CN103132163A - Fiber with multiple core-shell structures and preparation method thereof - Google Patents

Fiber with multiple core-shell structures and preparation method thereof Download PDF

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Publication number
CN103132163A
CN103132163A CN2013100774953A CN201310077495A CN103132163A CN 103132163 A CN103132163 A CN 103132163A CN 2013100774953 A CN2013100774953 A CN 2013100774953A CN 201310077495 A CN201310077495 A CN 201310077495A CN 103132163 A CN103132163 A CN 103132163A
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fiber
phase solution
passage
fluid
shell structure
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CN103132163B (en
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赵远锦
程瑶
商珞然
顾忠泽
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Southeast University
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Southeast University
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Abstract

The invention discloses a fiber with multiple core-shell structures. The fiber is provided with the multiple core-shell structures. The diameter of the fiber is 10 microns to 1*106 microns, and the length of the fiber is more than one 1 micron. The cross section of the fiber is in a circular shape or a hollow ring shape. The invention further provides a preparation method of the fiber. With the structure, the fiber with the multiple core-shell structures is controllable in morphology and structure, and the preparation method is convenient and fast to operate, and designability and piratical applicability of the fiber are strong. Packaging miscellaneous nano particles, medicines or living cells can be achieved. The fiber with the multiple core-shell structures can be applied in the fields of cell cultivation, medicine sustained release, tissue engineering and the like.

Description

A kind of fiber with multi-kernel shell structure and preparation method thereof
Technical field
The present invention relates to technical field of biological materials, particularly relate to a kind of fiber with multi-kernel shell structure and preparation method thereof.
Background technology
Fiber refers to the material that is comprised of continuous or discrete filament.Just there is natural fiber in occurring in nature, just can directly obtain from plant, animal and Minerals And Rocks, as flax, jute, wool, the rabbit hair, mineral fibres etc., in daily life everywhere as seen.With respect to natural fabric, chemical fibre is a kind of fiber that processes through chemical treatment, more than wide, the kind of its raw material, all is widely used in high-tech areas such as textile industry, military affairs, environmental protection, medicine, building, biotechnologies.Along with the development of science and technology, people are increasing to the needs of the 26S Proteasome Structure and Function of fiber, no longer are confined to the fiber of one-component, homogenous material, simple function, and it is particularly important that the preparation of composite fibre seems.And traditional preparation method as melt spinning, wet spinning, electrostatic spinning etc., due to the restriction of its technique and principle, has run into difficulty in the fiber preparation with labyrinth and function.Especially at biological technical field, the three-dimensional carrier that fiber is cultivated as cell is guaranteeing not destroy the preparation of synchronously completing parcel and the fiber of cell under the prerequisite of cytoactive, and traditional preparation method is difficult to realize.
Micro-fluidicly refer to a kind of technology of accurately controlling minute yardstick (especially referring to submicron-scale) fluid, have that device volume is little, liquid flow is controlled, consume sample and amount of reagent still less, be easy to control, be difficult for causing the advantage such as cross pollution.Utilize the micro-channel device of microflow control technique, can controllably prepare various shapes, structure functional carrier, can also realize the encapsulation of chemistry of different nature, biological sample, cultivate and the clinical diagnosis field is widely used at genomics, proteomics, combinatorial chemistry, drug screening and slowly-releasing, cell.
Therefore, utilizing microflow control technique is that the composite fibre that preparation has labyrinth and a function is the powerful measure that addresses the above problem.
Summary of the invention
The object of the invention is to provide a kind of fiber and method thereof of multi-kernel shell structure, and its preparation process is simple, and appearance and size is controlled, favorable repeatability.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of fiber with multi-kernel shell structure is provided, and described fiber has the multi-kernel shell structure, the diameter of described fiber be 10 microns to 1 * 10 6Micron, length is more than 1 millimeter, the cross section of described fiber is circle or hollow ring.
In a preferred embodiment of the present invention, the volume of described each nucleocapsid is identical.
In a preferred embodiment of the present invention, the volume of described each nucleocapsid is not identical.
For solving the problems of the technologies described above, another technical solution used in the present invention is: a kind of described method with fiber of multi-kernel shell structure for preparing is provided, and described fiber is by micro-fluidic method preparation, comprises the following steps:
At first, micro-fluidic chip build step:
Adopt micro-processing technology to set up the microfluidic channel network, perhaps select capillary glass tube, sheet glass and syringe needle to set up microfluid c-axial channel network, this channel network comprises three kinds of passages, is respectively fluid passage, continuous phase passage and coflow passage;
Secondly, the preparation process of fiber:
Fluid-phase solution and continuous phase solution are respectively charged into syringe, connect entrance separately, control each phase solution flow rate with the numerical control syringe pump, treat that decentralized photo presents stable fibrous in the coflow passage, curing is to be cured by physico-chemical process convection cell phase solution.
In a preferred embodiment of the present invention, described microfluidic channel network using silicon, glass, polymethyl methacrylate or dimethyl silicone polymer micro-fluid chip are made, the internal diameter size of passage be 1 micron to 1 * 10 6Micron.
In a preferred embodiment of the present invention, according to the nucleocapsid number of plies of described fiber, described fluid passage is one or more, and a plurality of decentralized photo passages independently of one another and coaxial nested layer by layer from inside to outside.
In a preferred embodiment of the present invention, described fluid-phase solution is selected from one or more in calcium alginate, agarose, shitosan, acrylic acid, acrylamide, N-isopropylacrylamide, polyethyleneglycol diacrylate, Ethylene glycol dimethacrylate, methyl methacrylate, poly hydroxy ethyl acrylate, acetylbutyrylcellulose, siloxanes methacrylate, fluorine silicon methacrylate, perfluor ether, N-vinylpyrrolidone, polyvinyl alcohol or glycidyl methacrylate.
In a preferred embodiment of the present invention, described fluid-phase solution is oil-soluble, and described continuous phase solution is selected from one or more in methyl-silicone oil, hexadecane, paraffin oil or soybean oil.
In a preferred embodiment of the present invention, described fluid-phase solution is water-soluble, and described continuous phase solution is selected from one or more in water, ethanol, polyvinyl alcohol, polyethylene glycol, glycerine, calcium ion salts solution, magnesium ion salting liquid or barium ions salting liquid.
In a preferred embodiment of the present invention, the curing of described fiber is selected one or more in thermal curing method, ultra-violet curing method or ion exchange method.
The invention has the beneficial effects as follows: pattern and the structure of fiber of the present invention are controlled, and designability and the practicality of preparation method's simple operation, fiber are stronger, can realize the parcel of nano particle of different nature, medicine or active somatic cell.
Description of drawings
Fig. 1 is that the present invention prepares microfluidic channel network diagram in the fiber process with multi-kernel shell structure;
Fig. 2 is the schematic diagram that the present invention has the fiber of multi-kernel shell structure;
In accompanying drawing, the mark of each parts is as follows: 1, coflow passage; 2, continuous phase passage; 3, fluid passage; 4, fiber.
The specific embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in detail, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that, protection scope of the present invention is made more explicit defining.
See also Fig. 1 and Fig. 2, the embodiment of the present invention provides following technical scheme
In one embodiment, a kind of fiber 4 with multi-kernel shell structure, described fiber 4 has the multi-kernel shell structure, the diameter of described fiber 4 be 10 microns to 1 * 10 6Micron, length is more than 1 millimeter, the cross section of described fiber 4 is circle or hollow ring.
Preferably, the volume of described each nucleocapsid is identical.
Preferably, the volume of described each nucleocapsid is not identical.
For solving the problems of the technologies described above, another technical solution used in the present invention is: a kind of described method with fiber 4 of multi-kernel shell structure for preparing is provided, and described fiber 4 is by micro-fluidic method preparation, comprises the following steps:
At first, micro-fluidic chip build step:
Adopt micro-processing technology to set up the microfluidic channel network, perhaps select capillary glass tube, sheet glass and syringe needle to set up microfluid c-axial channel network, this channel network comprises three kinds of passages, is respectively fluid passage 3, continuous phase passage 2 and coflow passage 1;
Secondly, the preparation process of fiber:
Fluid-phase solution and continuous phase solution are respectively charged into syringe, connect entrance separately, control each phase solution flow rate with the numerical control syringe pump, treat that decentralized photo presents stable fibrous in coflow passage 1, curing is to be cured by physico-chemical process convection cell phase solution.
Preferably, described microfluidic channel 3 network using silicon, glass, polymethyl methacrylate or dimethyl silicone polymer micro-fluid chip are made, the internal diameter size of passage be 1 micron to 1 * 10 6Micron.
Preferably, according to the nucleocapsid number of plies of described fiber 4, described fluid passage 3 is one or more, and a plurality of decentralized photo passages independently of one another and coaxial nested layer by layer from inside to outside.
Preferably, described fluid-phase solution is selected from one or more in calcium alginate, agarose, shitosan, acrylic acid, acrylamide, N-isopropylacrylamide, polyethyleneglycol diacrylate, Ethylene glycol dimethacrylate, methyl methacrylate, poly hydroxy ethyl acrylate, acetylbutyrylcellulose, siloxanes methacrylate, fluorine silicon methacrylate, perfluor ether, N-vinylpyrrolidone, polyvinyl alcohol or glycidyl methacrylate.
Preferably, described fluid-phase solution is oil-soluble, and described continuous phase solution is selected from one or more in methyl-silicone oil, hexadecane, paraffin oil or soybean oil.
Preferably, described fluid-phase solution is water-soluble, and described continuous phase solution is selected from one or more in water, ethanol, polyvinyl alcohol, polyethylene glycol, glycerine, calcium ion salts solution, magnesium ion salting liquid or barium ions salting liquid.
Preferably, the curing of described fiber 4 is selected one or more in thermal curing method, ultra-violet curing method or ion exchange method.
The present invention utilizes microflow control technique, according to the 26S Proteasome Structure and Function of multicomponent fibre, designs and build micro-fluidic chip, by composition and the flow velocity of regulating each phase solution, can prepare the fiber 4 with multi-kernel shell structure.Fiber 4 with multi-kernel shell structure, each layer with its material and function to show differentiation.Optionally adopt each fluid passage 3 materials, wrap up functional nano particle, medicine or cell, can be applied in the fields such as cell cultivation, medicament slow release, organizational project.With respect to traditional fiber preparation method, the method that the present invention proposes, device is simple, designability and the practicality of simple operation, fiber are stronger.Its concrete preparation method comprises the following steps:
(1) preparation process of micro-fluidic chip:
Utilize the method for micromachined, the preparation channel network, the material of passage can be selected silicon or the materials such as glass or polymethyl methacrylate or dimethyl silicone polymer; Perhaps select capillary glass tube, sheet glass and syringe needle to set up microfluid coflow formula channel network.Channel network comprises three kinds of passages, is respectively fluid passage 3, continuous phase passage 2 and coflow passage 1, and the internal diameter size of passage is between 1 micron to 1 millimeter.
(2) preparation process of fiber:
Certain density cell or nano particle or medicine or above any combination mixture are added before aquogel in aggressiveness, and vibration mixing or ultrasonic dispersion are as solution.before aquogel in fluid-phase solution, aggressiveness is selected from calcium alginate, agarose, shitosan, acrylic acid, acrylamide, N-isopropylacrylamide, Ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, methyl methacrylate, poly hydroxy ethyl acrylate, acetylbutyrylcellulose, the siloxanes methacrylate, fluorine silicon methacrylate, perfluor ether, the N-vinylpyrrolidone, polyvinyl alcohol, or one or more the material in glycidyl methacrylate.Nanometer particle material before aquogel in aggressiveness is selected from one or more the material in silica, polystyrene, polymethyl methacrylate, titanium dioxide, iron oxide, gold, silver, fluorescent dye or quantum dot.The selection of fluid-phase solution is depended in the selection of continuous phase solution: if fluid-phase solution is oil-soluble material, continuous phase solution is selected from one or more the material in methyl-silicone oil, hexadecane, paraffin oil or soybean oil; If fluid-phase solution is water miscible material, continuous phase solution is selected from one or more the material in water, ethanol, polyvinyl alcohol, polyethylene glycol, glycerine, calcium ion salts solution, magnesium ion salting liquid or barium ions salting liquid.
Mentioned solution is respectively charged into syringe, connects the entrance of passage separately.Control each phase solution flow rate with the numerical control syringe pump, treat that fluid-phase solution presents stable fibrous in coflow passage 1, characteristic according to front aggressiveness solution, select ion exchange method or ultra-violet curing method or heat cure to send out method decentralized photo solution is cured, and collect at the end of coflow passage 1.
Embodiment 1 has the preparation of the fiber 4 of two-layer nucleocapsid structure:
1. the preparation of micro-fluidic chip:
Utilize the method for micromachined, the PDMS channel network that preparation is circular, this channel network comprises two mutual 3, two of coaxial nested fluid passages continuous phase passages 2 and a coflow passage 1, each channel interior is done hydrophobic treatments.
2. the preparation of fiber:
(1) configuration of each phase solution:
Fluid-phase solution 1: the monodisperse silica nano particle that is 180 nanometers with diameter joins in the aqueous solution of polyethyleneglycol diacrylate, the mass fraction of regulating silica is 40%, the mass fraction of polyethyleneglycol diacrylate is 10%, ultrasonic dispersion is until colloidal particle solution produces vivid color; Add initator 2-hydroxy-2-methyl propiophenone (1%, volume ratio) in mentioned solution, fully after mixing, standby after sealing.
Fluid-phase solution 2: the single ferriferrous oxide nano-particle that disperses that with diameter is the carboxyl modified of 20 nanometers joins in the aqueous solution of polyethyleneglycol diacrylate, the mass fraction of regulating four oxidation trisomes is 5%, the mass fraction of polyethyleneglycol diacrylate is 10%, ultrasonic dispersion; Add initator 2-hydroxy-2-methyl propiophenone (1%, volume ratio) in mentioned solution, fully after mixing, standby after sealing.
Continuous phase solution: mass fraction is 10% Aqueous Solutions of Polyethylene Glycol.
(2) generation of fiber and curing
Mentioned solution is respectively charged into syringe, connect the entrance of passage separately, control each phase solution flow rate with the numerical control syringe pump, treat that fluid-phase solution presents stable fibrous in coflow passage 1, by the ultra-violet curing method, decentralized photo solution is cured, and collects at the end of coflow passage 1.
Embodiment 2 has the preparation of fiber of the hollow structure of two-layer nucleocapsid:
1. the preparation of micro-fluidic chip:
Draw instrument with acetylene burner or microelectrode and draw three kinds of capillary glass tubies, make the tapered sharp-crested of one end, and polish on sand paper, until the smooth sharp-crested internal diameter smooth and single tube of sharp-crested is respectively 40 microns, 100 microns, 200 microns, be placed in the alcohol ultrasonic cleaning, nitrogen dries up; Take sheet glass as substrate, be that to insert internal diameter be in the capillary of 580 microns for the capillary of 200 microns with internal diameter, adjust sharp-crested to the capillary axis, successively the capillary of 100 microns is nested in by above-mentioned steps in the pipe of 200 microns, the capillary of 40 microns is nested in the pipe of 100 microns, syringe needle is installed, and is fixed with quick-drying gelatin.
2. the preparation of fiber:
(1) configuration of each phase solution:
Fluid-phase solution 1: configuration 2wt% sodium alginate aqueous solution, after high-temperature sterilization, equal-volume mixes with the culture medium solution that contains the human liver cancer cell of 2 * 105/liter, and is standby after vibration evenly.
Fluid-phase solution 2: configuration 2wt% sodium alginate aqueous solution, after high-temperature sterilization, equal-volume becomes the culture medium solution of fiber 4 cells to mix with the mouse that contains 2 * 105/liter, standby after vibration evenly.
Fluid-phase solution 3: the configuration quality mark is 2% calcium chloride water respectively, and mass fraction is 10% polyvinyl alcohol water solution, and both after the equal-volume mixing, high-temperature sterilization is standby.
Continuous phase solution: mass fraction is 2% calcium chloride water, and is standby after high-temperature sterilization.
(2) generation of fiber 4 and curing
Under gnotobasis, mentioned solution is respectively charged into syringe, connects the entrance of passage separately, control each phase solution flow rate with the numerical control syringe pump, treat that fluid-phase liquid presents stable fibrous in coflow passage 1, collect calcium alginate fibre at the end of coflow passage 1.Collect complete after, rinse fiber with phosphate buffer and culture medium successively, fiber is immersed in is placed in incubator in culture medium solution at last.
The present invention utilizes microflow control technique, according to the 26S Proteasome Structure and Function of multi-kernel shell structure fiber, designs and build micro-fluidic chip, and composition and flow velocity by regulating each phase solution can prepare the fiber with multi-kernel shell structure.Fiber with multi-kernel shell structure, each component with its material and function to show differentiation.Optionally adopt each fluid passage 3 materials, wrap up functional nano particle, medicine or cell, can be applied in the fields such as cell cultivation, medicament slow release, organizational project.With respect to traditional fiber preparation method, the method that the present invention proposes, device is simple, designability and the practicality of simple operation, fiber are stronger, can realize the parcel of nano particle of different nature, medicine or active somatic cell.
The present invention is by microflow control technique, and the designability and the practicality that prepare the fiber with multi-kernel shell structure are stronger.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification of the present invention and accompanying drawing content to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.

Claims (10)

1. the fiber with multi-kernel shell structure, is characterized in that, described fiber has the multi-kernel shell structure, the diameter of described fiber be 10 microns to 1 * 10 6Micron, length is more than 1 millimeter, the cross section of described fiber is circle or hollow ring.
2. the fiber with multi-kernel shell structure according to claim 1, is characterized in that, the volume of described each nucleocapsid is identical.
3. the fiber with multi-kernel shell structure according to claim 1, is characterized in that, the volume of described each nucleocapsid is not identical.
4. one kind prepares the arbitrary described method with fiber of multi-kernel shell structure of claim 1-3, it is characterized in that, described fiber is by micro-fluidic method preparation, comprises the following steps:
At first, micro-fluidic chip build step:
Adopt micro-processing technology to set up the microfluidic channel network, perhaps select capillary glass tube, sheet glass and syringe needle to set up microfluid c-axial channel network, this channel network comprises three kinds of passages, is respectively fluid passage, continuous phase passage and coflow passage;
Secondly, the preparation process of fiber:
Fluid-phase solution and continuous phase solution are respectively charged into syringe, connect entrance separately, control each phase solution flow rate with the numerical control syringe pump, treat that decentralized photo presents stable fibrous in the coflow passage, curing is to be cured by physico-chemical process convection cell phase solution.
5. method according to claim 4, is characterized in that, described microfluidic channel network using silicon, glass, polymethyl methacrylate or dimethyl silicone polymer micro-fluid chip are made, the internal diameter size of passage be 1 micron to 1 * 10 6Micron.
6. method according to claim 4, is characterized in that, according to the nucleocapsid number of plies of described fiber, described fluid passage is one or more, and a plurality of decentralized photo passages independently of one another and coaxial nested layer by layer from inside to outside.
7. method according to claim 4, it is characterized in that, described fluid-phase solution is selected from one or more in calcium alginate, agarose, shitosan, acrylic acid, acrylamide, N-isopropylacrylamide, polyethyleneglycol diacrylate, Ethylene glycol dimethacrylate, methyl methacrylate, poly hydroxy ethyl acrylate, acetylbutyrylcellulose, siloxanes methacrylate, fluorine silicon methacrylate, perfluor ether, N-vinylpyrrolidone, polyvinyl alcohol or glycidyl methacrylate.
8. method according to claim 4, is characterized in that, described fluid-phase solution is oil-soluble, and described continuous phase solution is selected from one or more in methyl-silicone oil, hexadecane, paraffin oil or soybean oil.
9. method according to claim 4, it is characterized in that, described fluid-phase solution is water-soluble, and described continuous phase solution is selected from one or more in water, ethanol, polyvinyl alcohol, polyethylene glycol, glycerine, calcium ion salts solution, magnesium ion salting liquid or barium ions salting liquid.
10. method according to claim 4, is characterized in that, the curing of described fiber is selected one or more in thermal curing method, ultra-violet curing method or ion exchange method.
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CN103820425A (en) * 2014-01-21 2014-05-28 东南大学 Microfluidic device for preparing calcium alginate fibers
CN103820880A (en) * 2014-01-21 2014-05-28 东南大学 Calcium alginate fiber and preparation method thereof
CN105887241A (en) * 2016-05-27 2016-08-24 东莞市联洲知识产权运营管理有限公司 Phase-change temperature-regulating chitosan composite fiber and preparation method thereof
CN106215987A (en) * 2016-08-12 2016-12-14 四川大学 Multichannel also flows micro-fluid chip and the controlled spinning process of linear heterogeneous heterojunction structure fiber based on this chip
CN106222799A (en) * 2016-08-03 2016-12-14 耿云花 A kind of double-layer nested nanofiber and preparation method thereof
CN107849739A (en) * 2015-07-29 2018-03-27 纳幕尔杜邦公司 Yarn from the polymer with different decomposition temperature with and forming method thereof
CN107988657A (en) * 2017-12-25 2018-05-04 东华大学 A kind of continuous method for preparing magnetic field responsiveness photonic crystal fiber
CN108159976A (en) * 2018-01-03 2018-06-15 西南交通大学 A kind of Water-In-Oil Bao Shui(W/W/O)Monodisperse double emulsion preparation method and its micro fluidic device
CN108360088A (en) * 2018-02-28 2018-08-03 清华大学深圳研究生院 The method and apparatus for preparing calcium alginate fibre
CN109537071A (en) * 2018-12-06 2019-03-29 南通纺织丝绸产业技术研究院 A method of preparing the nanofiber of multilayered structure
CN109927282A (en) * 2019-04-17 2019-06-25 中国科学院长春应用化学研究所 A kind of Method of printing of 3D printing system and fiber
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CN112481721A (en) * 2020-12-28 2021-03-12 南京鼓楼医院 Microfluidic spinning device, linear type core-shell structure conductive fiber, and preparation method and application thereof
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CN103820880A (en) * 2014-01-21 2014-05-28 东南大学 Calcium alginate fiber and preparation method thereof
CN103820880B (en) * 2014-01-21 2016-04-20 东南大学 A kind of calcium alginate fibre and preparation method thereof
CN103820425A (en) * 2014-01-21 2014-05-28 东南大学 Microfluidic device for preparing calcium alginate fibers
US11932838B2 (en) 2014-11-25 2024-03-19 Corning Incorporated Cell culture media extending materials and methods
CN107849739A (en) * 2015-07-29 2018-03-27 纳幕尔杜邦公司 Yarn from the polymer with different decomposition temperature with and forming method thereof
CN107849739B (en) * 2015-07-29 2022-08-02 纳幕尔杜邦公司 Yarns from polymers having different decomposition temperatures and methods of forming the same
CN105887241A (en) * 2016-05-27 2016-08-24 东莞市联洲知识产权运营管理有限公司 Phase-change temperature-regulating chitosan composite fiber and preparation method thereof
CN106222799A (en) * 2016-08-03 2016-12-14 耿云花 A kind of double-layer nested nanofiber and preparation method thereof
CN106215987A (en) * 2016-08-12 2016-12-14 四川大学 Multichannel also flows micro-fluid chip and the controlled spinning process of linear heterogeneous heterojunction structure fiber based on this chip
CN107988657A (en) * 2017-12-25 2018-05-04 东华大学 A kind of continuous method for preparing magnetic field responsiveness photonic crystal fiber
CN107988657B (en) * 2017-12-25 2019-12-10 东华大学 Method for continuously preparing magnetic field responsive photonic crystal fiber
CN108159976A (en) * 2018-01-03 2018-06-15 西南交通大学 A kind of Water-In-Oil Bao Shui(W/W/O)Monodisperse double emulsion preparation method and its micro fluidic device
CN108360088A (en) * 2018-02-28 2018-08-03 清华大学深圳研究生院 The method and apparatus for preparing calcium alginate fibre
CN109537071A (en) * 2018-12-06 2019-03-29 南通纺织丝绸产业技术研究院 A method of preparing the nanofiber of multilayered structure
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