CN109989119A - A kind of preparation method and product and application with the porous fibre for being orientated pore structure - Google Patents
A kind of preparation method and product and application with the porous fibre for being orientated pore structure Download PDFInfo
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- CN109989119A CN109989119A CN201810004795.1A CN201810004795A CN109989119A CN 109989119 A CN109989119 A CN 109989119A CN 201810004795 A CN201810004795 A CN 201810004795A CN 109989119 A CN109989119 A CN 109989119A
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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
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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
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
Abstract
The present invention relates to a kind of preparation methods of porous fibre with orientation pore structure and product and application, preparation method to include the following steps: fibroin solutions and chitosan solution mixed preparing mixed solution 1)；2) mixed solution carries out solution-polymerized SBR, and when spinning is oriented freezing, and is collected to fiber；3) fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure.The preparation method, which passes through, combines orientation freezing and solution-polymerized SBR, and the pore structure of obtained porous fibre has orientation, it is made to have excellent heat-proof quality and electric heating property.
Description
Technical field
The present invention relates to the preparation fields of porous fibre, and in particular to a kind of system of the porous fibre with orientation pore structure
Preparation Method and product and application.
Background technique
Heat-barrier material is the material that can block hot-fluid transmitting, also known as heat insulator.Conventional insulation material, such as glass fibers
Dimension, asbestos, rock wool, silicate etc..Heat-insulation material, such as aerogel blanket, evacuated panel.Lasting solar radiation can make object
The excessively high burn into aging and degradation to accelerated material of the surface temperature of body, makes it be difficult to keep good mechanically and chemically property
Energy.
Although there are many existing cooling refrigeration equipment, the loss of the energy and the increasing of cost are largely caused
Add.Therefore, heat can be stopped to enter heat-barrier material from source, is increasingly becoming the hot spot that people competitively study.Currently, heat-insulated
The research of material is confined to the industries such as building, petroleum, transport, shipbuilding, military project, space flight mostly.And under hot summer, people couple
The demand of comfortable and easy to wear, cool clothes and shading sun-proof open air textile is also increasingly urgent to.Heat insulating function fabric passes through pair
Fabric is thermally shielded, and makes it to sunlight with barrier action or with high reflectance, high radiation.To inhibit fabric surface temperature
Degree rises to reduce internal temperature.
Heat-barrier material is divided into porous material, heat-reflecting material and vacuum material three classes.The former is using contained by material itself
Hole is heat-insulated, because the thermal coefficient of air or inert gas in gap is very low, such as foamed material, fibrous material；It is hot anti-
Material is penetrated with very high reflection coefficient, heat can be reflected away, polyester, polyamides such as gold, silver, nickel, aluminium foil or plating metal
Imines film etc..Vacuum heat insulation materials are to reach barrier convection current using the inner vacuum of material come heat-insulated.
The preparation method of barrier fabric is varied, mainly there is vapour deposition process, sol-gel technique, padding method and dry method
Direct coating.However these methods often have the shortcomings that time-consuming, energy consumption, complex process, environment be unfriendly, size limitation and
It is unable to get and is widely applied.
Orientation freezing is a kind of movement for being influenced using temperature gradient and controlling raw material and assembling to obtain orientation knot
The method of structure porous material.In recent years, people are successfully prepared the porous material that multiclass has orientation texture using orientation freezing
Material.Deville et al. (S.Deville, E.Saiz, A.P.Tomsia, Biomaterials 2006,27,5480.) successfully makes
For the timbering material of hydroxyapatite, the presence of orientation texture makes this material have the compression bigger than other structures strong
Degree.Wicklein et al. (B.Wicklein, A.Kocjan, G.Salazar-Alvarez, F.Carosio, G.Camino,
M.Antonietti, L.Bergstrom, Nat.Nanotechnol.2014,10,27791) utilize the stone of orientation freezing preparation
Black alkene/cellulose compound support frame material has better heat-insulated and flame retardant property because of orientation texture.
However, limitation of traditional orientation freezing due to its mold, cannot achieve continuous large-scale preparation, for needing
The occasion of porous fibre is continuously prepared on a large scale, this disadvantage seriously limits orientation freezing and prepares answering for porous fibre
With.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of porous fibre with orientation pore structure
Preparation method, by combining orientation freezing and solution-polymerized SBR, the pore structure of obtained porous fibre has orientation, has it
Excellent heat-proof quality.
Technical solution provided by the present invention are as follows:
A kind of preparation method of the porous fibre with orientation pore structure, includes the following steps:
1) by fibroin solutions and chitosan solution mixed preparing mixed solution；
2) mixed solution carries out solution-polymerized SBR, and when spinning is oriented freezing, and is collected to fiber；
3) fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure.
In the above technical solution, there is the porous fibre of orientation pore structure using orientation freezing and solution-polymerized SBR preparation,
With excellent heat-proof quality.After solution is squeezed out from extruder pump, due to the influence of temperature gradient, the nucleation and growth of ice crystal
It is all orientated in extrusion direction, forms orientation pore structure.
Simultaneously as micron-scale phase separation occurs for system, raw material squeezed by ice crystal, the gap that is compressed between ice crystal it
In.It is to be frozen completely after, then ice crystal removed by freeze-drying, just obtained using ice crystal as template, there is orientation hole to tie
The porous fibre of structure.
Preferably, in the step 1) fibroin solutions preparation: natural silk cocoon is sheared, is boiled in sodium carbonate liquor
Boiling drying, is dissolved in lithium-bromide solution, is made into fibroin solutions after dialysis completely.
Preferably, in the step 1) chitosan solution preparation: Chitosan powder is dissolved in acetic acid solution, match shelling
Glycan solution；The concentration of the chitosan solution is 40-60mg/ml.Further preferably, the mass concentration of the acetic acid solution is
0.5-1.5%.
Preferably, the quality proportioning of fibroin and chitosan is 8-10:1 in the step 1).Further preferably 9:
1.Fiber mechanical properties and heat-insulated can be influenced by adjusting the different quality of fibroin and chitosan proportion in mixed solution
Performance.To the intensity of fiber, elongation at break and heat-proof quality all have a major impact different ratio.When fibroin proportion is excessively high
When, tensile strength and the elongation at break that will lead to fiber are not high enough, this fiber is further woven into fabric generate it is unfavorable
It influences.When chitosan proportion is excessively high, the heat-proof quality that will lead to fiber is undesirable, because fibroin is a kind of even more ideal
Heat-barrier material.In view of effectively taking into account the engineering properties and heat-proof quality of fiber, the quality of fibroin and chitosan is found
When proportion is 9:1, the engineering properties and heat-proof quality of fiber have ideal as a result, it is possible to make fiber with excellent simultaneously
Heat-proof quality while guarantee the mechanical performance of fiber to a certain extent.
Preferably, when preparing mixed solution in the step 1), it is additionally added carbon nano-tube solution；The fibroin and carbon
The mass ratio of nanotube is 200-250:1.Further preferably 225:1.Carbon nanotube is added in mixed solution, its tool can be made
There is electric heating property, upon application of a voltage, own temperature increases.Further preferably, the carbon nano-tube solution is by carbon nanotube point
It dissipates and is made in neopelex solution；The concentration of the carbon nano-tube solution is 0.5-1.5mg/ml；The dodecane
The volumetric concentration of base benzene sulfonic acid sodium salt solution is 0.5-1.5%.
Preferably, orientation freezing specifically includes in the step 2): mixed solution passes through low temperature after squeezing out in extruder pump
Copper ring is oriented freezing；The temperature of the low temperature copper ring is -100~-40 DEG C.On the basis of traditional orientation freezing, with
Solution-polymerized SBR combines, and after mixed solution is squeezed out from extruder pump, low temperature copper ring is passed through, in the vertical direction of low temperature copper ring
With temperature gradient, when being cooled to the crystallization temperature lower than solvent, solvent starts to crystallize, final raw material squeezed by ice crystal,
It is compressed among the gap between ice crystal, above-mentioned temperature makes ice crystal be easily formed template.Cryogenic temperature is more to the orientation of formation
Pore structure has influence.Temperature is lower, and temperature gradient is bigger, and ice-crystal growth speed is faster, and the aperture of the porous structure of formation is got over
It is small.Temperature is higher, and temperature gradient is smaller, and ice-crystal growth speed is slower, and the aperture of the porous structure of formation is bigger.
The present invention provides a kind of porous fibre with orientation pore structure being prepared such as above-mentioned preparation method.This is more
The diameter of hole fiber is about 200 μm, and aperture is 15~85 μm.
The present invention provides a kind of porous fibre conduct with orientation pore structure being prepared such as above-mentioned preparation method
The application of heat-barrier material.
The present invention provides a kind of porous fibre conduct with orientation pore structure being prepared such as above-mentioned preparation method
The application of hot stealth material.Since porous fibre has excellent heat-proof quality, when the difference of material own temperature and ambient temperature
When smaller, object will not be detected by infrared camera, so as to for doing hot stealth material.
The present invention provides a kind of porous fibre conduct with orientation pore structure being prepared such as above-mentioned preparation method
The application of thermo electric material.The conductive materials such as carbon nanotube are further added in above-mentioned porous fibre, can make it have electric heating
Matter, upon application of a voltage, own temperature increase.To be applied to the management of human body self-energy, heat both can be actively discharged, together
When also can be heat-insulated, to further save and store energy, can be widely applied to human body wearable device, construction material is anti-
Shield, the fields such as military affairs, development prospect are wide.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) preparation method of the invention is simple, can continuous large scale preparation, be suitble to industry amplification application, while can basis
Actual needs designs different materials.
(2) the porous of different pore size can be prepared by adjusting the temperature of orientation freezing in preparation method of the invention
Fiber, furthermore the aperture of fiber multihole structure, porosity and hole pattern can also be adjusted on a large scale.
(3) porous fibre that preparation method of the invention is prepared, have orientation pore structure, make it have it is excellent every
Hot property.
Detailed description of the invention
Fig. 1 is present invention orientation freezing-spinning process schematic device；
Fig. 2 is the optical picture of porous fibre prepared by embodiment 1；
Fig. 3 is the Micro-CT figure of porous fibre prepared by embodiment 1；
Fig. 4 is the SEM figure of porous fibre prepared by embodiment 2；
Fig. 5 is the SEM figure of porous fibre prepared by embodiment 3；
Fig. 6 is the optical picture and SEM figure of porous fibre knitted thermal fabric prepared by embodiment 4；
Fig. 7 is the SEM figure of porous fibre prepared by comparative example 1；
Fig. 8 is the infrared figure a and absolute temperature difference b of barrier fabric prepared by application examples 1；
Fig. 9 is the optical picture a and infrared figure b for being used as the stealthy fabric of heat of barrier fabric prepared by application examples 2；
Figure 10 is the optics and SEM figure of doped carbon nanometer pipe porous fabric prepared by application examples 3；
Figure 11 is the infrared figure of doped carbon nanometer pipe porous fabric prepared by application examples 3；
Figure 12 is the making alive thermogenesis performance of doped carbon nanometer pipe porous fabric prepared by application examples 3.
Specific embodiment
The present invention is further explained in the light of specific embodiments:
Orientation freezing-spinning schematic device used in embodiment is as shown in Figure 1, wherein top has extrusion device
1, intermediate mixed solution is connect with cold source and (is not provided) by low temperature copper ring 2, copper ring 2, and bottom is motor collection device 3.Fig. 1 is right
Side is enlarged drawing of the mixed solution after freezing-spinning.
Used raw material in embodiment: natural silk cocoon (Silkworm cocoons, Yiwu Ruiheng Co., Ltd,
China.)；Chitosan powder (Chitosan, high viscosity, > 400mPas, Aladdin)；Carbon nanotube
(Carbon nanotubes, P3-SWNT)；Solvent: deionized water (H2O)。
Embodiment 1
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromination of 20ml
In lithium solution, dialysis is made into 22.5% fibroin solutions afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, is made into 5% chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein fibroin and chitosan mass proportion are 9:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure, optical photograph are as shown in Figure 2.
(4) characterization test
Micro-CT characterization is carried out for porous fibre obtained in the present embodiment, as shown in figure 3, illustrating that porous fibre has
There is orientation pore structure.
Embodiment 2
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromination of 20ml
In lithium solution, dialysis is made into 22.5% fibroin solutions afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, is made into 5% chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein fibroin and chitosan mass proportion are 9:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (respectively
It is -40, -60, -80, -100 DEG C) in, solution passes through copper ring and freeze-spinning process, and by the fiber motor after freezing
It collects.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.
(4) characterization test
SEM characterization is carried out for the porous fibre obtained under different temperatures in the present embodiment, as shown in figure 4, illustrating hole fibre
Dimension has orientation pore structure.
Embodiment 3
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromination of 20ml
In lithium solution, dialysis is made into 22.5% fibroin solutions afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, is made into 5% chitosan solution.
0.01g carbon nanotube powder is dissolved in the 1% neopelex solution of 10ml, by 20ml fibroin
Solution, 10ml chitosan solution and 20ml carbon nano-tube solution after mixing, obtain uniform solution after being centrifuged bubble removing, wherein
The quality proportioning of fibroin and chitosan is 9:1, and the quality proportioning of fibroin and carbon nanotube is 225:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (temperature
It is -100 DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.
(4) characterization test
SEM characterization is carried out for porous fibre obtained in the present embodiment, as shown in figure 5, after illustrating doped carbon nanometer pipe
Porous fibre have orientation pore structure.
Embodiment 4
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromination of 20ml
In lithium solution, dialysis is made into 22.5% fibroin solutions afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, is made into 5% chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein the quality proportioning of fibroin and chitosan is 9:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (temperature-
100 DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.
(4) porous fibre that step (3) obtains is woven into fabric.
(5) characterization test
Fabric is woven into for porous fibre obtained in the present embodiment and carries out SEM characterization, as shown in fig. 6, explanation is porous
Fiber can be woven into wearable textiles, for further keeping the temperature thermal-insulation function.
Comparative example 1
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromination of 20ml
In lithium solution, dialysis is made into 22.5% fibroin solutions afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, is made into 5% chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein fibroin and chitosan mass proportion are 9:1.
(2) mixed solution is placed in syringe, direct injection enters in liquid nitrogen (- 196 DEG C) freezings.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, is had random
Porous structure.
(4) characterization test
SEM characterization is carried out for porous fibre obtained in this comparative example, as shown in fig. 7, explanation has randomly porous
Structure, main reason is that freezing is multi-direction rather than single direction.
Application examples 1
Porous fibre prepared by Example 4 is woven into fabric as barrier fabric, due to the pore structure of fiber, fabric
The number of plies all has influence to the heat-proof quality of fabric.Therefore aperture from left to right, respectively may be about 85 μm by selection, and 65 μm, 45 μm,
30 μm of porous fibre is woven into woven, is 30 μm of fibrage into 3 and 5 layers of (area: 2 × 2mm by aperture；Thickness
Respectively 0.4,1.2 and 2mm) fabric, and test their heat-proof quality.
Six kinds of fabrics are placed in the same thermal station and are compared, as shown in Figure 8 a.When thermal station is heated to 80 from -20 DEG C
DEG C when, obtain a series of infrared images, when thermal station temperature be respectively -20 DEG C, 50 DEG C and 80 DEG C when, tool there are three typical image.
Fig. 8 b has counted the absolute temperature difference (| Δ T |) between fabric surface and thermal station.For the fabric that the fiber of smaller aperture due is made into, absolutely
It is bigger to temperature difference, there is preferable heat-proof quality.
Application examples 2
Porous fibre prepared by embodiment 4 is woven into fabric, is further woven into barrier fabric.With excellent thermal insulation
The Biomimetic Fabric of energy can become a selection well of hot stealth material.
As shown in figure 9, showing the rabbit for wearing single layer Biomimetic Fabric and commercial fabric in optics and infrared image
Son.The rabbit that can be detected by infrared camera by the body of the rabbit of the covering of commercial fabric, and be covered by Biomimetic Fabric
Body can hardly be detected by infrared camera, this is because the surface temperature of rabbit body connects very much with ambient temperature
Closely.Which demonstrate biomimetic porous fibrage barrier fabrics can be used for hot stealth material.
Equally, as shown in figure 9b, under different environment temperatures, the body of rabbit cannot all be detected by infrared camera
Out, illustrate that the hot stealth of fabric can use under -10 to 40 DEG C of extensive environment temperature.
Application examples 3
Porous fibre prepared by Example 3 is woven into fabric, since carbon nanotube being dispersed in silk fibroin protein solution,
It is set to form conductive network in bionic fiber, to generate electric heating property.As shown in the optics and SEM image in Figure 10, carbon is received
Mitron (CNTs) successfully disperses and is embedded in polymer substrate, the oriented porous structure without destroying bionic fiber.
When the fabric of doped carbon nanometer pipe is connected in circuit, as shown in the infrared image in Figure 11, applying 5V's
In the case where voltage, the surface temperature of fabric DEG C increases sharply from 20 DEG C to 36.1 in 45s.By changing the voltage applied,
Such as Figure 12, the temperature of the fabric of doped carbon nanometer pipe can be effectively adjusted.
Claims (10)
1. a kind of preparation method of the porous fibre with orientation pore structure, which comprises the steps of:
1) by fibroin solutions and chitosan solution mixed preparing mixed solution；
2) mixed solution carries out solution-polymerized SBR, and when spinning is oriented freezing, and is collected to fiber；
3) fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure.
2. the preparation method of the porous fibre with orientation pore structure according to claim 1, which is characterized in that the step
It is rapid 1) in fibroin solutions preparation: natural silk cocoon is sheared, drying is boiled in sodium carbonate liquor, is dissolved in lithium-bromide solution
In, fibroin solutions are made into after dialysis completely.
3. the preparation method of the porous fibre with orientation pore structure according to claim 1, which is characterized in that the step
It is rapid 1) in chitosan solution preparation: Chitosan powder is dissolved in acetic acid solution, chitosan solution is made into；The chitosan is molten
The concentration of liquid is 40-60mg/ml.
4. the preparation method of the porous fibre with orientation pore structure according to claim 1, which is characterized in that the step
It is rapid 1) in the quality proportioning of fibroin and chitosan be 8-10:1.
5. the preparation method of the porous fibre with orientation pore structure according to claim 1, which is characterized in that the step
When rapid 1) middle preparation mixed solution, it is additionally added carbon nano-tube solution；The fibroin and the mass ratio of carbon nanotube are 200-
250:1。
6. the preparation method of the porous fibre with orientation pore structure according to claim 1, which is characterized in that the step
Rapid 2) middle orientation freezing specifically includes: mixed solution passes through low temperature copper ring, is oriented freezing after squeezing out in extruder pump；Institute
The temperature for stating low temperature copper ring is -100~-40 DEG C.
7. the porous fibre with orientation pore structure that a kind of preparation method as described in claim 1~6 is any is prepared.
8. the porous fibre with orientation pore structure that a kind of preparation method as described in claim 1~6 is any is prepared
Application as heat-barrier material.
9. the porous fibre with orientation pore structure that a kind of preparation method as described in claim 1~6 is any is prepared
Application as hot stealth material.
10. what a kind of preparation method as claimed in claim 5 was prepared has the porous fibre of orientation pore structure as electricity
The application of hot material.
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| CN201810004795.1A CN109989119A (en) | 2018-01-03 | 2018-01-03 | A kind of preparation method and product and application with the porous fibre for being orientated pore structure |
| PCT/CN2018/096755 WO2019134359A1 (en) | 2018-01-03 | 2018-07-24 | Porous fiber having an oriented hole structure and preparation method, application and device |
| US16/817,630 US11674242B2 (en) | 2018-01-03 | 2020-03-13 | Fabrication, application and apparatus of fibers with aligned porous structure |
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| CN201810004795.1A CN109989119A (en) | 2018-01-03 | 2018-01-03 | A kind of preparation method and product and application with the porous fibre for being orientated pore structure |
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| CN110409006A (en) * | 2018-04-27 | 2019-11-05 | 浙江大学 | A kind of method that porous fibre is prepared by natural polymer and products thereof and application |
| CN110512300A (en) * | 2018-05-22 | 2019-11-29 | 浙江大学 | The preparation method and product of antibacterial porous fibre with orientation pore structure and application |
| CN110578182A (en) * | 2018-05-22 | 2019-12-17 | 浙江大学 | preparation method of anti-ultraviolet porous fiber with oriented pore structure, product and application |
| CN110578181A (en) * | 2018-05-22 | 2019-12-17 | 浙江大学 | Preparation method of radiation-proof porous fiber with oriented pore structure, product and application |
| CN112266620A (en) * | 2020-10-20 | 2021-01-26 | 江苏科技大学 | Silk-carbon nanotube composite material with directional through pore passage and preparation method thereof |
| CN114875579A (en) * | 2021-05-14 | 2022-08-09 | 南京大学 | Cellulose-based film radiation refrigeration material for passively slowing down ice melting under sunlight and application thereof |
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