CN106758135A - 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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- CN106758135A CN106758135A CN201611224269.3A CN201611224269A CN106758135A CN 106758135 A CN106758135 A CN 106758135A CN 201611224269 A CN201611224269 A CN 201611224269A CN 106758135 A CN106758135 A CN 106758135A
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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
- D06M10/06—Inorganic 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 method of metal composite fiber, the microwave technology for being possible to quick heating first is combined with the Microwave Absorption Properties and metallic fiber Surface microwave eddy heating for heating characteristic of Graphene derivative, the heat of high heat conduction ability and graphene layer in combination with Graphene is easy to be quickly exchanged the characteristic of transfer, enable that the Graphene derivative that metallic fiber surface is coated with is quick, Graphene is converted into low energy consumption so as 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 heating using microwave Graphene derivative
Solution coating metallic fiber and obtain core for metallic fiber shell for graphene layer composite fibre method.
Background technology
With the development of society, metallic fiber due to possess many merits such as good mechanical performance, electric property and
Wide spectrum obtains extensive use including electric wire, mechanical enhancing, electrode material, senser element etc..But metallic fiber sheet
The presence for some problems such as needing to be improved including etching problem, electric conductivity of body limits its further popularization and application.
Therefore the coating decoration of metallic fiber is paid high attention to by people, and including polymeric PTC materials, coatings, metal composite
Etc. aspect obtain fast-developing.And still further aspect, Graphene is used as a kind of two-dimentional conductive material, its 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 have 2.3% and excellent locked mode characteristic), surpass
Big theoretical specific surface area (2630m2.g-1) not only enable that it effectively plays metal and graphite in metal surface modification field
The superior function of alkene, and its lamellar structure also causes that its covered effect is good, therefore as 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 such as agent coating, graphene oxide solution coating carry out surface modification to metallic fiber, but what these method of modifying were present
Chemical vapor deposition needs the conditions such as high temperature and costly problem, and electrostatic powder coating is reunited and difficult due to graphene powder
To cause that graphene planes sprawl the problem of uniform covering material, Graphene adhesive will be influenceed due to the addition of macromolecular material
The problem that graphene conductive, the capacity of heat transmission are played, and the coating of simple graphene oxide solution then to there is graphene oxide performance remote
There is environmental pollution less than Graphene performance and electronation and metallic fiber may be damaged in itself and high temperature reduction energy consumption it is big,
The problems such as cycle is long, therefore people still expect that new coating technology occur enables graphene coated composite metal fiber at present
Enough preferably service societies.For this application is proposed on metallic fiber first by Graphene derivative solution coating first
The metal composite fiber of Graphene derivative layer cladding is obtained, then composite fibre is logical with setting speed in the case where atmospheric condition is set
Whole heating using microwave 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 causes Graphene derivative layer or graphene edge derivative layer and the metal surface of oxidation
Layer be rapidly heated due to microwave action and reduction-oxidation Graphene derivative or the edge of de- graphene edge derivative
Functional group and be converted into graphene layer, the form sprawled with Graphene basal plane due to the Graphene derivative layer of solution coating is layer by layer
Be coated on metallic fiber, and graphene layer that now high-temperature process is obtained due also to different graphene film interlayer pi-electron cloud it
Between interaction and preferable conductive, heat conduction and mechanical performance can be kept.Heating using microwave (time is in seconds) is due to selection
Property ground heating Graphene derivative layer and metallic fiber surface, therefore can avoid other heat up heating due to need for a long time
(time is in hours) and Heat transmission etc. and trigger high energy consumption.Composite fibre passes through whole micro-wave oven heating zone with setting speed
Mode, on the one hand can be with the microwave heating time of precise control composite fibre.The micro-wave oven heat time as is set with 30
Second is multiple class of unit, however, experimentation have shown that a whole shelves are heated under protective atmosphere may occur because intensification is too fast
And cause the Graphene derivative layer of coating at random or even come off, even if accurate micro-wave oven can set microwave pulse length, but
Also be difficult to setting may such as 1.2 seconds optimal heat time, and composite fibre then can be with by heating using microwave area with setting speed
The accurate optimal heat time is easily obtained according to heating using microwave area size.Composite fibre passes through heating using microwave area with setting speed
The heating that heating using microwave area different zones heating effect different band can also be avoided is uneven.In fact, composite fibre is placed
A period of time is heated in micro-wave oven, the composite fibre heating effect for being placed on different heating region can be clearly felt that after taking-up
Really different, this is relevant with the uniformity that electric field is heated in micro-wave oven, although can be by design such as curve antenna structure side
Formula improves micro-wave oven heating uniformity, but it also has certain limit.And composite fibre with setting speed by whole heating using microwave
Qu Ze obtains consistent heating effect due to all composite fibres by whole heating zone.Certain composite fibre is setting speed
Degree it can cool down opportunity by whole heating using microwave area with precise control.And composite fibre of the invention is passed through with setting speed
The method in whole heating using microwave area also with the process compatible of fiber process, hence help to the batch production of metal composite fiber.
And composite fibre leaves heating using microwave area and can be quickly cooled to design temperature, therefore greatly shorten process time.So this
Application coats metal composite fiber with setting speed using heating using microwave by the Graphene derivative floor in whole heating using microwave area
The method for preparing graphene layer cladding metal composite fiber can not only obtain surface and have the graphite of good conductive, antiseptic power
Alkene layer, and due to using open heat and heat selective microwave heating technique and can effectively reducing energy consumption be simultaneously
Shortening process time hence helps to the further research and development and popularization and application of the metal composite fiber of graphene layer coating decoration.
The content of the invention
Technical problem：Metal composite is obtained it is an object of the invention to provide a kind of metallic fiber surface coating graphene layer
The method of fiber, forms metal composite fiber, then metal by being coated with Graphene derivative layer in metallic fiber surface solution
Composite fibre under inert atmosphere, reducing atmosphere or vacuum environment with setting speed by whole micro-wave oven heating region with
Precise control heat time, cooling opportunity simultaneously avoid heating uneven, in heating Graphene derivative using microwave selective
Graphene microcell and metallic fiber surface (depth is a few micrometers) and high-temperature process Graphene derivative layer, so as to obtain in gold
Category fiber surface is coated with the composite fibre of graphene layer.The method can not only avoid the electrostatic powder spraying that presently, there are
The influence and chemistry of cladding inhomogeneities, macromolecule compo due to high molecular mixing to the presentation of Graphene derivative performance
The problems such as reducing the time-consuming and high energy consumption of the pollution problem and common high temperature reduction for existing, can be made with convenient, fast, low energy consumption
The metal composite fiber of standby graphene layer cladding, hence helps to the further development and application of metal composite fiber.
Technical scheme：A kind of preparation method of metal composite fiber of the invention is：It is molten that Graphene derivative is prepared first
Liquid, then answers Graphene derivative solution coating in the metal that selected metallic fiber surface forms Graphene derivative cladding
Condensating fiber, then causes that metal composite fiber causes metallic fiber table with setting speed by heating using microwave area in the case where atmosphere is set
Face is heated up because of eddy current effect, while Graphene derivative layer then heats up because microwave is absorbed and causes 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 heating using microwave
Area is simultaneously cooled, and then extrusion process can obtain 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
Gas such as nitrogen, helium, the argon gas not reacted with graphene oxide derivative；The reducing atmosphere refers to contain 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.
It refers to that high temperature action causes oxidation that the Graphene derivative layer is converted into graphene layer because of high temperature action
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 more than 90% in the metal composite fiber of the graphene layer cladding.
The metal composite fiber leaves heating using microwave area and is cooled, and refers to by cold atmosphere or additionally applies cold
Air-flow body and cool down.
When the metal composite fiber is heated by heating using microwave area with setting speed according to heating using microwave area size Control
Between.
It is described to cause that metal composite fiber causes metallic fiber surface because vortex is made by microwave treatment in the case where atmosphere is set
With and heat up, while Graphene derivative layer then heats up because microwave is absorbed and causes the Graphene on metal composite fiber surface
Derivative layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves heating using microwave area and is cooled,
The process can be repeated with multiple high temp treatment Graphene derivative layer.
It is described that Graphene derivative solution coating is formed into Graphene derivative cladding on selected metallic fiber surface
Metal composite fiber, then causes that metal composite fiber causes metallic fiber surface because whirlpool by microwave treatment in the case where atmosphere is set
Stream is acted on and heated up, while Graphene derivative layer then heats up because of absorption microwave and causes the stone on metal composite fiber surface
Black ene derivative layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves heating using microwave area and cold
But, then extrusion process, the process can repeat can be repeatedly coated with and microwave high-temperature treatment is to increase the thickness of graphene layer
Degree.
The coating includes dip-coating, spraying, brushing, foam coating, layer assembly coating, contact coating.
Beneficial effect：The present invention compared with prior art, with advantages below：
The application is possible to the tool Microwave Absorption Properties that the microwave technology of quick heating contains with Graphene derivative first
Graphene microcell and metal surface a few micrometers depth eddy heating for heating characteristic combine, in combination with the Graphene capacity of heat transmission high
And the heat of graphene layer is easy to be quickly exchanged the characteristic of transfer, metal composite fiber is coated by setting Graphene derivative
By whole heating using microwave area with precise control heat time, cooling opportunity and avoid heating it is uneven on the basis of so that gold
The Graphene derivative of category fiber surface coating can avoid the high energy consumption of long-time high-temperature heating and shorten process time
The metal composite fiber of graphene layer parcel is effectively converted into situation, by this kind of metal composite fiber of method preparation not
But there can be good conductive capability and metal erosion can be effectively prevented from, can be metallic fiber, grapheme material
Further development and application make contributions.
Brief description of the drawings
Fig. 1 is metal composite fiber preparation flow schematic diagram.
Fig. 2 is that fiber bypasses metal baffle schematic diagram by guide wheel.
Have in figure：1st, metallic fiber；2nd, immersion liquid pond, 2a, solution；3rd, liquid squeezing roll；4th, drying room；5th, metal baffle is 5a, small
Hole；6th, microwave oven, 6a, microwave input, 6b, heating cavity；7th, atmosphere chamber, 7a, gas population, 7b, gas vent；8th, after
Temperature control, 8a, temperature controlled fluid entrance, 8b, temperature controlled fluid outlet；9th, guide wheel；10th, compression roller.
Specific embodiment
The present invention is further illustrated below in conjunction with the accompanying drawings.
The nationality of metallic fiber 1 is coated with Graphene derivative solution by guide wheel 9 by solution 2a in immersion liquid pond 2 first, then
The metal composite fiber for being coated with Graphene derivative layer goes redundant solution by the way that liquid squeezing roll 3 is crowded, and subsequent composite fibre is by drying
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 is set atmosphere chamber 7 and is controlled in heating using microwave regional metal composite fibre using gas access 7a and gas vent 7b
The atmosphere of surrounding.Then nationality is input into microwave in the case where atmosphere is set to metal on metal composite fiber by microwave input 6a
Top layer and Graphene derivative layer are then passed through out foraminate metal baffle and are left micro-wave oven 6 and entered by heating using microwave
Afterwards the area of temperature control 8 and using temperature controlled fluid entrance 8a and temperature controlled fluid outlet 8b design temperatures circulation of fluid and at cooled microwave heating
The temperature of the metal composite fiber after reason, then passes through metal composite fiber the squeezing by compression roller 10 that microwave heating treatment is crossed
Press and obtain the metal composite fiber coated by graphene layer.
Wherein metal baffle 5 can be beneficial to by opening aperture fiber continuously operation be changed to guide fiber to bypass gold by guide wheel 9
Category baffle plate and continuously run so as to be conducive to stop microwave and strengthen 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 metallic fiber Surface coating Graphene derivative layer
War.Except extra high temperature long time treatment, after general chemistry reduction and high temperature reduction method treatment Graphene derivative its
The content of middle carbon is difficult more than 90%, and extra high temperature long time treatment not only energy consumption is big, but also Graphene can be spread out
Biological laminate structure causes to damage.Therefore it is converted into Graphene with by Graphene derivative layer in the urgent need to developing new technology
Layer.Have intensification quickly special for this present invention has Microwave Absorption Properties and microwave using Graphene derivative first in the world
Point, passes through heating using microwave area, so as to add in precise control in the case where atmosphere is set by by Graphene derivative floor with setting speed
The hot time and avoid heating inequality in the case of heat Graphene derivative layer and by Graphene derivative layer be converted into stone
Black alkene layer.In fact, microwave treatment is applied in Graphene associated materials some correlative studys.For example people prepare oxygen
A kind of method of graphite alkene is exactly microwave treatment graphite oxide, and high temperature of the nationality by heating using microwave up to more than 2,000 degrees Celsius causes oxygen
Graphite inside produces a large amount of gases and is separated from each other few layer even single-layer graphene oxide in graphite and comes.And 2,000 is Celsius
Degree high temperature above almost can thoroughly redox graphene and be translated into Graphene.Our experiences show that non-
Microwave heating treatment includes the stone 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 heats due to concentrating heating, therefore local
Temperature is high, causes vigorous reaction to produce gas and so that the structure of Graphene derivative material is destroyed, Graphene derivative
Layer becomes chip, it is therefore necessary to effectively control microwave heating process cause can either effective high-temperature process Graphene derivative, and
Destruction of the vigorous reaction to Graphene derivative material structure can be avoided.Our experiences show that the time is small in the case where atmosphere is set
Graphene derivative can be efficiently converted into Graphene in the of short duration heating using microwaves of 3 seconds, but produced due to reduction
Drastically expansion including the gas including aqueous vapor is an important pushing hands for causing Graphene derivative material structure to destroy, therefore
We just generate the thinking that rapid microwave heating, steam that subsequent quick cooling causes reduction to produce etc. avoid drastically expanding.
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 the gas of generation is reduced therefore, it is possible to preferably keeping the structure of Graphene derivative material and being eventually converted into Graphene material
Material.Certainly the nitrogen for being passed through cooling is cooled down while heating material, could be improved from from the point of view of energy ezpenditure.Graphene
The another question of derivant material microwave heating treatment is that uneven problem is heated in heating using microwave area, during this is with micro-wave oven
The uniformity for heating electric field is relevant, although can improve micro-wave oven homogeneous heating by designing such as curve antenna structure mode
Property, but electric field is uneven is difficult to avoid that, and the effect of non-uniform heat flux then causes Graphene derivative material to be converted into Graphene
Effect had differences in different zones and influence overall performance, and if improve the heat time if a part of stone may occur
Black ene derivative material is destroyed because of over-heating, and another part may not reduced also then well.So
In order to reduce one side heating using microwave, one side cooling fluid cooling zone carrys out the increase of energy consumption and improves the uniform of microwave heating treatment
Property, accurately controlled so that setting speed is heated by heating using microwave area in the case where atmosphere is set we consider Graphene derivative material
Heat time processed, the method for then quickly cooling down so that the Graphene derivative in all regions is by whole heating using microwave 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 heating using microwave
Micro-wave oven is cooled down so as to reduce the energy consumption of cooling by cooling device again.Experiment shows that our method works well, just
Graphene derivative layer be converted into for graphene layer, the content of the carbon of graphene layer more than 90%, due to common graphite absorption
There is 3% oxygen, therefore close to reducing completely, and show good electrical property.
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, keep
Mixture temperature is less 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 the temperature in oil bath increases to 90 degrees Celsius.300 milliliters of water are added in addition, and
It is stirred for one and a half hours.The color of mixture becomes brown.Mixture is then with 30% 300 milliliters of hydrogen peroxide and 30 liters
Hot water treatment and dilution.The mixture further with excessive water washing, until the pH value of filtrate is almost neutral so as to obtain
Obtain graphene oxide.Graphene oxide freeze-drying then can be obtained into graphene oxide powder.Then by graphene oxide
Powder disperses in water and is reduced 12 hours at 80 degrees Celsius with hydrazine hydrate.Redox graphene is formed with black precipitate, is used
0.45 μm of PTFE film is collected by filtration, and is rinsed with substantial amounts of water.Product is carried by methyl alcohol, tetrahydrofuran (THF) and water with Soxhlet
Follow the example of and be further purified.Finally, the redox graphene for being obtained is subzero 120 Celsius under 0.05 millimetres of mercury vacuum environment
Degree is lyophilized.The redox graphene aqueous solution of 0.5 mg/ml is then prepared with deionized water.
Secondly a diameter of 50 microns of copper wire 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 be coated to be formed surface be coated with redox graphene layer answer
Copper wire is closed, subsequent composite copper wire is that the liquid squeezing roll that 200 N/centimetre hardness are 90 degree removes unnecessary solution by line pressure, so
Composite copper wire enters 150 degrees Celsius of drying rooms and dries afterwards, obtains to surface and is coated with the composite copper wire of redox graphene layer.Then
Composite copper wire is by opening the heating using microwave area that foraminate stainless steel metal baffle plate is protected into argon gas.Heating using microwave area is by 10
Radiator is constituted and causes that heating zone length reaches 1 meter, and it is that 1000W is heated about 1 second then to adjust microwave power, then by gold
Aperture enters by circulating cooling water management temperature for the rear temperature control area of room temperature is cooled down on category baffle plate, and composite copper wire passes through thereafter
Line pressure is that the compression roller of 1300 Ns/centimetre carries out extrusion process.Above-mentioned heating using microwave-cooling-extrusion process three times is repeated to obtain
Obtain graphene layer carbon content and be more than 5000Sm more than 90% electrical conductivity-1Graphene layer cladding composite copper wire.The composite copper wire
There is no obvious corrosion phenomenon within one week in the salpeter solution of 1M in the case of not exposing exposed head end yet, show excellent
Corrosion resistance features.
Embodiment two：
A diameter of 1 millimeter of aluminum steel is obtained first, aluminum steel is then passed through into 30 centimeter lengths with the speed of 0.1 meter per second 10
The graphene oxide water solution of mg/ml, obtains the compound aluminum steel that surface is coated with graphene oxide layer after drying.This is answered
It is 55 that aluminum steel is closed in nitrogen and hydrogen ratio:Led at 200 degrees celsius with the speed of 0.1 meter per second under being protected under 1 reducing atmosphere
Overpower 10 centimetres of heating zones of micro-wave oven diameter of 1000W to be heated about 1 second, be then again introduced into room temperature region carry out it is cold
But, be then combined aluminum steel carries out extrusion process by the compression roller that line pressure is 1000 Ns/centimetre, repeat above-mentioned heating using microwave-
Cooling-extrusion process 20 times.Obtain graphene layer carbon content and be more than 5000Sm more than 90% electrical conductivity-1Graphene layer cladding
Compound aluminum steel.The compound aluminum steel does not occur significantly for one week in the hydrochloric acid solution of 1M in the case of not exposing exposed head end yet
Corrosion phenomenon, shows excellent corrosion resistance features.
Embodiment three：
The graphene platelet of edge carboxylated is prepared first.5 grams of graphite and 100 grams of dry ice are added and contain 1000 grams of diameter
In 5 millimeters of stainless steel capsules of stainless steel ball.Container is sealed and is fixed on planetary ball mill (F-P4000), and with 500rpm
(rev/min) speed is stirred 48 hours.Then, internal pressure is slowly discharged by a gas vent.Pass through at the end of ball milling
Container cover is opened in atmosphere, is triggered carboxylate that violent hydration reaction generation carboxylic acid occurs by the wet steam in air and is sent out sudden strain of a muscle
Light.Products obtained therefrom carries out soxhlet type with 1M hydrochloric acid solutions to be thoroughly acidified carboxylate and the presumable metal impurities of removal.Most
Eventually under 0.05 millimetres of mercury vacuum environment subzero 120 degrees Celsius obtain edge carboxylated graphene nanometer sheet within lyophilized 48 hours
Furvous powder.Edge carboxylated graphene nanometer sheet is obtained into the uniform of 0.1wt% in 30 minutes by the ultrasound in isopropanol
Scattered solution.
Then the filamentary silver of 100 microns of diameter 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 and is coated with edge carboxylated graphene layer after drying
Compound filamentary silver.Under helium protection under room temperature state it is 1000W by power with the speed of 0.02 meter per second by the compound filamentary silver
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, repeat above-mentioned solution coating-heating using microwave-cooling-
Extrusion process 3 times,.Obtain graphene layer carbon content and be more than 5000Sm more than 90% electrical conductivity-1Graphene layer cladding it is compound
Filamentary silver.There is no within one week in the salpeter solution of 1M obvious corrosion in the case of not exposing exposed head end in the compound filamentary silver yet
Phenomenon, shows excellent corrosion resistance features.
Example IV：
Edge halo graphene nanometer sheet is prepared first.5 grams of graphite are added and contain 1000 grams 5 millimeters of stainless steel balls of diameter
Stainless steel capsule in.Then capsule is sealed and five circulations charge and discharge argon gas under 0.05 millimetres of mercury vacuum pressure condition.
Hereafter, it is that 8.75atm adds chlorine from gas access by cylinder pressure.Container is sealed and is fixed on planetary ball mill (F-
P4000), and with 500rpm (rev/min) speed stir 48 hours.Products obtained therefrom successively carries out Soxhlet with methyl alcohol and 1M hydrochloric acid solutions
Extract thoroughly to remove small molecule organic impurities and presumable metal impurities.Finally zero under 0.05 millimetres of mercury vacuum environment
The lower 120 degrees Celsius furvous powder for obtaining edge chlorination graphene nanometer sheet for lyophilized 48 hours.Then 0.1 milligram/milli is prepared
The edge chloro Graphene N for rising, N '-dimethyl formamide DMF solution.
Secondly a diameter of 50 microns of nickel wire 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 obtains surface and is coated with edge after drying
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
Room is then again introduced into for 10 centimetres of heating zones of micro-wave oven diameter of 1000W are heated about 5 seconds by power under room temperature state
Temperature area is cooled down, and be then combined nickel wire carries out extrusion process by the compression roller that line pressure is 500 Ns/centimetre, in repetition
Solution coating-heating using microwave-cooling-extrusion process process 3 times is stated,.Obtain graphene layer carbon content big more than 90% electrical conductivity
In 5000Sm-1Graphene layer cladding compound nickel wire.The compound nickel wire does not expose the nitric acid in 1M in the case of exposed head end
There is no obvious corrosion phenomenon within one week in solution, show excellent corrosion resistance features yet.
Embodiment five
Edge nitridation graphene nanometer sheet is prepared first.5 grams of graphite are added and contain 1000 grams 5 millimeters of stainless steel balls of diameter
Stainless steel capsule in.Then capsule is sealed and five circulations charge and discharge nitrogen under 8bar pressure conditions.Then seal capsule
And planetary ball mill (F-P4000) is fixed on, then stirred 48 hours with 500rpm (rev/min) speed.Products obtained therefrom is successively used
Methyl alcohol and 1M hydrochloric acid solutions carry out soxhlet type thoroughly to remove presumable metal impurities.Then repeat to use ethylenediamine tetra-acetic acid
(EDTA), concentrated ammonia liquor and 1M hydrochloric acid solutions are processed, until XPS inspections do not measure metal residue.It is final true in 0.05 millimetres of mercury
The subzero 120 degrees Celsius 5.67 grams of edges nitridation graphene nanos for obtaining intake at least 0.67g nitrogen for lyophilized 48 hours 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 a diameter of 2 millimeters of cobalt silk is obtained.Then cobalt silk is run with the speed of 0.1 meter per second, and will by shower nozzle
0.1 mg/ml edge nitrogenizes graphene nanometer sheet DMA solution spraying thereon, reruns between 100 meters
Cobalt silk is sprayed with other shower nozzle every rear, after spraying 5 times, 50 degrees Celsius of vacuum drying obtain edge nitridation Graphene for 24 hours
The cobalt silk of layer parcel.It is by power under room temperature state with the speed of 0.02 meter per second under argon gas protection 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, Ran Houfu
Close cobalt silk carries out extrusion process by the compression roller that line pressure is 1300 Ns/centimetre, repeats above-mentioned heating using microwave-cooling-extruding
Processing procedure 5 times,.Obtain graphene layer carbon content and be more than 5000Sm more than 90% electrical conductivity-1Graphene layer cladding it is compound
Cobalt silk.There is no within one week in the salpeter solution of 1M obvious corrosion in the case of not exposing exposed head end in the compound cobalt silk yet
Phenomenon, shows excellent corrosion resistance features.
Embodiment six
A diameter of 1 millimeter of copper cash is obtained first, 1 milli that copper cash 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 drying.
Under the vacuum environment of 2KPa in room temperature condition it is the microwave of 800W by power with the speed of 0.02 meter per second by the composite copper wire
10 centimetres of heating zones of stove diameter are heated about 5 seconds, are then again introduced into room temperature region and are cooled down, the above-mentioned cooling of repetition-micro-
Wave heating-cooling procedure 5 times, then composite copper wire extrusion process is carried out by the compression roller that line pressure is 1200 Ns/centimetre, weight
Multiple above-mentioned heating using microwave-cooling-extrusion process 5 times,.Obtain graphene layer carbon content and be more than 5000Sm more than 90% electrical conductivity-1
Graphene layer cladding composite copper wire.The composite copper wire is not exposed in the case of exposed head end one week in the salpeter solution of 1M
There is no obvious corrosion phenomenon, show excellent corrosion resistance features yet.
Claims (8)
1. a kind of preparation method of metal composite fiber, it is characterised in that Graphene derivative solution is prepared first, then by stone
Black ene derivative solution coating forms the metal composite fiber of Graphene derivative cladding on selected metallic fiber surface, then
Cause that metal composite fiber causes metallic fiber surface because vortex with setting speed by heating using microwave area in the case where atmosphere is set
Effect and heats up, while Graphene derivative layer then heats up because of absorption microwave and causes the graphite on metal composite fiber surface
Ene derivative layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves heating using microwave area and cold
But, then extrusion process can obtain the metal composite fiber of graphene layer cladding.
2. the preparation method of a kind of metal composite fiber according to claim 1, it is characterised in that the Graphene derives
Thing refers to graphene oxide, the graphene oxide or graphene edge derivative of reduction.
3. the preparation method of a kind of metal composite fiber according to claim 1, it is characterised in that the setting atmosphere is
Refer to inert atmosphere, reducing atmosphere or vacuum state；The inert atmosphere refers to not anti-with graphene oxide derivative gas
The gas answered；The reducing atmosphere refers to contain the gas for being capable of reduced graphene derivative in gas；The vacuum state
Refer to that air pressure is less than 4KPa.
4. the preparation method of a kind of metal composite fiber according to claim 1, it is characterised in that the Graphene derives
It refers to that high temperature action causes the Graphene of oxidation to be reduced that nitride layer is converted into graphene layer because of high temperature action, and Graphene side
Then there is the reaction of off-clip edge functional group in edge derivative.
5. a kind of preparation method of metal composite fiber according to claim 1, it is characterised in that the graphene layer bag
The carbon content of graphene layer is more than 90% in the metal composite fiber for covering.
6. the preparation method of a kind of metal composite fiber according to claim 1, it is characterised in that the metal composite is fine
Dimension is left heating using microwave area and is cooled, and refers to by cold atmosphere or additionally applies cold air-flow body and cool down.
7. the preparation method of a kind 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 heating using microwave area,
Graphene derivative layer then heats up because microwave is absorbed and causes the Graphene derivative layer on metal composite fiber surface simultaneously
Graphene layer is converted into because of high temperature action, subsequent metal composite fiber leaves heating using microwave area and is cooled, and the process can
To repeat with multiple high temp treatment Graphene derivative layer.
8. the preparation method of a kind 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, then in setting
Cause that metal composite fiber causes metallic fiber surface because of eddy current effect with setting speed by heating using microwave area under atmosphere
Heat up, while Graphene derivative layer then heats up and cause that the Graphene on metal composite fiber surface derives because microwave is absorbed
Nitride layer is converted into graphene layer because of high temperature action, and subsequent metal composite fiber leaves heating using microwave area and is cooled, then
Extrusion process, the process can repeat can repeatedly be coated with and microwave high-temperature process to increase the thickness of graphene layer.
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| CN114737298A (en) * | 2022-03-31 | 2022-07-12 | 圣华盾防护科技股份有限公司 | High-barrier electromagnetic shielding protective clothing fabric and preparation method thereof |
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