CN107892784A - A kind of polymer based nanocomposites and preparation method thereof - Google Patents
A kind of polymer based nanocomposites and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of polymer based nanocomposites and preparation method thereof, belong to electronics technical field of composite materials, the carbon material that the functional composite material is wrapped up processing by polymer as matrix, silver nano-grain is mixed as filler, and the filling-material structure that processing is coated by silver nano-grain is uniformly attached to carbon material surface for silver nano-grain.The formula volume ratio of the polymer based nanocomposites is：Carbon material filler 10 ~ 20% through silver nano-grain parcel processing, polymer 80 ~ 90%.Polymer based nanocomposites prepared by the present invention have the remarkable advantages such as high thermal conductivity, low-k and low-dielectric loss, and preparation is simple for it, cost is cheap, is advantageous to be applied in large-scale electronic package material industrialized production.
Description
Technical field
The invention belongs to electronics technical field of composite materials, more particularly to different carbon material surfaces carry out metal nanoparticle
The preparation method of cladding, and using carbon material as polymer based nanocomposites of filler and preparation method thereof.
Background technology
At present, Heat Conduction Material is in necks such as telecommunications, heat exchange application, heating engineering application and generator applications
Domain.And mainly there are metal material and thermal conductive polymer based composites using more Heat Conduction Material.Wherein thermal conductive polymer base
Nano composite material because its it is corrosion-resistant, light, cheap, moulding process is simple the advantages that as the one of Heat Conduction Material field
The big focus of attention.It is wider by it for comprehensive utilization polymer based nanocomposites but the thermal conductivity factor of polymer is very small
General applies in Heat Conduction Material field, and it is to improve polymer-based nano composite wood to select and prepare the filler with high thermal conductivity
The key point of material.
Carbon material due to it there is the heat conductivility of superelevation and electric conductivity to be widely used in field of functional materials.This research
The materials such as the middle multi-walled carbon nanotube utilized, single-walled carbon nanotube, carbon nano-fiber, graphite flake, graphene are also current heat conduction
The focus of investigation of materials.Engineering application is had been carried out as mobile phone heat sink material currently with carbon material, how to improve performance
Also the emphasis of research in next step is turned into.
By the retrieval to document, the document identical with the present invention and patent are not yet found, retrieves some and the present invention
It is middle to test similar patent and document using silver nano-grain enveloped carbon nanometer tube, but mainly utilize what is synthesized mostly
Silver nano-grain is coated on carbon nano tube surface by mixed processing, and the silver nano material size coated is larger, and this hair
The preparation principle of bright middle filler is that the reduction of silver nano-grain and one step of cladding are completed, and reducing agent is used as simultaneously by the use of a kind of material
And coupling agent, and silver nano-grain particle diameter is about 10nm, this preparation technology substantially increases the efficiency of preparation, and reduces into
This.In conventional research, similar preparation technology is not found.Be below that applicant retrieves is related to the present invention special
Profit：
Wang Zhoucheng, Xu Xun, Wu Zhengtao, a kind of composite conducting glue used for electronic packaging and preparation method thereof, application number：
201410059910.7 application publication number：CN 103805118 A.
The content of the invention
It is an object of the invention to provide a kind of polymer based nanocomposites and preparation method thereof, this method utilizes gold
The carbon material belonged to after silver nano-grain cladding is filler, so as to improve the thermal conductivity of polymer based nanocomposites.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of polymer based nanocomposites, the carbon material conduct of processing is wrapped up as matrix, silver nano-grain by polymer
Filler is mixed, and wherein silver nano-grain is that direct-reduction obtains in the solution, and be uniformly adhered to the table of carbon material
Face, one layer of silver nano-grain clad is formed on its surface.
Further, the volume integral of the carbon material of processing is wrapped up in the polymer based nanocomposites through silver nano-grain
Number is 10 ~ 20%, and the volume fraction of polymeric matrix is 80 ~ 90%.
Further, the carbon material is multi-walled carbon nanotube, single-walled carbon nanotube, carbon nano-fiber, graphite flake, graphene
Material, and the mixing material of many of carbon material；The polymeric matrix be epoxy resin, polyimides, polyvinyl alcohol,
Polyethylene, polypropylene, polyvinylidene fluoride or its copolymer.
Further, a diameter of 30-50nm of the multi-walled carbon nanotube, length are 1-2 μm, the diameter of single-wall carbon nano tube
For 1nm-20nm, length is 1-2 μm, a diameter of 100 ~ 150nm of carbon nano-fiber, and length is 3-5 μm, the graphite flake
Thickness is 200nm, a diameter of 3 ~ 4 μm, and the graphene thickness is 2-5nm, a diameter of 2-3 μm, the clad silver nanoparticle
The particle diameter of grain is 5-10nm.
Further, the carbon material that processing is coated by silver nano-grain is prepared by sol-gal process, profit
By the use of benzyl mercaptan as coupling agent and reducing agent, by the use of silver nitrate as the presoma of silver nano-grain, under solution environmental, directly exist
Carbon material surface reduces to obtain silver nano-grain, and is uniformly attached to carbon material surface.
Further, the carbon material that processing is coated by silver nano-grain can be directly common by powder with polymeric matrix
Mixed method, solution mixing method carry out compound, and prepared by hot press forming technology or casting molding processes can test sample.
A kind of method for preparing above-mentioned polymer based nanocomposites, comprises the following steps：
Step 1：Carbon material powder is carried out to water bath sonicator ripple decentralized processing respectively；
Step 2：Prepare coupling agent solution and silver nano-grain precursor solution；
Step 3：Carbon material and coupling agent solution are mixed, first carry out magnetic agitation five minutes, utilizes ultrasonic disperse side afterwards
Method, coupling agent is evenly coated at carbon material surface, form coupling agent clad；
Step 4：Using sol-gal process, silver nano-grain precursor solution is added dropwise in above-mentioned mixed solution, and is mixed
Uniformly；
Step 5：Above-mentioned mixed solution is subjected to magnetic agitation, mixing time is 48 hours, and react fully progress, has reacted
After finishing, by gained mixed solution centrifugal treating, and washed 3-5 times with ethanol solution, be dried afterwards in 60 DEG C of baking ovens
Processing 12 hours, obtain the carbon material by silver nano-grain cladding processing；
Step 6：The carbon material powder obtained after step 5 is mixed with polymeric matrix, selects powder directly common
Mixed method is well mixed matrix and filler, and afterwards with hot press forming technology, mixed-powder is added in hot pressing grinding tool, heating
Pressurize is molded afterwards, obtains polymer matrix composite；
Step 7：After step 5, solution mixing method can be also used, by the carbon material powder of acquisition and water-soluble polymer
Matrix mixes under solution environmental, prepares film sample using the tape casting afterwards.
Further, for the sol-gal process to prepare the method for nano material under liquid environment, its step is in normal temperature
Or under conditions of heating, in ethanol solution environment, precursors and reduction agent material are added one by one, and utilize magnetic agitation
Method makes reactant be sufficiently mixed and react.
Further, the solvent is 99.7% absolute ethyl alcohol organic solvent, and silver nano-grain presoma is that silver nitrate is molten
Liquid, coupling agent and reducing agent are benzyl mercaptan solution.
Further, the step of pressure sintering moulding process is：Mixed-powder is added in hot pressing die, is in temperature
Apply 50MPa pressure, and pressurize 25 minutes in the environment of 250 DEG C.
The preparation principle of filler is that the reduction of silver nano-grain and one step of cladding are completed in the present invention, using benzyl mercaptan simultaneously
As reducing agent and coupling agent, and silver nano-grain particle diameter is 5 ~ 10nm, and this preparation technology substantially increases the efficiency of preparation,
And reduce cost.
The beneficial effects of the present invention are：
The present invention is handled by carrying out the cladding of surface silver nano-grain to carbon material, is improved carbon material and is being polymerize as filler
Dispersiveness in thing based nano composite material and the compatibility with polymeric matrix, it is compound so as to improve polymer-based nano
The thermal conductivity of material.On the other hand, the method for employing one-dimensional two-dimentional carbon material mixing addition, in the basic internal interaction of polymer
Link, forms effective thermal conducting path, so as to substantially increase the thermal conductivity of composite.
Polymer based nanocomposites prepared by the present invention have high thermal conductivity, low-k and low dielectric damage
The remarkable advantages such as consumption.Of the present invention preparation is simple, completes chemical synthesis process at normal temperatures substantially, and cost is low
It is honest and clean, it is plant-scale production（Such as electronic package material industrialized production）Possibility is brought with application.
Brief description of the drawings
Fig. 1 is that the multi-walled carbon nanotube TEM microstructures that processing is coated by silver nano-grain prepared by embodiment 1 are shone
Piece.
Fig. 2 is the graphene film TEM microsctructural photographs that processing is coated by silver nano-grain prepared by embodiment 4.
Embodiment
Below in conjunction with case study on implementation, the present invention is further described.It is pointed out that according to technical scheme,
The present invention is not limited to following embodiments, and those skilled in the art can make some non-according to the description below to the present invention
The modifications and adaptations of matter, it can reach the purpose of the present invention.
Embodiment 1：
There is provided in the present embodiment with PVA（Polyvinyl alcohol）For polymeric matrix, processing is coated to pass through silver nano-grain
Multi-walled carbon nanotube prepares polymer based nanocomposites as filler, volume integral shared by polymeric matrix in composite
Number is 90%, and volume fraction shared by filler is 10%, and conversion is weighed.Its preparation comprises the following steps：
1) multi-walled carbon nanotube 50mg is weighed, is determined through XRD test analysis free from foreign meter, carbon nanometer is determined through SEM scanning analysis
Pipe diameter is 10nm, and multi-walled carbon nanotube is dissolved in 100mL absolute ethyl alcohols, and the ultrasonic disperse 1h under 560W power；
2) silver nitrate solution is prepared：1.336g silver nitrate solids are weighed, 400mL absolute ethyl alcohols is measured as solvent, concentration is made
It is stand-by for 0.02M silver nitrate ethanol solution；
3) benzyl mercaptan solution is prepared：Measure the μ l of benzyl mercaptan liquid 20（About 1 drop）, measure absolute ethyl alcohol 7mL, by benzyl mercaptan liquid by
It is added dropwise in absolute ethyl alcohol and stirs, benzyl mercaptan solution for later use is made；
4) silver nitrate solution of above-mentioned preparation and benzyl mercaptan solution are mixed, and magnetic agitation 48h at normal temperatures, rotating speed are
600rpm；
5) scattered multi-walled carbon nanotube alcoholic solution is added to step（4）In the mixed solution of preparation, magnetic force stirs
15min is mixed, then mixed solution is placed under water bath sonicator environment and handles 6h, ultrasonic power 200w；
6) step will be passed through（5）The mixed solution of acquisition carries out centrifugal treating, and is washed 3 times with absolute ethyl alcohol；
7) step is passed through（6）Mixed solution is passed through into PTFE film（0.22µm）Filtering, then the solid for filtering acquisition is carried out true
Silver nano-grain is passed through in empty drying process, acquisition（Diameter 5nm）The multi-walled carbon nanotube powdered sample of cladding；
8) PVA solid 3g are weighed, the oil bath heating in the environment of 95 DEG C, make PVA solid dissolvings in deionized water, PVA is made
Solution 50mL, and it is stand-by after standing to bubble collapse；
9) by step（7）The filler powder of acquisition is added to step（8）In the PVA solution of preparation, magnetic agitation 30min, then
1h is ultrasonically treated, filler is well mixed in PVA matrixes, and shaping sample preparation is carried out after standing to bubble collapse；
10) step is passed through（9）The polymer matrix mixed solution of acquisition is molded by the tape casting, and polymerization is made after being dried at 50 DEG C
The film sample of thing based nano composite material.
The present embodiment is using benzyl mercaptan as coupling agent and the reducing agent of silver nano-grain, using absolute ethyl alcohol as reaction dissolvent, warp
Cross reaction and prepare the multi-wall carbon nano-tube tube material coated by silver nano-grain, and in this, as filler, using PVA as gathering
Compound matrix, prepare multi-walled carbon nanotube-silver nano-grain/PVA composites.
TEM microsctructural photographs such as Fig. 1 institutes of multi-wall carbon nano-tube tube material wherein by silver nano-grain cladding processing
Show.
In the polymer based nanocomposites of the structure with by silver nano-grain coat processing more wall carbon receive
Dispersiveness of the mitron filler in polymeric matrix is substantially better than the multi-wall carbon nano-tube tube material of uncoated processing.And filler exists
Good dispersive property also enables the good thermal conducting path that connection interaction is formed in matrix of filler inside polymeric matrix,
So that overall heat conductivility is improved.It is compound by the Determination of conductive coefficients analysis to sample, the polymer-based nano
The thermal conductivity of material is up to 11.2 W/mK.
Embodiment 2：
There is provided in the present embodiment using PVA as polymeric matrix, with by silver nano-grain cladding processing single
Pipe prepares polymer based nanocomposites, volume fraction shared by polymeric matrix is 80% in composite, is filled out as filler
Volume fraction shared by material is 20%, and conversion is weighed.Its preparation comprises the following steps：
1) single-walled carbon nanotube 50mg is weighed, is determined through XRD test analysis free from foreign meter, carbon nanometer is determined through SEM scanning analysis
Pipe diameter is 10nm, and single-walled carbon nanotube is dissolved in 100mL absolute ethyl alcohols, and the ultrasonic disperse 1h under 560W power；
2) silver nitrate solution is prepared：1.336g silver nitrate solids are weighed, 400mL absolute ethyl alcohols is measured as solvent, concentration is made
It is stand-by for 0.02M silver nitrate ethanol solution；
3) benzyl mercaptan solution is prepared：Measure the μ l of benzyl mercaptan liquid 20（About 1 drop）, measure absolute ethyl alcohol 7mL, by benzyl mercaptan liquid by
It is added dropwise in absolute ethyl alcohol and stirs, benzyl mercaptan solution for later use is made；
4) silver nitrate solution of above-mentioned preparation and benzyl mercaptan solution are mixed, and magnetic agitation 48h at normal temperatures, rotating speed are
600rpm；
5) scattered single-walled carbon nanotube alcoholic solution is added to step（4）In the mixed solution of preparation, magnetic force stirs
15min is mixed, then mixed solution is placed under water bath sonicator environment and handles 6h, ultrasonic power 200w；
6) step will be passed through（5）The mixed solution of acquisition carries out centrifugal treating, and is washed 4 times with absolute ethyl alcohol；
7) step is passed through（6）Mixed solution is passed through into PTFE film（0.22µm）Filtering, then the solid for filtering acquisition is carried out true
Silver nanoparticle is passed through in empty drying process, acquisition（5nm）The single-walled carbon nanotube powdered sample of grain cladding；
8) PVA solid 3g are weighed, the oil bath heating in the environment of 95 DEG C, make PVA solid dissolvings in deionized water, PVA is made
Solution 50mL, and it is stand-by after standing to bubble collapse；
9) by step（7）The filler powder of acquisition is added to step（8）In the PVA solution of preparation, magnetic agitation 30min, then
1h is ultrasonically treated, filler is well mixed in PVA matrixes, and shaping sample preparation is carried out after standing to bubble collapse；
10) step is passed through（9）The polymer matrix mixed solution of acquisition is molded by the tape casting, and polymerization is made after being dried at 50 DEG C
The film sample of thing based nano composite material.
By the preparation process of embodiment 2, the single-walled carbon nanotube/PVA obtained by silver nano-grain cladding processing is multiple
Condensation material.
Embodiment 3：
There is provided in the present embodiment using PVA as polymeric matrix, with by silver nano-grain cladding processing carbon nano-fiber
As filler, polymer based nanocomposites are prepared, volume fraction shared by polymeric matrix is 80% in composite, filler
Shared volume fraction is 20%, and conversion is weighed.Its preparation comprises the following steps：
1) carbon nano-fiber 50mg is weighed, is determined through XRD test analysis free from foreign meter, CNT is determined through SEM scanning analysis
A diameter of 10nm, carbon nano-fiber is dissolved in 100mL absolute ethyl alcohols, and the ultrasonic disperse 1h under 560W power；
2) silver nitrate solution is prepared：1.336g silver nitrate solids are weighed, 400mL absolute ethyl alcohols is measured as solvent, concentration is made
It is stand-by for 0.02M silver nitrate ethanol solution；
3) benzyl mercaptan solution is prepared：Measure the μ l of benzyl mercaptan liquid 20（About 1 drop）, measure absolute ethyl alcohol 7mL, by benzyl mercaptan liquid by
It is added dropwise in absolute ethyl alcohol and stirs, benzyl mercaptan solution for later use is made；
4) silver nitrate solution of above-mentioned preparation and benzyl mercaptan solution are mixed, and magnetic agitation 48h at normal temperatures, rotating speed are
600rpm；
5) scattered carbon nano-fiber alcoholic solution is added to step（4）In the mixed solution of preparation, magnetic agitation
15min, then mixed solution is placed under water bath sonicator environment and handles 6h, ultrasonic power 200w；
6) step will be passed through（5）The mixed solution of acquisition carries out centrifugal treating, and is washed 5 times with absolute ethyl alcohol；
7) step is passed through（6）Mixed solution is passed through into PTFE film（0.22µm）Filtering, then the solid for filtering acquisition is carried out true
Silver nano-grain is passed through in empty drying process, acquisition（10nm）The carbon nano-fiber powdered sample of cladding；
8) PVA solid 3g are weighed, the oil bath heating in the environment of 95 DEG C, make PVA solid dissolvings in deionized water, PVA is made
Solution 50mL, and it is stand-by after standing to bubble collapse；
9) by step（7）The filler powder of acquisition is added to step（8）In the PVA solution of preparation, magnetic agitation 30min, then
1h is ultrasonically treated, filler is well mixed in PVA matrixes, and shaping sample preparation is carried out after standing to bubble collapse；
10) step is passed through（9）The polymer matrix mixed solution of acquisition is molded by the tape casting, is made poly- after being dried at 50 DEG C
The film sample of compound based nano composite material.
By the preparation process of embodiment 3, the carbon nano-fiber/PVA obtained by silver nano-grain cladding processing is compound
Material.
Embodiment 4：
The present embodiment provide with PI（Polyimides）For matrix, the graphene handled is coated by silver nano-grain with two dimension
Material prepares polymer based nanocomposites as filler, and volume fraction shared by polymeric matrix is 80% in composite,
Volume fraction shared by filler is 20%, and conversion is weighed.Its preparation comprises the following steps：
1) graphene powder 50mg is weighed, is determined through XRD test analysis free from foreign meter, graphene material is determined through SEM scanning analysis
Material thickness is 9nm, and graphene powder is dissolved in 100mL absolute ethyl alcohols, and the ultrasonic disperse 1h under 560W power；
2) silver nitrate solution is prepared：1.336g silver nitrate solids are weighed, 400mL absolute ethyl alcohols is measured as solvent, concentration is made
It is stand-by for 0.02M silver nitrate ethanol solution；
3) benzyl mercaptan solution is prepared：Measure the μ l of benzyl mercaptan liquid 20（About 1 drop）, measure absolute ethyl alcohol 7mL, by benzyl mercaptan liquid by
It is added dropwise in absolute ethyl alcohol and stirs, benzyl mercaptan solution for later use is made；
4) silver nitrate solution of above-mentioned preparation and benzyl mercaptan solution are mixed, and magnetic agitation 48h at normal temperatures, rotating speed are
600rpm；
5) scattered graphene powder alcoholic solution is added to step（4）In the mixed solution of preparation, magnetic agitation
15min, then mixed solution is placed under water bath sonicator environment and handles 6h, ultrasonic power 200w；
6) step will be passed through（5）The mixed solution of acquisition carries out centrifugal treating, and is washed 3 times with absolute ethyl alcohol；
7) step is passed through（6）Mixed solution is passed through into PTFE film（0.22µm）Filtering, then the solid for filtering acquisition is carried out true
Silver nano-grain is passed through in empty drying process, acquisition（10nm）The graphene powder sample of cladding；
8) PI solid 3g are weighed, by step（7）The filler powder of middle acquisition is ground with PI to be mixed, and is subsequently placed in mould
Hot pressing on press, hot pressing temperature are 250 DEG C, pressure 50MPa, and the time is 25 minutes, can obtain adding stone after hot-forming
Black alkene-silver nano-grain/PI polymer based nanocomposites.
By implementing 4 preparation process, graphene/PI composites by silver nano-grain cladding processing are obtained, its
The TEM microsctructural photographs of the middle grapheme material handled by silver nano-grain are as shown in Figure 2.
Embodiment 5：
The present embodiment provide using PI as matrix, using by silver nano-grain cladding processing graphite flake be used as filler, prepare gather
Compound based nano composite material, volume fraction shared by polymeric matrix is 80% in composite, and volume fraction shared by filler is
20%, wherein each station 10% of graphene and multi-walled carbon nanotube, conversion is weighed.Its preparation comprises the following steps：
1) each 25mg of powdered graphite is weighed, is determined respectively through XRD test analysis free from foreign meter, is dissolved in after powdered graphite is mixed
In 100mL absolute ethyl alcohols, and the ultrasonic disperse 1h under 560W power；
2) silver nitrate solution is prepared：1.336g silver nitrate solids are weighed, 400mL absolute ethyl alcohols is measured as solvent, concentration is made
It is stand-by for 0.02M silver nitrate ethanol solution；
3) benzyl mercaptan solution is prepared：Measure the μ l of benzyl mercaptan liquid 20（About 1 drop）, measure absolute ethyl alcohol 7mL, by benzyl mercaptan liquid by
It is added dropwise in absolute ethyl alcohol and stirs, benzyl mercaptan solution for later use is made；
4) silver nitrate solution of above-mentioned preparation and benzyl mercaptan solution are mixed, and magnetic agitation 48h at normal temperatures, rotating speed are
600rpm；
5) alcoholic solution of scattered graphite flake is added to step（4）In the mixed solution of preparation, magnetic agitation
15min, then mixed solution is placed under water bath sonicator environment and handles 6h, ultrasonic power 200w；
6) step will be passed through（5）The mixed solution of acquisition carries out centrifugal treating, and is washed 4 times with absolute ethyl alcohol；
7) step is passed through（6）Afterwards, mixed solution is passed through into PTFE film（0.22µm）Filtering, then the solid for filtering acquisition is entered
Row vacuum drying treatment, obtain the powdered graphite sample by silver nano-grain cladding processing；
8) PI solid 3g are weighed, by step（7）The mixed fillers powder of middle acquisition is ground with PI to be mixed, and is subsequently placed in mould
In the hot pressing on press, hot pressing temperature be 250 DEG C, pressure 50MPa, the time be 25 minutes, it is hot-forming after i.e. can be added
Enter the polymer based nanocomposites of graphite/silver nano-grain/PI 1-2 composite constructions.
By the preparation process of embodiment 5, graphite/PI composites by silver nano-grain cladding processing are obtained.
Embodiment 6：
The present embodiment provide using PI as matrix, with the two-dimensional graphene material and one-dimensional more by silver nano-grain cladding processing
Wall carbon nano tube prepares polymer based nanocomposites as filler, volume fraction shared by polymeric matrix in composite
For 80%, volume fraction shared by filler is 20%, wherein each station 10% of graphene and multi-walled carbon nanotube, and conversion is weighed.It prepares bag
Include the following steps：
1) graphene and each 25mg of multi-wall carbon nano-tube pipe powder are weighed, determined respectively through XRD test analysis it is free from foreign meter, by graphite
It is dissolved in after alkene and the mixing of multi-wall carbon nano-tube pipe powder in 100mL absolute ethyl alcohols, and the ultrasonic disperse 1h under 560W power；
2) silver nitrate solution is prepared：1.336g silver nitrate solids are weighed, 400mL absolute ethyl alcohols is measured as solvent, concentration is made
It is stand-by for 0.02M silver nitrate ethanol solution；
3) benzyl mercaptan solution is prepared：Measure the μ l of benzyl mercaptan liquid 20（About 1 drop）, measure absolute ethyl alcohol 7mL, by benzyl mercaptan liquid by
It is added dropwise in absolute ethyl alcohol and stirs, benzyl mercaptan solution for later use is made；
4) silver nitrate solution of above-mentioned preparation and benzyl mercaptan solution are mixed, and magnetic agitation 48h at normal temperatures, rotating speed are
600rpm；
5) alcoholic solution that scattered graphene and multi-walled carbon nanotube mix is added to step（4）The mixing of preparation
In solution, magnetic agitation 15min, then mixed solution is placed under water bath sonicator environment and handles 6h, ultrasonic power 200w；
6) step will be passed through（5）The mixed solution of acquisition carries out centrifugal treating, and is washed 3 times with absolute ethyl alcohol；
7) step is passed through（6）Afterwards, mixed solution is passed through into PTFE film（0.22µm）Filtering, then the solid for filtering acquisition is entered
Row vacuum drying treatment, obtain graphene and multi-walled carbon nanotube powdered sample by silver nano-grain cladding；
8) PI solid 3g are weighed, by step（7）The mixed fillers powder of middle acquisition is ground with PI to be mixed, and is subsequently placed in mould
In the hot pressing on press, hot pressing temperature be 250 DEG C, pressure 50MPa, the time be 25 minutes, it is hot-forming after i.e. can be added
The polymer-based nano for entering multi-walled carbon nanotube/silver nano-grain-graphene/silver nano-grain/PI 1-2 composite constructions is compound
Material.
On the one hand the silver nano-grain cladding of passing through introduced in embodiment 1 and embodiment 4 is combined in the present embodiment to handle
Carbon material, can improve dispersiveness of the carbon material in polymeric matrix, on the other hand with the addition of peacekeeping two dimension knot simultaneously
The carbon material of structure, two-dimensional material is set to form thermal conducting path in polymeric matrix, one-dimensional material is between two-dimensional graphene
Play a part of interactive connection, make filler that effective ground three dimentional heat conduction path be integrally formed, so as to effectively improve leading for composite
Hot property.By the test analysis to sample heat conductivility, multi-walled carbon nanotube/silver nano-grain-graphene/silver nanoparticle
The thermal conductivity of grain/PI composites is up to 6 W/mK.
Above-described embodiment can also be enumerated a lot, no longer repeat one by one herein, as long as in scope disclosed by the invention
It is interior, i.e., by the use of the inorganic material of different carbon materials, the combination matching of different carbon materials or different high heat conductions as filler, with
And the organic solvent in preparation process, polymeric matrix, in the process parameters range that preparation method provides, it can be prepared into
Different filler materials and the polymer based nanocomposites with diverse microcosmic structure.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
Enclose not limited to this.The equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, in the present invention
Protection domain within.Protection scope of the present invention is defined by claims.
Claims (10)
1. a kind of polymer based nanocomposites, it is characterised in that by polymer as matrix, the processing of silver nano-grain parcel
Carbon material be mixed as filler, wherein silver nano-grain is that direct-reduction obtains in the solution, and is uniformly adhered to
On the surface of carbon material, one layer of silver nano-grain clad is formed on its surface.
2. a kind of polymer based nanocomposites according to claim 1, it is characterised in that the polymer-based nano is answered
The volume fraction for wrapping up the carbon material of processing in condensation material through silver nano-grain is 10 ~ 20%, and the volume fraction of polymeric matrix is
80~90%。
3. a kind of polymer based nanocomposites according to claim 1, it is characterised in that the carbon material is more wall carbon
Nanotube, single-walled carbon nanotube, carbon nano-fiber, graphite flake, grapheme material, and the mixing material of many of carbon material
Material；The polymeric matrix be epoxy resin, polyimides, polyvinyl alcohol, polyethylene, polypropylene, polyvinylidene fluoride or its
Copolymer.
4. a kind of polymer based nanocomposites according to claim 3, it is characterised in that the multi-walled carbon nanotube is straight
Footpath is 30-50nm, and length is 1-2 μm, the diameter of single-wall carbon nano tube 1nm-20nm, and length is 1-2 μm, the Nano carbon fibers
Tie up a diameter of 100 ~ 150nm, length is 3-5 μm, and the thickness of the graphite flake is 200nm, a diameter of 3 ~ 4 μm, the graphene
Thickness is 2-5nm, a diameter of 2-3 μm, and the particle diameter of the clad silver nano-grain is 5-10nm.
5. a kind of polymer based nanocomposites according to claim 1, it is characterised in that described to pass through silver nano-grain
The carbon material of cladding processing is prepared by sol-gal process, by the use of benzyl mercaptan as coupling agent and reducing agent, utilizes nitre
Presoma of the sour silver as silver nano-grain, under solution environmental, directly reduce to obtain silver nano-grain in carbon material surface, and
It is even to be attached to carbon material surface.
6. a kind of polymer based nanocomposites according to claim 1, it is characterised in that described to pass through silver nano-grain
The carbon material and polymeric matrix for coating processing can be compound by powder direct blending, solution mixing method progress, and pass through heat
Molded technique or casting molding processes are prepared can test sample.
A kind of 7. method for preparing polymer based nanocomposites as claimed in claim 1, it is characterised in that including following step
Suddenly：
Step 1：Carbon material powder is carried out to water bath sonicator ripple decentralized processing respectively；
Step 2：Prepare coupling agent solution and silver nano-grain precursor solution；
Step 3：Carbon material and coupling agent solution are mixed, first carry out magnetic agitation five minutes, utilizes ultrasonic disperse side afterwards
Method, coupling agent is evenly coated at carbon material surface, form coupling agent clad；
Step 4：Using sol-gal process, silver nano-grain precursor solution is added dropwise in above-mentioned mixed solution, and is mixed
Uniformly；
Step 5：Above-mentioned mixed solution is subjected to magnetic agitation, mixing time is 48 hours, and react fully progress, has reacted
After finishing, by gained mixed solution centrifugal treating, and washed 3-5 times with ethanol solution, be dried afterwards in 60 DEG C of baking ovens
Processing 12 hours, obtain the carbon material by silver nano-grain cladding processing；
Step 6：The carbon material powder obtained after step 5 is mixed with polymeric matrix, selects powder directly common
Mixed method is well mixed matrix and filler, and afterwards with hot press forming technology, mixed-powder is added in hot pressing grinding tool, heating
Pressurize is molded afterwards, obtains polymer matrix composite；
Step 7：After step 5, solution mixing method can be also used, by the carbon material powder of acquisition and water-soluble polymer
Matrix mixes under solution environmental, prepares film sample using the tape casting afterwards.
A kind of 8. method for preparing polymer based nanocomposites according to claim 7, it is characterised in that the colloidal sol
Gel method under liquid environment prepare nano material method, its step be under conditions of normal temperature or heating, it is molten in ethanol
In pendular ring border, one by one add precursors and reduction agent material, and using magnetic agitation method make reactant be sufficiently mixed and
Reaction.
A kind of 9. method for preparing polymer based nanocomposites according to claim 7, it is characterised in that the solvent
It is 99.7% absolute ethyl alcohol organic solvent, silver nano-grain presoma is silver nitrate solution, and coupling agent and reducing agent are benzyl sulphur
Alcoholic solution.
A kind of 10. method for preparing polymer based nanocomposites according to claim 7, it is characterised in that the heat
The step of platen press moulding process is：Mixed-powder is added in hot pressing die, applies 50MPa in the environment of being 250 DEG C in temperature
Pressure, and pressurize 25 minutes.
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