CN106758135B - A kind of preparation method of metal composite fiber - Google Patents
A kind of preparation method of metal composite fiber Download PDFInfo
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- CN106758135B CN106758135B CN201611224269.3A CN201611224269A CN106758135B CN 106758135 B CN106758135 B CN 106758135B CN 201611224269 A CN201611224269 A CN 201611224269A CN 106758135 B CN106758135 B CN 106758135B
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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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/003—Treatment with radio-waves or microwaves
Abstract
The invention discloses a kind of preparation methods of metal composite fiber, the microwave technology that will quickly heat for the first time is in conjunction with the Microwave Absorption Properties of Graphene derivative and metallic fiber Surface microwave eddy heating for heating characteristic, the heat of high thermal conductivity ability and graphene layer in combination with graphene is easy to be quickly exchanged the characteristic of transfer, the Graphene derivative that metallic fiber surface is coated with is quick, it is converted into graphene low energy consumption to obtain the composite metal fiber with good conductive ability and resistance to corrosion, it can be metallic fiber, the further development and application of grapheme material are made contributions.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of metal composite fiber especially by microwave heating Graphene derivative
Solution coating metallic fiber and obtain the method that core is the composite fibre that metallic fiber shell is graphene layer.
Background technique
With the development of society, metallic fiber due to possess many merits such as good mechanical performance, electric property and
It is widely applied including wide range of areas such as wire and cable, mechanical enhancing, electrode material, senser elements.However metallic fiber sheet
Body includes that etching problem, electric conductivity the presence of some problems such as need to be improved and limit its and further promote and apply.
Therefore highest attention of the coating decoration of metallic fiber by people, and including polymeric PTC materials, coating coating, metal composite
Etc. obtain it is fast-developing.And still further aspect, graphene is as a kind of two-dimentional conductive material, excellent mechanical property
(electron mobility is up to 10 for (Young's modulus is up to 1.0TPa), electrical properties6cm2.v-1s-1), (thermal conductivity coefficient is high for thermal property
Up to 5000w.m-1.k-1), optical property (visible absorption of single-layer graphene only has 2.3% and excellent mode locking characteristic), surpass
Big theoretical specific surface area (2630m2.g-1) it is not only enabled effectively to play metal and graphite in metal surface modification field
The superior function of alkene, and its lamellar structure is but also its covered effect is good, therefore becomes the weight of current metal surface modification
Point research field.It is developed at present including chemical vapor deposition cladding, electrostatic powder coating cladding, the compound gluing of graphene
The methods of agent coating, graphene oxide solution coating are surface modified metallic fiber, but existing for these method of modifying
Chemical vapor deposition needs the conditions such as high temperature and expensive problem, electrostatic powder coating are difficult due to graphene powder reunion
So that graphene planes are sprawled the problem of uniform covering material, graphene adhesive will affect due to the addition of high molecular material
The problem of graphene conductive, the capacity of heat transmission play, and then to there is graphene oxide performance remote for the coating of simple graphene oxide solution
Lower than graphene performance and electronation there are environmental pollution and may damage metallic fiber itself and high temperature reduction energy consumption is high,
The problems such as period is long, therefore people still expect that the new coating technology of appearance enables graphene coated composite metal fiber at present
Enough preferably service societies.The application is put forward for the first time on metallic fiber first through Graphene derivative solution coating thus
The metal composite fiber of Graphene derivative layer cladding is obtained, then composite fibre is logical with setting speed in the case where setting atmospheric condition
Entire microwave heating area is crossed, it is micro- using the microwave absorption capacity of graphene microcell in Graphene derivative and metallic fiber surface number
The eddy heating for heating characteristic of rice depth makes the Graphene derivative layer aoxidized or graphene edge derivative layer and metal surface
Layer is rapidly heated due to microwave action and the Graphene derivative of reduction-oxidation or the edge of de- graphene edge derivative
Functional group and be converted into graphene layer, due to solution coating Graphene derivative layer in the form of graphene basal plane is sprawled layer by layer
Be coated on metallic fiber, and the graphene layer that high-temperature process obtains at this time due also to different graphene film interlayer pi-electron cloud it
Between interaction and preferable conductive, thermally conductive and mechanical performance can be kept.Microwave heating (time is in seconds) is due to selection
Property heat Graphene derivative layer and metallic fiber surface, therefore can heat to avoid other heatings due to needing for a long time
(time is in hours) and Heat transmission etc. and cause high energy consumption.Composite fibre passes through entire micro-wave oven heating zone with setting speed
Mode, on the one hand can accurately control the microwave heating time of composite fibre.Micro-wave oven heating time is set with 30 as
Second is multiple class of unit, however, experimentation have shown that heating a whole shelves under protective atmosphere may occur since heating is too fast
And cause the Graphene derivative layer of coating at random or even fall off, even if accurate micro-wave oven can set microwave pulse length, but
Also be difficult to set may be optimal heating time such as 1.2 seconds, and composite fibre with setting speed by microwave heating Qu Zeke with
Accurate best heating time is easily obtained according to microwave heating area size.Composite fibre passes through microwave heating area with setting speed
Different zones heating effect difference bring heating in microwave heating area can also be avoided uneven.In fact, composite fibre is placed
A period of time is heated in micro-wave oven, and the composite fibre heating effect for being placed on different heating region can be clearly felt that after taking-up
Fruit is different, this is related with the uniformity of electric field is heated in micro-wave oven, although can be by designing such as curve antenna structure side
Formula improves micro-wave oven heating uniformity, but it also has certain limit.And composite fibre passes through entire microwave heating with setting speed
Qu Ze obtains consistent heating effect by entire heating zone due to all composite fibres.Certain composite fibre is to set speed
Degree can also accurately control its cooling opportunity by entire microwave heating area.And composite fibre of the invention is passed through with setting speed
The method in entire microwave heating area also with the process compatible of fiber process, therefore facilitates the batch production of metal composite fiber.
And composite fibre leaves microwave heating area can be quickly cooled to set temperature, therefore greatly shortens process time.So this
Application coats metal composite fiber by the Graphene derivative floor in entire microwave heating area with setting speed using microwave heating
The method for preparing graphene layer cladding metal composite fiber can not only obtain graphite of the surface with good conductive, anti-corrosion ability
Alkene layer, and heat and heat selective microwave heating technique due to using to open and can be effectively reduced energy consumption simultaneously
Therefore shortening process time facilitates the further research and development and popularization and application of metal composite fiber of graphene layer coating decoration.
Summary of the invention
Technical problem: metal composite is obtained the object of the present invention is to provide a kind of metallic fiber surface coating graphene layer
The method of fiber forms metal composite fiber by being coated with Graphene derivative layer in metallic fiber surface solution, then metal
Composite fibre under inert atmosphere, reducing atmosphere or vacuum environment with setting speed by entire micro-wave oven heating region with
Accurate control heating time, cooling opportunity simultaneously avoid heating uneven, using microwave selective heat in Graphene derivative
Graphene microcell and metallic fiber surface (depth a few micrometers) and high-temperature process Graphene derivative layer, to obtain in gold
Belong to the composite fibre that fiber surface is coated with graphene layer.This method not only can to avoid presently, there are electrostatic powder spraying
Cladding inhomogeneities, macromolecule compo mix the influence presented to Graphene derivative performance and chemistry due to high molecular
The problems such as time-consuming and high energy consumption of pollution problem existing for restoring and common high temperature reduction, it can be convenient, fast, low energy consumption make
The metal composite fiber of standby graphene layer cladding, therefore facilitate the further development and application of metal composite fiber.
Technical solution: a kind of metal composite fiber of the invention the preparation method comprises the following steps: first prepare Graphene derivative it is molten
Then liquid answers Graphene derivative solution coating in the metal that selected metallic fiber surface forms Graphene derivative cladding
Condensating fiber then makes metal composite fiber lead to metallic fiber table by microwave heating area with setting speed in the case where setting atmosphere
Face is heated up because of eddy current effect, while Graphene derivative layer then heats up because microwave is absorbed and makes metal composite fiber
The Graphene derivative layer on surface is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves microwave heating
Area is simultaneously cooled, and then extrusion process can be obtained the metal composite fiber of graphene layer cladding.
Wherein:
The Graphene derivative refers to the oxide i.e. graphene oxide of graphene and the graphene oxide and stone of reduction
Black alkene edge derivative.
The setting atmosphere refers to inert atmosphere, reducing atmosphere or vacuum state；The inert atmosphere refers to gas
The gas not reacted with graphene oxide derivative such as nitrogen, helium, argon gas；The reducing atmosphere, which refers to, contains energy in gas
Gas such as hydrogen, alcohols, the alkanes gas of enough reduced graphene derivatives；The vacuum state refers to that air pressure is less than 4KPa.
The Graphene derivative layer is converted into graphene layer because of high temperature action and refers to that high temperature action leads to oxidation
Graphene is reduced and is converted into graphene, and graphene edge derivative then occurs the reaction of off-clip edge functional group and is converted into
Graphene.
The carbon content of graphene layer is greater than 90% in the metal composite fiber of the graphene layer cladding.
The metal composite fiber leaves microwave heating area and is cooled, and refers to through cold atmosphere or additionally applies cold
Air-flow body and cool down.
When the metal composite fiber is heated by microwave heating area according to microwave heating area size Control with setting speed
Between.
It is described that metal composite fiber is made to lead to metallic fiber surface because vortex is made by microwave treatment in the case where setting atmosphere
With and heat up, while Graphene derivative layer then heats up and makes the graphene on metal composite fiber surface because microwave is absorbed
Derivative layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves microwave heating area and is cooled,
The process can repeat to handle Graphene derivative layer with multiple high temp.
It is described that Graphene derivative solution coating is formed into Graphene derivative cladding on selected metallic fiber surface
Metal composite fiber then makes metal composite fiber lead to metallic fiber surface because of whirlpool by microwave treatment in the case where setting atmosphere
Stream is acted on and is heated up, while Graphene derivative layer then heats up and make the stone on metal composite fiber surface because microwave is absorbed
Black ene derivative layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves microwave heating area and cold
But, then extrusion process, which can repeat repeatedly to be coated with and microwave high-temperature processing is to increase the thickness of graphene layer
Degree.
The coating includes dip-coating, spraying, brushing, foam coating, layer assembly coating, contact coating.
The utility model has the advantages that compared with prior art, the present invention having the advantage that
The tool Microwave Absorption Properties that the microwave technology and Graphene derivative that the application will be heated quickly for the first time contain
Graphene microcell and a few micrometers of metal surface depth eddy heating for heating characteristic combine, in combination with the high capacity of heat transmission of graphene
And the heat of graphene layer is easy to be quickly exchanged the characteristic of transfer, coats metal composite fiber by setting Graphene derivative
By entire microwave heating area with accurately control heating time, cooling opportunity and avoiding heat it is non-uniform on the basis of so that golden
The Graphene derivative for belonging to fiber surface coating can avoid the high energy consumption being heated at high temperature for a long time and shorten process time
Be effectively converted into situation graphene layer package metal composite fiber, by this kind of method prepare metal composite fiber not
But there can be good conductive capability and metal erosion can be effectively avoided, can be metallic fiber, grapheme material
It is further development and application make contributions.
Detailed description of the invention
Fig. 1 is metal composite fiber preparation flow schematic diagram.
Fig. 2 is that fiber passes through guide wheel around metal baffle schematic diagram.
Have in figure: 1, metallic fiber；2, immersion liquid pond, 2a, solution；3, liquid squeezing roll；4, drying chamber；5, metal baffle is 5a, small
Hole；6, microwave oven, 6a, microwave input, 6b, heating cavity；7, atmosphere chamber, 7a, gas population, 7b, gas vent；8, after
Temperature control, 8a, temperature controlled fluid entrance, 8b, temperature controlled fluid outlet；9, guide wheel；10, compression roller.
Specific embodiment
The present invention will be further described below with reference to the drawings.
1 nationality of metallic fiber is coated with Graphene derivative solution by solution 2a in immersion liquid pond 2 by guide wheel 9 first, then
The metal composite fiber for being coated with Graphene derivative layer is squeezed by liquid squeezing roll 3 goes redundant solution, and subsequent composite fibre passes through baking
Room 4 is dried, and subsequent composite fibre enters in the micro-wave oven 6 protected by the metal baffle 5 for being provided with aperture 5a.In micro-wave oven plus
Thermal region setting atmosphere chamber 7 is simultaneously controlled using gas access 7a and gas vent 7b in microwave heating regional metal composite fibre
The atmosphere of surrounding.Then nationality inputs microwave in the case where setting atmosphere to metal on metal composite fiber by microwave input 6a
Surface layer and Graphene derivative layer are then passed through out foraminate metal baffle and are left micro-wave oven 6 and entered by microwave heating
Afterwards 8th area of temperature control and using temperature controlled fluid entrance 8a and temperature controlled fluid outlet 8b set temperature circulation of fluid and at cooled microwave heating
The temperature of metal composite fiber after reason then passes through metal composite fiber the squeezing by compression roller 10 that microwave heating treatment is crossed
It presses and obtains the metal composite fiber coated by graphene layer.
Wherein metal baffle 5 can be conducive to fiber continuous operation and be changed to guide fiber around gold by guide wheel 9 by opening aperture
Belong to baffle and continuous operation to be conducive to stop microwave and enhances the protection to human body.As shown in Figure 2.
It is that people need one solved to choose that graphene layer is converted into after the coated graphite ene derivative layer of metallic fiber surface
War.In addition to extra high temperature long time treatment, after general chemistry reduction and high temperature reduction method processing Graphene derivative its
The content of middle carbon is difficult more than 90%, and not only energy consumption is high for extra high temperature long time treatment, but also can spread out to graphene
The laminate structure of biology causes to damage.Therefore there is an urgent need to develop new technologies to convert graphene for Graphene derivative layer
Layer.The present invention has heating quickly special using Graphene derivative tool Microwave Absorption Properties and microwave for the first time in the world thus
Point, by the way that Graphene derivative floor is passed through microwave heating area in the case where setting atmosphere with setting speed, to add in accurate control
It the hot time and avoids heating Graphene derivative layer in the case that heating is uneven and converts stone for Graphene derivative layer
Black alkene layer.In fact, microwave treatment is applied in graphene associated materials some correlative studys.Such as people prepare oxygen
A kind of method of graphite alkene is exactly microwave treatment graphite oxide, and high temperature of the nationality by microwave heating up to more than 2,000 degrees Celsius leads to oxygen
Bulk gas is generated inside graphite and layer few in graphite even single-layer graphene oxide is separated from each other and is come.And 2,000 is Celsius
Spend or more high temperature almost can thoroughly redox graphene and be translated into graphene.Our experiences show that non-
Stone of the microwave heating treatment including graphene oxide, redox graphene, graphene edge derivative under oxidizing atmosphere
Black ene derivative can efficiently be converted into graphene.Problem is that conventional microwave heat treatment is heated due to concentrating, part
Temperature is high, causes vigorous reaction to generate gas and the structure of Graphene derivative material is destroyed, Graphene derivative
Layer becomes clast, it is therefore necessary to effectively control microwave heating process make can either effective high-temperature process Graphene derivative, again
It can destruction to avoid vigorous reaction to Graphene derivative material structure.Our experiences show that the time is small in the case where setting atmosphere
Graphene derivative can be efficiently converted into graphene in of short duration microwave heatings in 3 seconds, but generated due to reduction
The sharply expansion of gas including aqueous vapor is an important pushing hands for causing Graphene derivative material structure to destroy, therefore
We just produce rapid microwave heating, and the steam etc. that being then quickly cooled down causes reduction to generate avoids the thinking sharply expanded.
In the case that experiment shows by being passed through cold nitrogen, Graphene derivative material is after by microwave fast heating due to fast quickly cooling
But it restores the gas of generation therefore can preferably keep the structure of Graphene derivative material and be eventually converted into graphene material
Material.Certainly heating material on one side being passed through while cooling nitrogen is cooling, could be improved from the point of view of energy consumption.Graphene
The another question of derivant material microwave heating treatment is that non-uniform problem is heated in microwave heating area, this in micro-wave oven
The uniformity for heating electric field is related, although can improve micro-wave oven homogeneous heating by designing such as curve antenna structure mode
Property, but electric field is unevenly difficult to avoid that, then causes Graphene derivative material to be converted into graphene without uniformly heated effect
Effect have differences and influence overall performance in different zones, and a part of stone may occur if improving heating time
Black ene derivative material is destroyed because of over-heating, and another part may then restore well not yet.So
In order to reduce one side microwave heating, one side cooling fluid cooling zone carrys out the increase of energy consumption and improves the uniform of microwave heating treatment
Property, it is heated with setting speed by microwave heating area we consider Graphene derivative material in the case where setting atmosphere and is accurately controlled
Heating time processed, the method being then quickly cooled down, so that the Graphene derivative of all areas passes through entire microwave heating area
And relatively uniform heating is obtained, and unless special requirement cooling just first room temperature cooling, is then departed from after the completion of microwave heating
Micro-wave oven passes through cooling device again and carries out cooling to reduce cooling energy consumption.Experiment shows that our method works well, just
Graphene derivative layer is converted into for graphene layer, and the content of the carbon of graphene layer is more than 90%, since common graphite adsorbs
There is 3% oxygen, therefore close to reduction completely, and shows good electrical property.
Below with reference to embodiment, the present invention is further illustrated.
Embodiment one:
Graphene oxide powder and redox graphene powder are prepared first.30 grams of graphite mixing 15g sodium nitrate and 750
The milliliter concentrated sulfuric acid.Mixture is cooled to 0 degree Celsius in ice bath, and after stirring 2h, is slowly added to 90 grams of potassium permanganate, is kept
Mixture temperature is lower than 5 degrees Celsius in mixed process.The mixture is stirred for a hour, and is heated to by removing ice bath
Room temperature.1 liter of distilled water is added in mixture and temperature in oil bath increases to 90 degrees Celsius.In addition 300 milliliters of water are added, and
It is stirred for one and a half hours.The color of mixture becomes brown.Mixture then use 30% 300 milliliters of hydrogen peroxide and 30 liters
Hot water treatment and dilution.The mixture further uses excessive water washing, until the pH value of filtrate is almost neutral to obtain
Obtain graphene oxide.Graphene oxide freeze-drying then be can be obtained into graphene oxide powder.Then by graphene oxide
Powder disperses in water and is restored 12 hours with hydrazine hydrate at 80 degrees Celsius.Redox graphene is formed with black precipitate, is used
0.45 μm of PTFE film is collected by filtration, and is rinsed with a large amount of water.Product is mentioned by methanol, tetrahydrofuran (THF) He Shuiyong Soxhlet
It follows the example of and is further purified.Finally, redox graphene obtained is subzero 120 Celsius under 0.05 millimetres of mercury vacuum environment
Degree freeze-drying.The redox graphene aqueous solution of 0.5 mg/ml is then prepared with deionized water.
Secondly the copper wire that diameter is 50 microns is obtained.Then above-mentioned copper wire is passed through into 0.5 milli with 60 ms/min of speed
The redox graphene aqueous solution immersion liquid pond of grams per milliliter, which is coated, to be formed surface and is coated with answering for redox graphene layer
Copper wire is closed, subsequent composite copper wire is that the liquid squeezing roll that 200 N/centimetre hardness are 90 degree removes extra solution by line pressure, so
Composite copper wire enters 150 degrees Celsius of drying chambers dryings afterwards, obtains to surface and is coated with the composite copper wire of redox graphene layer.Then
Composite copper wire enters the microwave heating area of argon gas protection by opening foraminate stainless steel metal baffle.Microwave heating area is by 10
Radiator forms so that heating zone length reaches 1 meter, and then adjusting microwave power is that 1000W is heated about 1 second, then passes through gold
Aperture, which enters, on category baffle is cooled down by recirculated cooling water controlled at the rear temperature control area of room temperature, and composite copper wire passes through thereafter
Line pressure is that the compression roller of 1300 Ns/centimetre carries out extrusion process.Above-mentioned microwave heating-cooling-extrusion process is repeated to obtain three times
It obtains graphene layer carbon content and is greater than 90% conductivity greater than 5000Sm-1Graphene layer cladding composite copper wire.The composite copper wire
It does not expose in the case where exposed head end that also there is no apparent corrosion phenomenons in one week in the nitric acid solution of 1M, shows excellent
Corrosion resistance features.
Embodiment two:
The aluminum steel that diameter is 1 millimeter is obtained first, and aluminum steel is then passed through the 10 of 30 centimeter lengths with the speed of 0.1 meter per second
The graphene oxide water solution of mg/ml obtains the compound aluminum steel that surface is coated with graphene oxide layer after dry.This is answered
Aluminum steel is closed to lead at 200 degrees celsius under protection with the speed of 0.1 meter per second in the case where nitrogen and hydrogen ratio are the reducing atmosphere of 55:1
Overpower is that 10 centimetres of heating zones of micro-wave oven diameter of 1000W are heated about 1 second, and it is cold to be then again introduced into room temperature region progress
But, then compound aluminum steel repeats above-mentioned microwave heating-by the compression roller progress extrusion process that line pressure is 1000 Ns/centimetre
Cooling-extrusion process 20 times.It obtains graphene layer carbon content and is greater than 90% conductivity greater than 5000Sm-1Graphene layer cladding
Compound aluminum steel.The compound aluminum steel does not expose in the case where exposed head end that also there is no apparent in one week in the hydrochloric acid solution of 1M
Corrosion phenomenon shows excellent corrosion resistance features.
Embodiment three:
The graphene platelet of edge carboxylated is prepared first.The diameter containing 1000 grams is added in 5 grams of graphite and 100 grams of dry ice
In the stainless steel capsule of 5 millimeters of stainless steel balls.Container is sealed and is fixed on planetary ball mill (F-P4000), and with 500rpm
(rev/min) speed stirs 48 hours.Then, internal pressure passes through a gas vent slow release.Pass through at the end of ball milling
Container cover is opened in air, and violent hydration reaction generation carboxylic acid is occurred by the wet steam initiation carboxylate in air and sends out sudden strain of a muscle
Light.Products obtained therefrom carries out soxhlet type with 1M hydrochloric acid solution to be thoroughly acidified carboxylate and remove presumable metal impurities.Most
Obtain edge carboxylated graphene nanometer sheet within subzero 120 degrees Celsius of freeze-dryings 48 hours under 0.05 millimetres of mercury vacuum environment eventually
Furvous powder.Edge carboxylated graphene nanometer sheet was obtained into the uniform of 0.1wt% by ultrasound 30 minutes in isopropanol
The solution of dispersion.
Then 100 microns of diameter of filamentary silver is obtained.Filamentary silver is then passed through into 50 centimeter lengths with the speed of 0.1 meter per second
The edge carboxylated graphene aqueous isopropanol of 0.1wt% obtains surface after dry and is coated with edge carboxylated graphene layer
Compound filamentary silver.It is 1000W that the compound filamentary silver is passed through power under helium protection with the speed of 0.02 meter per second under room temperature state
10 centimetres of heating zones of micro-wave oven diameter heated about 5 seconds, be then again introduced into room temperature region and cooled down, then composite silver
Silk carries out extrusion process by the compression roller that line pressure is 900 Ns/centimetre, repeats above-mentioned solution coating-microwave heating-cooling-
Extrusion process 3 times,.It obtains graphene layer carbon content and is greater than 90% conductivity greater than 5000Sm-1Graphene layer cladding it is compound
Filamentary silver.The compound filamentary silver does not expose in the case where exposed head end that also there is no significantly corroding in one week in the nitric acid solution of 1M
Phenomenon shows excellent corrosion resistance features.
Example IV:
The halogenated graphene nanometer sheet in edge is prepared first.5 millimeters of stainless steel balls of diameter containing 1000 grams are added in 5 grams of graphite
Stainless steel capsule in.Then capsule seals and five circulations charge and discharge argon gas under 0.05 millimetres of mercury vacuum pressure condition.
Hereafter, chlorine is added from gas access for 8.75atm by cylinder pressure.Container is sealed and is fixed on planetary ball mill (F-
P4000), and with 500rpm (rev/min) speed stirring 48 hours.Products obtained therefrom successively carries out Soxhlet with methanol and 1M hydrochloric acid solution
Extracting is to completely remove small molecule organic impurities and presumable metal impurities.Finally zero under 0.05 millimetres of mercury vacuum environment
Lower 120 degrees Celsius of freeze-dryings obtain the furvous powder of edge chlorination graphene nanometer sheet for 48 hours.Then 0.1 milligram/milli is prepared
The edge chloro graphene N risen, N '-dimethyl formamide DMF solution.
Secondly the nickel wire that diameter is 50 microns is obtained.Then nickel wire is passed through into 40 centimeter lengths with the speed of 0.5 meter per second
The edge chloro graphene N of 0.1 mg/ml, N '-dimethyl formamide DMF solution obtain surface after dry and are coated with edge
The compound nickel wire of chlorination graphene layer.The compound nickel wire is existed under the nitrogen protection containing 5% hydrogen with the speed of 0.02 meter per second
It is heated about 5 seconds under room temperature state by 10 centimetres of heating zones of micro-wave oven diameter that power is 1000W, is then again introduced into room
Temperature area is cooled down, and then compound nickel wire passes through line pressure for the compression roller progress extrusion process of 500 Ns/centimetre, in repetition
Solution coating-microwave heating-cooling-extrusion process process 3 times is stated,.It is big greater than 90% conductivity to obtain graphene layer carbon content
In 5000Sm-1Graphene layer cladding compound nickel wire.The compound nickel wire does not expose the nitric acid in the case where exposed head end in 1M
Also there is no apparent corrosion phenomenons within one week in solution, show excellent corrosion resistance features.
Embodiment five
Edge nitridation graphene nanometer sheet is prepared first.5 millimeters of stainless steel balls of diameter containing 1000 grams are added in 5 grams of graphite
Stainless steel capsule in.Then capsule seals and five circulations charge and discharge nitrogen under 8bar pressure condition.Then seal capsule
And it is fixed on planetary ball mill (F-P4000), then with 500rpm (rev/min) speed stirring 48 hours.Products obtained therefrom is successively used
Methanol and 1M hydrochloric acid solution carry out soxhlet type to completely remove presumable metal impurities.Then it repeats to use ethylenediamine tetra-acetic acid
(EDTA), concentrated ammonia liquor and the processing of 1M hydrochloric acid solution, until XPS inspection does not measure metal residue.It is finally true in 0.05 millimetres of mercury
Subzero 120 degrees Celsius of freeze-dryings 48 hours 5.67 grams of edges for obtaining intake at least 0.67g nitrogen nitrogenize graphene nano under Altitude
The furvous powder of piece.Edge nitridation graphene nanometer sheet is molten with 0.1 mg/ml of DMAC N,N' dimethyl acetamide solvent preparation
Liquid.
Secondly the cobalt silk that diameter is 2 millimeters is obtained.Then cobalt silk is run with the speed of 0.1 meter per second, and will by spray head
0.1 mg/ml edge nitrogenizes graphene nanometer sheet n,N-dimethylacetamide solution spraying thereon, reruns between 100 meters
Cobalt silk is sprayed with other spray head every rear, after spraying 5 times, 50 degrees Celsius of vacuum drying, 24 hours acquisition edges nitrogenize graphene
The cobalt silk of layer package.It is by power under room temperature state with the speed of 0.02 meter per second under protection of argon gas by the compound cobalt silk
10 centimetres of heating zones of micro-wave oven diameter of 800W are heated about 5 seconds, are then again introduced into room temperature region and are cooled down, then multiple
It closes cobalt silk and extrusion process is carried out by the compression roller that line pressure is 1300 Ns/centimetre, repeat above-mentioned microwave heating-cooling-extruding
Treatment process 5 times,.It obtains graphene layer carbon content and is greater than 90% conductivity greater than 5000Sm-1Graphene layer cladding it is compound
Cobalt silk.The compound cobalt silk does not expose in the case where exposed head end that also there is no significantly corroding in one week in the nitric acid solution of 1M
Phenomenon shows excellent corrosion resistance features.
Embodiment six
The copper wire that diameter is 1 millimeter is obtained first, 1 milli that copper wire is then passed through into 40 centimeter lengths with the speed of 0.1 meter per second
The redox graphene aqueous solution of grams per milliliter obtains the composite copper wire that surface is coated with redox graphene layer after dry.
The composite copper wire is passed through into the microwave that power is 800W in room temperature condition with the speed of 0.02 meter per second under the vacuum environment of 2KPa
10 centimetres of heating zones of furnace diameter are heated about 5 seconds, are then again introduced into room temperature region and are cooled down, and it is micro- to repeat above-mentioned cooling-
Wave heating-cooling procedure 5 times, then composite copper wire carries out extrusion process, weight by the compression roller that line pressure is 1200 Ns/centimetre
Multiple above-mentioned microwave heating-cooling-extrusion process 5 times,.It obtains graphene layer carbon content and is greater than 90% conductivity greater than 5000Sm-1
Graphene layer cladding composite copper wire.The composite copper wire does not expose in the case where exposed head end one week in the nitric acid solution of 1M
Also there is no apparent corrosion phenomenons, show excellent corrosion resistance features.
Claims (8)
1. a kind of preparation method of metal composite fiber, which is characterized in that preparation Graphene derivative solution first, then by stone
Black ene derivative solution coating forms the metal composite fiber of Graphene derivative cladding on selected metallic fiber surface, then
Make in the case where setting atmosphere metal composite fiber with 0.1 meter per second of setting speed or 0.02 meter per second by power reach 800 watts or
1000 watts of microwave heating areas, cause metallic fiber surface to be heated up because of eddy current effect, at the same Graphene derivative layer then because
It absorbs microwave and heats up and the Graphene derivative layer on metal composite fiber surface is made to be converted into graphite because of high temperature action
Alkene layer, subsequent metal composite fiber leave microwave heating area and are cooled, and then extrusion process can be obtained graphene layer cladding
Metal composite fiber；The setting atmosphere refers to inert atmosphere, reducing atmosphere or vacuum state.
2. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that the graphene is derivative
Object refers to graphene oxide, the graphene oxide of reduction or graphene edge derivative.
3. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that the inert atmosphere is
Refer to the gas that gas is not reacted with graphene oxide derivative；The reducing atmosphere, which refers to contain in gas, can restore graphite
The gas of ene derivative；The vacuum state refers to that air pressure is less than 4KPa.
4. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that the graphene is derivative
Nitride layer is converted into graphene layer because of high temperature action and refers to that high temperature action causes the graphene of oxidation to be reduced, and graphene side
The reaction of off-clip edge functional group then occurs for edge derivative.
5. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that the graphene layer packet
The carbon content of graphene layer is greater than 90% in the metal composite fiber covered.
6. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that the metal composite is fine
Dimension leaves microwave heating area and is cooled, and refers to through cold atmosphere or additionally applies cold air-flow body and cools down.
7. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that described in setting atmosphere
Down so that metal composite fiber causes metallic fiber surface to be heated up because of eddy current effect with setting speed by microwave heating area,
Graphene derivative layer then heats up and makes the Graphene derivative layer on metal composite fiber surface because microwave is absorbed simultaneously
Graphene layer is converted into because of high temperature action, subsequent metal composite fiber leaves microwave heating area and is cooled, which can
To repeat to handle Graphene derivative layer with multiple high temp.
8. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that described that graphene spreads out
Biological solution is coated on the metal composite fiber that selected metallic fiber surface forms Graphene derivative cladding, is then setting
Metal composite fiber is made to lead to metallic fiber surface by microwave heating area because of eddy current effect with setting speed under atmosphere
Heating, while Graphene derivative layer then heats up because microwave is absorbed and makes the graphene on metal composite fiber surface derivative
Nitride layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves microwave heating area and is cooled, then
Extrusion process, which can repeat repeatedly to be coated with and microwave high-temperature is handled to increase the thickness of graphene layer.
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| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN102815695A (en) * | 2012-08-02 | 2012-12-12 | 许子寒 | Preparation method of low-cost large-area graphene transparent conductive film |
| CN102839534A (en) * | 2012-08-30 | 2012-12-26 | 西北工业大学 | Surface modification method of carbon fiber by plasma treatment and coating of nano graphene |
| CN105271209A (en) * | 2015-11-05 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuously producing graphene film |
| KR20160132730A (en) * | 2015-05-11 | 2016-11-21 | 전관구 | Manufacturing process of graphene coated metal fine structures |
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|---|---|---|---|---|
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN102815695A (en) * | 2012-08-02 | 2012-12-12 | 许子寒 | Preparation method of low-cost large-area graphene transparent conductive film |
| CN102839534A (en) * | 2012-08-30 | 2012-12-26 | 西北工业大学 | Surface modification method of carbon fiber by plasma treatment and coating of nano graphene |
| KR20160132730A (en) * | 2015-05-11 | 2016-11-21 | 전관구 | Manufacturing process of graphene coated metal fine structures |
| CN105271209A (en) * | 2015-11-05 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuously producing graphene film |
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