CN107381555A - A kind of three-dimensional grapheme of structure-controllable and its preparation method of composite - Google Patents
A kind of three-dimensional grapheme of structure-controllable and its preparation method of composite Download PDFInfo
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Abstract
The invention belongs to graphene composite material preparation field, and disclose the three-dimensional grapheme and its composite material and preparation method thereof of a kind of structure-controllable.This method comprises the following steps：(a) design construction CAD model, and the three-dimensional resinous structure of corresponding structure is obtained by increasing material manufacturing；(b) three-dimensional resinous structure obtained in step (a) is used into chemical plating method in copper coating or nickel metal layer, and removes resin material and obtain the three-dimensional structure template of copper or nickel；(c) graphene is generated on three-dimensional structure metal form using chemical vapour deposition technique, the three-dimensional grapheme of required structure-controllable is thus made.By the graphene to obtaining, further processing obtains graphene composite material.By the present invention, the regulation and control of three-dimensional grapheme structure can be achieved, and obtain the high quality of effective, accurate control, multifunction three-dimensional graphene composite material product, this method is easy to operate, short preparation period, adapts to wide.
Description
Technical field
The invention belongs to graphene composite material preparation field, more particularly, to a kind of three-dimensional graphite of structure-controllable
The preparation method of alkene and its composite.
Background technology
Graphene is two dimension (2D) crystalline material being made up of single layer of carbon atom, has extremely excellent electricity, light, heat and machine
The specific surface area of tool performance and superelevation, it is assigned in scientific domains such as nano material, bioengineering, fine chemistry industry, energy stores
Very important application prospect.The composite prepared by graphene, also because it is to original mechanics of materials, heat conduction, electric conductivity
Improvement and receive much concern.
However, strong interaction force between 2D single-layer graphene films be present, easily assemble, we are generally made
Exist more than grapheme material with powder-form, this causes its excellent specific surface area and heat conduction to be limited with conductive characteristic
System.The preparation generally use graphene powder of existing graphene composite material as additive, due to graphene distribution can not
Control property, cause composite graphene addition larger (such as conductive plastics graphene addition is 4~10%) and composite
Performance optimization is limited, and (mechanical property of composite shows the change of first increases and then decreases with the increase of graphene addition
Trend).In order to solve this problem, multi-disc graphene is joined together to form three-dimensional honeycomb shape skeleton structure by researcher, i.e.,
Three-dimensional (3D) graphene.3D graphenes in addition to the physicochemical property intrinsic with graphene, its abundant hole, ultralight density,
The performances such as bigger serface, low thermal conductivity, high conductivity, good mechanics compressibility and structural stability assign the material
Have in fields such as hydrogen storage, catalysis, sensing technology, ultracapacitor and flexibility/scalable conducing composite materials compared with mono-layer graphite
The more excellent performance of alkene and broader practice prospect.
Therefore, some solutions are proposed to it in the prior art.For example, one is disclosed in CN102674321A
Kind chemical vapour deposition technique in three-dimensional foam nickel template surface deposited graphite alkene film, and through it is molten remove porous metals substrate after
To porous foam shape graphene, but, this method is using foam metal as template, pore characteristic and graphene sheet layer therein
Orientation can not be effectively controlled；CN105776186A discloses one kind and uses SLM form metal templates, and growth prepares knot
The controllable three-dimensional grapheme porous material preparation method of structure, this method prepare metal form growth stone with SLM increases material manufacturing technologies
Black alkene, metal form surface prepared by SLM is second-rate, therefore the graphene prepared is second-rate, it is difficult to applied to composite wood
The preparation of material；The three-dimensional graphene composite material that CN106349658A, CN105749865A and CN106349658A are announced
Preparation method, it is using powdered form three-dimensional grapheme as complexing agent, graphene dispersion is improved, but still can be rolled into a ball
It is poly-, and graphene sheet layer orientation can not realize regulation and control.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of three-dimensional grapheme of structure-controllable
And its preparation method of composite, by three-dimensional template design and manufacture shaping, electroless metal layer quality regulation and control and
The links such as the growth of graphene are studied and designed, and thus solve three-dimensional grapheme and its composite outer shape and interior
The uncontrollable technical problem of portion's structure.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of three-dimensional grapheme system of structure-controllable
Preparation Method, it is characterised in that this method comprises the following steps：
(a) the three-dimensional structure structure CAD model needed for three-dimensional grapheme to be prepared, by the CAD model by increasing material
Manufacture obtains the three-dimensional resinous structure of corresponding construction；
(b) by the three-dimensional resinous structure obtained in step (a) using chemical plating method in copper coating or nickel metal layer, by
This, which must arrive surface, the resin structure of the coat of metal, and the resin of the coat of metal is removed using chemical attack or heat-treating methods
Resin material in structure, obtain the three-dimensional structure template of copper facing or nickel；
(c) graphene is generated using chemical vapour deposition technique on the three-dimensional structure metal form that step (b) obtains, thus
Obtain required three-dimensional grapheme.
Include photocuring, fusion sediment and laser choosing it is further preferred that in step (a), the step of the increasing material manufacturing
Area sinters.
The copper plating bath used it is further preferred that in step (b), during the chemical plating method copper facing is copper sulphate, chlorination
One kind or combination in copper, basic copper carbonate, cupric tartrate or copper acetate；The nickel-plating liquid used during the chemical plating method nickel plating
For one kind in nickel sulfate or nickel acetate or combination；And the layer thickness range of the coat of metal is 1 μm~50 μm.
It is further preferred that in step (b), the method for removing resin material uses chemical attack or heat treatment, its
In, using acetone, ethanol or carbon tetrachloride as corrosive agent, the temperature of the heat treatment is 300 DEG C~900 for the chemical attack
℃。
It is further preferred that in step (c), carbon source used in the chemical vapor deposition be methane, ethene, acetylene or
One kind or combination in styrene.
According to another aspect of the present invention, there is provided a kind of preparation method of three-dimensional grapheme composite material, its
It is characterised by, the preparation method comprises the following steps：For as the three-dimensional grapheme obtained by claim any one of 1-5, adopting
With the mode of casting or high temperature insostatic pressing (HIP) by the metal filled space to its internal structure, the compound gold of three-dimensional grapheme is thus made
Belong to material.
According to it is still another aspect of the present invention to provide a kind of preparation method of three-dimensional grapheme compound resin, its feature
It is, the preparation method comprises the following steps：
(c1) it is directed to as the three-dimensional grapheme obtained by claim any one of 1-5, revolves one layer of resin branch of Tu on its surface
Layer is supportted, the metal form in corrosive liquid up to the three-dimensional grapheme is then immersed in and is completely dissolved, obtain the three-dimensional with supporting layer
Graphene, wherein, the resin support layer material uses polymethyl methacrylate (PMMA) or dimethyl silicone polymer
(PDMS)；The corrosive liquid uses one kind or combination in hydrochloric acid, sulfuric acid, nitric acid, iron chloride or ammonium persulfate, corrosion process temperature
It is 30 DEG C~90 DEG C to spend scope；
(c2) resin material is made to fill to the three-dimensional grapheme with supporting layer using the method for injection, solvent evaporation
Space in, three-dimensional grapheme composite resin material is thus made.
It is further preferred that in step (c2), the resin material is PMMA, PDMS, polyamide (PA), polyethylene
(PE), polypropylene (PP), polyvinyl chloride (PVC), makrolon (PC), acrylonitrile-butadiene-styrene copolymer (ABS), poly-
Styrene (PS), epoxy resin (EP), phenolic resin (PF), polyether-ether-ketone (PEEK) or one kind in polyvinyl alcohol (PVA) or
Combination.
According to it is still another aspect of the present invention to provide a kind of preparation method of three-dimensional grapheme composite ceramics, its feature
It is, the preparation method comprises the following steps：
(d1) it is directed to as the three-dimensional grapheme obtained by claim any one of 1-5, revolves one layer of resin branch of Tu on its surface
Layer is supportted, is then immersed in corrosive liquid up to the metal form of the three-dimensional grapheme is completely dissolved, thus obtains carrying supporting layer
Three-dimensional grapheme, wherein, the resin support layer material uses polymethyl methacrylate (PMMA) or polydimethylsiloxanes
Alkane (PDMS)；The corrosive liquid uses one kind or combination in hydrochloric acid, sulfuric acid, nitric acid, iron chloride or ammonium persulfate, corrosion process
Temperature range is 30 DEG C~90 DEG C；
(d2) using filling ceramic slurry, the method for colloidal formation, ceramic material is filled to described with supporting layer
In three-dimensional grapheme space, then removed using organic solvent corrosion or heat-treating methods in the preliminary ceramic composite
Resin supporting layer, and ceramic material is again filled with using filling ceramic slurry, the method for colloidal formation, finally to being again filled with
Product carries out high temperature insostatic pressing (HIP) or normal pressure-sintered, and three-dimensional grapheme composite ceramic material is thus made.
It is further preferred that in step (d2), the ceramic slurry material selection Al2O3、ZrO2、TiO2、SiO2Or SiC
In one kind or combination.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention by using increasing material manufacturing combination electroless metal layer as template, using chemical vapor deposition in gold
Belong to growing three-dimensional graphene in template, design can prepare given shape and the three-dimensional grapheme composite wood of structure as desired
Material, it can effectively overcome graphene skewness, graphene sheet layer in the graphene composite material in the presence of prior art
Uncontrollable defect is orientated, is laid the foundation for the lifting of three-dimensional graphene composite material performance；
2nd, chemical vapor deposition three-dimensional grapheme is used for for metal form with increasing material manufacturing combination chemically plating, due to chemistry
Metallized surfaces quality is better than increasing material manufacturing direct forming metal form surface quality, and therefore, the technology of the present invention is advantageous to grow
High quality three-dimensional grapheme, be advantageous to the preparation and performance boost of three-dimensional graphene composite material；
3rd, this method has the characteristics that short preparation period easy to operate and adaptation are wide, particularly suitable for designing as required,
The high quality of effective, accurate control, the production of multifunction three-dimensional graphene composite material can be obtained by preparing internal graphene composite structure
Product.
Brief description of the drawings
Fig. 1 is the three-dimensional grapheme and its composite according to the structure-controllable constructed by the preferred embodiments of the present invention
Preparation method flow chart.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
A kind of three-dimensional graphene composite material preparation method of structure-controllable provided by the invention, with reference to increasing material manufacturing, change
Learn plating and CVD technology prepares the three-dimensional grapheme material for meeting design requirement structure-controllable, it is then corresponding compound by adding
Material component configures the method that corrosive liquid dissolving or heat treatment are decomposed and got rid of in composite as supporting filling material
Unwanted component, finally prepare three-dimensional grapheme composition metal, resin, the ceramic material of structure-controllable.
Specifically include following steps：
(1) CAD model of three-dimensional porous structure needed for structure, and its outer shape and internal structure are set respectively
Meter；
CAD model described in step (1) is presented the periodicity loose structure of ordered arrangement or arranged according to design requirement
Interconnected three-dimensional structure, and its unit size, between 0.1~10mm, porosity is adjustable between 30~99%.
(2) based on the CAD model constructed by step (1), material system is increased by photocuring, fusion sediment or selective laser sintering
Make the three-dimensional resinous structure that respective shapes are made in technology；
Increases material manufacturing technology described in step (2) includes photocuring, fusion sediment, selective laser sintering technology；Into shape
Standby three-dimensional structure is resin material.
(3) by electroless copper or nickel chemical plating technology, in the three-dimensional resinous structure copper coating prepared by step (2)
Or nickel metal layer；Wherein used copper facing or nickel plating technology include resin structure cleaning, roughening, neutralize, are sensitized, after activation,
Using copper plating bath or nickel-plating liquid resin structure copper coating or nickel metal layer after treatment, the metal layer thickness plated is in 1~50 μ
Between m.Then the resin structure for being coated with metal level is removed into resin material using chemical attack or heat-treating methods, obtains copper
Or nickel three-dimensional structure template；
Copper plating bath employed in step (3) is using copper sulphate, copper chloride, basic copper carbonate, cupric tartrate, copper acetate as copper
Salt；The nickel-plating liquid used is using nickel sulfate, nickel acetate as nickel salt；The metal layer thickness plated is controlled between 1~50 μm.
Chemical corrosion method employed in step (3) is to corrode resin template using acetone, ethanol, carbon tetrachloride；Heat
Processing method is to decompose to remove resin structure at 300~900 DEG C.
(4) graphene is grown on the metal form obtained by step (3) by chemical vapour deposition technique：In this process
In, metal form is put into CVD tube furnaces, is passed through argon gas as protective gas；Then under the conditions of argon gas is passed through, sample is heated
Product are to reaction temperature；Argon gas and hydrogen heat-insulation are passed through after reaching reaction temperature；Then pass to methane and hydrogen and keep tube furnace
Interior pressure, proceeds by chemical vapour deposition reaction；Sample is cooled to by reaction after terminating in the case where being passed through argon gas and hydrogen atmosphere
Room temperature, the three-dimensional grapheme being grown on the metal form is thus made；
Chemical vapor deposition processes use carbon source as methane, ethene, acetylene, styrene in step (4)；In step (3)
The graphene number of plies of prepared 3-dimensional metal template surface growth is 1~20 layer.
(5) certain density corrosive liquid is configured, by product elder generation one layer of resin support of surface rotation Tu obtained by step (4)
Layer, is then immersed in the corrosive liquid of configuration, and backflow is until the metal form is completely dissolved at a temperature of 30~90 DEG C：Wherein
The copper metal template prepared using copper facing uses FeCl3Or (NH4)2S2O8Solution is as corrosive liquid；The nickel gold prepared using nickel plating
Belong to template using HCl solution as corrosive liquid.Obtain compound with three-dimensional grapheme material with supporting layer；
Resin supporting layer described in step (5) is PMMA, PDMS；Corrosive liquid is selected from one kind or its mixing of following material：
Hydrochloric acid, sulfuric acid, nitric acid, iron chloride and ammonium persulfate；Corrosion process controls temperature at 30 DEG C~90 DEG C.
(6) preparation of three-dimensional grapheme composite material, by metal of the surface with graphene obtained by step (4)
For structure as compound added material, the method using casting, high temperature insostatic pressing (HIP) makes metal filled stencil apertures, and three-dimensional grapheme is made
Composite material；
It is copper or nickel that metal is filled described in step (6)；Composite ratio shared by three-dimensional grapheme be 0.01~
10wt%.
(7) fill resin material using the method for injection, solvent evaporation the three-dimensional grapheme with resin supporting layer
Stencil apertures, three-dimensional grapheme composite resin material is made；By the three-dimensional grapheme with resin supporting layer using filling ceramics
The method of slurry, colloidal formation, ceramic material is filled space, then removed using organic solvent corrosion or heat-treating methods
Resin supporting layer, space, then high temperature insostatic pressing (HIP) or normal pressure-sintered obtained three are filled using the method for filling ceramic slurry, colloidal formation
Tie up graphene composite ceramic material.
Prepared described in step (7) three-dimensional grapheme composite resin material potting resin for PMMA, PDMS, PA, PE, PP,
One kind in PVC, PC, ABS, PS, EP, PF, PEEK, PVA；Preparing three-dimensional grapheme composite ceramic material institute packing material is
Al2O3、ZrO2、TiO2、SiO2、SiC；Composite ratio shared by three-dimensional grapheme is 0.01~10wt%.
In summary, general thought of the invention mainly includes three aspects, first, establishing CAD according to design of material demand
Model, the metal form for meeting CAD model is prepared by increasing material manufacturing and electroless plating technology；Second, in the metal form of preparation
On using the controllable three-dimensional grapheme of CVD technology growth structure；Filled out third, being used as support by adding corresponding nanocomposite constituents
Material is filled, while configures the method that corrosive liquid dissolving or heat treatment are decomposed and gets rid of unwanted component in composite, finally
It is made and meets design requirement, three-dimensional grapheme composition metal, resin, the ceramic material of structure-controllable.
The solution of the present invention is further detailed below in conjunction with specific embodiments.
Embodiment 1
(1) CAD software is used, the three-dimensional porous cell cube that unit size is 0.1mm is accordingly established, wherein by the cell cube
Array Design is that porosity is 30%, the periodicity loose structure of ordered arrangement, model external dimensions be 50mm × 50mm ×
10mm。
(2) resin structure of constructed CAD model is prepared using photocuring increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using chemical-copper-plating process
Resin structure copper coating metal level, chemical bronze plating liquid uses copper sulphate, and for mantoquita, formaldehyde is reducing agent, the metal copper layer plated
Thickness is 1 μm.By the obtained resin structure immersion for being coated with metal level in acetone, taken out after resin structure is completely dissolved,
Wash, dry again.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 900 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm conditions
Under 900 DEG C be incubated 35 minutes；In hydrogen flowing quantity 30sccm, methane gas flow 10sccm, and pressure 50Pa bars in tube furnace
Under part, metal form is incubated 15 minutes at 900 DEG C；Then it is cold under the conditions of argon flow amount 60sccm, hydrogen flowing quantity 50sccm
But to room temperature, the three-dimensional grapheme being grown on metal form is thus made, the graphene number of plies is 1 layer.
(5) steel structure of superficial growth graphene is put into mould, the copper of thawing is poured into a mould under the conditions of protective atmosphere
Space is filled, cooling and demolding, that is, obtains the compound copper product of three-dimensional grapheme.Test result shows that three-dimensional grapheme is needed by design
Ask and be evenly distributed in compound Copper substrate.
Embodiment 2
(1) CAD software is used, the three-dimensional porous cell cube that unit size is 10mm is accordingly established, wherein by the cell cube
Array Design is that porosity is 99%, the periodicity loose structure of ordered arrangement, model external dimensions be 100mm × 100mm ×
100mm。
(2) resin structure of constructed CAD model is prepared using fusion sediment increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using nickel chemical plating technology
Resin structure copper coating metal level, chemical nickel-plating liquid uses nickel sulfate, and for nickel salt, sodium phosphite is reducing agent, the metal plated
Nickel layer thickness is 50 μm.The obtained resin structure for being coated with metal level is heat-treated 3 hours for 900 DEG C under nitrogen protection atmosphere,
Resin structure is decomposed and removed.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 1050 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm bars
Under part 35 minutes are incubated at 1050 DEG C；In hydrogen flowing quantity 30sccm, acetylene gas flow 50sccm, and pressure in tube furnace
Under the conditions of 200Pa, metal form is incubated 15 minutes at 1100 DEG C；Then in argon flow amount 60sccm, hydrogen flowing quantity 50sccm
Under the conditions of be cooled to room temperature, be thus made and be grown in three-dimensional grapheme on metal form, the graphene number of plies is 20 layers.
(5) 3wt% PMMA ethanol solutions are configured, rotation Tu on metal form of the obtained surface with graphene,
Being incubated 30 minutes under the conditions of 150 DEG C solidifies PMMA.Configure 3mol/L FeCl3The aqueous solution, obtained product is immersed,
Backflow is until the metal form is completely dissolved at a temperature of 30 DEG C.
(6) using the method for injection by the space of material prepared by the PMMA implantation steps (5) of thawing, cooling obtains
The compound PMMA materials of three-dimensional grapheme.Test result shows that three-dimensional grapheme is evenly distributed in compound PMMA by design requirement
In matrix.
Embodiment 3
(1) CAD software is used, accordingly establishes the lamellar structure model that spacing is 1mm, lamellar spacing is outside 1mm models
Size is 50mm × 50mm × 50mm.
(2) resin structure of constructed CAD model is prepared using selective laser sintering increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using chemical-copper-plating process
Resin structure copper coating metal level, chemical bronze plating liquid uses copper chloride, and for mantoquita, formaldehyde is reducing agent, the metal copper layer plated
Thickness is 3 μm.By the obtained resin structure immersion for being coated with metal level in acetone, taken out after resin structure is completely dissolved,
Wash, dry again.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 1000 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm bars
Under part 35 minutes are incubated at 1000 DEG C；In hydrogen flowing quantity 30sccm, methane gas flow 20sccm, and pressure in tube furnace
Under the conditions of 130Pa, metal form is incubated 15 minutes at 1000 DEG C；Then in argon flow amount 60sccm, hydrogen flowing quantity 50sccm
Under the conditions of be cooled to room temperature, be thus made and be grown in three-dimensional grapheme on metal form, the graphene number of plies is 3 layers.
(5) 3wt% PMMA ethanol solutions are configured, rotation Tu on metal form of the obtained surface with graphene,
Being incubated 30 minutes under the conditions of 100 DEG C solidifies PMMA.Configure 3mol/L FeCl3The aqueous solution, obtained product is immersed,
Backflow is until the metal form is completely dissolved at a temperature of 50 DEG C.
(6) using the method for colloidal formation by Al2O3In the space of material prepared by slurry implantation step (5), heating is solid
Change, be then heat-treated 3 hours at 600 DEG C, PMMA supporting layers are decomposed and removed, by Al2O3Caused by slurry injection PMMA is removed
Space, be heating and curing simultaneously high temperature sintering, that is, obtains the compound Al of three-dimensional grapheme2O3Ceramic material.Test result shows, three-dimensional stone
Black alkene is evenly distributed in compound Al by design requirement2O3In matrix.
Embodiment 4
(1) CAD software is used, the three-dimensional porous cell cube that unit size is 3mm is accordingly established, wherein by the cell cube battle array
It is 85% that row, which are designed as porosity, and the periodicity loose structure of ordered arrangement, model external dimensions is 50mm × 50mm × 50mm.
(2) resin structure of constructed CAD model is prepared using photocuring increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using nickel chemical plating technology
Resin structure copper coating metal level, chemical bronze plating liquid uses copper sulphate, and for mantoquita, formaldehyde is reducing agent, the metal copper layer plated
Thickness is 5 μm.The obtained resin structure for being coated with metal level is heat-treated 5 hours for 300 DEG C under nitrogen protection atmosphere, by resin
STRUCTURE DECOMPOSITION removes.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 1050 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm bars
Under part 35 minutes are incubated at 1050 DEG C；In hydrogen flowing quantity 30sccm, acetylene gas flow 50sccm, and pressure in tube furnace
Under the conditions of 200Pa, metal form is incubated 15 minutes at 1100 DEG C；Then in argon flow amount 60sccm, hydrogen flowing quantity 50sccm
Under the conditions of be cooled to room temperature, be thus made and be grown in three-dimensional grapheme on metal form, the graphene number of plies is 1 layer.
(5) PDMS solidify liquids are configured, polymerized monomer and curing agent are with 10:1 mass ratio mixing, rotation Tu is in obtained surface
On metal form with graphene, under the conditions of 80 DEG C being incubated 30 minutes makes PDMS polymerizing curables.Configure 3mol/L (NH4)2S2O8Solution, obtained product is immersed, backflow is until the metal form is completely dissolved at a temperature of 30 DEG C.
(6) PDMS solidify liquids are configured, polymerized monomer and curing agent are with 10：1 mass ratio mixing, PDMS solidify liquids are injected
In the space of material prepared by step (5), cooling obtains the compound PDMS material of three-dimensional grapheme.Test result shows, three-dimensional
Graphene is evenly distributed in compound PDMS matrixes by design requirement.
Embodiment 5
(1) CAD software is used, the three-dimensional porous cell cube that unit size is 0.2mm is accordingly established, wherein by the cell cube
Array Design is that porosity is 50%, the periodicity loose structure of ordered arrangement, model external dimensions be 10mm × 10mm ×
10mm。
(2) resin structure of constructed CAD model is prepared using photocuring increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using nickel chemical plating technology
Resin structure plating nickel on surface metal level, chemical nickel-plating liquid uses nickel acetate, and for nickel salt, sodium phosphite is reducing agent, the metal plated
Nickel layer thickness is 10 μm.The obtained resin structure for being coated with metal level is immersed in carbon tetrachloride, treats that resin structure is completely molten
Taken out after solution, then wash, dry.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 1000 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm bars
Under part 30 minutes are incubated at 1000 DEG C；In hydrogen flowing quantity 30sccm, methane gas flow 10sccm, and pressure 50Pa in tube furnace
Under the conditions of, metal form is incubated 15 minutes at 900 DEG C；Then under the conditions of argon flow amount 60sccm, hydrogen flowing quantity 50sccm
Room temperature is cooled to, the three-dimensional grapheme being grown on metal form is thus made, the graphene number of plies is 5 layers.
(5) the nickel structure of superficial growth graphene is put into mould, nickel metal powder is filled under the conditions of protective atmosphere,
Densifying materials are made using hot isostatic pressing technique, cooling and demolding, that is, obtain the compound nickel material of three-dimensional grapheme.Test result table
Bright, three-dimensional grapheme is evenly distributed in compound Ni substrate by design requirement.
Embodiment 6
(1) CAD software is used, the three-dimensional porous cell cube that unit size is 0.1mm is accordingly established, wherein by the cell cube
Array Design is that porosity is 90%, the periodicity loose structure of ordered arrangement, model external dimensions be 100mm × 100mm ×
100mm。
(2) resin structure of constructed CAD model is prepared using fusion sediment increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using nickel chemical plating technology
Resin structure copper coating metal level, chemical nickel-plating liquid uses nickel sulfate, and for nickel salt, sodium phosphite is reducing agent, the metal plated
Nickel layer thickness is 25 μm.The obtained resin structure for being coated with metal level is heat-treated 4 hours for 800 DEG C under nitrogen protection atmosphere,
Resin structure is decomposed and removed.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 950 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm conditions
Under 950 DEG C be incubated 35 minutes；In hydrogen flowing quantity 30sccm, acetylene gas flow 50sccm, and pressure 200Pa bars in tube furnace
Under part, metal form is incubated 15 minutes at 1100 DEG C；Then it is cold under the conditions of argon flow amount 60sccm, hydrogen flowing quantity 50sccm
But to room temperature, the three-dimensional grapheme being grown on metal form is thus made, the graphene number of plies is 10 layers.
(5) configure 3wt% PMMA methyl phenyl ethers anisole solution, rotation Tu on metal form of the obtained surface with graphene,
Being incubated 40 minutes under the conditions of 100 DEG C solidifies PMMA.Configure 3mol/L FeCl3The aqueous solution, obtained product is immersed it
In, backflow is until the metal form is completely dissolved at a temperature of 50 DEG C.
(6) by ZrO2In the space of material prepared by slurry implantation step (5), it is heating and curing, then in 900 DEG C of heat treatments
2 hours, PMMA supporting layers are decomposed and removed, again by ZrO2Space caused by slurry injection PMMA removals, is heating and curing simultaneously
Using HIP sintering, that is, obtain the compound ZrO of three-dimensional grapheme2Ceramic material.Test result shows, three-dimensional grapheme is by setting
Meter demand is evenly distributed in compound ZrO2In matrix.
Embodiment 7
(1) CAD software is used, accordingly establishes the lamellar structure model that spacing is 3mm, lamellar spacing is outside 0.5mm models
Portion's size is 30mm × 30mm × 30mm.
(2) resin structure of constructed CAD model is prepared using selective laser sintering increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using chemical-copper-plating process
Resin structure copper coating metal level, chemical bronze plating liquid uses copper chloride, and for mantoquita, formaldehyde is reducing agent, the metal copper layer plated
Thickness is 2 μm.By the obtained resin structure immersion for being coated with metal level in ethanol, taken out after resin structure is completely dissolved,
Wash, dry again.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 1050 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm bars
Under part 35 minutes are incubated at 1050 DEG C；In hydrogen flowing quantity 30sccm, acetylene gas flow 50sccm, and pressure in tube furnace
Under the conditions of 200Pa, metal form is incubated 15 minutes at 1100 DEG C；Then in argon flow amount 60sccm, hydrogen flowing quantity 50sccm
Under the conditions of be cooled to room temperature, be thus made and be grown in three-dimensional grapheme on metal form, the graphene number of plies is 1 layer.
(5) configure 3wt% PMMA methyl phenyl ethers anisole solution, rotation Tu on metal form of the obtained surface with graphene,
Being incubated 30 minutes under the conditions of 100 DEG C solidifies PMMA.Configure 3mol/L FeCl3The aqueous solution, obtained product is immersed it
In, backflow is until the metal form is completely dissolved at a temperature of 50 DEG C.
(6) using the method for solvent evaporation by the space of material prepared by PMMA solution-injecting steps (5), evaporation solvent
Solidification, that is, obtain the compound PMMA materials of three-dimensional grapheme.Test result shows that three-dimensional grapheme is uniformly distributed by design requirement
In compound PMMA matrixes.
Embodiment 8
(1) CAD software is used, the three-dimensional porous cell cube that unit size is 1mm is accordingly established, wherein by the cell cube battle array
Row are designed as porosity as 35%, the periodicity loose structure of ordered arrangement, model external dimensions be 150mm × 150mm ×
50mm。
(2) resin structure of constructed CAD model is prepared using photocuring increases material manufacturing technology.
(3) by prepared resin structure it is cleaned, roughening, neutralize, sensitization, activation after, existed using nickel chemical plating technology
Resin structure copper coating metal level, chemical nickel-plating liquid uses nickel sulfate, and for nickel salt, sodium phosphite is reducing agent, the metal plated
Nickel layer thickness is 20 μm.The obtained resin structure for being coated with metal level is heat-treated 5 hours for 600 DEG C under nitrogen protection atmosphere,
Resin structure is decomposed and removed.
(4) metal form made from step (3) is put into CVD tube furnaces, is passed through argon gas as protective gas；In argon gas
Under the conditions of flow 300sccm, 950 DEG C are heated the sample within 50 minutes；In argon flow amount 50sccm, hydrogen flowing quantity 50sccm conditions
Under 950 DEG C be incubated 35 minutes；In hydrogen flowing quantity 30sccm, acetylene gas flow 50sccm, and pressure 50Pa bars in tube furnace
Under part, metal form is incubated 15 minutes at 1100 DEG C；Then it is cold under the conditions of argon flow amount 60sccm, hydrogen flowing quantity 50sccm
But to room temperature, the three-dimensional grapheme being grown on metal form is thus made, the graphene number of plies is 5 layers.
(5) PDMS solidify liquids are configured, polymerized monomer and curing agent are with 10:1 mass ratio mixing, rotation Tu is in obtained surface
On metal form with graphene, under the conditions of 60 DEG C being incubated 60 minutes makes PDMS polymerizing curables.Configure 3mol/L sulfuric acid
Solution, obtained product is immersed, backflow is until the metal form is completely dissolved at a temperature of 90 DEG C.
(6) PDMS solidify liquids are configured, polymerized monomer and curing agent are with 10:1 mass ratio mixing, PDMS solidify liquids are injected
In the space of material prepared by step (5), cooling obtains the compound PDMS material of three-dimensional grapheme.Test result shows, three-dimensional
Graphene is evenly distributed in compound PDMS matrixes by design requirement.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the three-dimensional grapheme of structure-controllable, it is characterised in that the preparation method comprises the following steps：
(a) the three-dimensional structure structure CAD model needed for three-dimensional grapheme to be prepared, passes through increasing material manufacturing by the CAD model
Obtain the three-dimensional resinous structure of corresponding construction；
(b) by the three-dimensional resinous structure obtained in step (a) using chemical plating method in copper coating or nickel metal layer, thus
There is the resin structure of the coat of metal to surface, removed using chemical attack or heat-treating methods in the coat of metal resin structure
Resin material, obtain the three-dimensional structure template of copper facing or nickel；
(c) thus obtained using chemical vapour deposition technique generation graphene on the three-dimensional structure metal form that step (b) obtains
Required three-dimensional grapheme.
A kind of 2. preparation method of the three-dimensional grapheme of structure-controllable as claimed in claim 1, it is characterised in that step (a)
In, include photocuring, fusion sediment and selective laser sintering the step of the increasing material manufacturing.
A kind of 3. preparation method of the three-dimensional grapheme of structure-controllable as claimed in claim 1 or 2, it is characterised in that step
(b) copper plating bath used in, during the chemical plating method copper facing is copper sulphate, copper chloride, basic copper carbonate, cupric tartrate or vinegar
One kind or combination in sour copper；The nickel-plating liquid used during the chemical plating method nickel plating for one kind in nickel sulfate or nickel acetate or
Combination；And the layer thickness range of the coat of metal is 1 μm~50 μm.
A kind of 4. preparation method of the three-dimensional grapheme of structure-controllable as described in claim any one of 1-3, it is characterised in that
In step (b), the method for removing resin material uses chemical attack or heat treatment, wherein, the chemical attack uses third
As corrosive agent, the temperature of the heat treatment is 300 DEG C~900 DEG C for ketone, ethanol or carbon tetrachloride.
A kind of 5. preparation method of the three-dimensional grapheme of structure-controllable as described in claim any one of 1-4, it is characterised in that
In step (c), carbon source used in the chemical vapor deposition is one kind or combination in methane, ethene, acetylene or styrene.
6. a kind of preparation method of three-dimensional grapheme composite material, it is characterised in that the preparation method comprises the following steps：
, will be metal filled by the way of casting or high temperature insostatic pressing (HIP) for as the three-dimensional grapheme obtained by claim any one of 1-5
Into the space of its internal structure, three-dimensional grapheme composite material is thus made.
7. a kind of preparation method of three-dimensional grapheme compound resin, it is characterised in that the preparation method comprises the following steps：
(c1) it is directed to as the three-dimensional grapheme obtained by claim any one of 1-5, revolves one layer of resin supporting layer of Tu on its surface,
It is then immersed in the metal form in corrosive liquid up to the three-dimensional grapheme to be completely dissolved, obtains the three-dimensional graphite with supporting layer
Alkene, wherein, the resin support layer material uses polymethyl methacrylate (PMMA) or dimethyl silicone polymer (PDMS)；Institute
State corrosive liquid is using one kind in hydrochloric acid, sulfuric acid, nitric acid, iron chloride or ammonium persulfate or combination, corrosion process temperature range
30 DEG C~90 DEG C；
(c2) resin material is made to fill to the sky of the three-dimensional grapheme with supporting layer using the method for injection, solvent evaporation
In gap, three-dimensional grapheme composite resin material is thus made.
8. a kind of preparation method of three-dimensional grapheme compound resin as claimed in claim 7, it is characterised in that in step (c2)
In, the resin material is PMMA, PDMS, polyamide (PA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), poly-
Carbonic ester (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), epoxy resin (EP), phenolic resin
(PF), polyether-ether-ketone (PEEK) or one kind in polyvinyl alcohol (PVA) or combination.
9. a kind of preparation method of three-dimensional grapheme composite ceramics, it is characterised in that the preparation method comprises the following steps：
(d1) it is directed to as the three-dimensional grapheme obtained by claim any one of 1-5, revolves one layer of resin supporting layer of Tu on its surface,
It is then immersed in corrosive liquid up to the metal form of the three-dimensional grapheme is completely dissolved, thus obtains the three-dimensional with supporting layer
Graphene, wherein, the resin support layer material uses polymethyl methacrylate (PMMA) or dimethyl silicone polymer
(PDMS)；The corrosive liquid uses one kind or combination in hydrochloric acid, sulfuric acid, nitric acid, iron chloride or ammonium persulfate, corrosion process temperature
It is 30 DEG C~90 DEG C to spend scope；
(d2) using filling ceramic slurry, the method for colloidal formation, ceramic material is filled to the three-dimensional with supporting layer
In graphene space, the resin in the preliminary ceramic composite is then removed using organic solvent corrosion or heat-treating methods
Supporting layer, and ceramic material is again filled with using filling ceramic slurry, the method for colloidal formation, the finally product to being again filled with
High temperature insostatic pressing (HIP) or normal pressure-sintered is carried out, three-dimensional grapheme composite ceramic material is thus made.
10. a kind of preparation method of three-dimensional grapheme composite ceramics as claimed in claim 8, it is characterised in that in step
(d2) in, the ceramic slurry material selection Al2O3、ZrO2、TiO2、SiO2Or one kind in SiC or combination.
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