CN110228248A - A kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof - Google Patents
A kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof Download PDFInfo
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- CN110228248A CN110228248A CN201910389657.4A CN201910389657A CN110228248A CN 110228248 A CN110228248 A CN 110228248A CN 201910389657 A CN201910389657 A CN 201910389657A CN 110228248 A CN110228248 A CN 110228248A
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Abstract
The present invention provides a kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof；The composite material has the stepped construction formed by hot pressing after several composite fibre layer stackups；The composite fibre layer is the composite fibre layer that heat filling is covered in the formation of polymer nanofiber surface.When preparation, heat filling dispersion solution inhalation syringe is subjected to high-pressure electrostatic splash, be attached on polymer nanofiber by electrostatic force and hydrogen bond action, form the network structure of the filler orientation arrangement contacted with each other, after stacking through cold pressing compression, hot-forming obtain the composite material.The special construction of the composite material can make filler form high-efficiency heat conduction access in the composite material of its filling, achieve the purpose that a small amount of high thermal conductivity filler of addition is remarkably improved Thermal Properties of Polymer-based Composites, the thermally conductive demand for preparing electronic electric equipment can be met.
Description
Technical field
The invention belongs to heat-conductive composite material preparation technical fields, and it is compound to be related to a kind of high thermal conductivity anisotropic polymer base
Material and preparation method thereof.
Background technique
With the miniaturization of hyundai electronics electrical equipment, highly integrated and multifunction has accumulated a large amount of heat in equipment
Amount, this may cause the thermal fault of these electronic electric equipments or even sets off an explosion.Therefore, these electric appliance and electronic devices are carried out
For effective heat management for its performance, reliability and service life are most important.In addition, in many frontier science and technology fields, especially under
Generation flexible electronic devices or aerospace sophisticated technology, opposite heat tube reason material then additionally have stringenter performance requirement, example
Such as electrical isolation, lateral thermal conductivity energy in the face of superelevation, flexibility and light etc..Most polymers material usually has on the market
Most of features described above, but its thermal conductivity wretched insufficiency, need to greatly improve its thermal conductivity, are greater than 10W/ (mK).However, mesh
Preceding preparation method is difficult to prepare super-high heat-conductive polymer composites at low levels, if too high levels, composite material can
Some critical problems are exposed, if processing performance is very poor, the distinctive flexible missing of polymer, Material Cost is high and material is close
Degree is big etc., hinders the practical application of polymer composites.Therefore, for such material, the Rational structure of filler is designed
As the key for realizing thermal resistance between high heat conductance and low particle, i.e., form the continuous of filler as much as possible in a polymer matrix
Heat-transfer path network.
It is well known that the interface resistance between thermal resistance or matrix and filler between filler and filler may seriously affect it is multiple
The final heating conduction of condensation material.Up to the present, by the effort of many scientists, it has been reported that several reduction filler heat
Resistance improves the technology that material thermal conductivity increases efficiency, wherein building three dimentional heat conduction filler network structure framework was seemingly in the past
The fruitful mode being concerned in several years.However, the preparation of these three-dimensional net structures in polymer composites,
Usually prepared by chemical vapor deposition (CVD) or by organic polymer as adhesive substance.As far as we know, severe
The condition at quarter and high cost limit the extensive use of CVD, and when constructing Percolation network, organic in three-dimensional filler structure
Connector can seriously reduce the contact area between filler and filler and increase its thermal resistance, hinder heating conduction and further mention
It is high.Therefore, still tight demand have bulky grain between contact area, little particle thermal resistance three-dimensional filler network structure, as
The effective ways of nanocomposite thermal conductivity are improved, especially two-dimentional filler.
Summary of the invention
It is an object of the invention to overcome existing filled-type thermally conductive composite material to improve heating conduction with filer content to increase
The problems such as thermal resistance is high between low efficiency and filler provides a kind of with low thermal resistance contacts, respectively between heating conduction, filler in superelevation face
The high thermal conductivity anisotropic polymer based composites and preparation method thereof of the features such as anisotropy structure and easily preparation.By to poly-
It closes object progress electrostatic spinning and prepares polymer nanofiber, then pass through the splash of high voltage electrostatic on this basis for heat filling
It is covered on polymeric fiber surface and forms polymer/heat filling assorted fibre.This assorted fibre be cut into fritter simultaneously
It is layering, and then forms assorted fibre felt.Finally, it is multiple to obtain polymer matrix by cold pressing compression and hot-forming
Condensation material.It in the composite material, contacts with each other and orientations, is distributed compared to uniform filling compound in sheet heat filling face
Material greatly reduces thermal resistance between filler, and it is high that this special construction can be such that filler is formed in the composite material of its filling
Thermal conducting path is imitated, achievees the purpose that a small amount of heat filling of addition is remarkably improved Thermal Properties of Polymer-based Composites.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention relates to a kind of high thermal conductivity anisotropic polymer based composites, the composite material has by several multiple
The stepped construction that hot pressing is formed after condensating fiber layer stackup；The composite fibre layer is that heat filling is covered in polymer nanofiber
The composite fibre layer that surface is formed.
In the present invention, the polymer nanofiber is the polymer nanofiber prepared by electrostatic spinning.
The polymer nanofiber be selected from polyvinyl alcohol, Kynoar, polymethyl methacrylate, polystyrene,
Chitosan, cellulose, polypropylene be fine, one of polyimides, polyurethane or a variety of.
In the present invention, the heat filling includes the mixed fillers of sheet heat filling, bar shape heat filling or both.
The sheet heat filling be selected from boron nitride nanosheet, stannic oxide/graphene nano piece, graphene, metal nano plate,
One of transition metal carbide, nitride (MXene) are a variety of.
The bar shape heat filling be selected from boron nitride nano-tube, carbon nanotube, silicon carbide nanometer line, MXene nanotube,
One of metal nanometer line is a variety of.
In the present invention, the packing volume of heat filling is 0.1-50% in the composite fibre layer；In the composite material
Heat filling orientations；Thermal conductivity has anisotropy.
The invention further relates to a kind of preparation method of above-mentioned high thermal conductivity anisotropic polymer based composites, the methods
Include the following steps:
A, it dissolves the polymer in progress electrostatic spinning in solvent A and prepares polymer nanofiber non-woven fabrics；
B, heat filling, which is dispersed in solvent B, is attached to the polymer nanofiber non-woven fabrics by high-pressure electrostatic splash
On, obtain composite fibre layer；
C, the composite fibre layer is cut into pre-set dimension, polymer composite felt is made in stacked in multi-layers；
D, by the polymer composite felt carry out room temperature molding after, be higher than the melting point polymer at a temperature of be hot pressed into
Type, annealing, obtains the high thermal conductivity anisotropic polymer based composites.
In step A, the solvent A includes n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, acetone, deionized water, two
One or more of methyl sulfoxide and ethyl acetate.
In step A, the electrostatic spinning time is 10-40 minutes, voltage 10-30kV, and temperature is 15-35 DEG C, spinning
Flow quantity is 0.1-2mL/h.
In step B, the solvent B include n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, isopropanol, deionized water,
One or more of dimethyl sulfoxide and ethyl acetate.
In step B, the high-pressure electrostatic splash time is 10-120 minutes, voltage 10-40kV, 15-35 DEG C of temperature, spraying liquid
Flow is 0.1-2mL/h.
The present invention uses high heat conductance two-dimensional sheet or the rodlike heat filling of one-dimensional pipe, is obtained first by method of electrostatic spinning
Heat filling dispersion solution inhalation syringe is carried out the splash of high voltage electrostatic, covers heat filling by polymer nanofiber
In polymer nanofiber surface.By the way that polymer/heat filling assorted fibre to be successively superimposed, compression molding is formed containing mutual
It is in contact and the filler network structure of orientations.This special construction can make filler shape in the composite material of its filling
At high-efficiency heat conduction access, reaches and add the mesh that a small amount of high thermal conductivity filler is remarkably improved Thermal Properties of Polymer-based Composites
, the preparation method of similar thermally conductive compounded mix has not been reported.
Compared with prior art, the invention has the following beneficial effects:
1, there is the two-dimensional sheet of high thermal conductivity coefficient and one-dimensional heat conduction filler to be covered in industry and make extensively for present invention selection
The polymer nanofiber surface prepared with method of electrostatic spinning forms the polymer composite of contact and orientation texture in filler face
Material, the structure have thermal resistance between lower particle, high-efficiency heat conduction network path can be realized in the composite material filled
Building, wherein carrier of the two-dimensional sheet filler of high thermal conductivity as high-efficiency heat conduction access, reaches and greatly improves compounded mix
The purpose of heating conduction；
2, the present invention constructed by filler face in contact and the composite material of orientation texture in, can contain in lesser filler
Reach direction thermal conductivity in high face under amount, thermal conductivity improve efficiency it is very high, to effectively reduce expensive high thermal conductivity filler
Additive amount, enable the production cost of composite material reduce；
3, the filler network structure for contacting and interconnecting in high voltage electrostatic splash preparation used in the present invention face, can
The heating conduction of material is significantly improved, there is wide thermally conductive application prospect；
4, thermal conductive polymer composite material preparation process of the present invention is simple, cost economy, is applicable to extensive
Industrialized production.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the high thermal conductivity anisotropic polymer composite material preparation process schematic diagram that the embodiment of the present invention 1 obtains；
Fig. 2 is polymer and polymer/filler composite fibre scanning electron microscope prepared by embodiment 1
(SEM) photo；Wherein Fig. 2 a is PVA nanofiber；Fig. 2 b-2d is followed successively by embodiment 1 in the BNNS electrostatic splash time
Prepared PVA/BNNS nano-composite fiber under 40min, 60min and 80min；
Fig. 3 is that the SEM of PVA/BNNS composite material section under BNNS 33wt% additive amount prepared by embodiment 1 shines
Piece；
Fig. 4 be the embodiment of the present invention 1 prepared by polymer matrix composite thermal conductivity, wherein Fig. 4 a be thermal conductivity with
The variation diagram of BNNS additive amount, figure b are the thermal conductivity anisotropy ratio of composite material, and illustration is its corresponding composite material section
SEM photograph.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Experimental test sample of the invention is under vulcanizing press (QLB-D type, Shanghai rubber machinery plant) by hot-forming.
The pattern of polymer prepared by the present invention and its composite fibre uses field emission scanning electron microscope (SEM)
(450 type of Nova NanoSEM, FEI Co., the U.S.) is observed.
The heating conduction of sample prepared by the present invention using laser heat conducting instrument (LFA 467HT HyperFlash@,
NanoFlash, Netzsch) it is measured.
Embodiment 1
The present embodiment is related to the preparation method of a kind of composite fibre and composite material, and the composite fibre is received by boron nitride
Rice piece covering PVA nanofiber composition, the composite material are made of composite fibre layer poststack hot pressing.The preparation of composite material
Journey by following steps as shown in Figure 1, prepared:
A, hexagonal boron nitride (h-BN) liquid phase removing: according to document (Chen, et al.,
Adv.Funct.Mater.2017,27,1604754. the method for the removing of liquid phase ultrasound and centrifugal classification) reported prepares nitrogen
Change boron nanometer sheet (BNNS)；
B, a certain amount of PVA white particle powder the electrostatic spinning of PVA: is dissolved in deionized water with the concentration of 18wt%
In, it is stirred in beaker at ambient temperature 1 hour.Then by the solution left standstill 0.5h after stirring, it is transferred to vacuum baking
Normal-temperature vacuum deaeration obtains the precursor solution for straight polymer electrostatic spinning in case.Clear solution after deaeration is drawn into
In syringe, with injection rate electrostatic spinning 15 minutes of 1mL per hour.During electrostatic spinning, syringe needle and collection cylinder
Between operating distance be 15 centimetres, voltage is set as 15 kilovolts.Pump is promoted to control liquid inventory per hour by injection
0.5ml.The revolving speed of rotatingcylindrical drum collector is 300 turns per minute.Whole process is carried out at 25 DEG C, and ambient humidity is relatively wet
Degree 45%, obtains PVA nanofiber.
C, the electrostatic splash of BNNS: being dispersed in deionized water and isopropanol (1/1) in the mixed solvent for the BNNS after drying,
Concentration is 20mg/ml.Then it is stirred in beaker under environment temperature 1 hour.Then by the solution left standstill 0.5h after stirring,
It is transferred to normal-temperature vacuum deaeration in vacuum drying oven and obtains the milk-white coloured suspension for BNNS vacuum splash.By the suspension after deaeration
Liquid is drawn into syringe, electrostatic splash BNNS is carried out on the PVA nanofiber basis prepared in stepb, with 1mL per hour
Injection rate high-pressure electrostatic splash, the splash time of BNNSs is respectively 40min, 60min or 80min.In electrostatic spinning process
In, the operating distance between syringe needle and collection cylinder is 15 centimetres, and voltage is set as 20 kilovolts.Promote pump by solution by injection
Flow control is in 0.5ml per hour.The revolving speed of rotatingcylindrical drum collector is 300 turns per minute.Whole process is carried out at 25 DEG C,
Ambient humidity is relative humidity 45%.After electrostatic splash, obtains and be covered with BNNS layers of PVA layers of nanofibers.By what is obtained
Nanofiber compound nonwoven cloth is so 12 hours dry that be covered with to surface in the vacuum drying oven for being placed in 70 DEG C from removing on aluminium foil
White BNNS layers of PVA nano-composite fiber non-woven fabrics is labeled as BNNS-C-PVA；
D, the preparation of PVA/BNNS nanocomposite: BNNS-C-PVA is cut, and becomes multiple fritter non-woven fabrics,
Size is about the square of 30mm long.Multiple nano fiber non-woven fabrics are subjected to overlapping covering layer by layer, it is fine to form stack-up array
Tie up felt.Finally, being first molded the stack-up array structure under 25 DEG C and 20MPa pressure 0.5 hour, then it is being higher than fusing point temperature
It is molded 0.5 hour under 95 DEG C of same pressure of degree.It is made annealing treatment 12 hours after taking-up in vacuum drying oven high temperature, stepped construction is made
PVA/BNNS nanocomposite.Through determination, the BNNS electrostatic splash time is that the PVA/BNNS of 40min, 60min and 80min receive
The BNNS mass content of nano composite material is respectively 23%, 28% and 33%, be respectively labeled as BNNS-40, BNNS-60 and
BNNS-80。
Implementation result: the present invention is prepared for the high-heat-conductive composite material containing orientation and the BNNS structure interconnected.
As shown in Fig. 2 scanning electron microscope (SEM) photo, in the PVA nanofiber prepared by embodiment 1, straight fiber phase
Mutually interweave, the direction random distribution of fiber, and the diameter distribution of fiber is relatively narrow, in 300-600nm.In addition, nanofiber
Surface be it is smooth, do not find apparent bead, fiber reunite or fibre matting.BNNS in the form of individual particle well
Uniform fold is on PVA fiber, and as the splash time increased to 80 minutes from 40 minutes, concentration of the BNNS on PVA fiber increases
Add.After the processing in the splash of BNNN electrostatic (40 minutes) of short period, BNNS is mutually isolated on PVA fiber, and BNNS's is quiet
EFI splashes that the time is longer, and contacting with each other for BNNS is more, and is face contact between BNNS, and contact area is bigger, until filler exists
(80 minutes) are interconnected in the form of overlapped by part on fiber, form apparent BNNS network.Fig. 3 shows PVA/BNNS
The SEM photograph of the cross section of composite material.The orientation of BNNS and face overlap joint contact with each other network structure and still obtain very after hot pressing
Retain well.Without apparent hole or aggregation in the surface of nanocomposite or on surface, illustrate that composite structure is complete
Good, defect is less.It is tested by the heating conduction to polymer composites prepared by the present invention, it can be found that compound
Material realizes thermal coefficient in face under less BNNS additive amount and is greatly improved, as shown in figure 4, PVA/BNNS is nano combined
Material in the face in BNNS splash time 80min (33wt%) thermal conductivity be up to 21.4W/ (mK), this superelevation thermal conductivity
Numerical value is even higher by two orders of magnitude than pure PVA, and shows higher anisotropic heat conductivity.The above results explanation, phase
Compared with the prior art, the network structure of BNNS orientation and face contact prepared by the present invention has prominent in terms of heating conduction raising
There is very high thermal conductivity to increase efficiency for advantage out, polymer matrix composite.
Comparative example 1
This comparative example is related to a kind of preparation method of thermally conductive PVA composite material, and the composite material is by 33wt% boron nitride
Nanometer sheet and 67wt%PVA composition.BNNS preparation process is same as Example 1, by grinding BNNS and PVA mixed-powder and
It is molded 0.5 hour under 95 DEG C and 20MPa pressure, makes annealing treatment 12 hours, be prepared in vacuum drying oven high temperature after taking-up
The PVA/BNNS nanocomposite of direct hot pressing.
Implementation result: it is tested by the heating conduction to polymer composites prepared by comparative example 1, Ke Yifa
Existing composite material realizes the larger raising of thermal coefficient under less BNNS additive amount, and PVA/BNNS nanocomposite exists
When BNNS mass fraction 33wt%, thermal conductivity reaches 4.87W/ (mK).It can be seen that under identical BNNS additive amount, comparative example 1
In the thermal conductivity of composite materials for being filled with direct hot pressing filler and polymer beads mixture it is relatively low.
Comparative example 2
This comparative example is related to a kind of preparation method of thermally conductive PVA composite material, and the composite material is by 33wt% boron nitride
Nanometer sheet and 67wt%PVA composition.BNNS preparation process is same as Example 1, BNNS and PVA mixed-powder is dissolved in anhydrous
In ethyl alcohol, it is stirred in beaker at ambient temperature 1 hour.Then it by the solution left standstill 0.5h after stirring, is transferred to true
Normal-temperature vacuum deaeration obtains BNNS and PVA mixed solution in empty baking oven, removes solvent 12 hours in 50 DEG C of baking ovens after taking-up, will
BNNS/PVA compound after drying carries out hot pressing, is molded 0.5 hour under 95 DEG C and 20MPa pressure.It is dried after taking-up in vacuum
Case high temperature makes annealing treatment 12 hours, and the equally distributed PVA/BNNS nanocomposite of BNNS is made.
Implementation result: it is tested by the heating conduction to polymer composites prepared by comparative example 2, Ke Yifa
For existing PVA/BNNS nanocomposite in BNNS mass fraction 33wt%, thermal conductivity is 0.67W/ (mK).It can be seen that
Under identical BNNS additive amount, the thermal conductivity of composite materials with Arbitrary distribution BNNS structure in comparative example 2 is with respect to embodiment 1
It is much lower with comparative example 1.
In conclusion preparing polymer nanofiber by carrying out electrostatic spinning to polymer, then lead on this basis
Heat filling is covered on polymeric fiber surface and forms polymer/heat filling assorted fibre by the splash of too high voltages electrostatic.Most
Afterwards, polymer matrix composite is obtained by molding.In the composite material, contacts with each other and be orientated in sheet heat filling face
Arrangement greatly reduces thermal resistance between filler, and it is high that this special construction can be such that filler is formed in the composite material of its filling
Thermal conducting path is imitated, achievees the purpose that a small amount of heat filling of addition is remarkably improved Thermal Properties of Polymer-based Composites.From
And improve the heating conduction of composite material.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of high thermal conductivity anisotropic polymer based composites, which is characterized in that the composite material has by several multiple
The stepped construction that hot pressing is formed after condensating fiber layer stackup；The composite fibre layer is that heat filling is covered in polymer nanofiber
The composite fibre layer that surface is formed.
2. high thermal conductivity anisotropic polymer based composites as described in claim 1, which is characterized in that the polymer nano
Rice fiber is the polymer nanofiber prepared by electrostatic spinning；The heat filling includes sheet heat filling, bar shape
The mixed fillers of heat filling or both.
3. high thermal conductivity anisotropic polymer based composites as claimed in claim 2, which is characterized in that the sheet is thermally conductive
Filler is selected from boron nitride nanosheet, stannic oxide/graphene nano piece, graphene, metal nano plate, transition metal carbide, nitride
One of (MXene) or it is a variety of；The bar shape heat filling is selected from boron nitride nano-tube, carbon nanotube, nanometer silicon carbide
One of line, MXene nanotube, metal nanometer line are a variety of.
4. high thermal conductivity anisotropic polymer based composites as claimed in claim 1 or 2, which is characterized in that the polymerization
Object nanofiber is selected from polyvinyl alcohol, Kynoar, polymethyl methacrylate, polystyrene, chitosan, cellulose, gathers
One of acrylonitrile, polyimides, polyurethane are a variety of.
5. high thermal conductivity anisotropic polymer based composites as described in claim 1, which is characterized in that the composite fibre
The packing volume of heat filling is 0.1-50% in layer；Heat filling orientations in the composite material；Thermal conductivity has each
Anisotropy.
6. a kind of preparation method of high thermal conductivity anisotropic polymer based composites as described in claim 1, feature exist
In described method includes following steps:
A, it dissolves the polymer in progress electrostatic spinning in solvent A and prepares polymer nanofiber non-woven fabrics；
B, heat filling is dispersed in solvent B is attached on the polymer nanofiber non-woven fabrics by high-pressure electrostatic splash,
Obtain composite fibre layer；
C, the composite fibre layer is cut into pre-set dimension, polymer composite felt is made in stacked in multi-layers；
D, by the polymer composite felt carry out room temperature molding after, be higher than the melting point polymer at a temperature of it is hot-forming,
Annealing, obtains the high thermal conductivity anisotropic polymer based composites.
7. the preparation method of high thermal conductivity anisotropic polymer based composites as claimed in claim 6, which is characterized in that step
In rapid A, the solvent A include n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, acetone, deionized water, dimethyl sulfoxide and
One or more of ethyl acetate.
8. the preparation method of high thermal conductivity anisotropic polymer based composites as claimed in claim 6, which is characterized in that step
In rapid A, the electrostatic spinning time is 10-40 minutes, voltage 10-30kV, and temperature is 15-35 DEG C, and spinning solution flow is
0.1-2mL/h。
9. the preparation method of high thermal conductivity anisotropic polymer based composites as claimed in claim 6, which is characterized in that step
In rapid B, the solvent B includes n,N-Dimethylformamide, tetrahydrofuran, ethyl alcohol, isopropanol, acetone, deionized water, dimethyl
One or more of sulfoxide and ethyl acetate.
10. the preparation method of high thermal conductivity anisotropic polymer based composites as claimed in claim 6, which is characterized in that
In step B, the high-pressure electrostatic splash time is 10-120 minutes, voltage 10-40kV, 15-35 DEG C of temperature, and splash flow quantity is
0.1-2mL/h。
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