CN105463613B - Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation - Google Patents
Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation Download PDFInfo
- Publication number
- CN105463613B CN105463613B CN201510953236.1A CN201510953236A CN105463613B CN 105463613 B CN105463613 B CN 105463613B CN 201510953236 A CN201510953236 A CN 201510953236A CN 105463613 B CN105463613 B CN 105463613B
- Authority
- CN
- China
- Prior art keywords
- cnt
- gqd
- quantum dot
- graphene quantum
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation, this method utilizes the molecular template effect of graphene quantum dot, first self assembled three-dimensional network structure is compounded to form with CNT, dislocation effect is formed between PA6 textures again, build conductive path, electric conductivity is improved in the case where not losing PA6 fibrous mechanical properties, while realizes that PA6 filamentary conductives can be with the lifting of mechanical property.And, due to graphene quantum dot and the compound and its self assembled three-dimensional network structure of CNT, the efficiency of transmission of electronics wherein is improved, the electric conductivity of fiber can be improved by adding a small amount of GQD/CNT, its transparency is improved simultaneously, is advantageous to the handling process such as dyeing in fiber manufacturing process.It is 0.52~0.81GPa to be prepared for tensile strength by traditional ripe PA6 melt spinning process, and line resistance is 106The good PA6 GQD/CNT composite fibres of the strength high electrical conductivity of magnitude, available for antistatic clothes, needle punched carpet, filter felt, Industrial Nonwovens, medical supplies etc..
Description
Technical field
The invention belongs to composite fibre technology field, be related to a kind of polyamide 6-graphene quantum dot/CNT prevent it is quiet
Electric fiber and preparation.
Background technology
Separated again after the object contact of any two unlike material, you can produce electrostatic.Static electric charge is not fearful, people
Electrostatic with it can run up to tens of thousands of volts sometimes, and fearful is the uneven and violent release of electrostatic, easily detonator circuit breakdown,
The malignant events such as fire, information interference, therefore the strick precaution of electrostatic is extremely important.It is harmful that the removing of antistatic textile is commonly used in life
Electrostatic, anti-static fabric mainly makes of antistatic fiber to knit.Antistatic fiber typically uses conductive fiber and antistatic fibre
Dimension.The antistatic effect of antistatic fibre and the humidity of environment are closely related, and when ambient humidity is very low, its antistatic effect is very
Weak or even disappearance, and quite a few antistatic fibre washability is poor, and persistence is poor.Conductive fiber have not against environment and
Stablize outstanding electric conductivity and excellent wear-resisting persistence, so increasingly carrying out the pro-gaze by people.
Conductive fiber can be divided into metallic fiber, carbon fiber, conductive polymer fiber, composite conducting fiber etc., wherein adopting
Electrically conductive particles are mixed into obtained composite conducting fiber in fiber stoste with composite spinning method neither influences the original physics of fiber
Performance, fiber is provided with electric conductivity again, therefore obtain more and more extensive research and application.Wherein polyamide 6 is conductive fine
Dimension is most widely used, and the method for preparing polyamide 6 conductive fiber at present is to add conductive filler in the matrix of fiber to enter
Row spinning, the conductive filler of use mainly include metal system and the major class of carbon system two.The electric conductivity of metal system composite conducting fiber
It is poor, and conductive materials are difficult to dispersed, spinning solution poor fluidity, difficulty in spinning, fiber mechanicses in polymeric matrix
Penalty.Carbon system filler mainly includes：Carbon black, CNT and graphene.Black grain diameter is larger, is difficult to disperse, is percolated valve
Value is higher, and obtained composite conducting fiber is in generally grey black, is not suitable for light textile, and mechanical performance is poor, therefore
Its application is restricted.The development for developing into composite conducting fiber of the new carbons such as CNT, graphene is widened
Road, makes it possible to have good mechanical property and electric conductivity concurrently simultaneously.
1991, the Iijima (S.Iijima, Nature, 1991,354,56) of Japanese NEC Corporation transmitted electricity with high-resolution
Caused by mirror analysis arc discharge during cathode deposition, it was found that there is the CNT (CNTs) of nano-scale, CNTs has
The advantages that size is small, draw ratio is big, intensity is high, electrical conductivity is high, good corrosion resistance and density are small.CNTs is by the C chain structure groups of C mono-
Into close with polymer chain structure, researcher is found through experiments that carries out compound, available by CNTs and high polymer material
The excellent nano composite material of energy.Since Ajayan etc. (P.M.Ajayan et al., Science, 1994,265,1212) is first
Since secondary report prepares polymer composites using CNTs as filler, CNTs and the compound of polymer turn into a research heat
Point.It is remote to assign it as a kind of new one-dimensional nano carbon system material in the unique texture of size, specific surface area etc. by CNTs
Be much better than the electrical properties of carbon black, it is oriented in polymeric matrix or orderly arrangement, by the electricity of composite and
Mechanical property produces strong influence.But because CNTs specific surface areas are big, draw ratio is big, in addition between each other strong Van der Waals force
Effect so that they are scattered relatively difficult in polymeric matrix usually into bulk or pencil aggregation, constrain it poly-
Commercial application in compound composite material.
Graphene (K.S.Novoselov, A.K.Geim, et since 2004 are found by Geim and Novoselov etc.
Al., Science, 2004,306,666), it is constantly subjected to the favor of researcher.Because it has very excellent mechanicalness
Can, such as：High Young's modulus and fracture strength, outstanding thermal conductivity and specific surface area, splendid electrical property, graphene are systems
The ideal filler of standby high tough conducting polymer based composites.Member of the graphene as newfound carbon-based material, it is comprehensive
The advantages of other carbon system fillers, there is the advantages that conductivity percolation threshold values is low, relative inexpensiveness, provided for being modified for polymer
New chance.In recent years, the research of polymer/graphene composite material has obtained development at full speed, has had both at home and abroad
Largely report (A.K.Geim, Science, 2009,19,1530；Tension force, Wu Juntao, Jiang Lei, chemical progress, 2014,26,
560).But because specific surface area and surface free energy are big, the piece interlayer of graphene has very strong electrostatic force and Van der Waals
Power, (S.Stankovich, et al., Carbon, 2007,45,1558) be present generally in the form of reunion.The aggregate of graphene
It is unfavorable for playing the excellent properties of itself, is easily caused polymer composites and produces defect, be unfavorable for the improvement of material property.
Therefore, it is one of the preferable nano composite material of manufacture to realize fine dispersion and peeling effect of the graphene in polymeric matrix
Important prerequisite.
In order to improve the dispersion effect of graphene and CNT in polymeric matrix, with reference to the advantages of both, people
By graphene and CNT be provided commonly for composite (M.A.Worsley, et al., J.Am.Chem.Soc.2010,132,
14067；W.H.Guo, et al., J.Mater.Chem.2012,22,903), build CNT-graphene composite structure.Carbon
Nanotube-graphene alkene composite forms tridimensional network (as shown in Figure 1) by wire-board junction, increases electrical-conductive nanometer material
Between effective contact, formed bridging structure.By the cooperative effect between them, the two collaboration is scattered, and CNT can be made
For the intercalation material of graphene, contribute to the scattered of the two, avoid the formation of microaggregate, show it more single than any one
The more excellent isotropic conductivity of material (V.C.Tung, et al., Nano Lett.2009,9,1949).It is but conventional
Graphene easily forms fold, the localized micro structure such as stacking because its radial dimension is big, cause CNT with its caused by have
Effect binding site is very few, and microscopic contact resistance is big, and the conductive advantage of graphene-carbon nano tube tridimensional network is difficult to play.
The content of the invention
It is an object of the invention to provide a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber and system
Standby, solving carbon nanomaterial dispersiveness and the imperfect problem of fibrous transparent degree, the fiber in composite fibre has weight
Gently, good conductivity, the advantages that transparency is high.
Graphene quantum dot (Graphene quantum dot, be abbreviated as GQD) is that the nano material of quasi-zero dimension is (two-dimentional flat
Face size<100nm), motion of its internal electron in all directions is more active, so quantum effect is particularly significant, has and is permitted
More unique properties, show more significant nanoscale effect.Found through our group studies, graphene quantum dot and carbon
The compound self assembled three-dimensional network structure of face-line that nanotube is formed has obvious enhancing effect to the electric conductivity of daiamid-6 fiber
Fruit, add a small amount of graphene quantum dot and CNT and also have simultaneously with regard to preferable effect, obtained composite fibre can be obtained
There are good mechanical property and transparency.
The present invention is using graphene quantum dot with carbon mano-tube composite as the fiber electrical-conductive nanometer filler of polyamide -6, profit
With graphene quantum dot radial dimension is small, marginal texture enriches, it is easy to the characteristics of CNT forms conducting three-dimensional network structure,
Solve the problems, such as that the easy fold of ordinary graphite alkene and stacking cause its difficulties in dispersion, obtain that transparency is preferable, electric conductivity is excellent
The composite conducting fiber of polyamide -6.
The present invention relates to a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber preparation method, this method
Comprise the following steps：
The first step, the preparation of graphene quantum dot/CNT (GQD/CNT) composite
(1) parts by weight of graphene quantum dot 0.1~1, the parts by weight of dispersant 0.1~1 are taken, are dissolved in 48~49.8 parts by weight
In deionized water, it is dispersed through, obtains dispersed graphene quantum dot dispersion；The graphite flake layer of the graphene quantum dot
It is 10~100nm for 1~3 layer, size；
(2) add in (1) parts by weight of CNT 0.1~1, the parts by weight of dispersant 0.1~1, deionized water 48~
49.8 parts by weight, it is dispersed through, centrifuges, filters, obtains dispersed GQD/CNT mixed liquors；The CNT be single wall and
Multi-walled carbon nanotube, 2~20nm of diameter, length are 0.1~2 μm；The scatter operation is ultrasonic wave or high-pressure homogeneous scattered, is adopted
With ultrasonic cell disruption instrument, 1000~4000W of its power；Or using superhigh-voltage homogenizing machine, its power is 2500W；
(3) above-mentioned GQD/CNT mixed liquors are obtained into GQD/CNT composite powders after being filtered by vacuum, being dried in vacuo；Institute
It is 0.5-2h to state the vacuum filtration time, and vacuum drying temperature is 60-100 DEG C, drying time 0.5-2h；
Second step, the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) parts by weight of caprolactam 79~97.5, above-mentioned GQD/CNT composite powders 2-20 parts by weight are taken, add initiator
0.5~1 parts by weight, stirring, ultrasonic disperse, are configured to caprolactam-GQD/CNT mixtures；The initiator be 6- amino oneself
One kind in acid, butyric acid, phosphoric acid；The dispersant is any one situation of statement in (a)~(c)：(a) polyethenoxy ether class
Or esters tween, (b) Sulfonates, Sulfates, phosphate or phosphite anionoid activating agent, (c) ammonia
The mixture of one or both of base acids, imidazoles, oxidation amine amphoteric surfactant any of the above ratio；
(2) PA6-GQD/CNT is made through steps such as prepolymerization, polymerization, granulation, washing, vacuum drying in above-mentioned mixed liquor
Master batch；The prepolymerization temperature is 150-200 DEG C, time 1-3h；Polymerization temperature is 250-270 DEG C, time 10-30h；Very
Empty drying temperature is 60-100 DEG C, drying time 2-5h；
3rd step, melt spinning
(1) the above-mentioned parts by weight of PA6-GQD/CNT master batches 1~10, the parts by weight of pure polyamide 6 about 10~20 are added screw rod and squeezed
Go out in machine and extruded after melt blending, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres；The melt is spun
Spinning temperature is 220~280 DEG C during silk；It is different according to purposes, PA6-GQD/CNT composite fibres are oiled, crimped
And/or cut-out.
The invention further relates to a kind of polyamide 6-graphene quantum dot/CNT antistatic fiber, the antistatic fiber
It is to be prepared by the above method.
The above method utilizes the molecular template effect of graphene quantum dot, is first compounded to form self assembled three-dimensional with CNT
Network structure, then dislocation effect is formed between PA6 textures, conductive path is built, is not losing PA6 fibrous mechanical properties
In the case of improve its electric conductivity, while realize PA6 filamentary conductives can and mechanical property lifting.Due to stone in the present invention
The compound and its self assembled three-dimensional network structure of black alkene quantum dot and CNT, substantially increase the transmission effect of electronics wherein
Rate, add a small amount of GQD/CNT and be greatly improved the electric conductivity of fiber, while improve its transparency, be advantageous to fiber preparation
During the handling process such as dyeing.By traditional ripe PA6 melt spinning process be prepared for tensile strength for 0.52~
0.81GPa, line resistance is 106The good PA6-GQD/CNT composite fibres of the strength high electrical conductivity of magnitude, available for it is antistatic clothes,
Needle punched carpet, filter felt, Industrial Nonwovens, medical supplies etc..
Brief description of the drawings
Fig. 1 is graphene quantum dot/CNT face-line complex three-dimensional network structure schematic diagram.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples, but should not be construed the above-mentioned theme of the present invention
Scope is only limitted to following embodiments.Without departing from the idea case in the present invention described above, known according to ordinary skill
Knowledge and customary means, make various replacements and change, all should include within the scope of the present invention.
Embodiment 1：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 8g, NPE (OP-10) 4g are taken, is dissolved in 488g deionized water, is passed through
Ultrasonic disperse (uses ultrasonic cell disruption instrument, its power 2000W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 4g, NPE (OP-10) 4g, deionized water 492g are added in (1), through super
Filtered after sound wave cell crushing instrument (power 2000W) ultrasonic disperse, 1000g centrifugal forces, obtain dispersed GQD/CNT
Mixed liquor.The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, carbon nanometer
It is 0.1~2 μm to manage as single-walled carbon nanotube, 2~10nm of diameter, length；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 0.5h drains moisture
GQD/CNT composite powders are obtained after vacuum drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 84.28g, above-mentioned GQD/CNT composite powders 14.88g are taken, adds 6-aminocaprolc acid 0.84g, is added
Heat coordinates ultrasonic disperse (power 2000W) to 100 DEG C, mechanical agitation 3h, is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres, melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.71GPa, and line resistance is 4.3 × 106Ω/cm。
Embodiment 2：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 10g, lauryl sodium sulfate 10g are taken, is dissolved in 480g deionized water, through homogeneous point
Dissipate (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtain the dispersed graphene quantum dot aqueous solution；
(2) CNT 2g, lauryl sodium sulfate 4g, deionized water 494g are added in (1), is broken through supersonic cell
Filtered after broken instrument (power 1000W) ultrasonic disperse, 1000g centrifugal forces, obtain dispersed GQD/CNT mixed solutions.
The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, and CNT is single wall
CNT, 2~10nm of diameter, length are 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 60 DEG C after vacuum filtration 2h drains moisture true
Sky obtains GQD/CNT composite powders after drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 82.32g, above-mentioned GQD/CNT composite powders 16.86g are taken, butyric acid 0.82g is added, is heated to 100
DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), it is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 150 DEG C of prepolymerization 3h, then polyase 13 0h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 5h is dried in vacuo at 60 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 30g, pure polyamide 6 section 300g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 220 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.70GPa, and line resistance is 9.0 × 106Ω/cm。
Embodiment 3：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 6g, APES 6g are taken, is dissolved in 488g deionized water, through ultrasound point
Dissipate (using ultrasonic cell disruption instrument, its power 4000W), obtain the dispersed graphene quantum dot aqueous solution；
(2) CNT 10g, APES 10g, deionized water 480g are added in (1), it is thin through ultrasonic wave
Born of the same parents filter after crushing instrument (power 2000W) ultrasonic disperse, 1000g centrifugal forces, and it is molten to obtain dispersed GQD/CNT mixing
Liquid.The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, and CNT is
Single-walled carbon nanotube, 2~10nm of diameter, length are 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 100 DEG C after vacuum filtration 1h drains moisture true
Sky obtains GQD/CNT composite powders after drying 1h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 79.0g, above-mentioned GQD/CNT composite powders 20.0g are taken, phosphatase 11 .0g is added, is heated to 100 DEG C,
Mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), it is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 200 DEG C of prepolymerization 1h, then polymerize 10h at 270 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 2h is dried in vacuo at 100 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 15g, pure polyamide 6 section 300g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 280 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.68GPa, and line resistance is 9.3 × 106Ω/cm。
Embodiment 4：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 4g, lauryl sodium sulfate 2.4g are taken, is dissolved in 493.6g deionized water, through ultrasound
Scattered (using ultrasonic cell disruption instrument, its power 2000W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 4g, lauryl sodium sulfate 1.6g, deionized water 494.4g are added in (1), through high-pressure homogeneous
Machine filters after disperseing (superhigh-voltage homogenizing machine JN-10HC, its power 2500W), 1000g centrifugal forces, obtains dispersed
GQD/CNT mixed solutions.The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size be 10~
100nm, CNT are single-walled carbon nanotube, and 2~10nm of diameter, length is 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 0.5h drains moisture
GQD/CNT composite powders are obtained after vacuum drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 91.16g, above-mentioned GQD/CNT composite powders 7.93g are taken, adds 6-aminocaprolc acid 0.91g, heating
To 100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), be configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.72GPa, and line resistance is 6.5 × 106Ω/cm。
Embodiment 5：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 4g, alkyl phenol polyethenoxy ether sodium sulfate 4g are taken, is dissolved in 488g deionized water, is passed through
Ultrasonic disperse (uses ultrasonic cell disruption instrument, its power 2000W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 2g, alkyl phenol polyethenoxy ether sodium sulfate 2g, deionized water 486g are added in (1), through high pressure
Homogenizer filters after disperseing (superhigh-voltage homogenizing machine JN-10HC, its power 2500W), 1000g centrifugal forces, is uniformly divided
Scattered GQD/CNT mixed solutions.The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size be 10~
100nm, CNT are single-walled carbon nanotube, and 2~10nm of diameter, length is 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 0.5h drains moisture
GQD/CNT composite powders are obtained after vacuum drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 89.20g, above-mentioned GQD/CNT composite powders 9.91g are taken, phosphoric acid 0.89g is added, is heated to 100
DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), it is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.69GPa, and line resistance is 7.1 × 106Ω/cm。
Embodiment 6：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 2g, lauryl sodium sulfate 1g are taken, is dissolved in 497g deionized water, through homogenous disperse
(using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 2g, lauryl sodium sulfate 1g, deionized water 497g are added in (1), is broken through supersonic cell
Filtered after broken instrument (power 2000W) ultrasonic disperse, 1000g centrifugal forces, obtain dispersed GQD/CNT mixed solutions.
The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, and CNT is single wall
CNT, 2~10nm of diameter, length are 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 0.5h drains moisture
GQD/CNT composite powders are obtained after vacuum drying 2h；
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 95g, above-mentioned GQD/CNT composite powders 4g are taken, butyric acid 1g is added, is heated to 100 DEG C, machinery stirs
3h is mixed, and coordinates ultrasonic disperse (power 2000W), is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.79GPa, and line resistance is 8.3 × 106Ω/cm。
Embodiment 7：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 1g, NPE (OP-10) 1g are taken, is dissolved in 497g deionized water, is passed through
Homogenous disperse (uses superhigh-voltage homogenizing machine JN-10HC, its power 2500W), and it is water-soluble to obtain dispersed graphene quantum dot
Liquid；
(2) CNT 1g, NPE (OP-10) 1g, deionized water 498g are added in (1), through equal
Matter filters after disperseing (using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), 1000g centrifugal forces, is uniformly divided
Scattered GQD/CNT mixed solutions.The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size be 10~
100nm, CNT are single-walled carbon nanotube, and 2~10nm of diameter, length is 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 100 DEG C after vacuum filtration 1h drains moisture true
Sky obtains GQD/CNT composite powders after drying 0.5h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 97.5g, above-mentioned GQD/CNT composite powders 2g are taken, 6-aminocaprolc acid 0.5g is added, is heated to 100
DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), it is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 160 DEG C of prepolymerization 3h, then polymerize 15h at 260 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 60 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 150g, pure polyamide 6 section 150g are added in screw extruder and melted altogether
Extruded after mixed, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 260 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.81GPa, and line resistance is 8.5 × 106Ω/cm。
Embodiment 8：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 8g, lauryl sodium sulfate 4g are taken, is dissolved in 488g deionized water, through homogenous disperse
(using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 2g, lauryl sodium sulfate 4g, deionized water 494g are added in (1), is broken through supersonic cell
Filtered after broken instrument (power 2000W) ultrasonic disperse, 1000g centrifugal forces, obtain dispersed GQD/CNT mixed solutions.
The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, and CNT is single wall
CNT, 2~10nm of diameter, length are 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 1h drains moisture true
Sky obtains GQD/CNT composite powders after drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 80g, above-mentioned GQD/CNT composite powders 19.2g are taken, 6-aminocaprolc acid 0.8g is added, is heated to
100 DEG C, mechanical agitation 3h, and coordinate ultrasonic disperse (power 2000W), it is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.52GPa, and line resistance is 4.6 × 106Ω/cm。
Embodiment 9：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 6g, lauryl sodium sulfate 3g are taken, is dissolved in 491g deionized water, through homogenous disperse
(using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 3g, lauryl sodium sulfate 3g, deionized water 494g are added in (1), is broken through supersonic cell
Filtered after broken instrument (power 2000W) ultrasonic disperse, 1000g centrifugal forces, obtain dispersed GQD/CNT mixed solutions.
The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, and CNT is single wall
CNT, 2~10nm of diameter, length are 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 0.5h drains moisture
GQD/CNT composite powders are obtained after vacuum drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 87g, above-mentioned GQD/CNT composite powders 12.1g are taken, phosphoric acid 0.9g is added, is heated to 100 DEG C, machine
Tool stirs 3h, and coordinates ultrasonic disperse (power 2000W), is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.71GPa, and line resistance is 6.3 × 106Ω/cm。
Embodiment 10：
A kind of preparation method of polyamide 6-graphene quantum dot/CNT antistatic fiber, comprises the following steps：
The preparation of graphene quantum dot/CNT 1. (GQD/CNT) composite
(1) graphene quantum dot 8g, lauryl sodium sulfate 6g are taken, is dissolved in 486g deionized water, through homogenous disperse
(using superhigh-voltage homogenizing machine JN-10HC, its power 2500W), obtains the dispersed graphene quantum dot aqueous solution；
(2) CNT 1g, lauryl sodium sulfate 2g, deionized water 497g are added in (1), is broken through supersonic cell
Filtered after broken instrument (power 2000W) ultrasonic disperse, 1000g centrifugal forces, obtain dispersed GQD/CNT mixed solutions.
The graphite flake layer of graphene quantum dot employed in this step is 1~3 layer, size is 10~100nm, and CNT is single wall
CNT, 2~10nm of diameter, length are 0.1~2 μm；
(3) above-mentioned GQD/CNT mixed liquors are put into vacuum drying chamber at 80 DEG C after vacuum filtration 0.5h drains moisture
GQD/CNT composite powders are obtained after vacuum drying 2h.
2. the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch
(1) caprolactam 85g, above-mentioned GQD/CNT composite powders 14.2g are taken, butyric acid 0.8g is added, is heated to 100 DEG C, machine
Tool stirs 3h, and coordinates ultrasonic disperse (power 2000W), is configured to PA6-GQD/CNT mixtures；
(2) above-mentioned mixed liquor is obtained into prepolymer in 180 DEG C of prepolymerization 3h, then polymerize 12h at 250 DEG C；Spend respectively
Ionized water and ethanol wash away the small molecule not polymerizeing fully or oligomer and initiator, and 4h is dried in vacuo at 80 DEG C, and PA6- is made
GQD/CNT master batches.
3. melt spinning
(1) above-mentioned PA6-GQD/CNT master batches 50g, pure polyamide 6 section 200g are added into melt blending in screw extruder
After extrude, section is made；
(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres.Melt spinning mistake
Spinning temperature is 250 DEG C in journey.
The fracture strength of composite fibre obtained by the present embodiment is 0.64GPa, and line resistance is 6.2 × 106Ω/cm。
Claims (2)
- A kind of 1. polyamide 6-graphene quantum dot/CNT antistatic fiber preparation method, it is characterized in that this method includes Following steps：The first step, the preparation of graphene quantum dot/CNT (GQD/CNT) composite(1) parts by weight of graphene quantum dot 0.1~1, the parts by weight of dispersant 0.1~1 are taken, be dissolved in 48~49.8 parts by weight go from In sub- water, it is dispersed through, obtains dispersed graphene quantum dot dispersion；The graphite flake layer of the graphene quantum dot is 1 ~3 layers, size be 10~100nm；(2) parts by weight of CNT 0.1~1, the parts by weight of dispersant 0.1~1, the weight of deionized water 48~49.8 are added in (1) Part is measured, is dispersed through, centrifuges, filters, obtain dispersed GQD/CNT mixed liquors；The CNT is single wall and more wall carbon Nanotube, 2~20nm of diameter, length are 0.1~2 μm；The scatter operation is ultrasonic wave or high-pressure homogeneous scattered, using ultrasound Ripple cell crushing instrument, 1000~4000W of its power；Or using superhigh-voltage homogenizing machine, its power is 2500W；(3) above-mentioned GQD/CNT mixed liquors are obtained into GQD/CNT composite powders after being filtered by vacuum, being dried in vacuo；It is described true The sky suction filtration time is 0.5-2h, and vacuum drying temperature is 60-100 DEG C, drying time 0.5-2h；Second step, the preparation of polyamide 6-graphene quantum dot/CNT (PA6-GQD/CNT) master batch(1) take the parts by weight of caprolactam 79~97.5, above-mentioned GQD/CNT composite powders 2-20 parts by weight, add initiator 0.5~ 1 parts by weight, stirring, ultrasonic disperse, are configured to caprolactam-GQD/CNT mixtures；The initiator is 6-aminocaprolc acid, fourth One kind in acid, phosphoric acid；The dispersant is any one situation of statement in (a)~(c)：(a) polyethenoxy ether class or ester Class tween, (b) Sulfonates, Sulfates, phosphate or phosphite anionoid activating agent, (c) amino acid The mixture of one or both of class, imidazoles, oxidation amine amphoteric surfactant any of the above ratio；(2) PA6-GQD/CNT master batches are made through prepolymerization, polymerization, granulation, washing, vacuum drying step in above-mentioned mixed liquor； The prepolymerization temperature is 150-200 DEG C, time 1-3h；Polymerization temperature is 250-270 DEG C, time 10-30h；Vacuum is done Dry temperature is 60-100 DEG C, drying time 2-5h；3rd step, melt spinning(1) the above-mentioned parts by weight of PA6-GQD/CNT master batches 1~10, the parts by weight of pure polyamide 6 10~20 are added into screw extruder Extruded after middle melt blending, section is made；(2) melt spinning is carried out using common melt spinning machine, prepares PA6-GQD/CNT composite fibres；The melt spinning mistake Spinning temperature is 220~280 DEG C in journey；It is different according to purposes, PA6-GQD/CNT composite fibres are oiled, crimp and/or Cut-out.
- A kind of 2. polyamide 6-graphene quantum dot/CNT antistatic fiber, it is characterized in that the antistatic fiber is to pass through The method of claim 1 is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953236.1A CN105463613B (en) | 2015-12-17 | 2015-12-17 | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953236.1A CN105463613B (en) | 2015-12-17 | 2015-12-17 | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105463613A CN105463613A (en) | 2016-04-06 |
| CN105463613B true CN105463613B (en) | 2018-03-09 |
Family
ID=55601754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510953236.1A Expired - Fee Related CN105463613B (en) | 2015-12-17 | 2015-12-17 | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105463613B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192192B (en) * | 2016-08-24 | 2017-04-12 | 福建省百凯经编实业有限公司 | Method for preparing patterned warp-knitted lace fabric |
| CN106435827B (en) * | 2016-09-21 | 2019-02-26 | 上海东北亚新纺织科技有限公司 | A kind of ceramics/resin/graphite alkene quantum dot composite fibre and preparation method thereof |
| CN106480532A (en) * | 2016-11-10 | 2017-03-08 | 过冬 | A kind of preparation method of Graphene reinforcing fiber |
| CN106675006A (en) * | 2017-01-05 | 2017-05-17 | 上海华峰超纤材料股份有限公司 | Conductive microfiber synthetic leather and production method thereof |
| CN108951177A (en) * | 2017-05-18 | 2018-12-07 | 安安(中国)有限公司 | A kind of processing method of the suede superfine fiber synthetic leather with higher scratch resistance wear-resisting property |
| CN107674385B (en) * | 2017-10-31 | 2019-07-12 | 西南石油大学 | A kind of preparation method of toughening drop resistance carbon fibre composite |
| CN110511375A (en) * | 2018-05-22 | 2019-11-29 | 上海杰事杰新材料(集团)股份有限公司 | A kind of static resistant polyamide composite material and preparation method |
| CN109592670A (en) * | 2018-12-20 | 2019-04-09 | 湖北工程学院 | The dispersing method of single-walled carbon nanotube |
| CN109930188A (en) * | 2019-01-31 | 2019-06-25 | 山东金宝电子股份有限公司 | A method of holey copper is prepared based on conductive fiber |
| CN110230109B (en) * | 2019-07-09 | 2021-09-10 | 杭州高烯科技有限公司 | Low-cost antistatic chinlon and preparation method thereof |
| CN110306250B (en) * | 2019-07-09 | 2021-09-24 | 杭州高烯科技有限公司 | Long-acting anti-static composite nylon fabric and preparation method thereof |
| CN110230110B (en) * | 2019-07-09 | 2020-09-29 | 杭州高烯科技有限公司 | Low-cost antistatic polyester and preparation method thereof |
| CN110359121B (en) * | 2019-07-09 | 2021-03-05 | 杭州高烯科技有限公司 | Flame-retardant antistatic polyamide and preparation method thereof |
| CN111411519B (en) * | 2020-03-27 | 2021-11-26 | 东华大学 | Early-warning type flame-retardant polylactic acid fabric and preparation method thereof |
| CN113493942A (en) * | 2020-04-03 | 2021-10-12 | 天津市职业大学 | Nanofiber material and preparation method thereof |
| CN112030269B (en) * | 2020-09-04 | 2023-02-03 | 安徽德和织造有限公司 | Special lasting electric heating self-heating composite functional fiber material for military police and preparation method and application thereof |
| CN112457558A (en) * | 2020-12-08 | 2021-03-09 | 浩珂科技有限公司 | Graphene quantum dot modified polymer master batch for functional fibers and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409424B (en) * | 2011-12-13 | 2013-07-03 | 中原工学院 | Method for preparing bamboo charcoal and polyamide composite fibers by in situ polymerization |
| CN103215689B (en) * | 2013-05-09 | 2015-02-18 | 苏州大学 | Preparation method of graphene modified nylon 6 fiber |
| CN104963022B (en) * | 2015-07-07 | 2017-06-27 | 中国科学院重庆绿色智能技术研究院 | The preparation method and product of a kind of high strength and modulus polyvinyl alcohol graphene quantum dot composite fibre |
| CN105063796B (en) * | 2015-07-21 | 2017-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of high molecular composite conductive fiber and preparation method thereof |
-
2015
- 2015-12-17 CN CN201510953236.1A patent/CN105463613B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105463613A (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105463613B (en) | Polyamide 6 graphene quantum dot/CNT antistatic fiber and preparation | |
| US10106420B2 (en) | Method for manufacturing graphene fiber | |
| Xue et al. | Electrically conductive yarns based on PVA/carbon nanotubes | |
| Choudhary et al. | Polymer/carbon nanotube nanocomposites | |
| Chou et al. | An assessment of the science and technology of carbon nanotube-based fibers and composites | |
| Zhang et al. | Magnetic and mechanical properties of polyvinyl alcohol (PVA) nanocomposites with hybrid nanofillers–graphene oxide tethered with magnetic Fe3O4 nanoparticles | |
| Su et al. | Chain conformation, crystallization behavior, electrical and mechanical properties of electrospun polymer-carbon nanotube hybrid nanofibers with different orientations | |
| Liu et al. | Tough and electrically conductive Ti3C2Tx MXene–based core–shell fibers for high–performance electromagnetic interference shielding and heating application | |
| CN1226472C (en) | Conducting fiber containing nano car bon tube and its prepn. method | |
| CN104164707A (en) | Graphene conductive polyester fibers and preparation method thereof | |
| CN106968026A (en) | A kind of preparation method of graphene carbon black composite conducting fiber | |
| CN105463612A (en) | Graphene quantum dot reinforced polyarmide fiber and preparation method thereof | |
| Kou et al. | A mini review on nanocarbon-based 1D macroscopic fibers: assembly strategies and mechanical properties | |
| CN104672502B (en) | Cyanoethyl cellulose based high-dielectric flexible nano-composite film and preparation method thereof | |
| Almuhamed et al. | Measuring of electrical properties of MWNT-reinforced PAN nanocomposites | |
| CN108611918B (en) | Carbon nano composite conductive paper and preparation method thereof | |
| Wang et al. | Conducting MWNT/poly (vinyl acetate) composite nanofibres by electrospinning | |
| EP1910220A1 (en) | Nanocomposite polymers | |
| CN103046157B (en) | A kind of carbon nano tube/polyurethane/polypropylene conductive fiber and preparation method thereof | |
| CN106003934A (en) | Anti-static nanofiber non-woven material and preparation method | |
| Rahaman et al. | Preparation/processing of polymer–carbon composites by different techniques | |
| Al Habis et al. | Intelligent design of conducting network in polymers using numerical and experimental approaches | |
| Hu et al. | Conjugated electrospinning toward a dual conductive network Janus-shaped microfiber array film with enhanced green luminescence and high aeolotropic conduction | |
| Dweiri | The Potential of Using Graphene Nanoplatelets for Electrically Conductive Compression-Molded Plates. | |
| Dorneanu et al. | Photophysical and surface characteristics of electrospun polysulfone/nickel fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180309 Termination date: 20211217 |