, 3);
FIG. 2 is a scanning electron micrograph of a silica/cesium tungsten bronze near infrared shielding composite fiber of example 1 of the present invention;
FIG. 3 is a near infrared absorption curve of the near infrared shielding composite fiber of examples 2, 3 of the present invention;
FIG. 4 is XPS full spectrum (a) and W4f peak-splitting fitted spectrum (b) of the near-infrared shielding composite fiber of example 3 of the present invention;
FIG. 5 is a tensile stress-strain curve of the near infrared shielding composite fiber of examples 2, 3 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The embodiment of the invention provides a preparation method of a silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber, which comprises the following steps:
1) Preparing an electrostatic spinning precursor: uniformly mixing tetraethoxysilane with absolute ethyl alcohol, adding oxalic acid (serving as a catalyst), and hydrolyzing to prepare tetraethoxysilane hydrolysate; adding tungsten (W) powder into hydrogen peroxide (H) 2 O 2 ) Filtering after stirring, heating the filtrate in water bath to obtain a pale yellow solution, adding CsCl powder into the pale yellow solution, and stirring to obtain sol A; uniformly mixing the sol A with the tetraethoxysilane hydrolysate, and adding an organic branched salt into the mixed solution to adjust the conductivity of the spinning precursor solution so as to obtain an electrospinning precursor solution;
2) Controlling the environment temperature to be room temperature, carrying out electrostatic spinning by utilizing the electrospinning precursor solution to obtain a hybrid fiber membrane, preferably moving the electrospinning precursor solution to a 10mL injector, placing the injector in a full-automatic electrostatic spinning machine, and setting corresponding spinning parameters to carry out electrostatic spinning;
3) And drying the hybrid fiber membrane, and performing heat treatment to obtain the silicon dioxide/cesium tungsten bronze near infrared shielding composite fiber.
In the embodiment of the invention, the mass ratio of the tetraethoxysilane, the absolute ethyl alcohol and the oxalic acid in the step 1) is 1:0.5: (0.05-0.1), and the hydrolysis time is 10-12 h.
In the embodiment of the invention, the mass ratio of the tungsten powder to the tetraethoxysilane in the step 1) is 1:50, at the same time, to dissolve the W powder completely, H is added 2 O 2 Excessive, H 2 O 2 The concentration was 30wt%.
In the embodiment of the invention, after the tungsten powder is added in the step 1), in order to completely dissolve the W powder, the stirring time is 3-5 hours, and in order to avoid excessive boiling of the exothermic reaction solution, the dissolution process is carried out in a cold water bath.
In the embodiment of the invention, the water bath temperature in the step 1) is 80-95 ℃ and the heating time is 4.5-5.5 h.
In the embodiment of the invention, the atomic coefficient ratio n (Cs): n (W) =0.3-0.5 is ensured after the CsCl powder is added in the step 1).
In the embodiment of the invention, the organic branched salt in the step 1) is tetrabutylammonium chloride, and the addition amount is 2-5wt% (the addition amount is based on the mass of the mixed solution).
In an embodiment of the present invention, the electrospinning parameters in step 2) are: the common needle head of 21G is adopted, the distance between the receiver and the needle head is 15-20 cm, the liquid inlet rate is 1-1.5 mL/h, the positive pressure of the power supply is 15-18 kV, the negative pressure is 2.5kV, and the rotating speed of the collecting roller is 20-40 r/min.
In the embodiment of the invention, the drying temperature in the step 3) is 50-60 ℃ and the time is 5-8 h.
In the embodiment of the invention, the heating rate of the heat treatment in the step 3) is less than 5 ℃/min, the final temperature is 600-800 ℃, and the heat preservation time is 1-2 h.
In the examples of the present invention, room temperature refers to 25.+ -. 2 ℃.
Example 1
The preparation method of the silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber comprises the following steps:
1) Uniformly mixing 5g of ethyl orthosilicate with 2.5g of absolute ethyl alcohol, adding 0.05g of oxalic acid as a catalyst, and stirring for 10 hours by using a magnetic stirrer to fully hydrolyze the mixture to obtain ethyl orthosilicate hydrolysate; 0.1g tungsten powder was added to 1.5mL 30wt% H 2 O 2 Fully dissolving the solution until the black tungsten powder completely disappears, filtering the dissolved liquid, and heating the filtrate in a water bath at 80 ℃ for 5 hours to obtain a pale yellow solution; adding 0.23g of CsCl powder into the pale yellow solution, stirring to obtain yellow sol, fully mixing the yellow sol with the obtained tetraethoxysilane hydrolysate, and adding 0.15g of tetrabutylammonium chloride;
2) Carrying out electrostatic spinning on the obtained precursor solution at room temperature, wherein the spinning parameters are as follows: adopting a 21G single-shaft spinning needle, wherein the liquid inlet rate is 1mL/min, connecting the needle with the positive electrode of a high-voltage direct-current power supply, the voltage of the positive electrode is 15kV, the voltage of the negative electrode is 2.5kV, and selecting a roller receiver, wherein the distance between the roller receiver and the needle is 15cm, and the rotating speed is 20r/min;
3) And (3) placing the fiber membrane prepared by electrostatic spinning in a vacuum drying oven, vacuum drying at 60 ℃ for 5 hours, transferring into a vacuum resistance furnace, respectively heating to 700 ℃ at a speed of 2 ℃/min, calcining, preserving heat for 2 hours, and cooling to room temperature along with the furnace.
Example 2
The preparation method of the silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber comprises the following steps:
1) Uniformly mixing 5g of ethyl orthosilicate with 2.5g of absolute ethyl alcohol, adding 0.05g of oxalic acid as a catalyst, and stirring for 12 hours by using a magnetic stirrer to fully hydrolyze the mixture to obtain ethyl orthosilicate hydrolysate; 0.1g tungsten powder was added to 1.5mL 30wt% H 2 O 2 Fully dissolving the solution until the black tungsten powder completely disappears, filtering the dissolved liquid, and heating the filtrate in a water bath at 90 ℃ for 4.5 hours to obtain a pale yellow solution; adding 0.18g of CsCl powder into the pale yellow solution, stirring to obtain yellow sol, fully mixing the yellow sol with tetraethoxysilane hydrolysate, and adding 0.2g of tetrabutylammonium chloride;
2) Carrying out electrostatic spinning on the obtained precursor solution at room temperature, wherein the spinning parameters are as follows: adopting a 21G single-shaft spinning needle, wherein the liquid inlet rate is 1.2mL/min, connecting the needle with the positive electrode of a high-voltage direct-current power supply, the voltage of the positive electrode is 17kV, the voltage of the negative electrode is 2.5kV, and selecting a roller receiver, wherein the distance between the roller receiver and the needle is 18cm, and the rotating speed is 25r/min;
3) And (3) placing the fiber membrane prepared by electrostatic spinning in a vacuum drying oven, vacuum drying at 55 ℃ for 6 hours, transferring into a vacuum resistance furnace, respectively heating to 600 ℃ at a speed of 2 ℃/min, calcining, preserving heat for 1.5 hours, and cooling to room temperature along with the furnace.
Example 3
The preparation method of the silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber comprises the following steps:
1) Uniformly mixing 10g of ethyl orthosilicate with 5g of absolute ethyl alcohol, adding 0.1g of oxalic acid as a catalyst, and stirring for 12 hours by using a magnetic stirrer to fully hydrolyze the mixture to obtain ethyl orthosilicate hydrolysate; 0.2g tungsten powder was added to 3mL 30wt% H 2 O 2 Fully dissolving the solution until the black tungsten powder completely disappears, filtering the dissolved liquid, and heating the filtrate in a water bath at 95 ℃ for 4.5 hours to obtain a pale yellow solution; adding 0.37g of CsCl powder into the pale yellow solution, stirring to obtain yellow sol, fully mixing the yellow sol with tetraethoxysilane hydrolysate, and adding 0.3g of tetrabutylammonium chloride;
2) Carrying out electrostatic spinning on the obtained precursor solution at room temperature, wherein the spinning parameters are as follows: adopting a 21G single-shaft spinning needle, wherein the liquid inlet rate is 1mL/min, connecting the needle with the positive electrode of a high-voltage direct-current power supply, the voltage of the positive electrode is 18kV, the voltage of the negative electrode is 2.5kV, and selecting a roller receiver, wherein the distance between the roller receiver and the needle is 15cm, and the rotating speed is 20r/min;
3) And (3) placing the fiber membrane prepared by electrostatic spinning in a vacuum drying oven, vacuum drying at 60 ℃ for 5 hours, transferring into a vacuum resistance furnace, respectively heating to 700 ℃ at a speed of 2 ℃/min, calcining, preserving heat for 2 hours, and cooling to room temperature along with the furnace.
In fig. 1, a, b and c are X-ray diffraction curves of the near-infrared shielding composite fibers of the silicon dioxide/cesium tungsten bronze according to examples 1 to 3 of the present invention, respectively, as can be seen from fig. 1: the main component of cesium tungsten bronze in the composite fiber prepared by the invention is Cs 0.33 WO 3 High calcination temperature and Cs + The concentration has a remarkable promoting effect on crystallization of the opacifier particles. The XRD diffraction peaks are observed to be progressively sharpen in example 3 due to the increased driving force for crystal growth at high temperatures, sufficient Cs + Also ensure WO 3 The hexahedral duct structure is completely filled.
FIG. 2 is a scanning electron micrograph of a near infrared shielding composite fiber of example 1 of the present invention, and it can be seen from FIG. 2 that the calcined fiber still maintains a three-dimensional network structure, and the surface of the fiber is smooth and has no cracks.
Fig. 3 is a near infrared absorption curve of the near infrared shielding composite fiber of examples 2, 3 of the present invention, silica/cesium tungsten bronze, as can be seen from fig. 3: the fiber has a good shielding effect against near infrared light, and as can be seen in connection with fig. 1, the outer shielding ability of the sample magenta has a positive correlation with the crystallinity of the opacifier particles. Cs (cells) + Is added to [ WO ] 6 ]The tunnel contains a large number of free carriers which are confined to the W sites by the lattice energy and create small polarons to the surrounding lattice, which transition between different W sites will absorb light in the near infrared band. The large number of carriers causes Cs 0.33 WO 3 With some characteristics similar to those of metals, electron clusters formed by gathering a large number of free electrons can be regarded as plasmas, and when the frequency of incident light rays is close to the natural frequency of the plasmas, strong coupling occurs, so that localized surface plasma waves are generated. The energy in the plasma wave is absorbed by the material in the process of propagation, and the near infrared rays are shielded.
FIG. 4 is a graph showing XPS full spectrum and W4f peak splitting fitting of the near infrared shielding composite fiber of example 3 of the present invention, as can be seen from FIG. 4: there was a peak of the binding energy of Cs, W, O, si in the sample. Description of the preparation of relatively pure SiO 2 /Cs 0.33 WO 3 The product has good agreement with XRD test results. The W4f orbit is subjected to peak separation treatment, so that a W4f peak separation fitting spectrogram can be obtained, and the split peaks of W4f are seen from the graph in FIG. 4 b to be located at 34.28eV and 35.98eV 5+ Bimodal and W at 35.58eV, 37.68eV 6+ Bimodal composition。Cs + The valence of part of W ions is changed by adding the catalyst, so that electrons are transferred between W with different valence states, and the near infrared absorption performance of the composite fiber is improved.
Fig. 5 is a tensile stress-strain curve of the inventive example 2, 3 silica/cesium tungsten bronze near infrared shielding composite fiber, as can be seen from fig. 5, the lower heat treatment temperature helps the fiber film maintain good flexibility and strength. Cs in the fiber as the calcination temperature increases 0.33 WO 3 Overgrowth of the lattice structure of (C) at high temperatures, destruction of amorphous SiO 2 Thereby reducing the toughness and strength of the fiber.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. The preparation method of the silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber is characterized by comprising the following steps of:
1) Preparing an electrostatic spinning precursor: uniformly mixing ethyl orthosilicate with absolute ethyl alcohol, adding oxalic acid, and hydrolyzing to prepare ethyl orthosilicate hydrolysate; adding tungsten powder into hydrogen peroxide, stirring, filtering, heating the filtrate in a water bath to obtain a pale yellow solution, adding CsCl powder into the pale yellow solution, and stirring to obtain sol A; uniformly mixing the sol A with the tetraethoxysilane hydrolysate, and adding organic branched salt into the mixed solution to obtain an electrospinning precursor solution;
2) Controlling the environment temperature to be room temperature, and carrying out electrostatic spinning by utilizing the electrospinning precursor solution to obtain a hybrid fiber membrane;
3) Drying the hybrid fiber membrane, and performing heat treatment to obtain a silicon dioxide/cesium tungsten bronze near-infrared shielding composite fiber;
in the step 1), the mass ratio of the tetraethoxysilane to the absolute ethyl alcohol to the oxalic acid is 1:0.5: (0.05-0.1), and the hydrolysis time is 10-12 h; the mass ratio of the tungsten powder to the tetraethoxysilane is 1:50; after CsCl powder is added, the atomic coefficient ratio n (Cs) is ensured to be n (W) =0.3-0.5; the organic branched salt is tetrabutylammonium chloride, and the addition amount is 2-5 wt%.
2. The method according to claim 1, wherein the stirring time is 3 to 5 hours after the tungsten powder is added in step 1).
3. The preparation method according to claim 1, wherein the water bath temperature in step 1) is 80-95 ℃ and the heating time is 4.5-5.5 h.
4. The method according to claim 1, wherein the electrospinning parameters in step 2) are: the common needle head of 21G is adopted, the distance between the receiver and the needle head is 15-20 cm, the liquid inlet rate is 1-1.5 mL/h, the positive pressure of the power supply is 15-18 kV, the negative pressure is 2.5kV, and the rotating speed of the collecting roller is 20-40 r/min.
5. The preparation method according to claim 1, wherein the drying temperature in step 3) is 50-60 ℃ and the time is 5-8 h.
6. The preparation method according to claim 1, wherein the heating rate of the heat treatment in the step 3) is less than 5 ℃/min, the final temperature is 600-800 ℃, and the heat preservation time is 1-2 h.
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| CN108483934B (en) * | 2018-03-29 | 2021-02-02 | 东南大学 | Tungsten bronze/silica gel heat insulation functional material and preparation method thereof |
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