CN106676653B - Core fluid carries two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid - Google Patents
Core fluid carries two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid Download PDFInfo
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- CN106676653B CN106676653B CN201611021148.9A CN201611021148A CN106676653B CN 106676653 B CN106676653 B CN 106676653B CN 201611021148 A CN201611021148 A CN 201611021148A CN 106676653 B CN106676653 B CN 106676653B
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Classifications
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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
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- 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
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
-
- 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
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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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)
- Manufacturing & Machinery (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of core fluids to carry two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid, this method is to be support using the spinnability of polymer core liquid, it carries that the functional fluid without spinning properties is middle layer and pure organic solvent is outermost layer fluid in a manner of outer ring sheath fluid, implements three-level coaxial high pressure electrostatic spinning process.Outer layer organic solvent can effectively ensure that three-level coaxial electrically spun technique stabilization and it is lasting implement simultaneously guarantee prepare high quality core sheath structure nanofiber product.Spinnable functional fluid is effectively introduced into three-level coaxial electrically spun technique by the method for the present invention, is greatly expanded the nanostructure preparative capacibility of the technique；This method single step simultaneously is effective, and the nanofiber core sheath structure prepared is clear, nanofiber diameter is small, good linearity, diameter are evenly distributed, fiber surface is smooth.Numerous function ingredients can be mounted in polymer nanofiber surface by this method, obtain new function nanofiber product.
Description
Technical field
The present invention relates to a kind of processing of micro Nano material, in particular to a kind of core fluid, which carries two kinds, can not spin outer sheath fluid
Three-level coaxial electrically spun method.
Background technique
High-voltage electrostatic spinning technology (electrospinning) is the nano-fabrication technique of a kind of (top-down) from top to bottom, by additional
Electric field force overcome spray head tip drop surface tension of liquid and viscoelastic power and form jet stream, in electrostatic repulsion, Coulomb force and table
Under the tension collective effect of face, the liquid jet after being atomized is drafted thousand by high frequency flexural, drawing, division within a few tens of milliseconds
Wan Bei obtains nano-scale fiber in receiving end through solvent volatilization or melt are cooling.The technical matters process is simple, manipulation is convenient,
Selection material ranges are extensive, controllability is strong, are considered as a kind of most possible side for realizing continuous nano-fibre industrialized production
Method prepares functional nano-fiber with good prospect using the technology.
But there are two the extensive uses that aspect reason significantly limits the technology at present.One is only 100 kinds of left sides
Right polymer has a good spinning properties, and these polymer to spin concentration window narrow；The second is due to making
Be easy to volatilize organic solvent deploy spinning solution, therefore have many materials (including be easy be precipitated small molecule function ingredients,
Binder, the protein easily to interact with spinneret etc.) it is very easy to blocking spinneret.These problems effectively overcome
The nano structural material preparative capacibility of electrospinning processes will greatly be expanded, be guided out the polymer matrix function of a series of new
Micro-nano rice product.
Summary of the invention
The present invention be directed to material limited problems when the use of high-voltage electrostatic spinning technology, propose a kind of core fluid carrying
Two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid, this method to be support using the spinnability of polymer core liquid, with
The mode of outer ring sheath fluid carries that the functional fluid without spinning properties is middle layer and pure organic solvent is outermost layer fluid, real
Apply three-level coaxial high pressure electrostatic spinning process.
The technical solution of the present invention is as follows: a kind of core fluid carries two kinds of three-level coaxial electrically spun sides that can not spin outer sheath fluid
Method specifically comprises the following steps:
1) build preparation facilities: in the coaxial spinneret of three-level by three capillaries of different sizes form it is interior, in, outer three
It is corresponding on layer axis outlet, internal layer fluid syringe pump and intermediate layer fluid syringe pump to be fixedly installed with internal layer and intermediate layer fluid note
Emitter, internal layer and middle layer fluid injector pass through high resiliency silica gel hose in the coaxial spinneret of three-level internal layer and centre
Layer capillary inlet be connected, the outer layer fluid injector being fixedly mounted on outer layer fluid syringe pump directly with the coaxial spinning of three-level
Outer capillary tube entrance in head is connected, and high pressure generator is connected with the coaxial spinneret of three-level, the coaxial spinneret exit orifices of three-level
The fiber that the hardboard of the useful aluminium foil package in lower end is made into receives plate；
2) inner operative fluid is made into using spinnable polymer solution, is the Core support fluid of three-level coaxial electrically spun,
Inject internal layer fluid injector；
3) middle layer working fluid is made into using not spinnable function ingredients solution, injects middle layer fluid injector；
4) outer operative fluid is made into using pure organic solvent, injects outer layer fluid injector；
5) high pressure generator is opened, controls the stream of three kinds of fluids in the coaxial spinneret of three-level respectively by three syringe pumps
Speed, under the action of high-pressure electrostatic, the coaxial spinneret exit orifices of three-level generate the nanofiber with core sheath structure feature, pass through fibre
Dimension receives plate and receives.
The step 2) with core sheath structure feature nanofiber, 3) allotment with 4) three layers of working fluid: by 15 grams
Cellulose acetate is put into 120 grams of in the mixed solvents, is made into the Core support fluid with favorable spinning quality, mixed solvent is by 20
Gram n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone mix；Outer operative fluid is by 20 grams of N, N- dimethyl methyl
Amide, 20 grams of ethyl alcohol and 80 grams of acetone mix；10 grams of gliadins are dissolved in the in the mixed solvent of 100 grams of acetic acid and ethyl alcohol,
Volume ratio acetic acid: ethyl alcohol 1:3 constitutes middle layer working fluid；
Step 5) control requires after the allotment: internal layer, middle layer, outer layer fluid flow are respectively 0.5,0.5,2.0
ML/h, it is 20 cm, 18 kV of high pressure generator voltage with a distance from spinning nozzle that fiber, which receives plate,；Environment temperature is 24 ± 2 DEG C,
Ambient humidity is 55 ± 5%.
And 4) described with core sheath structure feature nanofiber is step 2) when drug directly wrap up polymer fiber, 3)
The allotment of three layers of working fluid: 15 grams of cellulose acetates are put into 120 grams of in the mixed solvents, are made into favorable spinning quality
Core support fluid, mixed solvent are mixed by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone；Outer layer work
Make fluid to be mixed by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone；10 grams of drug Ketoprofens are dissolved
In the mixed solvent being made of 80 grams of acetone and 20 grams of ethyl alcohol be middle layer working fluid；
Step 5) control requires after the allotment:: internal layer, middle layer, outer layer fluid flow are respectively 0.5,1.0,2.0
ML/h, it is 20 cm with a distance from spinning nozzle that fiber, which receives plate, and 20 kV of high pressure generator voltage, environment temperature is 24 ± 2
DEG C, ambient humidity is 55 ± 5%.
The beneficial effects of the present invention are: core fluid of the present invention carries two kinds of three-level coaxial electrically spuns that can not spin outer sheath fluid
Method, outer layer organic solvent can effectively ensure that three-level coaxial electrically spun technique stabilization and it is lasting implementation and meanwhile guarantee to prepare
High quality core sheath structure nanofiber product out.Spinnable functional fluid is effectively introduced three-level coaxial electrically spun by the method for the present invention
In technique, it is greatly expanded the nanostructure preparative capacibility of the technique；This method single step simultaneously is effective, the Nanowire prepared
Dimension core sheath structure is clear, nanofiber diameter is small, good linearity, diameter are evenly distributed, fiber surface is smooth.It can be with by this method
Numerous function ingredients are mounted in polymer nanofiber surface, obtain new function nanofiber product.
Detailed description of the invention
Fig. 1 is the coaxial spinneret schematic diagram of three-level of the present invention；
Fig. 2 is that core fluid of the present invention carries two kinds of three-level coaxial electrically spun method implementing device signals that can not spin outer sheath fluid
Figure；
Fig. 3 is that core fluid of the present invention carries two kinds of taylor cones that can not spin the three-level coaxial electrically spun process shooting of outer sheath fluid
Figure；
Fig. 4 can not spin outer sheath fluid three-level coaxial electrically spun using two kinds of the carrying of core fluid for the present invention and prepare nanofiber
Scanning electron microscope diagram；
Fig. 5 is that the present invention applies core fluid two kinds of three-level coaxial electrically spuns that can not spin outer sheath fluid of carrying to prepare nanofiber
Transmission electron microscope figure.
Specific embodiment
The coaxial spinneret of the three-level that the present invention uses as shown in Figure 1, by of different sizes, in, outer three layers of coaxial capillary
Pipe is constituted, comprising: outer capillary tube 1, middle layer capillary 2, internal layer capillary 3,1 end rubber entry connector of outer capillary tube
4, interior, middle capillary 2,3 ends bulge loop connector 5 and adhesive epoxy resin 6 for fixing.Three-level coaxial electrically spun technology is real
Device figure is applied as shown in Fig. 2, including high pressure generator 7, the coaxial spinneret 8 of three-level, outer layer fluid syringe pump 9, intermediate fluid layer body
Syringe pump 10, internal layer fluid syringe pump 11, fiber receiver board 12, ground connection 13, middle layer fluid conveying high resiliency silica gel hose 14,
Internal layer fluid conveying high resiliency silica gel hose 15.
Internal layer fluid injector 18 and centre are separately installed on internal layer fluid syringe pump 11 and central fluid syringe pump 10
Layer fluid syringe 17 fills internal layer and middle layer working fluid in syringe respectively, and it is soft that syringe passes through high resiliency silica gel respectively
Pipe 15 and high resiliency silica gel hose 14 in the coaxial spinneret 8 of three-level internal layer capillary and middle layer capillary be connected.Outside
Installation outer layer fluid injector 16 on layer fluid syringe pump 9, the built-in outer operative fluid of syringe, the coaxial spinneret 8 of three-level
Outer capillary tube is connected directly between outer layer fluid injector.The high pressure generator 7 and the coaxial spinneret 8 of three-level connect
It connects, coaxial 8 lower end of spinneret of the three-level is provided with a receiver board 12, and receiver sheet 12 is equipped with ground connection 13.Fiber receives
Plate 12 is the hardboard of aluminium foil package.
The allotment of three layers of working fluid: being put into 120 grams of in the mixed solvents for 15 grams of cellulose acetates, and being made into has good spin
The operating core fluid of silk performance.Mixed solvent by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone mixing and
At.Outer layer solvent is mixed by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone.10 grams of gliadins are dissolved in
The in the mixed solvent (volume ratio acetic acid: ethyl alcohol 1:3) of 100 grams of acetic acid and ethyl alcohol constitutes middle layer working fluid.
The implementation of three-level coaxial high pressure electrostatic spinning process: above-mentioned three kinds of working fluids are respectively charged into internal layer, middle layer
In the syringe of outer operative fluid, each layer fluid is connected into the coaxial spinneret of three-level according to Fig. 2 shown device, is connected high
Press spinneret and HV generator.
Implement three-level coaxial high pressure electrostatic spinning process: internal layer/centre/outer laminar fluid flow according to following technological parameter
Amount is 0.5/0.5/2.0 mL/h, and receiver board is 20 cm, 18 kV of voltage with a distance from spinning nozzle.Environment temperature is (24 ± 2)
DEG C, ambient humidity is 55 ± 5%.Fiber wraps up cardboard by the aluminium foil being grounded and is collected.In the above operating condition, to electricity
Spinning process carries out bust shot in situ, as a result as shown in figure 3, being collectively formed one from the three-layer fluid that the coaxial spinneret of three-level comes out
The top of a compound Taylor cone, cone issues a straight jet.
The analysis and characterization of nanofiber: it is seen after carrying out surface metal spraying to prepared fiber using field scan Electronic Speculum (FESEM)
It examines, as a result as shown in Figure 4.Prepared fiber is presented good linear condition, does not have bead structure, fiber surface light
Cunning, fiber accumulations are uniform.Diameter is 470 ± 50 nm, and distribution is relatively uniform, and concentration is compared in diameter distribution.
Prepared fibrous inner structure is observed using high-resolution projection electron microscope (TEM), as a result such as Fig. 5 institute
Show, the core sheath structure of nanofiber is clear.
Drug directly wraps up the core sheath structure preparation of polymer fiber: it is molten that 15 grams of cellulose acetates being put into 120 grams of mixing
In agent, it is made into the operating core fluid with favorable spinning quality.Mixed solvent is by 20 grams of n,N-Dimethylformamide, 20 grams of second
Pure and mild 80 grams of acetone mixes.Outer layer solvent by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone mixing and
At.10 grams of drug Ketoprofens are dissolved in, middle layer workflow is constituted by the mixed solvent that 80 grams of acetone and 20 grams of ethyl alcohol form
Body.
Above-mentioned three kinds of working fluids are respectively charged into the syringe of internal layer, middle layer and outer operative fluid, according to reality
It applies example 1 and connects each layer fluid into the coaxial spinneret of three-level, connect high-pressure spinning head and HV generator.According to following work
Skill conditional parameter implements three-level coaxial high pressure electrostatic spinning process: internal layer/centre/outer layer fluid flow is 0.5/1.0/2.0
ML/h, receiver board are 20 cm, 20 kV of voltage with a distance from spinning nozzle.Environment temperature be (24 ± 2) DEG C, ambient humidity be 55 ±
5%.Fiber wraps up cardboard by the aluminium foil being grounded and is collected.In the above operating condition, Ketoprofen can be effectively prevent in electricity
Spinning process is precipitated and blocks spinneret, prepares the core sheath structure nanofiber that fiber surface wraps up one layer of small-molecule drug.
Claims (2)
1. a kind of core fluid carries two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid, which is characterized in that specifically include
Following steps:
1) build preparation facilities: in the coaxial spinneret of three-level by three capillaries of different sizes form it is interior, in, outer three layers it is same
It is corresponding on axial outlet, internal layer fluid syringe pump and intermediate layer fluid syringe pump to be fixedly installed with internal layer and intermediate layer fluid injection
Device, internal layer and middle layer fluid injector pass through high resiliency silica gel hose and the internal layer and middle layer in the coaxial spinneret of three-level
Capillary inlet is connected, the outer layer fluid injector being fixedly mounted on outer layer fluid syringe pump directly with the coaxial spinneret of three-level
In outer capillary tube entrance be connected, high pressure generator is connected with the coaxial spinneret of three-level, under the coaxial spinneret exit orifices of three-level
The fiber for holding the hardboard of useful aluminium foil package to be made into receives plate；
2) inner operative fluid is made into using spinnable polymer solution, is the Core support fluid of three-level coaxial electrically spun, injection
Internal layer fluid injector；
3) middle layer working fluid is made into using not spinnable function ingredients solution, injects middle layer fluid injector；
4) outer operative fluid is made into using pure organic solvent, injects outer layer fluid injector；
5) high pressure generator is opened, controls the flow velocity of three kinds of fluids in the coaxial spinneret of three-level respectively by three syringe pumps,
Under the action of high-pressure electrostatic, the coaxial spinneret exit orifices of three-level generate the nanofiber with core sheath structure feature, are connect by fiber
It is closed flat plate reception；
The step 2) of the nanofiber with core sheath structure feature, 3) allotment with 4) three layers of working fluid: by 15 grams of vinegar
Acid cellulose is put into 120 grams of in the mixed solvents, is made into the Core support fluid with favorable spinning quality, mixed solvent is by 20 grams
N,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone mix；Outer operative fluid is by 20 grams of N, N- dimethyl formyl
Amine, 20 grams of ethyl alcohol and 80 grams of acetone mix；10 grams of gliadins are dissolved in the in the mixed solvent of 100 grams of acetic acid and ethyl alcohol, body
Product is than acetic acid: ethyl alcohol 1:3 constitutes middle layer working fluid；
Step 5) control requires after the allotment: internal layer, middle layer, outer layer fluid flow are respectively 0.5,0.5,2.0mL/h, fibre
It is 20cm, high pressure generator voltage 18kV with a distance from spinning nozzle that dimension, which receives plate,；Environment temperature is 24 ± 2 DEG C, and ambient humidity is
55 ± 5%.
2. core fluid carries two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid, feature according to claim 1
Be, the nanofiber with core sheath structure feature is drug when directly wrap up polymer fiber, the step 2), 3) with
4) the allotment replacement of three layers of working fluid are as follows: 15 grams of cellulose acetates are put into 120 grams of in the mixed solvents, being made into has good spin
The Core support fluid of silk performance, mixed solvent by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone mixing and
At；Outer operative fluid is mixed by 20 grams of n,N-Dimethylformamide, 20 grams of ethyl alcohol and 80 grams of acetone；By 10 grams of drug ketone
It is middle layer working fluid that ibuprofen, which is dissolved in by the mixed solvent that 80 grams of acetone and 20 grams of ethyl alcohol form,；
Step 5) control requires after the allotment: internal layer, middle layer, outer layer fluid flow are respectively 0.5,1.0,2.0mL/h, fibre
It is 20cm with a distance from spinning nozzle that dimension, which receives plate, and high pressure generator voltage 20kV, environment temperature is 24 ± 2 DEG C, and ambient humidity is
55 ± 5%.
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| CN201611021148.9A CN106676653B (en) | 2016-11-21 | 2016-11-21 | Core fluid carries two kinds of three-level coaxial electrically spun methods that can not spin outer sheath fluid |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106757502B (en) * | 2017-01-06 | 2019-08-30 | 上海理工大学 | A kind of electro spinning nano fiber and preparation method thereof that distribution characteristics being radially isolated with drug |
| CN109295511B (en) * | 2018-09-26 | 2022-05-31 | 上海理工大学 | Detachable coaxial nozzle, electrospinning device and preparation method of core-sheath nanofiber |
| CN110004506B (en) * | 2019-04-17 | 2021-03-02 | 中国科学院长春应用化学研究所 | Microfluidic spinning device and method |
| CN113897691A (en) * | 2021-11-16 | 2022-01-07 | 上海理工大学 | Preparation method of bead nanofiber with composite structure |
| CN114351284A (en) * | 2022-01-18 | 2022-04-15 | 上海理工大学 | Method for preparing porous nano polymer fiber through improved coaxial electrospinning process |
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| CN102234846A (en) * | 2010-04-28 | 2011-11-09 | 中国科学院化学研究所 | Core/shell fiber with nanowire-embedded microtube structure and preparation method thereof |
| CN103526336A (en) * | 2013-10-15 | 2014-01-22 | 东华大学 | Preparation method of oriented shell-core structural superfine composite fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101274662B1 (en) * | 2011-12-02 | 2013-06-13 | 서울대학교산학협력단 | Preparation method of multilayered carbon nano-fiber using electrospinning and multilayered carbon nano-fiber formed therefrom |
| KR101506513B1 (en) * | 2013-02-20 | 2015-03-27 | 서울대학교산학협력단 | Core-cut nozzle for co-axial electrospinning and electrospinning apparatus including the same |
| US20180044817A1 (en) * | 2015-03-17 | 2018-02-15 | Nanospun Technologies Ltd. | Multi-layered microfibers and use thereof |
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| CN102234846A (en) * | 2010-04-28 | 2011-11-09 | 中国科学院化学研究所 | Core/shell fiber with nanowire-embedded microtube structure and preparation method thereof |
| CN103526336A (en) * | 2013-10-15 | 2014-01-22 | 东华大学 | Preparation method of oriented shell-core structural superfine composite fiber |
| CN103668485A (en) * | 2013-12-03 | 2014-03-26 | 大连海洋大学 | Coaxial three-layer high-activity bio-enzyme-embedded electrostatic spinning nano-fiber membrane and preparation method thereof |
| CN105525385A (en) * | 2015-12-24 | 2016-04-27 | 杭州市第三人民医院 | Multilayer core-shell nano-fiber scaffold, and method for constructing tissue engineering material by using multilayer core-shell nano-fiber scaffold and melanocyte |
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