CN106381532A - Electric spinning preparation method of nanometer fiber with material gradient distribution features - Google Patents
Electric spinning preparation method of nanometer fiber with material gradient distribution features Download PDFInfo
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- CN106381532A CN106381532A CN201611021134.7A CN201611021134A CN106381532A CN 106381532 A CN106381532 A CN 106381532A CN 201611021134 A CN201611021134 A CN 201611021134A CN 106381532 A CN106381532 A CN 106381532A
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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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
-
- 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
-
- 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
- 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
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- 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
- D01F6/54—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 polymers of unsaturated nitriles
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention relates to an electric spinning preparation method of nanometer fiber with material gradient distribution features. A spinning polymer solution is used as mother liquid; the mother liquid is uniformly divided into three parts; additives are sequentially added into the three parts of mother liquid in a way that the content is gradually increased or gradually decreased; the materials are uniformly stirred; inner layer work fluid, middle layer work fluid and outer layer work fluid are formed, and are correspondingly charged into inner, middle and outer fluid injectors; the three fluid injectors are connected with one three-stage coaxial spinning head; the three kinds of work fluid respectively flows into coaxial capillaries of the three-stage coaxial spinning heads; the three-stage coaxial spinning heads generates the nanometer fiber with the material gradient distribution features under the effect of high-voltage static electricity; the nanometer fiber is collected by an aluminum foil covering paper board. The electric spinning preparation method provided by the invention has the advantages that the preparation process is simple; the single step is effective; the prepared inner/middle/outer three-layer structure of the prepared nanometer fiber is clear; in addition, the nanometer diameter is small; the linearity is good; the diameter distribution is uniform; the fiber surface is smooth. Through the material gradient distribution features, the effective implementation method can be provided for the design and the preparation of various novel nanometer materials.
Description
Technical field
The present invention relates to a kind of novel nano-material preparation, particularly to one kind, there is material gradient distribution characteristicss Nanowire
The electro spinning method for preparing of dimension.
Background technology
High-voltage electrostatic spinning technology（Electrospinning）It is the nano-fabrication technique of one kind (top-down) from top to bottom, by additional
Electric field force overcomes the shower nozzle tip surface tension of liquid of drop and viscoelastic power to form jet, in electrostatic repulsion, Coulomb force and table
Under the tension force collective effect of face, the liquid jet after being atomized by high frequency flexural, drawing, division, drafted thousand within a few tens of milliseconds
Wan Bei, obtains nano-scale fiber through solvent volatilization or melt cooling in receiving terminal.This technical matters process is simple, manipulation is convenient,
Select that material ranges are extensive, controllability strong, be considered as one kind side most possibly realizing continuous nano-fibre industrialized production
Method, applies this technology to prepare functional nano-fiber and has good prospect.
In all of " top-down " nano-fabrication technique, the advantageous feature of electrospinning can be by Macro
The design of secondary spinning header structure, the nanofiber with corresponding microstructure characteristic is prepared in single step effectively, such as by inside and outside two
Layer sleeve structure spinneret prepares core sheath structure nanofiber（DG Yu,LM Zhu,C Branford-White,JH Yang,X
Wang, Y Li, W Qian. Solid dispersions in the form of electrospun core-sheath
nanofibers. International Journal of Nanomedicine, 2011, 6: 3271-3280.）, pass through
Two capillaries prepare parallel construction nanofiber for spinneret side by side（Jalani G, Jung CW, Lee JS,Lim
DW.Fabrication and characterization of anisotropic nanofiber scaffolds for
advanced drug delivery systems. International journal of nanomedicine,2014, 9
(Suppl 1), 33.）.But this advantageous feature of electrospinning just just starts at present, at present generally research report for two
The manipulation preparation of fluid streams has the micro-nano rice product of second structure characteristic.The micro-nano with labyrinth feature but more
Rice fiber（As three-level core sheath structure feature nanofiber）Need to be studied out further with their multi-fluid electro spinning method for preparing
Send out.
Content of the invention
The present invention be directed to the micro nanometer fiber of labyrinth feature lacks the problem of suitable preparation method it is proposed that one
Plant the electro spinning method for preparing with material gradient distribution characteristicss nanofiber, the method can regulate and control electric spinning polymer nanofiber
Internal component is distributed according to the feature radially increasing in gradient from outside to inside or gradient reduces.
The technical scheme is that：A kind of electro spinning method for preparing with material gradient distribution characteristicss nanofiber, tool
Body comprises the steps：
1）Build preparation facilitiess：The coaxial spinneret of three-level by of different sizes, in, outer three layers coaxial capillary tube constitute, internal layer
On fluid syringe pump and central fluid syringe pump, correspondence is installed with internal layer and central fluid syringe, internal layer and central fluid
Syringe is all connected by the internal layer capillary tube in the coaxial spinneret of high resiliency silica gel hose and three-level and intermediate layer capillary tube；
Outer capillary tube phase in the direct spinneret coaxial with three-level of hard-wired outer layer fluid injector on outer layer fluid syringe pump
Connect, high tension generator and the coaxial spinneret of three-level connect, the cardboard of the useful aluminium foil in three-level coaxial spinneret exit orifices lower end parcel
The fiber that plate is made receives flat board；
2）Mother solution is made into using spinnable polymer solution, and the mother solution after preparing is divided into three parts；
3）Three partial mother liquid are successively decreased successively by content or is incremented by and add additive, stir, form inner, middle and outer layer work
Make fluid, and corresponding load in, in, outer three fluid injectors；
4）Open high tension generator, control the injection speed of three-layer fluid in the coaxial spinneret of three-level by three syringe pumps respectively
Degree, in the presence of high-pressure electrostatic, with the coaxial spinneret exit orifices of three-level as masterplate, prepares and has material gradient distribution characteristicss
Nanofiber, and flat board reception is received by fiber.
The allotment of three layers of working fluid of the described nanofiber with material gradient distribution characteristicss：By 66 grams of ethyl celluloses
Element is put in 300 grams of ethanol, is made into the mother solution with favorable spinning quality, above-mentioned mother solution is divided into three parts, wherein
Be separately added into 8 grams of Polyvinylpyrrolidone, 4 grams and 1 gram, through being stirred into transparent solution altogether, be used separately as internal layer, in
Interbed and the working fluid of outer layer；
Step 4 after described allotment）Control and require：Regulate and control the flow velocity difference of internal layer, intermediate layer, outer layer fluid by three syringe pumps
For 0.5,0.5,1.0 mL/h, it is 15 cm with three-level coaxial spinneret exit orifices distance that fiber receives flat board, and high-pressure electrostatic occurs
Device voltage 15 kV, ambient temperature is 23 ± 1 DEG C, and ambient humidity is 54 ± 4%, can be prepared by polyvinyl pyrrole under this condition
Alkanone radial direction is from the interior ethyl cellulose nanofiber successively decreasing successively outward.
The allotment of three layers of working fluid of the described nanofiber with material gradient distribution characteristicss：By 45 grams of polyacrylonitrile
Put in 300 grams of DMFs, be made into the mother solution with favorable spinning quality, above-mentioned mother solution is divided into three portions
Point, be separately added into wherein 8 grams of molecular weight 10000 Polyethylene Glycol, 4 grams and 1 gram, through being stirred into transparent altogether solution,
Use the working fluid of outer layer, intermediate layer and internal layer respectively；
Step 4 after described allotment）Control and require：Regulate and control the flow velocity difference of internal layer, intermediate layer, outer layer fluid by three syringe pumps
For 0.5,0.5,1.0 mL/h, it is 15 cm with three-level coaxial spinneret exit orifices distance that fiber receives flat board, and high-pressure electrostatic occurs
Device voltage 20 kV, ambient temperature is 24 ± 1 DEG C, and ambient humidity is 61 ± 5%, can be prepared by Polyethylene Glycol footpath under this condition
To the polyacrylonitrile nanofiber being from inside to outside incremented by distribution.
The beneficial effects of the present invention is：The present invention has the electro spinning method for preparing of material gradient distribution characteristicss nanofiber
And device, preparation process is simple, single step effectively, in the nanofiber of preparation/in/outer three-decker is clear and nanometer diameter
Little, good linearity, diameter Distribution are uniform, fiber surface is smooth.This gradient-structure feature can be setting of numerous novel nano-materials
Meter and preparation provide effective.
Brief description
The three-level coaxial spinneret schematic diagram that Fig. 1 uses for the present invention；
Fig. 2 is three-level coaxial electrically spun technology implementation schematic device of the present invention；
Fig. 3 has the electro-spinning process shooting figure of the nanofiber of material gradient distribution characteristicss for the present invention；
Fig. 4 has the scanning electron microscope diagram of the nanofiber of material gradient distribution characteristicss for the present invention；
Fig. 5 has the transmission electron microscope figure of the nanofiber of material gradient distribution characteristicss for the present invention.
Specific embodiment
There is material gradient outwards successively decrease the nanofiber of distribution characteristicss, the coaxial spinneret of three-level that the present invention uses is such as
Shown in Fig. 1, by of different sizes, in, outer three layers coaxial capillary tube constitute, including：Outer capillary tube 1, intermediate layer capillary tube
2, internal layer capillary tube 3, outer capillary tube 1 end rubber entry joint 4, interior, middle capillary tube 2, the bulge loop joint 5 of 3 ends and use
In fixing adhesive epoxy resin 6.Three-level coaxial electrically spun technology implementation installation drawing as shown in Fig. 2 include high tension generator 7,
The coaxial spinneret of three-level 8, outer layer fluid syringe pump 9, middle fluid layer body syringe pump 10, internal layer fluid syringe pump 11, fiber receive
Plate 12, is grounded 13, middle layer fluid conveys high resiliency silica gel hose 14, internal layer fluid conveys high resiliency silica gel hose 15.
Internal layer fluid injector 18 and centre are separately installed with internal layer fluid syringe pump 11 and central fluid syringe pump 10
Fluid injector 17, the built-in internal layer of syringe and intermediate layer working fluid, syringe passes through high resiliency silica gel hose 15 He respectively
Internal layer capillary tube in high resiliency silica gel hose 14 spinneret 8 coaxial with three-level and intermediate layer capillary tube are connected.Outer layer fluid
Outer layer fluid injector 16, syringe built-in outer operative fluid, the outer layer hair of the coaxial spinneret of three-level 8 are installed on syringe pump 9
Tubule is connected directly between outer layer fluid injector.Described high tension generator 7 and the coaxial spinneret of described three-level 8 connect, institute
The coaxial spinneret of three-level 8 lower end stated is provided with a receiver board 12, and receiver sheet 12 is provided with ground connection 13.Fiber receives flat board 12
Hardboard for aluminium foil parcel.
The allotment of three layers of working fluid：66 grams of ethyl celluloses are put in 300 grams of ethanol, is made into and there is good spinnability
The mother solution of energy.Above-mentioned mother solution is divided into three parts, is separately added into 8 grams of Polyvinylpyrrolidone, 4 grams and 1 gram, warp wherein
Cross and be stirred into transparent solution altogether, be used separately as the working fluid of internal layer, intermediate layer and outer layer.
Three-level coaxial high pressure electrostatic spinning process：Above-mentioned three kinds of deployed working fluids are respectively charged into internal layer, centre
In the syringe of layer and outer operative fluid, connect each layer fluid in the coaxial spinneret of three-level 8 according to implementation Fig. 1, connect
The coaxial spinneret 8 of logical three-level and HV generator 7.
Implement three-level coaxial high pressure electrostatic spinning process according to following technological parameter：Internal layer/intermediate/outer layer fluid
Flow is 0.5/0.5/1.0 mL/h, and receiver board is sent out for 15 cm, high-pressure electrostatic with a distance from the coaxial spinneret of three-level 5 spinning nozzle
Raw device voltage 15 kV.Ambient temperature is (23 ± 1) DEG C, and ambient humidity is 54 ± 4%.Fiber passes through the aluminium foil coated papers of ground connection
Plate is collected.In the above operating condition, original position bust shot is carried out to electro-spinning process, result as shown in figure 3, from three-level with
Axle spinneret 8 three-layer fluid out is collectively forming a compound Taylor cone, and the top of cone sends a straight jet.
There is the analysis and characterization of the nanofiber of material gradient distribution characteristicss：Using field scanning Electronic Speculum（FESEM）To above-mentioned
Prepared fiber is observed after carrying out surface metal spraying, and result is as shown in Figure 4.Prepared fiber assumes good linear condition, does not have
Bead structure is had to occur, fiber surface is smooth, fiber accumulations are uniform.A diameter of 540 ± 70 nm, distribution ratio is more uniform, diameter
Concentration is compared in distribution.
Using high-resolution projection electron microscope（TEM）Prepared fibrous inner structure is observed, result such as Fig. 5 institute
Show, nanofiber interior/in/outer three-decker is clear.
There is the nanofiber that material gradient is outwards incremented by distribution characteristicss
The implementation of three-level coaxial electrically spun technology is installed by Fig. 2.45 grams of polyacrylonitrile are put into 300 grams of N, N- dimethyl formyl
In in amine, it is made into the mother solution with favorable spinning quality.Above-mentioned mother solution is divided into three parts, is separately added into molecule wherein
Measure 8 grams of 10000 Polyethylene Glycol, 4 grams and 1 gram, through being stirred into transparent solution altogether, use respectively outer layer, intermediate layer and
The working fluid of internal layer.Above-mentioned three kinds of working fluids are respectively charged in the syringe of outer layer, intermediate layer and inner operative fluid,
Connect each layer fluid in the coaxial spinneret of three-level according to implementation Fig. 2, connect high-pressure spinning head and HV generator.
Implement three-level coaxial high pressure electrostatic spinning process according to following technological parameter：Outer layer/centre/internal layer fluid flow is 0.5/
0.5/1.0 mL/h, receiver board is with a distance from spinning nozzle for 15 cm, voltage 20 kV.Ambient temperature is (24 ± 1) DEG C, environmental wet
Spend for 61 ± 5%.Fiber wraps up cardboard by the aluminium foil of ground connection and is collected.Prepared nanofiber has Polyethylene Glycol footpath
To from inside to outside incremental distribution characteristicss.
The present invention adopts three-level coaxial electrically spun technique to prepare；Prepared nanofiber is tied by the three-level core sheath of interior outer wrapping
Structure feature；Adding ingredient in fiber polymer base material has Gradient Features distribution；This Gradient Features refers to from internal layer to outer layer,
In fiber, additive increases in gradient or reduces.
Claims (3)
1. a kind of electro spinning method for preparing with material gradient distribution characteristicss nanofiber is it is characterised in that specifically include as follows
Step：
1）Build preparation facilitiess：The coaxial spinneret of three-level by of different sizes, in, outer three layers coaxial capillary tube constitute, internal layer
On fluid syringe pump and central fluid syringe pump, correspondence is installed with internal layer and central fluid syringe, internal layer and central fluid
Syringe is all connected by the internal layer capillary tube in the coaxial spinneret of high resiliency silica gel hose and three-level and intermediate layer capillary tube；
Outer capillary tube phase in the direct spinneret coaxial with three-level of hard-wired outer layer fluid injector on outer layer fluid syringe pump
Connect, high tension generator and the coaxial spinneret of three-level connect, the cardboard of the useful aluminium foil in three-level coaxial spinneret exit orifices lower end parcel
The fiber that plate is made receives flat board；
2）Mother solution is made into using spinnable polymer solution, and the mother solution after preparing is divided into three parts；
3）Three partial mother liquid are successively decreased successively by content or is incremented by and add additive, stir, form inner, middle and outer layer work
Make fluid, and corresponding load in, in, outer three fluid injectors；
4）Open high tension generator, control the injection speed of three-layer fluid in the coaxial spinneret of three-level by three syringe pumps respectively
Degree, in the presence of high-pressure electrostatic, with the coaxial spinneret exit orifices of three-level as masterplate, prepares and has material gradient distribution characteristicss
Nanofiber, and flat board reception is received by fiber.
2. there is the electro spinning method for preparing of material gradient distribution characteristicss nanofiber according to claim 1 it is characterised in that
The allotment of three layers of working fluid of the described nanofiber with material gradient distribution characteristicss：66 grams of ethyl celluloses are put into
In 300 grams of ethanol, it is made into the mother solution with favorable spinning quality, above-mentioned mother solution is divided into three parts, add respectively wherein
Enter 8 grams of Polyvinylpyrrolidone, 4 grams and 1 gram, through being stirred into transparent solution altogether, be used separately as internal layer, intermediate layer and
The working fluid of outer layer；
Step 4 after described allotment）Control and require：Regulate and control the flow velocity difference of internal layer, intermediate layer, outer layer fluid by three syringe pumps
For 0.5,0.5,1.0 mL/h, it is 15 cm with three-level coaxial spinneret exit orifices distance that fiber receives flat board, and high-pressure electrostatic occurs
Device voltage 15 kV, ambient temperature is 23 ± 1 DEG C, and ambient humidity is 54 ± 4%, can be prepared by polyvinyl pyrrole under this condition
Alkanone radial direction is from the interior ethyl cellulose nanofiber successively decreasing successively outward.
3. there is the electro spinning method for preparing of material gradient distribution characteristicss nanofiber according to claim 1 it is characterised in that
The allotment of three layers of working fluid of the described nanofiber with material gradient distribution characteristicss：45 grams of polyacrylonitrile are put into 300
In gram DMF, it is made into the mother solution with favorable spinning quality, above-mentioned mother solution is divided into three parts, at it
In be separately added into 8 grams of molecular weight 10000 Polyethylene Glycol, 4 grams and 1 gram, through being stirred into transparent altogether solution, use respectively
The working fluid of outer layer, intermediate layer and internal layer；
Step 4 after described allotment）Control and require：Regulate and control the flow velocity difference of internal layer, intermediate layer, outer layer fluid by three syringe pumps
For 0.5,0.5,1.0 mL/h, it is 15 cm with three-level coaxial spinneret exit orifices distance that fiber receives flat board, and high-pressure electrostatic occurs
Device voltage 20 kV, ambient temperature is 24 ± 1 DEG C, and ambient humidity is 61 ± 5%, can be prepared by Polyethylene Glycol footpath under this condition
To the polyacrylonitrile nanofiber being from inside to outside incremented by distribution.
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| CN201611021134.7A CN106381532B (en) | 2016-11-21 | 2016-11-21 | Electro spinning method for preparing with material gradient distribution characteristics nanofiber |
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| CN201611021134.7A CN106381532B (en) | 2016-11-21 | 2016-11-21 | Electro spinning method for preparing with material gradient distribution characteristics nanofiber |
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Cited By (7)
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| CN106757502A (en) * | 2017-01-06 | 2017-05-31 | 上海理工大学 | A kind of electro spinning nano fiber for radially isolating distribution characteristics with medicine and preparation method thereof |
| CN106801294A (en) * | 2017-02-27 | 2017-06-06 | 上海理工大学 | A kind of nanofiber bank for shipwreck soluble drug and preparation method thereof |
| CN106929928A (en) * | 2017-02-27 | 2017-07-07 | 上海理工大学 | One kind has drug material radial direction contrary distribution feature nanofiber and preparation method |
| WO2019113348A1 (en) * | 2017-12-07 | 2019-06-13 | 4C Air, Inc. | Bicomponent or multicomponent fibers and methods of making the same |
| CN111575916A (en) * | 2020-05-13 | 2020-08-25 | 贵州大学 | Preparation method of electrostatic spinning fiber membrane with continuous gradient |
| CN111910290A (en) * | 2020-07-27 | 2020-11-10 | 陕西科技大学 | Cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and preparation method and application thereof |
| CN112481708A (en) * | 2019-09-11 | 2021-03-12 | 宁波国际材料基因工程研究院有限公司 | High-flux polymer fiber preparation equipment and preparation method thereof |
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| CN106757502A (en) * | 2017-01-06 | 2017-05-31 | 上海理工大学 | A kind of electro spinning nano fiber for radially isolating distribution characteristics with medicine and preparation method thereof |
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| WO2019113348A1 (en) * | 2017-12-07 | 2019-06-13 | 4C Air, Inc. | Bicomponent or multicomponent fibers and methods of making the same |
| CN111417749A (en) * | 2017-12-07 | 2020-07-14 | 四清空气公司 | Bicomponent or multicomponent fibers and methods for making same |
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| CN111417749B (en) * | 2017-12-07 | 2022-11-01 | 四清空气公司 | Bicomponent or multicomponent fibers and methods for making same |
| CN112481708A (en) * | 2019-09-11 | 2021-03-12 | 宁波国际材料基因工程研究院有限公司 | High-flux polymer fiber preparation equipment and preparation method thereof |
| CN112481708B (en) * | 2019-09-11 | 2022-08-12 | 宁波国际材料基因工程研究院有限公司 | High-flux polymer fiber preparation equipment and preparation method thereof |
| CN111575916A (en) * | 2020-05-13 | 2020-08-25 | 贵州大学 | Preparation method of electrostatic spinning fiber membrane with continuous gradient |
| CN111910290A (en) * | 2020-07-27 | 2020-11-10 | 陕西科技大学 | Cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and preparation method and application thereof |
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| CN106381532B (en) | 2018-07-31 |
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