CN109295615A - A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film - Google Patents
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film Download PDFInfo
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- CN109295615A CN109295615A CN201811155837.8A CN201811155837A CN109295615A CN 109295615 A CN109295615 A CN 109295615A CN 201811155837 A CN201811155837 A CN 201811155837A CN 109295615 A CN109295615 A CN 109295615A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- Life Sciences & Earth Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of durability graphene conductive silk fibroin nano-fiber film, by preparing redox graphene and fibroin albumen formic acid mixed liquor, redox graphene/silk fibroin nano-fiber film is prepared using method of electrostatic spinning, the nano fibrous membrane is placed in protein enzyme solution, hydrolyze the fibroin albumen of film surface, and the graphene on surface is made to obtain " exposed ", form fine and close conductive layer.Flexible, durability conduction silk fibroin nano-fiber film preparation is realized by means of the present invention, the nano fibrous membrane can be used for the wearable clothing fabric of intelligence, can also be used for the multiple fields such as flexible electronic device, health care, smart motion, and the conductive film excellent in te pins of durability prepared.
Description
Technical field
The invention belongs to textile chemistry fields, and in particular to a kind of method of electrostatic spinning durability graphene conductive fibroin albumen
The preparation method of nano fibrous membrane.
Background technique
Electrostatic spinning is a kind of special fiber fabrication process, and polymer solution or melt carry out injection spinning in strong electrical field
Silk.Under electric field action, the drop at syringe needle can be become conical (i.e. " taylor cone ") from spherical shape, and be extended from conical tip
To fiber filaments.This mode can produce the polymer filaments of nanometer grade diameter.Nanometer is prepared by electrostatic spinning technique
Fibrous material is one of most important academic and technical activity of world's material science and technology field in recent ten years.Electrostatic spinning
And it is simple with its manufacturing device, cost of spinning is cheap, can spin the advantages that substance classes are various, technique is controllable, it has also become effectively system
One of the main path of standby nano-fiber material.The wearable intelligent textile material of graphene is also the hot spot of current research, wherein
Electric conductivity and flexibility are its most important performances, and the most effectual way that flexibility obtains is to prepare substrate using electrostatic spinning,
Therefore the research of graphene flexible conductive electrostatic spinning textile material merits attention.
103938366 A of patent of invention CN discloses a kind of electrostatic spinning, and to prepare graphene oxide compound with polyvinyl alcohol
The spinning solution electrostatic spinning of graphene oxide and polyvinyl alcohol is obtained graphene oxide and polyvinyl alcohol is multiple by the method for film
Film is closed, finally by graphene oxide and composite membrane of polyvinyl alcohol in the mixed solution of acetone, deionized water, hydrochloric acid and crosslinking agent
It is handled to obtain the graphene oxide and composite membrane of polyvinyl alcohol by crosslinking, it is wet which mainly solves polyvinyl alcohol film
The defects of film-strength is poor, poor water resistance.104761737 B of patent of invention CN discloses a kind of method of electrostatic spinning and prepares collagen egg
The method of white/stannic oxide/graphene nano composite fiber membrane, the patent mainly utilize graphene oxide large specific surface area and excellent
Mechanical characteristic improves and improves the mechanical property of collagen nano fibrous membrane.Both the above method adds graphene oxide
Into electrostatic spinning liquid, the performances such as electrostatic spinning film strength are improved, are not involved with the electric conductivity of static spinning membrane.Invention
104878590 A of patent CN discloses a kind of preparation method of graphene conductive nano fibrous membrane, first prepares electrostatic spinning nano
Tunica fibrosa, then graphene oxide is filtered on electrostatic spinning film, finally by the graphene oxide conductive-nano-fibers of preparation
Film is restored with hydroiodic acid, obtains conductive film.105803672 A of patent of invention CN discloses a kind of conductive-nano-fibers film
Polyacrylonitrile and cellulose acetate, are dissolved in the polar organic solvent for being used for electrostatic spinning by preparation method, first prepare polyacrylonitrile/
Cellulose acetate composite nano-fiber membrane, then polyacrylonitrile/cellulose acetate composite nano-fiber membrane is carried out with strong base solution
It is hydrolyzed modified to prepare polyacrylonitrile/regenerated cellulose composite nano-fiber membrane, it is finally compound to polyacrylonitrile/regenerated cellulose to receive
Rice tunica fibrosa carries out silver mirror reaction and handles up to conductive-nano-fibers film.(the good of Cao's machine is based on graphene oxide flexibility and leads document
Electric fibrous material preparation and performance [D] Southern Yangtze University, 2017.) disclose a kind of graphene oxide or reduction-oxidation graphite
Alkene and fibroin albumen mixed liquor carry out electrostatic spinning, graphene nano fiber film are made, due to graphene quilt in static spinning membrane
Fibroin albumen is coated on fibrous inside, thus graphene oxide or redox graphene content are enough in gained nano fibrous membrane
It is still unable to test out electric conductivity when high, after impregnating GO solution again using the higher specific surface area of nanofiber and restore, can have
Effect improves the electric conductivity of nano fibrous membrane.Three of the above method is all first to prepare static spinning membrane, then conducting medium is applied to
Static spinning membrane film obtains conductive static spinning membrane.104674362 B of patent of invention CN discloses kind fibroin/stone
The preparation method of black alkene conductive fiber film, first prepares graphene oxide and silk fibroin composite membrane, then by graphene oxide with
Silk fibroin composite membrane is placed in solvent, is stirred to being completely dissolved, ultrasound obtains spinning solution, and spinning solution is placed in electrostatic spinning and is set
In standby container, high pressure electrospinning obtains composite fibre, and fibroin/graphene conductive fiber is obtained after steam treatment.The method needs elder generation
Film, then film is dissolved, then electrostatic spinning, last steam treatment obtain conductive film.Graphene is added to currently, having no
In fibroin albumen spinning solution, graphene silk fibroin nano-fiber film is obtained by electrostatic spinning, then post-process through protease
Obtain the preparation method of graphene conductive silk fibroin nano-fiber film.
Summary of the invention
The technical problem to be solved by the present invention is to for current graphene oxide or redox graphene and fibroin egg
Nano fibrous membrane made from white mixed liquor electrostatic spinning can not be shown since graphene is coated by fibroin albumen in film surface
The problem of electric conductivity, provides a kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, by graphite
Alkene/fibroin albumen Electrospun nano-fibers film Protease Treatment, hydrolyzes the fibroin albumen of film surface, and makes the stone on surface
Black alkene obtains " exposed ", forms fine and close conductive layer, obtains compliant conductive nano fibrous membrane, especially realizes conductive durability effect
Fruit.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 0.2~
The aqueous solution of 10g/L, stirring is warming up to 80~100 DEG C under ultrasound condition, and 2~20g/L reducing agent is added, continues to be stirred by ultrasonic,
10~120min is kept the temperature, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 0.5~5 g redox graphene super
It is scattered under the conditions of sound in 30 ml formic acid solutions, obtains dispersion liquid A, 10~40 g fibroin albumens is taken to disperse under ultrasound condition
In 170 ml formic acid solutions, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 10~60 min of stir process under 0~30 DEG C of ultrasound condition, for use；
(4) electrostatic spinning: electrostatic spinning liquid obtained by (3) is subjected to spinning on electrostatic spinning machine, spinning terminates on receiver board
Obtain redox graphene silk fibroin nano-fiber film；
(5) post-process: will redox graphene silk fibroin nano-fiber film obtained by (4) in 50~80 DEG C of vacuum drying 30~
Then 200min is placed it in the protein enzyme solution of 1~10g/L, adjust pH value be 3~10,30~70 DEG C processing 10~
100min, then sufficiently washing, drying.
The preparation process of graphene oxide uses ultrasound in the step (1), and the list of graphene oxide can be improved in ultrasound
Layer rate.
Reducing agent is the one or more of sodium hydrosulfite, hydrazine hydrate, rongalite, thiourea dioxide etc. in the step (2), and
The preparation process of redox graphene uses ultrasound, and the single layer rate of redox graphene can be improved in ultrasound, reduces reduction
The aggregation of graphene oxide.
The mass concentration of formic acid solution is 98% in the step (3).
In the step (3) ultrasonic purpose be in order to make redox graphene and fibroin albumen it is evenly dispersed or dissolution
In the formic acid solution that mass concentration is 98%, redox graphene dispersion liquid is added slowly in silk fibroin protein solution, it can
Redox graphene is dispersed in fibroin albumen.
8~20kV of spinning voltage when step (4) electrostatic spinning, pin hole and 6~15cm of receiver board distance, spinneret speed
0.5~4 ml/h of rate.
In the step (4) electrostatic spinning can make redox graphene and fibroin albumen spinning solution high pressure effect under with
Filament shape is sprayed on receiver board, and nano-fiber film is formed on receiver board.
Protease is one of neutral proteinase, acid protease, alkali protease or a variety of in the step (5).
In the step (5) protease post-process purpose be by the fibroin albumen corrosion dissolution of nanofiber film surface,
And the nano fibrous membrane of redox graphene conductive layer is left, improve the electric conductivity of nano fibrous membrane.
Beneficial effects of the present invention: redox graphene and fibroin albumen mixing formic acid solution are carried out electrostatic by the present invention
Spinning, be made redox graphene/silk fibroin nano-fiber film, due to redox graphene by fibroin albumen coat and
Can not show electric conductivity in film surface, using protein enzyme solution to graphene/fibroin albumen Electrospun nano-fibers film at
Reason, hydrolyzes the fibroin albumen of film surface, and the graphene on surface is made to obtain " exposed ", forms fine and close conductive layer, obtains soft
Property, durable conductive nano fibrous membrane.Technical solution of the present invention simple process is feasible, wants to raw material, auxiliary agent, fabric without special
It asks, achieves that large-scale production using conventional electrospinning device, have broad application prospects.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
The preparation method of durability graphene conductive silk fibroin nano-fiber film of the invention, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 0.2~
The aqueous solution of 10g/L, stirring is warming up to 80~100 DEG C under ultrasound condition, and 2~20g/L reducing agent is added, continues to be stirred by ultrasonic,
10~120min is kept the temperature, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 0.5~5 g redox graphene super
It is scattered under the conditions of sound in the formic acid solution of 30 ml 98%, obtains dispersion liquid A, take 10~40 g fibroin albumens in ultrasound condition
Under be scattered in the formic acid solution of 170 ml 98%, obtain thick solution B, continue under ultrasound condition that dispersion liquid A is slow
It pours into thick liquid B, continues 10~60 min of stir process under 0~30 DEG C of ultrasound condition, for use；
(4) electrostatic spinning liquid obtained by (3) electrostatic spinning: is subjected to spinning, 8~20kV of spinning voltage, needle on electrostatic spinning machine
Hole and 6~15cm of receiver board distance, 0.5~4 ml/h of spin rate, spinning terminate to obtain reduction-oxidation graphite on receiver board
Alkene silk fibroin nano-fiber film；
(5) post-process: will redox graphene silk fibroin nano-fiber film obtained by (4) in 50~80 DEG C of vacuum drying 30~
Then 200min is placed it in the protein enzyme solution of 1~10g/L, adjust pH value be 3~10,30~70 DEG C processing 10~
100min, then sufficiently washing, drying.
Embodiment 1
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 5g/L's
Aqueous solution, stirring is warming up to 90 DEG C under ultrasound condition, and 10g/L reducing agent sodium hydrosulfite is added, continues to be stirred by ultrasonic, and keeps the temperature 40min,
After, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 5 g redox graphenes in ultrasound condition
Under be scattered in the formic acid solution of 30 ml 98%, obtain dispersion liquid A, 20 g fibroin albumens taken to be scattered in 170 under ultrasound condition
In the formic acid solution of ml 98%, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 30 min of stir process under 10 DEG C of ultrasound conditions, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 10kV, pin hole with
Receiver board distance 8cm, 2 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen nanometer on receiver board
Tunica fibrosa；
(5) post-process: will (4) gained redox graphene silk fibroin nano-fiber film in 60 DEG C of 60 min of vacuum drying,
Then it placing it in the acidic protein enzyme solutions of 3 g/L, adjusting pH value is 3,70 DEG C of 10 min of processing, then sufficiently wash,
Drying.
Embodiment 2
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 0.2g/L
Aqueous solution, stirring is warming up to 80 DEG C under ultrasound condition, and 2g/L reducing agent rongalite is added, continues to be stirred by ultrasonic, and keeps the temperature
10min, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 0.5 g redox graphene in ultrasonic item
It is scattered under part in the formic acid solution of 30 ml 98%, obtains dispersion liquid A, 10 g fibroin albumens is taken to be scattered under ultrasound condition
In the formic acid solution of 170 ml 98%, thick solution B is obtained, continues to be poured slowly into dispersion liquid A under ultrasound condition sticky
In shape liquid B, continue 10 min of stir process under 30 DEG C of ultrasound conditions, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 8kV, pin hole with
Receiver board distance 6cm, 0.5 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen on receiver board to receive
Rice tunica fibrosa；
(5) it post-processes: by redox graphene silk fibroin nano-fiber film obtained by (4) in 50 DEG C of vacuum drying 30min, so
It is placed it in the neutral protein enzyme solutions of 1g/L afterwards, adjusting pH value is 7,30 DEG C of processing 100min, then sufficiently washing, baking
It is dry.
Embodiment 3
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 10g/L's
Aqueous solution, stirring is warming up to 100 DEG C under ultrasound condition, and 20g/L reducing agent hydrazine hydrate is added, continues to be stirred by ultrasonic, and keeps the temperature
120min, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 5 g redox graphenes in ultrasound condition
Under be scattered in the formic acid solution of 30 ml 98%, obtain dispersion liquid A, 40 g fibroin albumens taken to be scattered in 170 under ultrasound condition
In the formic acid solution of ml 98%, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 60 min of stir process under 0 DEG C of ultrasound condition, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 20kV, pin hole with
Receiver board distance 15cm, 4 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen on receiver board to receive
Rice tunica fibrosa；
(5) post-process: will (4) gained redox graphene silk fibroin nano-fiber film in 80 DEG C of vacuum drying 200min,
Then it placing it in the alkaline protease solution of 10g/L, adjusting pH value is 10,60 DEG C of processing 10min, then sufficiently wash,
Drying.
Embodiment 4
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 4g/L's
Aqueous solution, stirring is warming up to 90 DEG C under ultrasound condition, is added 5g/L reducing agent (2 g/L thiourea dioxides, 3 g/L sodium hydrosulfites),
Continue to be stirred by ultrasonic, keeps the temperature 60min, after, it filters, washes, freeze-drying obtains the uniform reduction-oxidation graphite of fineness
Alkene；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 2 g redox graphenes in ultrasound condition
Under be scattered in the formic acid solution of 30 ml 98%, obtain dispersion liquid A, 20 g fibroin albumens taken to be scattered in 170 under ultrasound condition
In the formic acid solution of ml 98%, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 40 min of stir process under 10 DEG C of ultrasound conditions, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 10kV, pin hole with
Receiver board distance 8cm, 1 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen nanometer on receiver board
Tunica fibrosa；
(5) post-process: will (4) gained redox graphene silk fibroin nano-fiber film in 70 DEG C of vacuum drying 100min,
Then it places it in the alkaline protease solution of 1 g/L, adjusting pH value is 10,40 DEG C of 100 min of processing, then abundant water
It washes, dry.
Embodiment 5
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 3g/L's
Aqueous solution, stirring is warming up to 80 DEG C under ultrasound condition, is added 10g/L reducing agent (5g/L sodium hydrosulfite, 5g/L hydrazine hydrate), continues to surpass
Sound stirring, keeps the temperature 10 min, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 4 g redox graphenes in ultrasound condition
Under be scattered in the formic acid solution of 30 ml 98%, obtain dispersion liquid A, 30 g fibroin albumens taken to be scattered in 170 under ultrasound condition
In the formic acid solution of ml 98%, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 10 min of stir process under 0 DEG C of ultrasound condition, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 12kV, pin hole with
Receiver board distance 12cm, 1.6 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen on receiver board
Nano fibrous membrane；
(5) post-process: will (4) gained redox graphene silk fibroin nano-fiber film in 50 DEG C of vacuum drying 200min,
Then it places it in the acidic protein enzyme solutions of 3g/L, adjusting pH value is 5,50 DEG C of processing 30min, then sufficiently washing, baking
It is dry.
Embodiment 6
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, it is characterised in that steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 2g/L's
Aqueous solution, stirring is warming up to 100 DEG C under ultrasound condition, and 4g/L reducing agent sodium hydrosulfite is added, continues to be stirred by ultrasonic, and keeps the temperature 10min,
After, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 2.5 g redox graphenes in ultrasonic item
It is scattered under part in the formic acid solution of 30 ml 98%, obtains dispersion liquid A, 18 g fibroin albumens is taken to be scattered under ultrasound condition
In the formic acid solution of 170 ml 98%, thick solution B is obtained, continues to be poured slowly into dispersion liquid A under ultrasound condition sticky
In shape liquid B, continue 60 min of stir process under 20 DEG C of ultrasound conditions, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 16kV, pin hole with
Receiver board distance 10cm, 3 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen on receiver board to receive
Rice tunica fibrosa；
(5) post-process: will (4) gained redox graphene silk fibroin nano-fiber film in 50 DEG C of vacuum drying 200min,
Then it placing it in the neutral protein enzyme solutions of 1g/L, adjusting pH value is 7.5,30 DEG C of processing 100min, then sufficiently wash,
Drying.
Embodiment 7
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 0.2g/L
Aqueous solution, stirring is warming up to 80 DEG C under ultrasound condition, and 2g/L reducing agent hydrazine hydrate is added, continues to be stirred by ultrasonic, and keeps the temperature
10min, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 5 g redox graphenes in ultrasound condition
Under be scattered in the formic acid solution of 30 ml 98%, obtain dispersion liquid A, 20 g fibroin albumens taken to be scattered in 170 under ultrasound condition
In the formic acid solution of ml 98%, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 10 min of stir process under 0 DEG C of ultrasound condition, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 20kV, pin hole with
Receiver board distance 8cm, 1 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen nanometer on receiver board
Tunica fibrosa；
(5) post-process: will (4) gained redox graphene silk fibroin nano-fiber film in 50 DEG C of vacuum drying 200min,
Then it places it in the protein enzyme solution of 5 g/L, adjusting pH value is 10,50 DEG C of processing 30min, then sufficiently washing, drying.
Embodiment 8
A kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide (GO), be centrifuged
The graphene oxide precipitating of 4000~10000 r/min is left and taken, freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by (1) is made into 3g/L's
Aqueous solution, stirring is warming up to 85 DEG C under ultrasound condition, and 6g/L reducing agent rongalite is added, continues to be stirred by ultrasonic, and keeps the temperature 100min,
After, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 3 g redox graphenes in ultrasound condition
Under be scattered in the formic acid solution of 30 ml 98%, obtain dispersion liquid A, 25 g fibroin albumens taken to be scattered in 170 under ultrasound condition
In the formic acid solution of ml 98%, thick solution B is obtained, dispersion liquid A is poured slowly into thick liquid B under ultrasound condition by continuation
In, continue 10 min of stir process under 30 DEG C of ultrasound conditions, for use；
(4) electrostatic spinning: carrying out spinning for electrostatic spinning liquid obtained by (3) on electrostatic spinning machine, spinning voltage 10kV, pin hole with
Receiver board distance 13cm, 0.5 ml/h of spin rate, spinning terminate to obtain redox graphene fibroin albumen on receiver board
Nano fibrous membrane；
(5) it post-processes: by redox graphene silk fibroin nano-fiber film obtained by (4) in 70 DEG C of vacuum drying 80min, so
It is placed it in the alkaline protease solution of 6g/L afterwards, adjusting pH value is 9,55 DEG C of processing 50min, then sufficiently washing, drying.
Implementation result of the invention
After the processing of embodiment 1 ~ 8, nano fibrous membrane is tested as follows, test result is shown in Table 1.
1) fastness to washing measures
Experimental test is carried out according to GB/T3921-2008 " textile color stability fastness to soaping ".
2) conducting performance test
Nano fibrous membrane sheet resistance measures in (Suzhou Electronics Co., Ltd. of Tontru) on SZT-2A four-point probe.
The test result of 1 embodiment nano fibrous membrane of table
As shown in Table 1, technical solution provided by the present invention can assign the excellent electric conductivity of nano fibrous membrane and excellent lead
Electric washability, electric conductivity has almost no change after washing 50 times.Nano fibrous membrane and document (the good base of Cao's machine is made in this method
In the preparation of graphene oxide compliant conductive fibrous material and performance [D] Southern Yangtze University, 2017.) compared to only needing in preparation process
Using a graphene, and the document need to respectively use a graphene or graphene oxide in spinning and last handling process, this
Inventive method only needs to carry out a Protease Treatment after obtaining spinning nano fibrous membrane, and document needs after obtaining nano fibrous membrane
With multiple working procedures processing such as graphene oxide solution dipping nano fibrous membrane, drying, reduction, drying, it is seen then that the technique of the document
It is more complicated；The sheet resistance value that the method for the present invention obtains nano fibrous membrane is lower than 100 Ω/cm, most far below above-mentioned document
Low 3.5 k Ω/cm, therefore the electric conductivity of nano fibrous membrane of the present invention is more preferably；Furthermore after use is already mentioned above in above-mentioned document chapter 3
The sheet resistance that graphene is coated on the conductive silk that silk surface obtains by the method for handling oxide impregnation graphene can be with
The increase of washing times and increase, i.e. electric conductivity reduces, thus ins conjunction with table 1 according to nano fibrous membrane of the present invention it is conductive water-fastness
Property is more excellent.It can be seen that silk fibroin nano-fiber film electric conductivity produced by the present invention and conductive superior in durability.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (6)
1. a kind of preparation method of durability graphene conductive silk fibroin nano-fiber film, it is characterised in that steps are as follows:
(1) it prepares graphene oxide: taking ultrasonic Hummers method, using graphite as raw material, prepare graphene oxide, centrifugation is left and taken
The graphene oxide of 4000~10000 r/min precipitates, and freeze-drying obtains evenly dispersed graphene oxide；
(2) it prepares redox graphene: taking sonochemistry reduction method, graphene oxide prepared by step (1) is made into 0.2
The aqueous solution of~10g/L, stirring is warming up to 80~100 DEG C under ultrasound condition, and 2~20g/L reducing agent is added, and continues ultrasound and stirs
It mixes, keeps the temperature 10~120min, after, it filters, washes, freeze-drying obtains the uniform redox graphene of fineness；
(3) redox graphene and fibroin albumen electrostatic spinning solution are prepared: taking 0.5~5 g redox graphene super
It is scattered under the conditions of sound in 30 ml formic acid solutions, obtains dispersion liquid A, 10~40 g fibroin albumens is taken to disperse under ultrasound condition
In the formic acid solution of 170 ml, thick solution B is obtained, continues to be poured slowly into dispersion liquid A under ultrasound condition thick
In solution B, 10~60 min of stir process under 0~30 DEG C of ultrasound condition, for use；
(4) electrostatic spinning: electrostatic spinning liquid obtained by step (3) is subjected to spinning on electrostatic spinning machine, spinning terminates receiving
Redox graphene silk fibroin nano-fiber film is obtained on plate；
(5) it post-processes: redox graphene silk fibroin nano-fiber film obtained by step (4) is dried in vacuo in 50~80 DEG C
Then 30~200min is placed it in the protein enzyme solution of 1~10g/L, adjusting pH value is 3~10,30~70 DEG C of processing 10
~100min, then sufficiently washing, drying.
2. the preparation method of durability graphene conductive silk fibroin nano-fiber film according to claim 1, feature
Be: the preparation process of graphene oxide uses ultrasound in the step (1).
3. the preparation method of durability graphene conductive silk fibroin nano-fiber film according to claim 1, feature
Be: reducing agent is one of sodium hydrosulfite, hydrazine hydrate, rongalite, thiourea dioxide or a variety of in the step (2), and is gone back
The preparation process of former graphene oxide uses ultrasound.
4. the preparation method of durability graphene conductive silk fibroin nano-fiber film according to claim 1, feature
Be: the mass concentration of formic acid solution is 98% in the step (3).
5. the preparation method of durability graphene conductive silk fibroin nano-fiber film according to claim 1, feature
It is: 8~20kV of spinning voltage when step (4) electrostatic spinning, pin hole and 6~15cm of receiver board distance, spin rate
0.5~4 ml/h.
6. the preparation method of durability graphene conductive silk fibroin nano-fiber film according to claim 1, feature
Be: protease is one of neutral proteinase, acid protease, alkali protease or a variety of in the step (5).
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