A kind of manufacturing method of the metal-base composites of containing graphene interlayer
Technical field
The invention belongs to metal-base composites forming fields, and in particular to the metal-base composites of containing graphene interlayer
Molding fabrication techniques, especially a kind of the ultrasonic welding manufacturing method and base of the metal-base composites of containing graphene interlayer
The metal-base composites of containing graphene interlayer made from the method.
Background technique
The demands of the manufacturing industry to high-performance metal sill such as fast-developing aerospace, automobile, electronics become more next
It is more urgent.The good metal_based material of electrical and thermal conductivity performance has the wide market demand.Graphene (graphene) earliest by
Novoselov of Univ Manchester UK et al. was obtained in the method with adhesive tape removing highly oriented pyrolytic graphite in 2004, it
It is by the new material of the closelypacked two-dimentional bee type lattice structure of carbon atom.Its according to the number of plies can be divided into single-layer graphene and
Multi-layer graphene, thickness is generally in 100nm or less.Since graphene is by since manually preparing, it becomes physics and materialogy
The primary study topic on boundary, causes the extensive concern of scholar and industry personage.Graphene is known most thin in the world at present
Material, it possesses many extremely excellent physical properties, such as light transmittance is high, and thermal coefficient is high, and electron mobility is high, resistance
Rate is that known materials are the smallest, and Hall effect, etc. can also be presented at room temperature.In order to efficiently use a series of excellent of graphene
Performance has a series of technology of metals of the preparation comprising graphene or ceramic base composite powder in the world, and is applied to various
Field.It is one of main method using reaction solution chemical synthesis, for example, patent CN102130334A is proposed molysite
Solution and graphene oxide mixed solution carry out hydro-thermal reaction in a kettle, and dry reaction product obtains the oxidation of graphene iron
Object composite material.Although a greater variety of containing graphene composite material granulars can be obtained using electrochemistry method, and disperse effect
Fruit is preferable, but that there are yield is very low, and particle size is unable to control, and the drawbacks of consume a large amount of electric energy.Patent CN104862508A
It describes and Al alloy powder is added in graphene solution, be then charged into ball milling and fill progress mechanical ball mill, Ball-milling Time is
It 20 40 hours, mixed solution is fitted into beaker after ball milling is placed in baking oven and dry, obtain graphene/aluminum alloy composite powder
End can be used for subsequent powder compacting process.Patent WO2015149385A1 is described monodispersed graphene solution and metal
Ball milling is carried out after powder mixing, the process that then mixed-powder is packed into jacket and is sealed, products obtained therefrom can be used for hot isostatic pressing
Manufacture sheet metal.Although the method for ball milling mixing can be suitable for mixing the metal powder and graphene of most of types, and
Yield is higher, but their often there is preparation process cumbersome, high energy consumptions, time-consuming it is equal the disadvantages of.In addition, being ground in mechanical milling process
Ball can also be such that the quality of composite powder declines the destruction of matrix powder and graphene.Moreover, in drying and transportational process
Reuniting again for middle graphene also will affect graphene in the uniformity of composite powder.
Summary of the invention
The present invention is based on graphene in the prior art and metal composite there are the problem of, invented a kind of completely new graphene
With the complex technique of metal_based material, innovation proposes a kind of ultrasonic welding manufacture of the metal-base composites of containing graphene interlayer
Method and metal-base composites based on containing graphene interlayer made from the manufacturing method.The method of the invention overcomes
In existing graphene reinforced metal based composites manufacturing process graphene be unevenly distributed, be easy to reunite, structural failure, arrangement
The disadvantages of uncontrollable, and the pioneering graphene that realizes is compound in metal_based material with sandwich format, changes the prior art
In powder complex technique.The gold prepared using the metal-base composites of containing graphene interlayer made from the method for the invention
Belong to part, because having benefited from the excellent physical and mechanical properties of graphene, so that the electrical and thermal conductivity performance of metal parts is promoted very
Obviously, good mechanical properties, microstructure is uniform, and the completely compatible subsequent machining of molded part, punching press reshaping etc., fits
The applications such as production, the heat dissipation of highly integrated electronic equipment casing of high-end electronic device part are closed, there is wide promotion prospect.
It is as follows that the present invention solves the technical solution that above-mentioned technical problem is taken:
A kind of manufacturing method of the metal-base composites of containing graphene interlayer, specifically includes the following steps:
Step 1: it is several to prepare metal foil, and level is spread out, and keeps surfacing;
Step 2: cleaning all metal foils, it is dried after having cleaned;
Step 3: graphene is dispersed in dispersing agent according to predetermined ratio, graphene suspension is formed;
Step 4: graphene suspension is passed through the surface that ultrasonic spraying method is uniformly sprayed on each metal foil;
Step 5: the metal foil merging vacuum drying box that surface is attached with graphene suspension is dried, dry
Equally distributed graphene layer is formed in metal foil surface afterwards;
Step 6: together by all metal foil stacked on top after drying, keeping the stone of each metal foil surface
Black alkene layer forms metal foil stack assemblies towards same direction;
Step 7: carrying out ultrasonic welding to metal foil stack assemblies using ultrasonic welding device, metal foil is stacked
The integral molded part of components welding, and graphene interlayers are formed between adjacent metal paillon, the gold of containing graphene interlayer is made
Metal-matrix composite material.
According further to manufacturing method of the present invention, wherein several metal foils in step 1 be equidimension,
The thickness of the paillon made of the metal_based material for being applicable to ultrasonic bonding of equal thickness, the metal foil is less than or equal to
1 millimeter, the quantity of the metal foil is within 50.
According further to manufacturing method of the present invention, wherein the metal foil in step 1 be metallic aluminium paillon,
Metallic iron paillon, metallic copper foil, almag paillon, cochrome paillon, nickel-base alloy paillon, stainless steel paillon, titanium close
Gold foil or aluminium alloy paillon;The metal foil with a thickness of 0.1-0.5mm.
According further to manufacturing method of the present invention, wherein in step 3, the graphene that is scattered in dispersing agent
For graphene of the number of plies within 10 layers, the dispersing agent selects organic solvent or aqueous liquid dispersion, the graphene suspension
The weight percent concentration of middle graphene is less than or equal to 5%.
According further to manufacturing method of the present invention, wherein in step 3, the graphene that is scattered in dispersing agent
For single-layer graphene, the dispersing agent selects ethyl alcohol, isopropyl acetone or dimethylformamide, graphene in the graphene suspension
Weight percent concentration be 1-4%.
According further to manufacturing method of the present invention, wherein in step 4, utilized by ultrasonic spray equipment super
Graphene suspension is broken up the upper surface for being uniformly sprayed to each metal foil afterwards, ultrasound in ultrasonic spray equipment by acoustic wave energy
At 1-3g/ minutes, the working frequency of ultrasonic spray nozzle was controlled in 10-30KHz, ultrasonic spray nozzle for the spraying flow control of wave spray head
By graphene suspension at uniform sprinkling 1-5 times of all standing of each metal foil upper surface.
According further to manufacturing method of the present invention, wherein in step 5, it is suspended that surface is attached with graphene
The metal foil merging vacuum drying box of liquid is dried, and controls the drying temperature of vacuum drying box at 50-70 degrees Celsius, to gold
Belong to after the dispersing agent in the graphene suspension of foil surfaces attachment volatilizees completely and take out metal foil, on the surface of metal foil
Remain with equally distributed graphene layer.
According further to manufacturing method of the present invention, wherein in step 6, by all metal foils after drying
Together, the surface for making each metal foil be formed with graphene layer is upward for stacked on top, and makes the shape of the top metal foil
At having the surface of graphene layer downward or the metal foil of graphene layer is not formed in the selection of uppermost metal foil.
According further to manufacturing method of the present invention, wherein in step 7, metal foil stack assemblies are placed
Below the welding impact head in the support base of ultrasonic welding device, and in ultrasonic welding device, welding ginseng needed for setting
Start ultrasonic welding device after number, adjacent metal paillon is issued in ultrasonic energy and action of compressive stress in metal foil stack assemblies
Raw interface is local melting and solidifies, and the graphene layer at welding process median surface is melted metallic cover and permeates and be retained in
In solidified structure, so that fusion has graphene interlayers between adjacent metal paillon.
According further to manufacturing method of the present invention, wherein in step 7, the maximum power of ultrasonic welding device
It is 5000 watts, the normal pressure that pressurizing device loads in ultrasonic welding device is less than or equal to 500 newton, ultrasound in ultrasonic welding device
The supersonic frequency that generator provides is 30-60KHz, and welding impact head is in each welding zone of metal foil surface in ultrasonic welding device
Single welding the duration be 5-20 seconds.
A kind of metal-base composites of containing graphene interlayer, which is characterized in that the Metal Substrate of the containing graphene interlayer
Composite material is made using manufacturing method of the present invention.
Technical solution of the present invention has following technical characteristic and technical effect:
(1) present invention proposes the complex method of a kind of completely new graphene and metal_based material, is based on ultra-sonic welding techniques
Graphene interlayers are compound in metal_based material, the method overcomes existing graphene reinforced metal based composites manufacture
Graphene is unevenly distributed, is easy to reunite, structural failure, arranging the disadvantages of uncontrollable in the process, and that initiates realizes graphite
Alkene is compound in metal_based material with sandwich format, it is entirely avoided the inherent shortcoming of powder complex technique in the prior art.
(2) present invention proposes a kind of completely new easy to operate, high efficiency, the high thermal conductivity suitable for producing containing graphene interlayer, height
Conductive, strong mechanical performance metal-base composites manufacturing process, the manufacturing process it is innovative by metal foil ultrasonic welding
Combine with graphene spraying process, realizes graphene controllable orderly arrangement inside metal-base composites, completely
Avoid graphene under conventional casting techniques in the agglomeration traits of intrinsic silicon, and ultrasonic welding is lower than the molding temperature of melting point metal
Degree, efficiently avoids the formation of structural failure and constituent phases of the graphene in recombination process compared with the existing technology.
(3) metal-base composites for the containing graphene interlayer that through the invention prepared by the method, electrical and thermal conductivity
Excellent, the good mechanical properties of energy, microstructure uniform, controllable, and completely compatible subsequent material machine-shaping, such as cut, punching press,
Drilling etc., is suitable for high-volume industrial production and application, and popularization and application foreground is good.
Detailed description of the invention
Attached drawing 1 is ultrasonic welding device schematic diagram used in the present invention;
Attached drawing 2 is ultrasonic spray equipment schematic diagram used in the present invention;
Attached drawing 3 is the schematic diagram of internal structure of the metal-base composites of containing graphene interlayer prepared by the present invention;
The meaning of each appended drawing reference is as follows in figure:
1- ultrasonic generator, 2- pressurizing device, 3- energy converter, 4- luffing device, 5- weld impact head, 6- metal foil heap
Stacked group part, 7- pedestal, 8- ultrasonic spray nozzle, the suspended liquid storage tank of 9- graphene, 10- graphene interlayers, 11- metal foil.
Specific embodiment
Technical solution of the present invention is described in detail below in conjunction with attached drawing, so that those skilled in the art can be more
The protection scope for adding and being clearly understood from the present invention, but be not intended to limit the present invention.
What the ultrasonic welding manufacturing method of the metal-base composites of containing graphene interlayer of the present invention was initiated will be ultrasonic
Welding procedure and ultrasonic spraying process combine, and are sprayed using ultrasonic welding device as shown in Fig. 1 and attached ultrasound shown in Fig. 2
Coating device.The ultrasonic welding device includes ultrasonic generator 1, pressurizing device 2, energy converter 3, luffing device 4, welding impact head
5 and pedestal 7, as shown in Fig. 1, ultrasonic generator 1 is connected to energy converter 3, and pressurizing device 2 is connected to energy converter 3, energy converter 3
It is connected to luffing device 4, luffing device 4 is connected to welding impact head 5, and pedestal 7 is in 5 lower section of welding impact head, socket part to be welded
Part such as metal foil stack assemblies 6 are placed on pedestal 7, carry out ultrasound to metal foil stack assemblies 6 by welding impact head 5
Welding.Ultrasonic welding is a kind of quick, clean, effective welding procedure, by ultrasonic generator 1 by 30-60 hertz of electric current
It is converted into high-frequency electrical energy and exports the machinery fortune being again converted to by energy converter 3 to energy converter 3, high-frequency electrical energy as equal frequencies
Dynamic, the mechanical movement after being converted by energy converter 3 is after the pressurization of pressurizing device 2, in the luffing device 4 by can change amplitude
Be transmitted to welding impact head 5, the vibrational energy received is transmitted to by welding impact head 5 be placed in it is to be welded on pedestal 7
The joint portion of workpiece, in the region, the vibrational energy for welding impact head 5 is converted into thermal energy by friction mode, by portion to be welded
Part fusion realizes that ultrasonic welding, ultrasonic welding belong to a kind of welding technique of relative maturity, and metal is carrying out ultrasonic bonding
When, electric current neither is conveyed to workpiece, also high temperature heat source is not imposed to workpiece, only under static pressure, vibrational energy is changed
Frictional work, deformation energy and limited temperature rise between workpiece, phenomena such as overcoming generated splashing when resistance welding and aoxidize.This
Innovation uses ultrasonic welding, compared to traditional high energy beam welding technique, so that welding zone temperature is substantially reduced, therefore graphene knot
Structure can be effectively retained and avoid the harmful constituent phases generated due to high temperature.
Ultrasonic spray equipment used in the present invention is as shown in Fig. 2, including ultrasonic generator 1,8 and of ultrasonic spray nozzle
The suspended liquid storage tank 9 of graphene, the ultrasonic generator 1 are connected to ultrasonic spray nozzle 8, and the ultrasonic spray nozzle 8 is connected by pipeline
It is connected to the suspended liquid storage tank 9 of graphene, ultrasonic generator 1 provides ultrasonic energy to ultrasonic spray nozzle 8, passes through 8 benefit of ultrasonic spray nozzle
The liquid in the suspended liquid storage tank 9 of graphene is broken up with ultrasonic energy, the atomized particles for forming micron dimension are uniformly sunk
Product is in being sprayed-on object surface.Ultrasound spraying as emerging spraying process, effectively nano material uniformly can be coated to
Graphene can effectively be broken up in dispersing agent and be sprayed at metal foil by the surface of all kinds of substrates, the ultrasonic vibration at spray head
Piece surface, as the volatilization graphene of dispersing agent just remains in metal foil surface to be welded, what the present invention initiated utilizes ultrasound
Spraying realizes graphene being uniformly distributed in metal foil surface.
The ultrasonic welding manufacturing method of the metal-base composites of containing graphene interlayer of the present invention, specifically includes following
Step:
Step 1: the metal foil of preparation equidimension equal thickness is several, and level is spread out, and keeps surfacing.It can use
It include all kinds of being applicable to paillon made of the metal_based material of ultrasonic bonding, such as proof gold in " metal foil " of the invention
Belong to paillon or alloy material made of (such as iron, copper, aluminium etc.) (such as almag, cochrome, nickel-base alloy, stainless steel,
Titanium alloy etc.) made of paillon.The thickness of metal foil is preferably less than 1 millimeter, more preferably less than 0.5 millimeter, such as 0.1-
0.5mm.The size of metal foil there is no limit, may depend on the size of ultrasonic welding stage, within generally 500 × 500mm because
The common consecutive maximum weld size of ultrasonic bond is generally 500mm.The quantity of metal foil can determine according to actual needs, such as 20
Piece, 30,50.
Step 2: cleaning all metal foils, is preferably cleaned using acetone soln, cleaned and be dried, and kept
Level spreads out state.
Step 3: configuration graphene suspension, is added evenly dispersed in dispersing agent be made according to predetermined ratio for graphene
Graphene suspension;The graphene is graphene of the number of plies within 10 layers, and the preferred graphene is single-layer graphene;
The dispersing agent is to commonly use organic solvent or aqueous liquid dispersion, preferably ethyl alcohol, isopropyl acetone, dimethylformamide etc., most
Preferred dispersing agent is ethyl alcohol;Adding proportion of the graphene in dispersing agent can be selected according to actual needs, still
The weight percent concentration of graphene is less than etc. 5% in preferred graphene suspension, because graphene adding proportion is higher than 5%
Graphene easily occurs to reunite, and influences interface welding quality.The mass percent of graphene in preferred graphene suspension
For 0.5-4%, preferably 1-4%, more preferably 1-2%.
Step 4: graphene suspension is passed through the surface that ultrasonic spraying method is uniformly sprayed at each metal foil.Tool
The usable ultrasonic spray equipment as shown in Fig. 2 of body, ultrasonic generator 1 provide ultrasonic energy to ultrasonic spray nozzle 8, ultrasound
Wave spray head 8 is uniformly sprayed to after being broken up the graphene suspension in the suspended liquid storage tank 9 of graphene using ultrasonic energy
The surface of each metal foil 11, fountain height of the graphene suspension on 11 surface of metal foil can need to carry out true according to application
Fixed, preferably uniform sprinkling 1-5 times by graphene suspension in metal foil surface all standing can satisfy most needs, surpass
Need real-time monitoring quantity for spray to complete accurately Composition Control in sound spraying process, the preferred spraying for controlling ultrasonic spray nozzle
For flow at 1-3g/ minutes, the working frequency of ultrasonic spray nozzle was 10-30KHz.Preferably on the single surface of each metal foil
Spraying graphite alkene suspension.
Step 5: all metal foils that surface is attached with graphene suspension are placed in vacuum drying box, dried,
Drying temperature is preferably at 50-70 degrees Celsius, and more preferably 60 DEG C, to point in the graphene suspension of metal foil surface
Powder takes out all metal foils after volatilizing completely, be attached with equally distributed graphite on the surface of each metal foil in this way
Alkene forms graphene layer.
Step 6: together by all metal foil stacked on top after drying, metal foil stack assemblies 6 are formed, and
Keep the graphene layer of each metal foil surface towards same direction, the graphene layer of preferred each metal foil is upward
It is arranged at (back side that graphene layer is not formed of the graphene layer contact upper metal paillon of each metal foil), it is uppermost
The graphene layer of metal foil is arranged downward or uppermost metal foil selects the metal foil of non-spraying graphite alkene.
Step 7: metal foil stack assemblies 6 are placed on the pedestal 7 of ultrasonic welding device, it is placed in welding impact
Under head, welding parameter needed for setting starts ultrasonic welding device, is carried out by welding impact head to metal foil stack assemblies 6
Disposable ultrasonic welding, the maximum power for being preferable to provide ultrasonic welding device is 5000 watts (being less than or equal to 5000W), pressurization dress
It sets 2 load normal pressures and (is less than or equal to 500N) within 500 newton, ultrasonic generator 1 provides supersonic frequency 30-60KHz, metal
The each welding zone of foil surfaces welds maintenance 5-20 seconds every time, and then mobile base welds next welding zone, and repeats this step extremely
All metal foils are all closely fused together.If metal foil area is too big, mobile welding impact head may be selected also to ensure
All metal foils all merge completely.Ultrasonic welding process is foregoing, is not necessarily to extra solder, the metal foil contacted up and down
Generation interface is local melting under ultrasonication and pressure and welding, and the graphene at welding process median surface are completed in solidification
Thin layer is melted metallic cover and permeates and be retained in solidified structure, to be each formed with stone between every double layer of metal paillon 11
Black alkene interlayer 10 simultaneously because welding fabrication process carries out under compression always, guarantees molded part invariably as shown in Fig. 3
Good residual stress.
Step 8: removing, being contained from ultrasonic welding device after metal foil stack assemblies 6 complete ultrasonic welding
The metal-base composites molded part of graphene interlayers.
As described above, what the present invention initiated is coated to graphene uniform using ultrasonic spraying process as pioneering technology
Each metal foil surface to be welded, and the distributional pattern of graphene is maintained in whole process, while the present invention initiates
The metal foil that multi-disc is coated with graphene is stacked into welding fabrication based on Ultrasonic welding processes, weldment is under high-frequency vibration super
Acoustic energy gathers the face of weld, and generating localized hyperthermia merges material, so the present invention initiate propose a kind of easy to operate, high efficiency
The metal-base composites manufacturing process for being suitable for producing containing graphene interlayer, composite material produced contains multilayer and uniformly divides
The controllable graphene interlayers of cloth, arrangement, the very effective thermal conductivity for improving material, electric conductivity and mechanical property.
Following for the better statement present invention, with AlSi10For Mg cast aluminium alloy gold, it is specific to provide of the invention one
(note: involved design parameter numerical value is representative value to embodiment, only the more preferably application implementation of statement the invention, not
Limit effective use scope of the invention):
Embodiment 1
The present embodiment provides a kind of ultrasonic welding manufacturing methods of the Al alloy composite of containing graphene interlayer, specific to wrap
Include following steps:
(1) horizontal after being cleaned and dried the aluminium alloy paillon of 0.5mm thickness (10 × 10mm of area) 20 with acetone soln
It spreads out.
(2) alcohol dispersant is added in certain content single-layer graphene, graphene suspension is made, wherein graphene quality
Percentage composition is 1% or so.
(3) graphene suspension is uniformly sprayed to each aluminium alloy foil surfaces, all standing sprinkling 1 using ultrasonic nozzle
It is secondary, it controls flow 2g/ minutes, ultrasonic nozzle frequency 20KHz.
(4) will be attached with graphene aluminium alloy paillon merging vacuum drying box, 60 degrees Celsius of set temperature, to dispersing agent
It is taken out after volatilization completely.
(5) will all aluminium alloy paillons stack after disposably welded, when stacking each aluminium alloy paillon spraying
Surface is upward.The power that ultrasonic welding device is arranged is 1000 watts, load 200 newton of normal pressure, supersonic frequency 30KHz, often
A welding zone welds maintenance 10 seconds every time, and then mobile base welds next welding zone and repeats this step to all Aluminum alloy foils all
Close fusion, ultrasonic welding process are not necessarily to extra solder, and the aluminium alloy paillon contacted up and down occurs under ultrasonication and pressure
Interface is local melting and welding is completed in solidification, and the graphene thin layer at welding process median surface is melted metallic cover infiltration simultaneously
It is retained in solidified structure, forms graphene interlayers.
The present invention proposes the complex method of a kind of completely new graphene and metal_based material, is led in the form of graphene interlayers
It crosses ultrasonic welding to make an addition to graphene in metal-base composites, it is multiple that the method overcomes existing graphene reinforced metal base
Graphene is unevenly distributed, is easy to reunite, structural failure, arranging the disadvantages of uncontrollable in condensation material manufacturing process, and initiate
It realizes graphene to be compound in metal_based material with sandwich format, changes powder complex technique in the prior art.Using this
The metal parts of the metal-base composites preparation of containing graphene interlayer made from invention the method, it is excellent because having benefited from graphene
Different physical and mechanical properties, so that the electrical and thermal conductivity performance of metal parts is promoted clearly, good mechanical properties, microcosmic group
It knits uniformly, and the completely compatible subsequent machining of molded part, punching press reshaping etc., is suitble to the life of high-end electronic device part
The applications such as production, the heat dissipation of highly integrated electronic equipment casing, have wide promotion prospect.
The above is only the preferred embodiment of the present invention is described, technical solution of the present invention is not limited to
This, those skilled in the art's made any known deformation on the basis of major technique design of the invention belongs to the present invention
Claimed technology scope, the specific protection scope of the present invention are subject to the record of claims.