CN105442072A - Method for preparing super tough fibers of shell-simulation structures and helical structures simultaneously in batches - Google Patents
Method for preparing super tough fibers of shell-simulation structures and helical structures simultaneously in batches Download PDFInfo
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- CN105442072A CN105442072A CN201511014843.8A CN201511014843A CN105442072A CN 105442072 A CN105442072 A CN 105442072A CN 201511014843 A CN201511014843 A CN 201511014843A CN 105442072 A CN105442072 A CN 105442072A
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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
- D01D13/00—Complete machines for producing artificial threads
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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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- 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
- D01F6/94—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 other polycondensation products
Abstract
The invention discloses a method for preparing super tough fibers of shell-simulation structures and helical structures simultaneously in batches. The method comprises the steps of combining the microscopic scale, the mesoscopic scale and the macroscopic scale, preparing out fibers of the shell-simulation structure in a layer-by-layer assembly mode in the first place, then weaving the fibers into the continuous helical structures through the dry spinning technology, and thereby integrating the shell-simulation structures and the helical structures into the same fibers. When the fibers are subjected to axial pulling force, external force acting is resisted through open loops of the helical structures on the mesoscopic scale and multiscale deformation such as slippage among graphene pieces on the microscopic scale, the superhigh elongation and tensile strength are achieved, and superhigh toughness is further achieved. The fibers of the shell-simulation structures and the helical structures simultaneously prepared through the method have superhigh elongation (>400%) and superhigh toughness (-640 J/g), raw materials are wide, the process is simple and continuous, and the method can be applied to fibers made of different two-dimensional inorganic nanosheets without polymer and has universality and portability.
Description
Technical field
The invention belongs to machine-building and material science field of engineering technology, relate to the method that the preparation of a kind of batch has the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously.
Background technology
High-performance fiber, compared to chemical fibres such as natural fabric and terylene such as traditional cotton, hair, silks, has the excellent properties such as high strength, high elasticity, heat resistance, rub resistance, resistance to chemical attack.Therefore, play an important role in various aspects such as national defense and military, communications and transportation, industrial and agricultural production, daily lifes.The continuous pursuit of high-performance fiber and fabric is promoted to the continuous progress of the preparation level of fiber.Two-dimension nano materials (as Graphene etc.) has the excellent specific properties such as low defect, large specific area, high strength, how to be extended in the body material of macroscopic view by the excellent properties that these materials show on nanoscale, be the significant challenge that material science and engineering field face for a long time.For graphene fiber, existing research is raw material usually with graphene oxide, can prepare graphene oxide fiber by wet spining technology; Graphene fiber is prepared further by restoring operation.Because the graphene oxide itself used has very high defect, and be only more weak Van der Waals force between graphene oxide sheet, make but the percentage elongation of this fibrid is generally less than 6%, tensile strength is less than 450MPa, thus it is lower to result in tenacity of fibre.Therefore, how by improving material performance and fibre structure reasonable in design is two importances improving fibre property.
Summary of the invention
The object of this invention is to provide the method that the preparation of a kind of batch has the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously.Raw material of the present invention is extensive, and technique is simply continuous, can prepare high-performance fiber in batches, designs and preparation provides a kind of universal method for allied fiber.
The object of the invention is to be achieved through the following technical solutions:
Batch preparation has a method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, comprises the steps:
One, Two-dimensional Inorganic nanometer sheet mixed by a certain percentage with polymer, obtain the stoste as wet spinning silk, the mass fraction controlling Two-dimensional Inorganic nanometer sheet in stoste is 0 ~ 100%, and concrete mixed method is as follows:
(1) first by polymer dissolution in deionized water, prepare mass fraction 1 ~ 10% aqueous solutions of polymers.
(2) Two-dimensional Inorganic nanometer sheet is mixed with aqueous solutions of polymers, then at 20 ~ 30 DEG C, stir 24 ~ 36h with 400 ~ 1000 revs/min, obtain homodisperse Two-dimensional Inorganic nanometer sheet/mixed with polymers solution.
(3) Two-dimensional Inorganic nanometer sheet/mixed with polymers solution heated at 60 ~ 90 DEG C and stir 30 ~ 120min, evaporation excessive moisture, thus forming liquid crystal gel, as the stoste of wet spinning silk.
Two, the stoste obtained in step one is moved in the container of 1 ~ 25mL, be the spinning pin hole of 10 ~ 500 μm by internal diameter with the extruded velocity of 0.1 ~ 100mL/h, the stoste extruded enters in condensation water solidifies 0.5 ~ 15min, again the fiber solidified is taken out, wash 3 ~ 5 times, and in 50 ~ 80 DEG C of baking ovens dry 12 ~ 24h, obtain the Two-dimensional Inorganic nanometer sheet/polymer fiber with imitative clam shell feature.
Three, fiber step 2 obtained is weaved in dry spinning equipment, and adjustment moment of torsion is 0.001 ~ 10N/m, axial tension 0.1 ~ 50N, and weaving 10 ~ 120min, forms the fiber with continuous helical structure.So far, obtain the Two-dimensional Inorganic nanometer sheet/polymer fiber simultaneously with imitative clam shell feature and helical structure, its microcosmic is the structure layer by layer of imitative shell, and being situated between on seeing and having helical structure, is macroscopically fibre structure.
In the present invention, described Two-dimensional Inorganic nanometer sheet comprises numerous material, as Graphene, calcium carbonate, alundum (Al2O3), clay, imvite, molybdenum bisuphide, two selenizing molybdenums, gallium selenide, sulfuration gallium, telluride gallium, tungsten disulfide, two tungsten selenide etc.Their preparation method is different, can adopt chemical vapour deposition technique, chemical stripping method, electrochemical stripping method, ultrasonic stripping method, mechanical stripping method etc.
In the present invention, the Typical Representative using graphene film as Two-dimensional Inorganic nanometer sheet, its preparation method is: adopt electrochemical method to peel off, prepare the high-quality graphene nanometer sheet of low defect, as the raw material preparing fiber, concrete steps are as follows:
(1) natural graphite flakes or highly oriented pyrolytic graphite is adopted to be raw material, and as an electrode.By in the diluting concentrated sulfuric acid of 0.5 ~ 5.0ml98% to 20 ~ 190ml deionized water and with 10 ~ 30% pH value to 0.8 ~ 1.5 of sodium hydrate regulator solution, as electrolyte.Platinized platinum, as another electrode, forms electrochemical stripping Graphene system.Suitable pH value can make to ionize out a large amount of sulfate ions in electrolyte, as intercalation thing under the effect of electric field, between the lamella being constantly inserted into graphite.
(2) before electrolysis, pre-oxidation is carried out to graphite extremely important in this experiment, adopt+1.0 ~+2.5V voltage to graphite pre-oxidation 0.5 ~ 3min, graphite flake layer spacing to be increased, be conducive to oxidation and the reduction reaction of follow-up graphite flake.
(3), after pre-oxidation, graphite and platinum plate electrode apply+8 ~ 12V, 2 ~ 5s and-8 ~-12V, 5 ~ 10s cycle alternation change voltage respectively and carries out electrolysis.Under+8 ~ 12V, graphite flake be inflated peel off and by dilute sulfuric acid slight oxidation; Under-8 ~-12V, oxidized graphite flake is reduced into Graphene and disperses in the electrolytic solution, and cycle alternation oxidation like this and reduction are until graphite is complete by electrolysis.
(4) after electrolysis, mixed solution is filtered and spends deionized water 3 ~ 5 times, the precipitation obtained is distributed in organic solvent (as DMF etc.) again, under the rotating speed of 2500 ~ 4000 revs/min, centrifugal 3 ~ 5min removes the graphite flake be not fully exfoliated out again, thus form low defect graphene nanometer sheet, i.e. the Graphene of electrochemical stripping.
In the present invention, described polymer comprises polyvinyl alcohol, dimethyl silicone polymer, polyacrylic acid, epoxy resin, polyacrylonitrile, Aromatic polyester, chliorinated polyvinyl chloride, liquid crystal polymer etc.
In the present invention, described condensation water comprises one or more of calcium chloride, NaOH, ethanol, saturated sodium sulphate, 5% NaOH ethanolic solution, sodium nitrate, calcium nitrate, chlorination molten iron or water/alcohol mixeding liquid.
Microcosmic-Jie's sight-macro-scale combines by the present invention, first the fiber of imitative clam shell feature is prepared by the mode of layer assembly, by dry spining technology, this fibrous woven is become continuous print helical structure again, thus imitative shell and helical structure are integrated in same fiber.When being subject to axial tension, in the open loop and microcosmic of seeing upper helical structure by being situated between, between graphene film, the multiple dimensioned distortion opposing external force such as slippage is done work, and realizes superelevation percentage elongation and tensile strength, and then realizes superhigh tenacity.Compared to prior art, the present invention has following technique effect:
1, Two-dimensional Inorganic nanometer sheet wide material sources enrich, cheap, and can the acquisition of low cost, ensure that fiber can the acquisition of low cost batch.
2, by controlling the content of Two-dimensional Inorganic nanometer sheet, can realize that there is imitative shell and helical structure fiber simultaneously easily.
3, in fiber manufacturing process, equipment therefor is simple, and Modulatory character is high, is easy to batch production.
The fiber while 4, prepared with imitative clam shell feature and helical structure has percentage elongation (>400%) and the superpower toughness (~ 640J/g) of superelevation; Can carry out weaving or becoming types of functionality fabric with other fiber shuffling, especially in physical protection, there is significant application value.
5, method of the present invention can be applied to different Two-dimensional Inorganic nanometer sheet and the fiber formed without polymer, and have universality and portability, this is also the most important feature of the present invention.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram that continuous production has imitative clam shell feature and helical structure simultaneously;
Fig. 2 is that the scanning electronic microscope of fiber characterizes.(a) helical structure fiber surface pattern, (b) fibre section low power pattern, (c) fibre section high power number form looks;
Fig. 3 is stress-strain curves, comprises pure graphene fiber, Graphene/66%PVA film and Graphene/66%PVA spiral fiber mechanical property contrast;
Fig. 4 is Graphene/PVA fiber macroscopic view digital camera photo;
Fig. 5 is the partial enlargement scanning electron microscope image of Fig. 4;
Fig. 6 is calcium carbonate/PVA fiber macroscopic view digital camera photo;
Fig. 7 is the partial enlargement scanning electron microscope image of Fig. 6.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Detailed description of the invention one: present embodiments provide for the method that the preparation of a kind of batch has the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, its preparation process is as follows:
One, Two-dimensional Inorganic nanometer sheet is prepared
Typical Representative using graphene film as Two-dimensional Inorganic nanometer sheet, its preparation method is: adopt electrochemical method to peel off, prepare the high-quality graphene nanometer sheet of low defect, as the raw material of fiber, concrete steps are as follows:
(1) highly oriented pyrolytic graphite is adopted to be raw material, and as an electrode.By the diluting concentrated sulfuric acid of 0.5 ~ 5.0mL98% in 20 ~ 190mL deionized water, and pH value to 0.8 ~ 1.5 of sodium hydrate regulator solution with 10 ~ 30%, as electrolyte.Platinized platinum, as another electrode, forms electrochemical stripping Graphene system.Suitable pH value can make to ionize out a large amount of sulfate ions in electrolyte, as intercalation thing under the effect of electric field, between the lamella being constantly inserted into graphite.
(2) before electrolysis, pre-oxidation is carried out to graphite extremely important in this experiment, adopt+1.0 ~+2.5V voltage to graphite pre-oxidation 0.5 ~ 3min, graphite flake layer spacing to be increased, be conducive to oxidation and the reduction reaction of follow-up graphite flake.
(3), after pre-oxidation, graphite and platinum plate electrode apply+8 ~ 12V, 2 ~ 5s and-8 ~-12V, 5 ~ 10s cycle alternation change voltage respectively and carries out electrolysis.Under+8 ~ 12V, graphite flake be inflated peel off and by dilute sulfuric acid slight oxidation; Under-8 ~-12V, oxidized graphite flake is reduced into Graphene and disperses in the electrolytic solution, and cycle alternation oxidation like this and reduction are until graphite is complete by electrolysis.
(4) after electrolysis, mixed solution is filtered and spends deionized water 3 ~ 5 times, the precipitation obtained is distributed in organic solvent (as DMF etc.) again, under the rotating speed of 2500 ~ 4000 revs/min, centrifugal 3 ~ 5min removes the graphite flake be not fully exfoliated out again, thus form low defect graphene nanometer sheet, i.e. the graphene film of electrochemical stripping.
Two, the graphene film of electrochemical stripping is mixed by a certain percentage with polyvinyl alcohol (PVA), control the mass fraction of Graphene from 0 ~ 100%.Concrete steps are as follows:
(1) first PVA dissolves in deionized water, and mass fraction is 1 ~ 10%.
(2) by the graphene film of certain mass and above-mentioned PVA aqueous solution, the mixed liquor of certain Graphene content is prepared.
(3) at 20 ~ 30 DEG C, stir 24 ~ 36h with 400 ~ 1000 revs/min, obtain homodisperse Graphene/PVA solution.
(4) by mixed solution agitating heating 30 ~ 120min at 60 ~ 90 DEG C, evaporation excessive moisture, thus form the liquid crystal gel of 10 ~ 30mg/mL, as the stoste of wet spinning silk.
Three, Graphene/PVA spinning solution will be obtained in step 2, move in the container of 1 ~ 25mL, be the spinning pin hole of 10 ~ 500 μm by internal diameter with the extruded velocity of 0.1 ~ 100mL/h, the stoste extruded enters in condensation water solidifies 0.5 ~ 15min, the fiber removal will solidified again, wash 3 ~ 5 times, and in 50 ~ 80 DEG C of baking ovens dry 12 ~ 24h, obtain the Graphene/PVA fiber with imitative clam shell feature.Condensation herein can be ethanol, saturated sodium sulphate, 5% NaOH ethanolic solution etc.
Four, fiber step 3 obtained, weaves further at dry spinning equipment, and adjustment moment of torsion is 0.001 ~ 10N/m, axial tension 0.1 ~ 50N, and weaving 10 ~ 120min, forms the fiber with continuous helical structure.So far, the Graphene/PVA fiber simultaneously with imitative clam shell feature and helical structure is obtained.
In present embodiment, described dry spinning equipment comprises syringe, the main stoste holding spinning, and its volume can design as required and manufacture, and changes within the scope of 1 ~ 25mL.There is push rod syringe rear end, is connected with peristaltic pump, controls the extruded velocity of stoste, can coordinate not isometric syringe by peristaltic pump, regulates extruded velocity at 0.1 ~ 100mL/h.There is long and thin metal pin syringe front portion, and there is pin hole inside, extruding for stoste, and the diameter of pin hole, by changing the kind of metal needle, changes in 10 ~ 500 μm.Syringe bottom is a container filling condensation water, and its volume, in 100 ~ 10000mL scope, adds the condensation water of respective volume as required.The fiber solidified is undertaken transporting and changing direction of advance by godet roller, enter torsion device, torsion device body interior has a hole, and the rotatable device in axial line position with two godet rollers, godet roller can regulate fiber hold down power, torsion device rotating speed can by regulating and controlling with its meshed gears and motor, and moment of torsion can be adjustable in 0.001 ~ 10N/m scope.Low order end dead block, for gathering screw structural fibers, its direction of rotation and speed can regulate, and provide an axial tension simultaneously, make helical structure be able to continuous print and are formed.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: adopt highly oriented pyrolytic graphite to be raw material, by pH value to 1.0 ~ 1.3 of the sodium hydrate regulator solution in the diluting concentrated sulfuric acid of 1.0 ~ 4.0mL98% to 50 ~ 150mL deionized water and with 20 ~ 30%.
Detailed description of the invention three: present embodiment and detailed description of the invention one, two unlike: adopt+1.5 ~+2.0V voltage to graphite oxidation 0.5 ~ 1.5min, graphite flake layer spacing to be increased, be conducive to oxidation and the reduction reaction of follow-up graphite flake.After pre-oxidation, graphite and platinum plate electrode apply+9 ~ 11V, 2 ~ 4s and-9 ~-11V, 8 ~ 10s cycle alternation change voltage respectively.
Detailed description of the invention four: present embodiment and detailed description of the invention one ~ tri-unlike: after electrolysis, mixed solution is filtered and spends deionized water 3 ~ 5 times, the precipitation obtained is distributed in organic solvent (as DMF etc.) again, under the rotating speed of 3000 ~ 4000 revs/min, centrifugal 4 ~ 5min removes the graphite flake be not fully exfoliated out again, thus forms low defect graphene nanometer sheet.
Detailed description of the invention five: present embodiment and detailed description of the invention one ~ tetra-unlike: first PVA dissolves in deionized water, and mass fraction is 5 ~ 10%.
Detailed description of the invention six: present embodiment and detailed description of the invention one ~ five unlike: Graphene mixes by a certain percentage with polyvinyl alcohol, and mixed proportion is 20 ~ 70%.
Detailed description of the invention seven: present embodiment and detailed description of the invention one ~ six unlike: Graphene and polyvinyl alcohol mixing liquid, at 25 ~ 30 DEG C, stir 24 ~ 36h with 500 ~ 800 revs/min, obtain homodisperse Graphene/PVA solution.Further by mixed solution agitating heating 30 ~ 120min at 70 ~ 80 DEG C, evaporation excessive moisture, thus form the liquid crystal gel of 10 ~ 30mg/mL, as the stoste of wet spinning silk.
Detailed description of the invention eight: present embodiment and detailed description of the invention one ~ seven unlike: move in the container of 1 ~ 25mL by obtaining Graphene/PVA spinning solution in step 2, as shown in Figure 1.Be the spinning pin hole of 50 ~ 400 μm by internal diameter with the extruded velocity of 1 ~ 50mL/h, the stoste extruded enters in condensation water solidifies 0.5 ~ 15min, then is taken out by the fiber solidified, and washs 3 ~ 5 times, and in 50 ~ 80 DEG C of baking ovens dry 12 ~ 24h, obtain the Graphene/PVA fiber with imitative clam shell feature.
Detailed description of the invention nine: present embodiment and detailed description of the invention one ~ eight unlike: described condensation water is 5% NaOH ethanolic solution.
Detailed description of the invention ten: present embodiment and detailed description of the invention one ~ nine unlike: syringe volume is 10mL, extruded velocity 1 ~ 10mL/h, and extruding pin hole internal diameter is 200 ~ 300 μm, and setting time is 5 ~ 10min.
Detailed description of the invention 11: present embodiment and detailed description of the invention one ~ ten unlike: the mass fraction of Graphene is 0, and gained fiber is straight polymer fiber.
Detailed description of the invention 12: present embodiment and detailed description of the invention one ~ 11 unlike: the mass fraction of Graphene is 100%, and gained fiber is for be made up of pure Two-dimensional Inorganic nanometer sheet.
Detailed description of the invention 13: present embodiment and detailed description of the invention one ~ 12 unlike: as shown in Figure 1, clamping force is regulated by two godet roller spacing on torsion device, and then change moment of torsion is 0.01 ~ 10N/m, axial tension is regulated by dead block and torsion device, axial tension 0.5 ~ 20N, weaving 10 ~ 120min, forms the fiber with continuous helical structure.
Detailed description of the invention 14: present embodiment and detailed description of the invention one ~ 13 unlike: for Graphene/PVA fiber, moment of torsion is 0.1 ~ 5N/m, and axial tension is 0.5 ~ 10N.
Detailed description of the invention 15: present embodiments provide for the method that the preparation of a kind of batch has the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, its preparation process is as follows:
(1) adopting highly oriented pyrolytic graphite to be raw material, will be the pH value to 1.2 of sodium hydrate aqueous solution regulator solution of 30% in the diluting concentrated sulfuric acid of 2.6mL98% to 100mL deionized water and with mass fraction.
(2) adopt+1.5V voltage to graphite oxidation 1.5min, graphite flake layer spacing to be increased, be conducive to oxidation and the reduction reaction of follow-up graphite flake.After pre-oxidation, on graphite and platinum plate electrode, applying+10V, 2s and-10V, 10s cycle alternation change voltage respectively.
(3) after electrolysis, mixed solution is filtered and spends deionized water 3 times, the precipitation obtained is distributed in organic solvent (as DMF etc.) again, more centrifugal 5min removes the graphite flake be not fully exfoliated out under the rotating speed of 3600 revs/min, thus forms low defect graphene nanometer sheet.
(4) first PVA dissolves in deionized water, and mass fraction is 5%.
(5) Graphene mixes by a certain percentage with PVA, and mixed proportion is 20 ~ 46%.
(6) Graphene and PVA mixed liquor are at 25 DEG C, stir 24h, obtain homodisperse Graphene/PVA solution with 500 revs/min.Further by mixed solution agitating heating 60min at 70 ~ 80 DEG C, evaporation excessive moisture, thus form the liquid crystal gel of 10 ~ 30mg/mL, as the stoste of wet spinning silk.
(7) Graphene/PVA spinning solution will be obtained, move in the container of 10mL, be the spinning pin hole of 400 μm by internal diameter with the extruded velocity of 10mL/h, the stoste extruded enters 5% NaOH ethanolic solution and solidifies 10min, again the fiber solidified is taken out, wash 3 ~ 5 times, and in 50 ~ 80 DEG C of baking ovens dry 12 ~ 24h, obtain the Graphene/PVA fiber with imitative clam shell feature.
(8) as shown in Figure 1, regulate clamping force by two godet roller spacing on torsion device, and then change moment of torsion is 5N/m, axial tension is regulated by dead block and torsion device, axial tension 10N, and weaving 80min, forms the fiber with continuous helical structure.
Have imitative shell and helical structure Graphene/PVA fiber while prepared by present embodiment as shown in Figure 2, as can be seen from the figure graphene nanometer sheet and PVA polymer layers are assembled, and form imitative clam shell feature.Fig. 2 a is typical helical structure, characterizes and confirms that Graphene and PVA form the imitative clam shell feature of layer assembly, as shown in Figure 2 c to its cross sectional scanning electron microscope.
Fig. 3 compared for the mechanical property of pure graphene fiber, Graphene/66%PVA film and Graphene/66%PVA helical structure fiber.As can be seen from Figure 3, Graphene prepared by present embodiment/66%PVA helical structure fiber, tensile strength, percentage elongation and toughness are greatly improved, compared to pure graphene fiber, percentage elongation and toughness have the raising of 3 ~ 4 orders of magnitude, maximum elongation rate can more than 400%, and toughness can reach 640J/g.
Not only can be prepared the Graphene/PVA fiber (as illustrated in figures 4-5) simultaneously with imitative clam shell feature and helical structure by present embodiment in batches, also can prepare the calcium carbonate/PVA fiber (as shown in fig. 6-7) with imitative clam shell feature and helical structure.Illustrate thus, the method described in present embodiment has good universality and portability, and the preparation for high performance composite fibre provides a kind of new method.
Claims (9)
1. batch preparation has a method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that described method step is as follows:
One, Two-dimensional Inorganic nanometer sheet mixed by a certain percentage with polymer, obtain the stoste as wet spinning silk, the mass fraction controlling Two-dimensional Inorganic nanometer sheet in stoste is 0 ~ 100%;
Two, the stoste obtained in step one is moved in the container of 1 ~ 25mL, be the spinning pin hole of 10 ~ 500 μm by internal diameter with the extruded velocity of 0.1 ~ 100mL/h, the stoste extruded enters in condensation water solidifies 0.5 ~ 15min, again the fiber solidified is taken out, wash 3 ~ 5 times, and in 50 ~ 80 DEG C of baking ovens dry 12 ~ 24h, obtain the Two-dimensional Inorganic nanometer sheet/polymer fiber with imitative clam shell feature;
Three, fiber step 2 obtained is weaved in dry spinning equipment, adjustment moment of torsion is 0.001 ~ 10N/m, axial tension 0.1 ~ 50N, weaving 10 ~ 120min, form the fiber with continuous helical structure, so far, the Two-dimensional Inorganic nanometer sheet/polymer fiber simultaneously with imitative clam shell feature and helical structure is obtained.
2. batch preparation according to claim 1 has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that described Two-dimensional Inorganic nanometer sheet is Graphene, calcium carbonate, alundum (Al2O3), clay, imvite, molybdenum bisuphide, two selenizing molybdenums, gallium selenide, sulfuration gallium, telluride gallium, tungsten disulfide or two tungsten selenide.
3. batch preparation according to claim 1 and 2 has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that the preparation method of described Two-dimensional Inorganic nanometer sheet can adopt chemical vapour deposition technique, chemical stripping method, electrochemical stripping method, ultrasonic stripping method or mechanical stripping method.
4. batch preparation according to claim 1 and 2 has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, when it is characterized in that described Two-dimensional Inorganic nanometer sheet is Graphene, electrochemical method is adopted to peel off, prepare the high-quality graphene nanometer sheet of low defect, as the raw material of fiber, concrete steps are as follows:
(1) natural graphite flakes or highly oriented pyrolytic graphite is adopted to be raw material, and as an electrode; By in the diluting concentrated sulfuric acid of 0.5 ~ 5.0ml98% to 20 ~ 190ml deionized water and with 10 ~ 30% pH value to 0.8 ~ 1.5 of sodium hydrate regulator solution, as electrolyte; Platinized platinum, as another electrode, forms electrochemical stripping Graphene system;
(2) adopt+1.0 ~+2.5V voltage to graphite pre-oxidation 0.5 ~ 3min;
(3), after pre-oxidation, graphite and platinum plate electrode apply+8 ~ 12V, 2 ~ 5s and-8 ~-12V, 5 ~ 10s cycle alternation change voltage respectively and carries out electrolysis;
(4) after electrolysis, mixed solution is filtered and spends deionized water 3 ~ 5 times, the precipitation obtained is distributed in organic solvent again, more centrifugal 3 ~ 5min removes the graphite flake be not fully exfoliated out under the rotating speed of 2500 ~ 4000 revs/min, thus forms low defect graphene nanometer sheet.
5. batch preparation according to claim 1 has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that the concrete steps of described step one are as follows:
(1) first by polymer dissolution in deionized water, prepare mass fraction 1 ~ 10% aqueous solutions of polymers;
(2) Two-dimensional Inorganic nanometer sheet is mixed with aqueous solutions of polymers, then at 20 ~ 30 DEG C, stir 24 ~ 36h with 400 ~ 1000 revs/min, obtain homodisperse Two-dimensional Inorganic nanometer sheet/mixed with polymers solution;
(3) Two-dimensional Inorganic nanometer sheet/mixed with polymers solution heated at 60 ~ 90 DEG C and stir 30 ~ 120min, evaporation excessive moisture, thus forming liquid crystal gel, as the stoste of wet spinning silk.
6. batch preparation according to claim 5 has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that the concentration of described liquid crystal gel is 10 ~ 30mg/mL.
7. batch preparation has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously according to claim 1 or 5, it is characterized in that described polymer is polyvinyl alcohol, dimethyl silicone polymer, polyacrylic acid, epoxy resin, polyacrylonitrile, Aromatic polyester, chliorinated polyvinyl chloride or liquid crystal polymer.
8. batch according to claim 1 preparation has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that described condensation water is one or more of calcium chloride, NaOH, ethanol, saturated sodium sulphate, 5% NaOH ethanolic solution, sodium nitrate, calcium nitrate, chlorination molten iron or water/alcohol mixeding liquid.
9. batch preparation according to claim 1 has the method for the superpower toughness fiber of imitative clam shell feature and helical structure simultaneously, it is characterized in that the structure layer by layer for imitative shell on described Two-dimensional Inorganic nanometer sheet/polymer fiber microcosmic, being situated between on seeing and having helical structure, is macroscopically fibre structure.
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