CN113322532A - Structural color fiber and preparation method thereof - Google Patents
Structural color fiber and preparation method thereof Download PDFInfo
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- CN113322532A CN113322532A CN202110703288.9A CN202110703288A CN113322532A CN 113322532 A CN113322532 A CN 113322532A CN 202110703288 A CN202110703288 A CN 202110703288A CN 113322532 A CN113322532 A CN 113322532A
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- 239000000835 fiber Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 70
- 238000009987 spinning Methods 0.000 claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 48
- 239000006185 dispersion Substances 0.000 claims abstract description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000002166 wet spinning Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 58
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000002077 nanosphere Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract description 5
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000012209 synthetic fiber Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- 239000004753 textile Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 229920006240 drawn fiber Polymers 0.000 description 1
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- 238000005562 fading Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Images
Classifications
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- 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
- D01D5/06—Wet spinning methods
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a structural color fiber and a preparation method thereof, and relates to the technical field of synthetic fibers. The preparation method of the structural color fiber provided by the invention comprises the following steps: mixing the silicon dioxide nano-microspheres, water, polyvinyl alcohol and graphene water dispersion to obtain spinning solution; and carrying out wet spinning on the spinning solution to obtain the structural color fiber. According to the invention, the silicon dioxide nano microspheres are used as microspheres for generating structural colors, the silicon dioxide nano microspheres are mixed with the polyvinyl alcohol and graphene water dispersion liquid to be used as spinning liquid, and the structural color fibers are prepared by adopting a wet spinning process, so that the silicon dioxide nano microspheres can be wrapped in the fibers, the microspheres are prevented from falling off, the prepared structural color fibers are not easy to fade, and the service life is long.
Description
Technical Field
The invention relates to the technical field of synthetic fibers, in particular to a structural color fiber and a preparation method thereof.
Background
The current synthetic dyed fiber industry causes serious pollution to water resources and atmospheric environment, and the appearance of structural color fibers can become a substitute product of synthetic dyed fibers. Pai Guomai et al deposited PS (polystyrene microspheres) on the surface of silk fabric in a face-centered cubic (FCC) manner by using a vertical sedimentation method to finally obtain fibers with structural colors (Pai Guomai, Liu Guojin, Huangjiang Peak, etc.. study on photonic crystal self-assembly process on silk fabric [ J ]. proceedings of Zhejiang university of science and technology, 2013,30(4): 467-. The Wang group used a quartz glass capillary and a polyimide overcoat as a microchannel, and silica fibers were put into a microcapillary, and silica suspensions uniformly dispersed at 215nm and 240nm were injected into the capillary, respectively, and dried to obtain blue and green structural color fibers having 3D effect structural colors, respectively (Liu Z, Zhang Q, Wang H, et al structural colored fiber textile by a textile color selected-assembly method in micro-space [ J ]. Chemical communications,2011,47(48): 12801-12803).
All the researches are that microspheres generating structural color are assembled on the surface of the fiber, and the structural color fiber is easy to fade.
Disclosure of Invention
The invention aims to provide structural color fibers and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of structural color fiber, which comprises the following steps:
mixing the silicon dioxide nano-microspheres, water, polyvinyl alcohol and graphene water dispersion to obtain spinning solution;
and carrying out wet spinning on the spinning solution to obtain the structural color fiber.
Preferably, the average particle size of the silicon dioxide nano-microspheres is 230-270 nm or 300-430 nm.
Preferably, the concentration of graphene in the graphene aqueous dispersion is 0.05-0.1%.
Preferably, the mass ratio of the silica nanospheres to the polyvinyl alcohol to the graphene water dispersion is 1: 0.8-1.5: 0.03 to 0.07.
Preferably, the using amount ratio of the silicon dioxide nano microspheres to water is 25-36 g: 100-164 mL.
Preferably, the method for mixing the silica nano-microspheres, the water, the polyvinyl alcohol and the graphene aqueous dispersion comprises the following steps: dispersing the silicon dioxide nano microspheres in water to obtain silicon dioxide dispersion liquid; mixing the silicon dioxide dispersion liquid with polyvinyl alcohol to obtain a mixed liquid; and mixing the mixed solution with the graphene aqueous dispersion.
Preferably, the mixing of the silicon dioxide dispersion liquid and polyvinyl alcohol is carried out under the heating condition, and the heating temperature is 70-98 ℃; the heating time is 2-6 h.
Preferably, the step of wet spinning comprises:
extruding the spinning solution from a spinneret into a first coagulation bath to form a fiber stream;
placing the fiber trickle in a second coagulating bath to obtain nascent fiber;
and (3) sequentially drafting and shaping the nascent fiber to obtain the structural color fiber.
The invention provides a structural color fiber prepared by the preparation method in the technical scheme, and the structural color fiber comprises a fiber matrix, and silica nano microspheres and graphene which are coated in the fiber matrix.
Preferably, the structural color fibers are non-iridescent structural color fibers.
The invention provides a preparation method of structural color fiber, which comprises the following steps: mixing the silicon dioxide nano-microspheres, water, polyvinyl alcohol and graphene water dispersion to obtain spinning solution; and carrying out wet spinning on the spinning solution to obtain the structural color fiber. In the present invention, polyvinyl alcohol is a raw material for forming fibers; the graphene is black, so that a light source which needs to be scattered out can be absorbed, only the structural color assembled by the silicon dioxide nano microspheres is reflected, and the vividness of the fiber color of the structural color is improved. According to the invention, the silicon dioxide nano microspheres are used as microspheres for generating structural colors, the silicon dioxide nano microspheres are mixed with the polyvinyl alcohol and graphene water dispersion liquid to be used as spinning liquid, and the structural color fibers are prepared by adopting a wet spinning process, so that the silicon dioxide nano microspheres can be wrapped in the fibers, the microspheres are prevented from falling off, the prepared structural color fibers are not easy to fade, and the service life is long.
Moreover, the preparation method provided by the invention is simple and convenient, and is easy for industrial popularization and application.
Drawings
FIG. 1 is a schematic representation of the spinning solutions prepared in examples 1 to 4;
FIG. 2 is a chromaticity diagram of the spinning solutions prepared in examples 1 to 4;
FIG. 3 is an optical micrograph of the structural color fibers prepared in examples 2 and 4;
FIG. 4 is a surface SEM image of a structural color fiber prepared in example 2;
FIG. 5 is a cross-sectional SEM image of a structural color fiber made according to example 2;
FIG. 6 is a surface SEM image of a structural color fiber prepared in example 4;
FIG. 7 is a cross-sectional SEM image of a structural color fiber made in example 4;
FIG. 8 is an infrared spectrum of the structural color fibers prepared in examples 2 and 4;
FIG. 9 is a graph of thermal performance analysis of the structural color fibers prepared in examples 2 and 4.
Detailed Description
The invention provides a preparation method of structural color fiber, which comprises the following steps:
mixing the silicon dioxide nano-microspheres, water, polyvinyl alcohol and graphene water dispersion to obtain spinning solution;
and carrying out wet spinning on the spinning solution to obtain the structural color fiber.
In the present invention, if not specifically required, the starting materials for the preparation are commercially available products known to those skilled in the art.
According to the invention, the spinning solution is obtained by mixing the silicon dioxide nano-microspheres, water, polyvinyl alcohol and graphene water dispersion. In the invention, the average particle size of the silicon dioxide nano-microspheres is preferably 230-270 nm or 300-430 nm. In a specific embodiment of the present invention, the average particle size of the silica nanospheres is 250nm or 430 nm. In the specific embodiment of the invention, when the average particle size of the silica nano-microspheres is 250nm, the color of the prepared structural color fiber is grayish blue; when the average particle size of the silicon dioxide nano microspheres is 430nm, the color of the prepared structural color fiber is green.
In the present invention, the water is preferably deionized water. In the invention, the preferable dosage ratio of the silicon dioxide nano microspheres to water is 25-36 g: 100-164 mL, more preferably 25-36 g: 140-164 mL.
In the present invention, the polyvinyl alcohol preferably has an average polymerization degree of 1700 to 1800.
In the invention, the mass concentration of graphene in the graphene aqueous dispersion is preferably 0.05-0.1%, and more preferably 0.05-0.08%. In the invention, the mass ratio of the silica nanospheres, the polyvinyl alcohol and the graphene aqueous dispersion is preferably 1: 0.8-1.5: 0.03 to 0.07, more preferably 1: 1: 0.03 to 0.07.
The preparation method of the graphene aqueous dispersion liquid has no special requirements, and the preparation method which is well known by the technical personnel in the field can be adopted. In the invention, the graphene aqueous dispersion is preferably prepared by adopting a modified Hummers method. In a specific embodiment of the present invention, a preparation method of the graphene aqueous dispersion includes:
mixing graphite powder, concentrated sulfuric acid, potassium nitrate and potassium permanganate to obtain a graphite dispersion liquid;
diluting the graphite dispersion liquid with dilute sulfuric acid, adding hydrogen peroxide, and carrying out oxidation reaction to obtain graphite oxide;
dispersing the graphite oxide in water, and sequentially centrifuging, cleaning and drying to obtain graphene oxide;
and dispersing the graphene oxide in water, adding sodium borohydride, and carrying out reduction reaction to obtain the graphene aqueous dispersion.
In the invention, graphite powder, concentrated sulfuric acid, potassium nitrate and potassium permanganate are preferably mixed to obtain the graphite dispersion liquid.
In the present invention, the mixing of the graphite powder, the concentrated sulfuric acid, the potassium nitrate and the potassium permanganate is preferably performed at 0 ℃. In the invention, the dosage ratio of the graphite powder, the concentrated sulfuric acid, the potassium nitrate and the potassium permanganate is preferably 2 g: 50mL of: 1 g: 6g of a mixture; the mass concentration of the concentrated sulfuric acid is preferably 98%. In the present invention, the mixing is preferably performed at room temperature; the mixing time is preferably 2 h.
After obtaining the graphite dispersion liquid, the invention preferably uses dilute sulfuric acid to dilute the graphite dispersion liquid, and adds hydrogen peroxide to carry out oxidation reaction to obtain the graphite oxide. In the present invention, the mass concentration of the dilute sulfuric acid is preferably 5%; the dilution is preferably carried out under stirring, the stirring time preferably being 0.5 h. In the present invention, the concentration of graphite in the dispersion obtained after dilution is preferably 0.05 to 0.1%. In the invention, the dosage ratio of the hydrogen peroxide to the graphite powder is preferably 6 mL: 2g of the total weight of the mixture; the mass concentration of the hydrogen peroxide is preferably 15-30%. After the hydrogen peroxide is added, the solution turns into bright yellow. In the present invention, the time of the oxidation reaction is preferably 2 hours. In the present invention, it is preferable to perform centrifugation after completion of the stirring, and the obtained precipitate is washed and dried in this order to obtain graphite oxide. In the present invention, the washing preferably includes a hydrochloric acid washing and a water washing in this order; the drying is preferably vacuum drying.
After obtaining the graphite oxide, the invention preferably disperses the graphite oxide in water, and then sequentially performs centrifugation, washing and drying to obtain the graphene oxide. In the present invention, it is preferable to disperse the graphite oxide in water by using ultrasound; the time of the ultrasound is preferably 3 hours. In the present invention, the color of the dispersion liquid obtained by dispersing the graphite oxide in water is yellowish brown. In the present invention, the temperature of the drying is preferably 40 ℃. In the present invention, the graphene oxide has a lamellar structure.
After graphene oxide is obtained, the graphene oxide is preferably dispersed in water, and sodium borohydride is added to perform a reduction reaction, so that a graphene aqueous dispersion is obtained. In the invention, the graphene oxide is preferably dispersed in water to obtain a graphene oxide dispersion liquid. In the present invention, the pH of the graphene oxide dispersion is preferably adjusted to 10 with a sodium hydroxide solution. In the present invention, the dispersion is preferably carried out under ultrasonic conditions, and the ultrasonic time is preferably 1 h. In the present invention, the color of the graphene oxide dispersion liquid is yellowish brown. According to the invention, after sodium borohydride is preferably added, the obtained mixed solution is stirred for 30min and uniformly mixed.
In the present invention, the temperature of the reduction reaction is preferably 135 ℃; the time for the reduction reaction is preferably 6 hours.
In the present invention, the method for mixing the silica nanospheres, water, polyvinyl alcohol and the graphene aqueous dispersion preferably comprises: dispersing the silicon dioxide nano microspheres in water to obtain silicon dioxide dispersion liquid; mixing the silicon dioxide dispersion liquid with polyvinyl alcohol to obtain a mixed liquid; and mixing the mixed solution with the graphene aqueous dispersion. In the invention, the method for dispersing the silicon dioxide nano microspheres in water is preferably ultrasonic mixing; the power of the ultrasonic wave is preferably 20-40 kHz; the time is preferably 2 h. In the invention, the mixing of the silicon dioxide dispersion liquid and the polyvinyl alcohol is preferably carried out under the heating condition, and the heating temperature is preferably 70-98 ℃, and more preferably 80-98 ℃; the heating time is preferably 2-6 h, and more preferably 4 h. In a specific embodiment of the present invention, the silica dispersion and polyvinyl alcohol are heated and refluxed at 70 ℃ for 3 hours, and then heated to 98 ℃ and refluxed for 1 hour to obtain a mixed solution.
In the invention, the spinning solution is preferably subjected to heat preservation at 70-98 ℃, and more preferably, the spinning solution is placed in a charging barrel and subjected to heat preservation by using circulating water at 70-98 ℃. The spinning solution is preferably left overnight to discharge bubbles in the spinning solution and then used for wet spinning.
After the spinning solution is obtained, the spinning solution is subjected to wet spinning to obtain the structural color fiber. The invention has no special requirements on the specific process of the wet spinning, and the wet spinning process known by the technical personnel in the field can be adopted. In the present invention, the step of wet spinning preferably comprises:
extruding the spinning solution from a spinneret into a first coagulation bath to form a fiber stream;
placing the fiber trickle in a second coagulating bath to obtain nascent fiber;
and (3) sequentially drafting and shaping the nascent fiber to obtain the structural color fiber.
In the present invention, the temperature from the spinneret to the barrel is preferably maintained at 98 ℃ during the extrusion of the spinning dope from the spinneret. In the present invention, the first coagulation bath and the second coagulation bath are preferably anhydrous sodium sulfate aqueous solutions; the concentration of the anhydrous sodium sulfate aqueous solution is preferably 370-410 g/L. In the present invention, the drawing preferably includes preliminary drawing, preheating and hot drawing which are sequentially performed. In the present invention, the medium for the pre-drawing, preheating and hot-drawing is preferably water; the temperature of the pre-drawing, pre-heating and hot-drawing is preferably room temperature. The present invention utilizes drafting to wash salts on the fibers.
In the invention, the setting temperature is preferably 45-90 ℃, and the time is preferably 2-5 min.
In the present invention, it is preferable that the drawn fiber obtained by drawing is dried before setting. In the invention, the drying temperature is preferably 100-120 ℃; the drying time is preferably 1-2 min.
The invention also provides the structural color fiber prepared by the preparation method in the technical scheme, and the structural color fiber comprises a fiber matrix, and silicon dioxide nano microspheres and graphene which are coated in the fiber matrix. In the invention, most of the silicon dioxide nano microspheres and graphene are coated in the fiber matrix, and only a small amount of the silicon dioxide nano microspheres and graphene are distributed on the surface of the fiber matrix. In the invention, the mass of the silicon dioxide nano microspheres coated in the fiber matrix preferably accounts for more than 80% of the total mass of the silicon dioxide nano microspheres; the mass of the graphene coated in the fiber matrix is preferably more than 80% of the total mass of the graphene.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 36g of silica nano microspheres with the average particle size of 250nm and 164mL of deionized water, and carrying out ultrasonic treatment for 2h under the power of 30kHz to obtain silica dispersion; adding 36g of polyvinyl alcohol (PVA) into the silicon dioxide dispersion liquid, heating and refluxing for 3h at 70 ℃, and then heating to 98 ℃ for refluxing for 1h to obtain a mixed liquid; adding 1.08g of graphene aqueous dispersion while mechanically stirring the mixed solution to obtain a spinning solution; the mass concentration of graphene in the graphene aqueous dispersion is 0.05%.
And (3) putting the spinning solution into a charging barrel, keeping the temperature by using circulating water at 98 ℃, and standing for one night to discharge bubbles in the spinning solution for wet spinning in the next day.
Opening a metering pump, and extruding the spinning solution out of a spinning nozzle by using the thrust of the pump, wherein the temperature from the spinning nozzle to a material cylinder is kept at 98 ℃ in the process; the spinning solution directly enters 370g/L anhydrous sodium sulfate aqueous solution from a spinning nozzle to form fiber trickle; the fiber trickle enters a 370g/L anhydrous sodium sulfate aqueous solution of a second coagulating bath through a driving roller to obtain nascent fiber; the nascent fiber is sequentially passed through a pre-drawing groove, a preheating groove and a hot drawing groove, the solutions of the three grooves are all water, and the temperature is normal temperature; and finally, drying the fiber at 120 ℃ for 2min by a drying box to reach a silk collecting machine, and shaping the fiber at 45 ℃ for 2min to obtain the structural color fiber.
Example 2
Mixing 36g of silica nano microspheres with the average particle size of 250nm and 164mL of deionized water, and carrying out ultrasonic treatment for 2h under the power of 30kHz to obtain silica dispersion; adding 36g of polyvinyl alcohol (PVA) into the silicon dioxide dispersion liquid, heating and refluxing for 3h at 70 ℃, and then heating to 98 ℃ for refluxing for 1h to obtain a mixed liquid; adding 2.52g of graphene aqueous dispersion while mechanically stirring the mixed solution to obtain a spinning solution; the mass concentration of graphene in the graphene aqueous dispersion is 0.05%.
And (3) putting the spinning solution into a charging barrel, keeping the temperature by using circulating water at 98 ℃, and standing for one night to discharge bubbles in the spinning solution for wet spinning in the next day.
Opening a metering pump, and extruding the spinning solution out of a spinning nozzle by using the thrust of the pump, wherein the temperature from the spinning nozzle to a material cylinder is kept at 98 ℃ in the process; the spinning solution directly enters 370g/L anhydrous sodium sulfate aqueous solution from a spinning nozzle to form fiber trickle; the fiber trickle enters a 370g/L anhydrous sodium sulfate aqueous solution of a second coagulating bath through a driving roller to obtain nascent fiber; the nascent fiber is sequentially passed through a pre-drawing groove, a preheating groove and a hot drawing groove, the solutions of the three grooves are all water, and the temperature is normal temperature; and finally, drying the fiber at 120 ℃ for 2min by a drying box to reach a silk collecting machine, and shaping the fiber at 45 ℃ for 2min to obtain the structural color fiber.
Example 3
Mixing 36g of silica nano microspheres with the average particle size of 430nm and 164mL of deionized water, and carrying out ultrasonic treatment for 2h under the power of 30kHz to obtain silica dispersion; adding 36g of polyvinyl alcohol (PVA) into the silicon dioxide dispersion liquid, heating and refluxing for 3h at 70 ℃, and then heating to 98 ℃ for refluxing for 1h to obtain a mixed liquid; adding 1.08g of graphene aqueous dispersion while mechanically stirring the mixed solution to obtain a spinning solution; the mass concentration of graphene in the graphene aqueous dispersion is 0.05%.
And (3) putting the spinning solution into a charging barrel, keeping the temperature by using circulating water at 98 ℃, and standing for one night to discharge bubbles in the spinning solution for wet spinning in the next day.
Opening a metering pump, and extruding the spinning solution out of a spinning nozzle by using the thrust of the pump, wherein the temperature from the spinning nozzle to a material cylinder is kept at 98 ℃ in the process; the spinning solution directly enters 370g/L anhydrous sodium sulfate aqueous solution from a spinning nozzle to form fiber trickle; the fiber trickle enters a 370g/L anhydrous sodium sulfate aqueous solution of a second coagulating bath through a driving roller to obtain nascent fiber; the nascent fiber is sequentially passed through a pre-drawing groove, a preheating groove and a hot drawing groove, the solutions of the three grooves are all water, and the temperature is normal temperature; and finally, drying the fiber at 120 ℃ for 2min by a drying box to reach a silk collecting machine, and shaping the fiber at 45 ℃ for 2min to obtain the structural color fiber.
Example 4
Mixing 36g of silica nano microspheres with the average particle size of 430nm and 164mL of deionized water, and carrying out ultrasonic treatment for 2h under the power of 30kHz to obtain silica dispersion; adding 36g of polyvinyl alcohol (PVA) into the silicon dioxide dispersion liquid, heating and refluxing for 3h at 70 ℃, and then heating to 98 ℃ for refluxing for 1h to obtain a mixed liquid; adding 2.52g of graphene aqueous dispersion while mechanically stirring the mixed solution to obtain a spinning solution; the mass concentration of graphene in the graphene aqueous dispersion is 0.05%.
And (3) putting the spinning solution into a charging barrel, keeping the temperature by using circulating water at 98 ℃, and standing for one night to discharge bubbles in the spinning solution for wet spinning in the next day.
Opening a metering pump, and extruding the spinning solution out of a spinning nozzle by using the thrust of the pump, wherein the temperature from the spinning nozzle to a material cylinder is kept at 98 ℃ in the process; the spinning solution directly enters 370g/L anhydrous sodium sulfate aqueous solution from a spinning nozzle to form fiber trickle; the fiber trickle enters a 370g/L anhydrous sodium sulfate aqueous solution of a second coagulating bath through a driving roller to obtain nascent fiber; the nascent fiber is sequentially passed through a pre-drawing groove, a preheating groove and a hot drawing groove, the solutions of the three grooves are all water, and the temperature is normal temperature; and finally, drying the fiber at 120 ℃ for 2min by a drying box to reach a silk collecting machine, and shaping the fiber at 45 ℃ for 2min to obtain the structural color fiber.
Test example 1
FIG. 1 shows schematic diagrams of the spinning solutions prepared in examples 1 to 4. Wherein the leftmost in fig. 1 a is a real image of a mixed solution of the silica dispersion and PVA in example 1; in the middle of a in fig. 1 is a physical representation of the spinning solution prepared in example 1; the rightmost side in a of fig. 1 is a physical diagram of the spinning solution prepared in example 2; the leftmost in fig. 1 b is a real image of a mixed liquid of the silica dispersion and PVA in example 3; in b of FIG. 1, the middle is a physical representation of the spinning solution prepared in example 3; the rightmost panel in b of fig. 1 is a physical diagram of the spinning solution prepared in example 4.
The chromaticity diagram of the spinning solutions prepared in examples 1 to 4 is shown in FIG. 2.
As can be seen from fig. 1 to 2, the spinning solution added with the graphene aqueous dispersion shows different colors due to different particle sizes, and the color of the spinning solution is gradually obvious as the graphene aqueous dispersion increases. This is because the black graphene absorbs the light source that would otherwise be scattered out, and reflects only the structural color of the silica nanosphere assembly. When the structural color is constructed artificially, if the colloidal microspheres forming the structural color film are in a light color system and are influenced by interference stray light and background light, multiple reflected lights are generated, the intensity of forbidden light reflection is weakened, and the relative intensity of the reflected lights generating the structural color is weakened, so that the structural color is whitened and is not bright enough, and the phenomenon is more obvious particularly under the irradiation of natural light. The invention can improve the color quality by using the graphene aqueous dispersion.
Test example 2
Optical micrographs of the structural color fibers prepared in example 2(250nm) and example 4(430nm) are shown in FIG. 3, where a in FIG. 3 is the structural color fiber prepared in example 2; b in fig. 3 is the structural color fiber prepared in example 4. As can be seen from fig. 3, the structural color fiber prepared using the silica nanospheres having an average particle size of 250nm is grayish blue, while the structural color fiber prepared using the silica nanospheres having an average particle size of 430nm is green. This is because the difference in particle size of the silica nanospheres causes the fibers to produce different photonic band gaps, thereby emitting visible light of different wavelengths. The structural color fiber prepared by the invention has soft color, shows the characteristics of an amorphous photonic crystal structure, and is a non-iridescent structural color fiber.
Comparing the color of the structural color fiber with the spinning dope, the color of the structural color fiber was found to appear slightly lighter to the naked eye than the color of the spinning dope.
Test example 3
SEM images of the surface and the cross section of the structural color fiber prepared in the examples 2 and 4 are shown in FIGS. 4-7, wherein FIG. 4 is the surface SEM image of the structural color fiber prepared in the example 2; FIG. 5 is a cross-sectional SEM image of a structural color fiber made according to example 2; FIG. 6 is a surface SEM image of a structural color fiber prepared in example 4; fig. 7 is a cross-sectional SEM image of a structural color fiber prepared in example 4.
As can be seen from fig. 4 to 7, the surface of the structural color fiber prepared by using the silica nanoparticles having an average particle size of 250nm and the surface of the structural color fiber prepared by using the silica nanoparticles having an average particle size of 430nm have almost no silica nanoparticles exposed outside, and the silica nanoparticles are wrapped by PVA, so that the silica nanoparticles are prevented from falling off and fading inside the structural color fiber.
The cross section of the structural color fiber prepared by the invention presents a short-range ordered and long-range disordered structure, because the fiber is extruded and drawn in the wet spinning process, so that the silicon dioxide nano microspheres are arranged in a certain order in the prepared structural color fiber than in the spinning solution, and the color of the structural color fiber is lighter than the color of the spinning solution by naked eyes.
The structural color fiber prepared by the invention is soft in color development and has no iridescence effect.
Test example 4
The infrared spectra of the structural color fibers prepared in examples 2 and 4 are shown in fig. 8. The silicon dioxide nano-microsphere is 3440cm-1There is a peak due to the residual moisture between the microspheres; at 1068cm-1And 801cm-1The peaks at (A) are caused by antisymmetric stretching vibration and symmetric stretching vibration of Si-O-Si bond, respectively. The most obvious characteristic peak of the PVA fiber is 3532cm-1、2924cm-1、1655cm-1、1430cm-1And 1090cm-1To (3). 3532cm-1The absorption peak is due to the presence of-OH, which may originate from the PVA fiber or from residual moisture in the fiber. 2924cm-1And 1430cm-1Tensile vibration and bending vibration of the C-H bond at the absorption peak; 1655cm-1And 1090cm-1The absorption peak at (A) is due to the C-O bond. By comparing silica nanospheres, PVA fibers and structural color fibers (SiO)2PVA/graphene composite fiber) and SiO can be found2the/PVA/graphene composite fiber is 1657cm-1A peak newly appears due to vibration caused by C ═ C in graphene, indicating that the six-membered ring structure of graphene contains a C double bond structure. SiO 22The infrared spectrum of the/PVA/graphene composite fiber is caused by the superposition of the three, and the peak value of the superposed curve is correspondingly weakened compared with that of the pure silica nano microsphere and the PVA fiber, which shows that the SiO 22The interior of the/PVA/graphene composite fiber is not simply physically mixed, but has a certain bonding effect.
Test example 5
A thermal analysis of the structural color fibers prepared in examples 2 and 4 is shown in FIG. 9. As can be seen from FIG. 9, the structural color fibers (SiO)2+ PVA + graphene composite fiber), the first weight loss occurs below 200 ℃, which is partly caused by the evaporation of water molecules in the structural color fiber; the second weight loss is 200-380 ℃, the reason for the partial weight loss is that PVA molecules are degraded in the temperature range, the third weight loss is 400-500 ℃, and the partial weight loss is mainly the further degradation of PVA and SiO2Xerogel formation. The weight loss curve is compared to find that the decomposition temperature of the structural color fiber is higher than that of the pure PVA fiber, and the residual carbon amount at 700 ℃ is higher, which indicates that the thermal stability of the structural color fiber is superior to that of the pure PVA fiber, and also indicates that the silicon dioxide nano-microspheres, the PVA and the graphene are not purely physically blended and have chemical bonding effect, and the conclusion is consistent with the infrared spectrum analysis result.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the structural color fiber is characterized by comprising the following steps of:
mixing the silicon dioxide nano-microspheres, water, polyvinyl alcohol and graphene water dispersion to obtain spinning solution;
and carrying out wet spinning on the spinning solution to obtain the structural color fiber.
2. The preparation method of claim 1, wherein the average particle size of the silica nanospheres is 230-270 nm or 300-430 nm.
3. The preparation method according to claim 1, wherein the concentration of graphene in the graphene aqueous dispersion is 0.05-0.1%.
4. The preparation method according to claim 3, wherein the mass ratio of the silica nanospheres to the polyvinyl alcohol to the graphene aqueous dispersion is 1: 0.8-1.5: 0.03 to 0.07.
5. The preparation method according to claim 1 or 2, wherein the ratio of the silicon dioxide nano-microspheres to water is 25-36 g: 100-164 mL.
6. The preparation method of claim 1, wherein the method for mixing the silica nano-microspheres, the water, the polyvinyl alcohol and the graphene aqueous dispersion comprises: dispersing the silicon dioxide nano microspheres in water to obtain silicon dioxide dispersion liquid; mixing the silicon dioxide dispersion liquid with polyvinyl alcohol to obtain a mixed liquid; and mixing the mixed solution with the graphene aqueous dispersion.
7. The preparation method according to claim 6, wherein the mixing of the silica dispersion and the polyvinyl alcohol is carried out under heating at a temperature of 70 to 98 ℃; the heating time is 2-6 h.
8. The method of manufacturing according to claim 1, wherein the step of wet spinning comprises:
extruding the spinning solution from a spinneret into a first coagulation bath to form a fiber stream;
placing the fiber trickle in a second coagulating bath to obtain nascent fiber;
and (3) sequentially drafting and shaping the nascent fiber to obtain the structural color fiber.
9. The structural color fiber prepared by the preparation method of any one of claims 1 to 8, which comprises a fiber matrix, and silica nano-microspheres and graphene coated inside the fiber matrix.
10. The structural color fiber of claim 9 wherein the structural color fiber is a non-iridescent structural color fiber.
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