CN106332520A - Graphite film composite body and preparation method thereof - Google Patents
Graphite film composite body and preparation method thereof Download PDFInfo
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- CN106332520A CN106332520A CN201610598159.7A CN201610598159A CN106332520A CN 106332520 A CN106332520 A CN 106332520A CN 201610598159 A CN201610598159 A CN 201610598159A CN 106332520 A CN106332520 A CN 106332520A
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- graphite film
- graphite
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- complex
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
- B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
- B32B2038/047—Perforating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
Abstract
The present invention provides a preparation method of a graphite film composite body. According to the preparation method, a polymer binder is infiltrated into a plurality of layers of graphite films by means of dipping and punching processes, so that the graphite film composite body can be formed. The method has the advantages of simplicity, reliability and high operability, and can be applied to the preparation of graphite film polymer composite bodies. The graphite film composite body prepared by using the method has the advantages of small density, adjustable thickness, high thermal conductivity, good mechanical properties, strong interlayer bonding strength and the like, and can be widely applied to the thermal management of electronic products.
Description
Technical field
The present invention relates to field of compound material, particularly relate to a kind of graphite film polymer composite and manufacture method thereof.
Background technology
Along with the fast development of electronic technology, electronic devices and components volume constantly reduces, and chip integration is continuously increased, hot-fluid
Density is the most increasing.High-power electronic component can produce substantial amounts of heat, if not taking effective heat management measure, by heat
Passing, device can sustain damage and even damage.Graphite is a kind of well Heat Conduction Material, has layer structure, respectively to different
Property, its plane thermal conductivity is up to 50-1800W/ (m K).And, the density of graphite is relatively low, and solid density only has ~ 2.2g/cm3,
It it is a kind of Heat Conduction Material with broad prospect of application.The graphite film developed in recent years or graphite flake, it is micro-that thickness can be as thin as tens
Rice, and there is preferable flexibility, relatively low-density, higher heat-conductivity, it is pasted on above chip or chipset, can be by chip heat
Amount is delivered to surrounding, significantly reduces chip temperature, has been applied to the electronics such as smart mobile phone, panel computer, notebook, display
Product.
Conventional graphite film or graphite flake include following several big class: the 1) first kind, by the expansion of expanded graphite roll-in
Graphite film, also known as expanded graphite paper, flexible graphite paper, is to prepare expanded graphite with graphite for raw material, then by expanded graphite roller
Pressure (having another name called calendering) graphite film, such as patent of invention CN1926060 B(exfoliated graphite sheet) representated by expanded graphite
Film；2) Equations of The Second Kind, by the graphite film of macromolecule membrane carbonization, graphitization roll-in, also referred to as pyrolytic graphite film, refers to height
Molecular film is raw material, such as polyimides, polyamide, through the graphite film of carbonization, graphitization roll-in, such as patent of invention
The manufacture method of a CN102838107 B(high conduction graphite film and system) and patent of invention CN103193221 B(graphite film
And manufacture method) representated by graphite film；3) the 3rd class, by graphene oxide through film forming, reduction graphite film, also known as
RGO graphite film (rGO, reduced graphene oxide) or title graphene oxide reduction film, refer to natural scale stone
Ink is raw material, is prepared into graphene oxide, then by graphene oxide film forming, then forms through electronation or thermal reduction
Graphite film, also referred to as graphene film, such as article Ultrathin Flexible Graphene Film:An Excellent
Thermal Conducting Material with Efficient EMI Shielding (Advanced Functional
Materials, 24 (2014), 4,542 4548) and article Thermally reduced graphene oxide films
as flexible lateral heat spreaders (J. Mater. Chem. A, 2(2014), 16563-16568)
The graphite film reported；4) the 4th class, other conduction graphite film based on graphite, refer to beyond above-mentioned three class graphite films
Conduction graphite film based on graphite, carbon nanometer as based on nano graphite sheet in patent of invention CN102874795 B(mono-kind
Thin film and preparation method thereof) graphite film reported.The plane thermal conductivity of all these graphite films is more than 50W/ (m K), graphite
The thickness of film is 1-2000 μm.
Graphite film is lamellar, presents obviously anisotropy, plane thermal conductivity 50-1800W/ (m K), is perpendicular to
The thermal conductivity of in-plane is less than 10W/ (m K).The in-plane of graphite film refers to be perpendicular to the direction of thickness, is also graphite
The direction that film thermal conductivity is the highest.
But graphite film has again many deficiencies, limit it and extensively apply.First, the hot strength of graphite film is the highest,
General at 3-30MPa, though there being certain flexibility, but easily broken, frangible；Secondly, the finite thickness of current various graphite films, typically several
Ten microns, expandable graphite sheet, up to millimeter rank, causes its heat flux less, limits its range of application.Therefore, anxious
Need a kind of have some strength, certain thickness, high conductive graphite composite block material that density is less, solve some heat radiation difficulties
Topic.
For overcoming the problems referred to above, frequently with the method that graphite film is compound with metal, inorganic matter or macromolecular material.Invention
Patent CN103258802A(patent documentation 1, graphite structure and use the electronic device of this graphite structure) method be
Punch on Multi-layer graphite film, regrowth layer of metal layer, prepare graphite film metal structure.Patent of invention CN103663407A
(carbon paper lamination compound heat-insulation liner) coats high polymer binder and high-temperature resistant coating on graphite film, cured, carbonization, one-tenth
Type, purification, prepare carbon paper laminated composite.Patent of invention CN104691036 A(patent documentation 2, a kind of high conductive graphite is combined
Block and preparation method thereof) graphite film that bend one end by polymer bond layer made high conductive graphite under pressure and answers
Closing block, but technique is complex, needs to be alternately stacked graphite film from level to level with binding agent, workload is relatively big, and prepare
The inter-layer bonding force of graphite film composite block is the highest.Apply for a patent CN104669702 A(patent documentation 3, accept, a kind of graphite guide
Hotting mask composite block and preparation method thereof), also can will lead in addition to connecting graphite film with adhesive film lamination, adhesive film after graphite film punching
Cross through hole to ooze out, be connected with thermal source, play the effect of the thermal contact resistance reduced between graphite film and thermal source, but the graphite of preparation
Pore within film heat conduction composite block is more, and thickness is too small, only 5-100 μm, and during heat transfer, heat flux is the least, the purest graphite
Film is the most crisp, is difficult to punching.
Summary of the invention
When preparing graphite film polymer composite, existing method technique is complex, and graphite film complex is anti-
Curved intensity is the highest, layer by layer between be easily peeled off.
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of technique is simple, reliable, and graphite film interlayer is not
Be easily peeled, graphite film polymer composite that bending strength is higher and preparation method thereof.
To achieve the above object, the invention discloses the preparation method of a kind of graphite film complex, including following step
Rapid:
S101, stacking: by the successively superposition of some graphite films, make graphite film duplexer；
S102, single-steeping: control condition makes high polymer binder become liquid, and makes it be impregnated into described graphite film duplexer
Lamellar spacing in；
S103, one-step solidification: to the graphite film duplexer through described single-steeping, control condition makes high polymer binder solid
Change, obtain graphite film complex.
Further, the method for the present invention can also comprise the following steps:
S104, punching: get some dipping holes on the graphite film complex that described one-step solidification is formed；
S105, double-steeping: control condition makes high polymer binder become liquid so that it is be impregnated into described graphite by dipping hole
In the lamellar spacing of film composite, and it is distributed in dipping hole；
S106, secondary solidifies: to the graphite film complex through double-steeping, control condition makes high polymer binder solidify.
Further, in described S101 step use graphite film, plane thermal conductivity more than 50W/ (m K), graphite film
Thickness is 1-2000 μm；And/or
Described graphite film includes expandable graphite sheet, pyrolytic graphite film, graphene oxide reduction film and other are based on graphite
Conduction graphite film in one or more；And/or
It is 10-99% that described graphite film accounts for the volume fraction of graphite film complex.
Further, binding agent used in described S102 and/or S105 step is high polymer binder.
Further, high polymer binder composition used in described S102 and/or S105 step is identical or different,
Selected from epoxy resin, phenolic resin, alkyd resin, polyurethane, polysiloxanes, cyanate ester resin, acrylic resin, polyether-ketone,
Polyether-ether-ketone, polyamide, polyamidoimide, polyimides, polyester, Merlon, polyolefin, polyphenylene oxide, polyphenylene sulfide, benzene
Polyvinyls, polysulfones, polrvinyl chloride, polyvinylidene chloride, chliorinated polyvinyl chloride, phenylpropyl alcohol cyclobutane, ethene-vinyl acetate
Copolymer, politef, fluorinated ethylene-propylene resin, perfluoroalkoxy compound, polyethylene-tetrafluoroethene, polyvinylidene fluoride, poly-
In CTFE, polyethylene-CTFE, polyvinyl fluoride, acrylonitrile-butadiene-styrene copolymer, polyformaldehyde one
Plant or multiple.
Further, if described high polymer binder is at room temperature liquid, then it is added to firming agent or solidification
Agent and diluent, then impregnate；
If described high polymer binder is at room temperature solid-state, then it is heated to become liquid, then impregnates.
Further, the temperature of described heating is 50 DEG C-400 DEG C.
Further, in described S102 and/or S105 step, dip time is 0.1-24h, and dipping temperature is 20-400 DEG C,
Apply pressure 0-100MPa.
The dipping hole that the most described S104 step is formed is through hole or blind hole, is by drill bit punching, laser boring
Or other hole knockouts obtain, the width in described dipping hole is 0.1-5mm, and the density in described dipping hole is 1-20/square
Centimetre.
Further, in described S103 and/or S106 step, the hardening time of binding agent is 1-72h, and solidification temperature is
20-180℃。
Further, in described S103 and/or S106 step, to graphite film duplexer or graphite while binding agent solidification
Film composite applies the pressure vertical with graphite film plane, and described pressure is 0-100MPa.
The invention also discloses a kind of graphite film complex, its by mentioned earlier method prepare.
The present invention uses dipping drilling technology to prepare graphite film complex, overcomes the difficult point that graphite film macromolecule is compound, main
Advantage is wanted to have:
1) preparation method of the present invention is simple, reliable, and strong operability can be applicable to the graphite film polymer composite of numerous system
Preparation；
2) the graphite film complex prepared by, in addition to graphite film has high polymer binder between layer by layer, dipping is also filled in hole
High polymer binder, the high polymer binder in dipping hole is had just like the effect of " rivet ", to be tightly coupled by each layer graphite film
Together, it is possible to more effectively strengthening the intensity of graphite film complex, its bending strength is higher, inter-layer bonding force is more preferable, mechanical property
Can be excellent；
3) this method impregnates hole to be formed after graphite film with high polymer binder one-step solidification, effectively avoid
The difficult point of directly punching on graphite film；
4) the graphite film complex density of this method gained is little, thickness is adjustable, and thermal conductivity can be by the kind of graphite film and graphite
The percent by volume of film controls.
In a word, the method for the present invention is simple, reliable, strong operability, and the graphite film macromolecule that can be applicable to numerous system is multiple
Fit preparation, and the graphite film complex prepared of the method has, and density is little, thickness scalable, thermal conductivity high, mechanical property
The advantages such as energy is preferable, inter-layer bonding force is stronger, can be widely applied in the heat management of electronic product.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing skill
During art describes, required accompanying drawing is briefly described.
Fig. 1 is the schematic flow sheet of preparation method disclosed in this invention, and Figure 1A is the flow process signal of step S101-S103
Figure, Figure 1B is the schematic flow sheet of step S101-S106.
Fig. 2 is the structural representation with the graphite film complex prepared by preparation method disclosed in this invention, and Fig. 2 A is
Through the structural representation of the graphite film complex prepared by step S101-S103, Fig. 2 B is through prepared by step S101-S106
The structural representation of graphite film complex.
Fig. 3 is the sectional schematic diagram with the graphite film complex prepared by preparation method disclosed in this invention, wherein 31
For dipping through hole, 32 is dipping blind hole.
Fig. 4 is the surface optical photo of the graphite film epoxy resin composite disclosed in the embodiment of the present invention 1.
Fig. 5 is the section optical photograph of the graphite film epoxy resin composite disclosed in the embodiment of the present invention 1.
Fig. 6 is that the cross-sectional scanning electron microscope of the graphite film epoxy resin composite disclosed in the embodiment of the present invention 1 shines
Sheet.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with specific embodiment, but the present invention is not limited to implement as follows
Content described in example, other embodiments based on inventive concept, the most all among protection scope of the present invention.
Figure 1A is the schematic flow sheet of step S101-S103, and expression sequentially passes through stacking, single-steeping step, once consolidates
Changing step and form graphite film complex, its high polymer binder is located only within graphite film interlayer.Figure 1B is step S101-S103
Schematic flow sheet, represent sequentially pass through stacking, single-steeping step, one-step solidification step, punch out step, double-steeping step and
Secondary curing schedule forms graphite film complex, and its high polymer binder is not exclusively located in the lamellar spacing of graphite film, is also located at
In dipping hole.
In Fig. 2,21 is graphite film, and 22 is the high polymer binder of graphite film interlayer, and 23 is dipping hole, and 24 is dipping hole
High polymer binder.Fig. 2 A is the structural representation through the graphite film complex prepared by step S101-S103, represents graphite film
Combined by the high polymer binder in graphite film lamellar spacing.Fig. 2 B is through the graphite prepared by step S101-S106
The structural representation of film composite, expression graphite film is not only by the high polymer binder in graphite film lamellar spacing, also by leaching
High polymer binder in stain hole combines, and the bending strength of the graphite film composite block of formation is higher.
Fig. 3 represents that the dipping hole that in claims, step S104 is formed can be through hole, it is also possible to is blind hole, also may be used
With part be throughhole portions be blind hole.
Embodiment 1
1. S101, stacking, is 10cm × 10cm by size, and thickness is 300 commercialization expandable graphite sheet (first kind of 50 μm
Graphite film), successively superposition, make graphite film duplexer.
2. S102, single-steeping, take 200g n-butyl alcohol and 600g dimethylbenzene, by the diluent of 1:3 proportional arrangement 800g,
Then 800g diluent is joined in 800g bisphenol f type epoxy resin, and stir, add 200g polyamide and make
For firming agent, and stir, obtain the high polymer binder of liquid；Being placed in mould by graphite film duplexer, mould is placed on
In vacuum impregnation stove, vacuum impregnation stove starts evacuation, is 10Pa to pressure, and dipping in-furnace temperature is 25 DEG C, opens Vaccum Permeating
The Fluid valve of stain stove, is flowed into liquid macroimolecule binding agent in mould, closes Fluid valve, impregnates 3h, and pressure is 10Pa,
Liquid macroimolecule binding agent is by the edge impregnation of graphite film to the lamellar spacing of graphite film.
3. S103, one-step solidification, the graphite film duplexer through single-steeping step to be taken out, level puts into another mould
In solidify, apply the pressure vertical with graphite film in-plane to impregnated graphite film duplexer during solidification
(0.08MPa), solidifying 4h at 80 DEG C, after solidification, high polymer binder becomes solid-state.
4. S104, punching, the graphite film complex formed through one-step solidification step is removed from the molds, thick with 2mm
Drill bit, along being perpendicular to the direction of graphite film plane, extend to lower surface from the upper surface of complex and bore circular dipping hole, leaching
The width in stain hole is 2mm, and the density in dipping hole is 4/square centimeter, and dipping hole is blind hole.
5. S105, double-steeping, take 200g n-butyl alcohol and 600g dimethylbenzene, by the diluent of 1:3 proportional arrangement 800g,
Then 800g diluent is joined in 800g bisphenol f type epoxy resin, and stir, add 200g polyamide and make
For firming agent, and stir, obtain the high polymer binder of liquid；The graphite film obtained through punch out step is combined
Body is again placed in mould, and mould is placed in vacuum impregnation stove, and vacuum impregnation stove starts evacuation, is 10Pa to pressure, dipping
In-furnace temperature is 25 DEG C, opens the Fluid valve of vacuum impregnation stove, is flowed in mould by liquid adhesive, closes fluid valve
Door, impregnates 6h, and pressure is 10Pa, and liquid adhesive is impregnated in the lamellar spacing of graphite film by dipping hole, and is distributed in dipping
Kong Zhong.
6. S106, secondary solidifies, and is taken out by the graphite film complex through double-steeping step, and level puts into another mould
In tool, apply the pressure (0.08MPa) vertical with graphite film in-plane to graphite film complex, 100oC solidifies 3h, allows viscous
Knot agent solidification, forms final graphite film complex.
The density of the graphite film complex obtained through step S101-S103 is 1.6g/cm3, plane thermal conductivity is 240W/
(m K), bending strength is 6MPa.Through step S101-S106, the density of the graphite film complex of formation is 1.5g/cm3, flat
Fever sensation of the face conductance is 220W/ (m K), and bending strength is 20MPa.Contrast data above understands, through punching, double-steeping and two
Secondary solidification, it is possible to significantly improve the bending strength of graphite film complex.Fig. 4 be disclosed in the present embodiment through step S101-
The surface optical photo of the graphite film epoxy resin composite that S106 is formed, dipping hole is filled out by high polymer binder as seen from the figure
Full.Fig. 5 is the section light of the graphite film epoxy resin composite formed through step S101-S106 disclosed in the present embodiment
Learning photo, the pattern in dipping hole is high-visible, and dipping hole is filled up by high polymer binder.Fig. 6 is the warp disclosed in the present embodiment
Cross the cross-sectional scanning electron microphotograph of the graphite film epoxy resin composite that step S101-S106 is formed.Sheet in figure
Dark areas be graphite film, the light tone region of wire is epoxy resin layer.
Embodiment 2
1. S101, stacking, is 5cm × 5cm by size, and thickness is 200 commercialization pyrolytic graphite film (Equations of The Second Kind stones of 40 μm
Ink film) successively superposition, make graphite film duplexer.
2. S102, single-steeping, take 200g n-butyl alcohol and 600g dimethylbenzene, by the diluent of 1:3 proportional arrangement 800g,
Then 800g diluent is joined in 800g bisphenol f type epoxy resin, and stir, add 200g polyamide and make
For firming agent, and stirring, obtain the high polymer binder of liquid, be placed in mould by graphite film duplexer, mould is placed on
In vacuum impregnation stove, vacuum impregnation stove starts evacuation, is 10Pa to pressure, and dipping in-furnace temperature is 25 DEG C, opens Vaccum Permeating
The Fluid valve of stain stove, is flowed into liquid macroimolecule binding agent in mould, closes Fluid valve, impregnates 1.5h, and pressure is
10Pa, liquid macroimolecule binding agent is by the edge impregnation of graphite film to the lamellar spacing of graphite film.
3. S103, one-step solidification, the graphite film duplexer through single-steeping step to be taken out, level puts into another mould
In, apply the pressure (0.1MPa) vertical with graphite film in-plane to impregnated graphite film duplexer, 120oC solidifies
1h, allows high polymer binder solidify.
4. S104, punching, the graphite film complex formed through one-step solidification step is removed from the molds, uses 0.5mm
Thick drill bit, edge is perpendicular to the direction of graphite film plane, extends to lower surface from the upper surface of complex and bores circular dipping hole,
The width in dipping hole is 0.5mm, and the density in dipping hole is 20/square centimeter, and dipping hole is blind hole, and the degree of depth is 7mm.
5. S105, double-steeping, take 200g dehydrated alcohol as diluent, join in 100g phenolic resin, and stir
Uniformly, add 15g hexamethylenetetramine as firming agent, and stir, obtain liquid adhesive；Will be through once punching
The graphite film complex that step obtains is again placed in mould, and mould is placed in vacuum impregnation stove, and vacuum impregnation stove starts to take out very
Sky, is 10Pa to pressure, and dipping in-furnace temperature is 25 DEG C, opens the Fluid valve of vacuum impregnation stove, is flowed into by liquid adhesive
In mould, closing Fluid valve, impregnate 6h, pressure is 10Pa, and liquid adhesive is impregnated into the layer of graphite film by dipping hole
In gap, and it is distributed in dipping hole.
8. S106, secondary solidifies, and is taken out by the graphite film complex through double-steeping step, and level puts into another mould
In tool, apply the pressure (0.1MPa) vertical with graphite film in-plane to graphite film complex, 60oC solidifies 12h, allows viscous
Knot agent solidification, forms final graphite film complex.
Through step S101-S103, the density of the graphite film complex of formation is 1.7g/cm3, plane thermal conductivity is
650W/ (m K), bending strength is 8MPa.Through step S101-S106, the density of the graphite film complex of formation is 1.6g/
cm3, plane thermal conductivity is 625W/ (m K), and bending strength is 30MPa, and bending strength substantially increases.
Embodiment 3
1.S101, stacking, is 5cm × 5cm by size, and thickness is 100 homemade graphite film successively superpositions of 20 μm, makes stone
Ink film duplexer.Graphite film used is the 3rd class graphite film, prepares with graphene oxide, and concrete grammar sees Ultrathin
Flexible Graphene Film: An Excellent Thermal Conducting Material with
Efficient EMI Shielding(Advanced Functional Materials, 24 (2014), 4,542 4548),
Specifically comprising the following steps that 1) graphene oxide that takes 5g is dissolved in 5000mL deionized water, ultrasonic agitation 1h；2) then it is poured upon
In ptfe surface ware, it is dried 10h at 50 DEG C, removes moisture removal, bottom surface plate, just obtain graphene oxide membrane, because
Graphene oxide membrane is very poor with the politef adhesion of bottom, it is possible to graphene oxide membrane peeled off, obtains independence
Graphene oxide membrane；3) subsequently, graphene oxide membrane is placed in graphitizing furnace, argon shield, with the intensification speed of 5 DEG C/min
Rate is warming up to 2000 DEG C, and is incubated 1h.Afterwards, stop heating, under argon shield, naturally cool to room temperature, take out sample, machinery
After process, obtain the graphite film of 20 μ m-thick.
2. S102, single-steeping, take 500g acrylonitrile-butadiene-styrene copolymer (ABS) resin, dry at 85 DEG C
Dry 3h removes moisture, is subsequently heated to 220oC, and it is incubated 0.5h so that it is it is fused into liquid macroimolecule binding agent；By graphite film layer
Stack is placed in mould, and mould is heated to 180 DEG C, utilizes press to be pressed in mould by liquid macroimolecule binding agent, and pressure is
90MPa, liquid macroimolecule binding agent by the edge impregnation of graphite film to the lamellar spacing of graphite film, dwell time 8min.
3. S103, one-step solidification, it is cooled to room temperature through the graphite film duplexer of single-steeping step with mould, cold
But, during, the pressure (8Mpa) vertical with graphite film in-plane, cool time are applied to impregnated graphite film duplexer
1h, high polymer binder solidification after cooling.
4. S104, punching, the graphite film complex formed through one-step solidification step is removed from the molds, uses 1.0mm
Thick drill bit, edge is perpendicular to the direction of graphite film plane, extends to lower surface from the upper surface of complex and bores circular dipping hole,
The width in dipping hole is 1.0mm, and the density in dipping hole is 10/square centimeter, and dipping hole is through hole.
5. S105, double-steeping, take 200g acrylonitrile-butadiene-styrene copolymer (ABS) resin, dry at 85 DEG C
Dry 3h removes moisture, is subsequently heated to 220oC, and it is incubated 0.5h so that it is it is fused into liquid macroimolecule binding agent；Will be through once
The graphite film complex that punch out step obtains is again placed in mould, mold temperature 180 DEG C, utilizes press to be glued by liquid macroimolecule
Knot agent is pressed in mould, and pressure is 90MPa, and liquid macroimolecule binding agent is impregnated into the lamellar spacing of graphite film by dipping hole
In, dwell time 8min.
6. S106, secondary solidifies, and is cooled to room temperature through the graphite film complex of double-steeping step with mould, cold
But during, applying the pressure (8Mpa) vertical with graphite film in-plane to graphite film complex, cool time, 0.5h, cooled down
Rear high polymer binder solidifies.
Through step S101-S103, the density of the graphite film complex of formation is 1.8g/cm3, plane thermal conductivity is
840W/ (m K), bending strength is only 6MPa.Through step S101-S106, the density of the graphite film complex of formation is
1.7g/cm3, plane thermal conductivity is 770W/ (m K), and bending strength is 20MPa, and bending strength substantially increases.
Embodiment 4
1. S101, stacking, is 5cm × 5cm by size, and thickness is that 200 homemade nanometer sheet graphite films of 10 μm are successively folded
Add, make graphite film duplexer.Homemade nanometer sheet graphite film used belongs to the 4th class graphite film, is former with nano graphite sheet
Material preparation, concrete grammar (sees Chinese patent CN102874795 B, a kind of carbon nanometer thin based on nano graphite sheet as follows
Film and preparation method thereof): 1) 20 DEG C, natural flake graphite is joined concentrated sulphuric acid with in the mixed liquor I of concentrated nitric acid, with 300r/
Stir speed (S.S.) mechanical agitation 12hh of min, filters, and solid deionized water rinsing to the pH value after filtering is 6.5, so
After, it is dried at a temperature of 90 DEG C to constant weight, obtains the graphite granule being dried；Wherein, the mass percent concentration of concentrated sulphuric acid is
95%, the mass percent concentration of concentrated nitric acid is 65%, and concentrated sulphuric acid is 3.6:1, concentrated sulphuric acid and concentrated nitric acid with the volume ratio of concentrated nitric acid
The volume of mixed liquor I be 10mL:1g with the ratio of the quality of natural flake graphite；2) graphite being dried step 1) obtained
Granule, puts in Muffle furnace, at a temperature of 1000 DEG C, and constant temperature 50s, it is cooled to 20 DEG C, obtains expanded graphite；3) by step
3) expanded graphite obtained joins in the mixed liquor II of concentrated sulphuric acid and concentrated nitric acid, at 40 DEG C, with the stirring speed of 300r/min
Rate mechanical agitation 1h, then, with the frequency ultrasound 3h of 40kHz, it is 2 that addition deionized water is diluted to the pH value of solution, is received
Rice graphite flake dispersion liquid；Wherein, concentrated sulphuric acid is 2.6:1 with the volume ratio of concentrated nitric acid, concentrated sulphuric acid and the mixed liquor II of concentrated nitric acid
The ratio of volume and the quality of expanded graphite be 6mL:1mg；4) microporous filter membrane is laid in suction funnel, in the condition of sucking filtration
Under, take the nano graphite sheet dispersion liquid that step 3) obtains and be added on microporous filter membrane, and upper to nano graphite sheet dispersion liquid
Surface applies the pressure of 0.7MPa, pressurize 5min, obtains the graphite film being laid on microporous filter membrane；5) step 4) is obtained
The graphite film deionized water rinsing being laid on microporous filter membrane to pH value be 7, then, will rinse after be laid in micro-
The graphite film of hole filter membrane, at 70 DEG C, is dried 20h, sloughs microporous filter membrane, obtain the graphite film being dried, i.e. complete nanometer
The preparation of sheet graphite film.
2. S102, single-steeping, take 600g Merlon, at 110 DEG C, be dried 8h remove moisture, be subsequently heated to
300oC, and it is incubated 0.5h so that it is being fused into liquid macroimolecule binding agent, be placed in mould by graphite film duplexer, mould heats
To 250 DEG C, utilizing press to be pressed in mould by liquid macroimolecule binding agent, pressure is 60MPa, and liquid macroimolecule binding agent leads to
Cross the edge impregnation of graphite film in the lamellar spacing of graphite film, dwell time 10min.
3. S103, one-step solidification, it is cooled to room temperature through the graphite film duplexer of single-steeping step with mould, cold
But, during, the pressure (10Mpa) vertical with graphite film in-plane, cool time are applied to impregnated graphite film duplexer
1h, high polymer binder solidification after cooling.
4. S104, punching, the graphite film complex formed through one-step solidification step is removed from the molds, uses 0.5mm
Thick drill bit, edge is perpendicular to the direction of graphite film plane, extends to lower surface from the upper surface of complex and bores circular dipping hole,
The width in dipping hole is 0.5mm, and the density in dipping hole is 20/square centimeter, and dipping hole is through hole.
5. S105, double-steeping, take 300g ethylene-vinyl acetate copolymer (EVA), be heated to 200oC, and be incubated
0.5h makes it be fused into liquid macroimolecule binding agent；The graphite film complex obtained through punch out step is again placed in mould
In tool, mould is heated to 150 DEG C, utilizes injection machine to be expelled in mould by binding agent, and injection pressure is 40MPa, and binding agent leads to
Cross dipping hole to be impregnated in the lamellar spacing of graphite film, and be distributed in dipping hole, dwell time 3min.
6. S106, secondary solidifies, and is cooled to room temperature through the graphite film complex of double-steeping step with mould, cold
But during, applying the pressure (10Mpa) vertical with graphite film in-plane to graphite film complex, cool time, 1h, cooled down
Rear high polymer binder solidifies.
Through step S101-S103, the density of the graphite film complex of formation is 1.8g/cm3, plane thermal conductivity is
170W/ (m K), bending strength is 15MPa.Through step S101-S106, the density of the graphite film complex of formation is 1.7g/
cm3, plane thermal conductivity is 150W/ (m K), and bending strength is 30MPa, and bending strength substantially increases.
Various embodiments above illustrates, graphite film complex prepared by the present invention has that density is little, thickness scalable, thermal conductivity high,
The advantages such as bending strength is higher, inter-layer bonding force is stronger.
Claims (12)
1. a preparation method for graphite film complex, comprises the following steps:
S101, stacking: by the successively superposition of some graphite films, make graphite film duplexer；
S102, single-steeping: control condition makes high polymer binder become liquid, and makes it be impregnated into described graphite film duplexer
Lamellar spacing in；
S103, one-step solidification: to the graphite film duplexer through described single-steeping, control condition makes high polymer binder solid
Change, obtain graphite film complex.
2. the method for claim 1, further includes steps of
S104, punching: get some dipping holes on the graphite film complex that described one-step solidification is formed；
S105, double-steeping: control condition makes high polymer binder become liquid so that it is be impregnated into described graphite by dipping hole
In the lamellar spacing of film composite, and it is distributed in dipping hole；
S106, secondary solidifies: to the graphite film complex through double-steeping, control condition makes high polymer binder solidify.
3. the method for claim 1, it is characterised in that
The graphite film used in described S101 step, plane thermal conductivity is 1-2000 μ more than 50W/ (m K), the thickness of graphite film
m；And/or
Described graphite film includes expandable graphite sheet, pyrolytic graphite film, graphene oxide reduction film and other are based on graphite
Conduction graphite film in one or more；And/or
It is 10-99% that described graphite film accounts for the volume fraction of graphite film complex.
4. method as claimed in claim 1 or 2, it is characterised in that
Binding agent used in described S102 and/or S105 step is high polymer binder.
5. method as claimed in claim 4, it is characterised in that
High polymer binder composition used in described S102 and/or S105 step is identical or different, selected from epoxy resin, phenol
Urea formaldehyde, alkyd resin, polyurethane, polysiloxanes, cyanate ester resin, acrylic resin, polyether-ketone, polyether-ether-ketone, polyamide,
Polyamidoimide, polyimides, polyester, Merlon, polyolefin, polyphenylene oxide, polyphenylene sulfide, styrenic polymer, poly-
Sulfone, polrvinyl chloride, polyvinylidene chloride, chliorinated polyvinyl chloride, phenylpropyl alcohol cyclobutane, ethylene-vinyl acetate copolymer, polytetrafluoroethyl-ne
Alkene, fluorinated ethylene-propylene resin, perfluoroalkoxy compound, polyethylene-tetrafluoroethene, polyvinylidene fluoride, polytrifluorochloroethylene, poly-second
One or more in alkene-CTFE, polyvinyl fluoride, acrylonitrile-butadiene-styrene copolymer, polyformaldehyde.
6. the method as described in claim 4 or 5, it is characterised in that
If described high polymer binder is at room temperature liquid, then it is added to firming agent or firming agent and diluent, so
After impregnate；
If described high polymer binder is at room temperature solid-state, then it is heated to become liquid, then impregnates.
7. method as claimed in claim 6, it is characterised in that:
The temperature of described heating is 50 DEG C-400 DEG C.
8. method as claimed in claim 1 or 2, it is characterised in that
In described S102 and/or S105 step, dip time is 0.1-24h, and dipping temperature is 20-400 DEG C, applies pressure 0-
100MPa。
9. method as claimed in claim 2, it is characterised in that
The dipping hole that described S104 step is formed is through hole or blind hole, is by drill bit punching, laser boring or other punchings
Mode obtains, and the width in described dipping hole is 0.1-5mm, and the density in described dipping hole is 1-20/square centimeter.
10. method as claimed in claim 1 or 2, it is characterised in that
In described S103 and/or S106 step, the hardening time of binding agent is 1-72h, and solidification temperature is 20-180 DEG C.
11. methods as claimed in claim 11, it is characterised in that
In described S103 and/or S106 step, apply to graphite film duplexer or graphite film complex while binding agent solidification
The pressure vertical with graphite film plane, described pressure is 0-100MPa.
12. 1 kinds of graphite film complexs, it is characterised in that
Described graphite film complex is to be prepared by the method any one of claim 1-12.
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| CN107499047A (en) * | 2017-09-26 | 2017-12-22 | 北华大学 | A kind of snow deposit stacking method for 3D printing snow carving |
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| CN112937011A (en) * | 2019-12-11 | 2021-06-11 | 国家纳米科学中心 | Heat-conducting gasket and preparation method and application thereof |
| CN111497367A (en) * | 2020-04-26 | 2020-08-07 | 哈尔滨工业大学（威海） | High-heat-conductivity body and preparation method thereof |
| CN111978931A (en) * | 2020-08-27 | 2020-11-24 | 清华大学深圳国际研究生院 | Graphene composite slurry, graphite heat dissipation film structure and preparation method thereof |
| CN112225929A (en) * | 2020-10-19 | 2021-01-15 | 王楠 | Graphene film reinforced heat-conducting composite film and preparation method and application thereof |
| CN112225929B (en) * | 2020-10-19 | 2023-11-24 | 苏州南诣科技有限公司 | Graphene film reinforced heat conduction composite film and preparation method and application thereof |
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