CN106366402A - Method for preparing high-heat-conductivity boron nitride reinforced polymer based composite material - Google Patents
Method for preparing high-heat-conductivity boron nitride reinforced polymer based composite material Download PDFInfo
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- CN106366402A CN106366402A CN201610747049.2A CN201610747049A CN106366402A CN 106366402 A CN106366402 A CN 106366402A CN 201610747049 A CN201610747049 A CN 201610747049A CN 106366402 A CN106366402 A CN 106366402A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/56—Compression moulding under special conditions, e.g. vacuum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/56—Compression moulding under special conditions, e.g. vacuum
- B29C2043/561—Compression moulding under special conditions, e.g. vacuum under vacuum conditions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a method for preparing a boron nitride reinforced polymer based composite material. The method comprises the steps of mixing laminar hexagonal boron nitride powder and polymer powder so as to obtain a mixture, then, vibrating the mixture on a rotary type vibrating table, and then, carrying out vacuum hot-pressing, thereby obtaining the boron nitride reinforced polymer based composite material. The composite material prepared by the method provided by the invention has the advantages that the heat conductivity is high, the mechanical properties are good, the preparation method is simple, the controllability is high, the forming time is short, and long-time curing is not required.
Description
Technical field
The invention belongs to engineering field of polymer composite material.In particular it relates to a kind of high heat conduction boron nitride strengthens polymerization
The preparation method of thing based composites.
Background technology
Fast-developing with electronic technology industry ground, the heat that unit area distributes gets more and more, and the miniaturization of equipment makes
Effectively area of dissipation reduces increasingly, and the performance that opposite heat tube manages material proposes more strict requirements.The opening of electronic package material
Send out with pyroconductivity as an important ring it is desirable to material has high thermal conductivity, low-expansion coefficient, lightweight, the feature of low cost.
On the one hand polymer-based composite has the advantages that light weight, inexpensive, easy to process at this.But due to macromolecule originally
The thermal conductivity of body is low, leads to the radiating effect poor performance of product, significantly limit the use of product.With polyethylene (pe) it is
Example, it is a kind of excellent performance and widely used engineering plastics, has the advantages that above-mentioned light weight, inexpensive, easy to process, but
Its thermal conductivity is very low, typically only 0.42w/m k about.
Studies have reported that boron nitride powder as packing material.Using after being mixed under organic solution in air
In hot-forming technique prepared hexagonal boron nitride/Kapton, boron nitride volume fraction be 60% when, obtain
To heat conductivity value be up to 7w/m k.Obtained on etch substrate by adopting semar technique after being mixed in organic solution
Arrive polyvinyl alcohol/boron nitride nm composite material, the thermal conductivity value finally obtaining when boron nitride volume fraction is 50% is
30w/m·k.By the fiber with the degree of orientation as the selection of reinforcing agent, then carry out hot pressing, Ke Yiti with macromolecule matrix
The degree of orientation of high composite and intensity.In addition also by the method for twin-roll mixing, some mechanical mixture of screw mixes, in mould
Prepare the composite of anti-corrosion and high strength in pressure crosslinking, but the capacity of heat transmission is not high.What these preparation methoies obtained answers
Condensation material all has powder body skewness, and production cost is high, complicated process of preparation, or can inevitably introduce variousization
The undesirable element that one or more of compound ion etc..
Therefore, this area is badly in need of finding a kind of simple and effective preparation high heat conductance boron nitride powder enhancing polymer matrix
The method of insulating heat-conductive composite.
Content of the invention
It is an object of the invention to provide the boron nitride that a kind of interface bond strength is suitable, hot property is excellent strengthens polymer
The preparation method of based composites, solves that existing process is complicated, cycle time length and also the heat conductivity that obtains is not high
The problems such as, and be intended to widen the range of application of composite, improve heat and the mechanical property of material, solve existing boron nitride/
In polymer composites, aligning property of boron nitride is poor, the problems such as polymer uniform bad dispersibility,
A first aspect of the present invention, provides a kind of boron nitride to strengthen the preparation method of polymer matrix composite, including with
Lower step:
A) in the presence of double center mixing dispersion machines, mixing stratiform hexagonal boron nitride powder and polymer powder are mixed
Compound is so that polymer powder sticks on boron nitride powder；
B) mixture that vibrating step a) obtains on swinging vibration table is so that sheet boron nitride powder realizes lamella
The preferential arrangement in direction；
C) mixture that vacuum hotpressing is vibrated through step b), obtains described composite.
In another preference, the planar dimension of layered hexagonal boron nitride powder is 10～500 microns, and thickness is
0.1～10 micron.
In another preference, the planar dimension of layered hexagonal boron nitride powder is 50～400 microns, preferably
100～300 microns.
In another preference, the thickness of layered hexagonal boron nitride powder is 0.5～8 μm, preferably 1～5 μm.
In another preference, described polymer is polyethylene, polypropylene, nylon, polyimides or polyphenylene sulfide.
In another preference, described polymer powder is graininess.
In another preference, planar dimension≤300 micron of described polymer powder, preferably≤100 microns, more preferably
For 1～75 micron.
In the present invention, in the presence of the rotation mixing of step a) Zhong Shuan center mixing dispersion machine, mixed described polymerization
Powder is evenly distributed on described six side's layered nitride boron powder surfaces.
In another preference, the volume of layered hexagonal boron nitride powder account for layered hexagonal boron nitride powder and
The 30～60% of the cumulative volume of the mixture of polymer powder, preferably 40～60%, more preferably 50～60%.
In another preference, the mass ratio of layered hexagonal boron nitride powder and described polymer is 1:1～5:1.
In another preference, the rotating speed of described pair of center mixing dispersion machine is 1000～2000rpm.
In another preference, the described rotating speed in double center mixing dispersion machines is 1000～1500rpm, more preferably 1100
～1300rpm.
In another preference, described step a) in the presence of double center mixing dispersion machines, time of mixing is 30～
150 seconds, preferably 30～120 seconds, more preferably 30～90 seconds, even 30～60 seconds.
In another preference, in described step b), frequency of vibration is 40～200 revs/min, preferably 60～190 turns/
Minute, more preferably 60～180 revs/min.
In another preference, in described step b), time of vibration is 5～100min, preferably 10～60min.
In another preference, described mixed powder is carried out on swinging vibration table.By this type games, provide nitridation
The concordance of boron arrangement.
In another preference, described vacuum hotpressing is under vacuum, and the mixture through step b) oscillation crosswise is warmed up to
100～400 DEG C are pressurizeed, and pressure is 10～80mpa, and the dwell time is 10～60min.
In another preference, described warming temperature is pressurizeed for 100～200 DEG C.
In another preference, the vacuum≤250pa of described vacuum, preferably≤200pa.
In another preference, the step that composite that described preparation method also includes obtaining vacuum hotpressing is cooled down
Suddenly.
A second aspect of the present invention, provides a kind of boron nitride to strengthen polymer matrix composite, by the stratiform aligning
Hexagonal boron nitride powder and polymer powder hot pressed sintering form, and have following one or more feature:
1) density of described composite is 1～2g/cm3；
2) described composite is 20～40w/m k along the thermal conductivity perpendicular to hot pressing direction；
3) described composite is 1.7～18mm along the thermal diffusion coefficient perpendicular to hot pressing direction2/s；
4) described composite is 1～6mm along the thermal diffusion coefficient parallel to hot pressing direction2/s；
5) described composite is 8～50mpa along the bending strength parallel to hot pressing direction；
6) in described composite, the mass ratio of boron nitride and polymer is 1:1-5:1.
In the present invention, described hot pressing direction refers to the z direction of composite, that is, perpendicular to the side of powder body planar arrangement
To.
In another preference, thermal conductivity >=20w/m k perpendicular to hot pressing direction for the described composite edge, preferably
>=30w/m k, more preferably >=37w/m k.
In another preference, the bending strength of described composite is 10～40mpa or 10～35mpa
A third aspect of the present invention, provides the boron nitride described in second aspect to strengthen the purposes of polymer matrix composite,
As electronic package material or heat sink material.
A fourth aspect of the present invention, provides a kind of product, comprises composite described in second aspect or by second aspect
Described composite is made.
The technical method that the present invention adopts is that boron nitride powder is uniform through double center mixing dispersion machines with polymer powder
After mixing, it is put into the arrangement of vibration control high heat conduction lamella boron nitride powder on mechanical vibration generator system, then enter through vacuum hotpressing stove
Row Thermocompressed sintering and forming, obtains highly directional boron nitride and strengthens polymer matrix composite.The boron nitride of high heat conduction strengthens polymerization
In thing based composites, the highly directional arrangement of lamella boron nitride powder is to vibrate by swinging to be formed, and polymer is in composite wood
Being uniformly distributed in material is to rotate mixing procedure by double center mixing dispersion machines to control.
Strengthen polymer matrix composite thermal deformation by the use of the boron nitride that boron nitride powder prepares as packing material
Temperature is high, molding shrinkage is low, can be used for making the aspects such as fine heat-resisting performance, the solar water heater of excellent thermal conductivity tool
There is very big prospect.And these performances of composite can also be applied in the processing heat consumption assembly of microelectronics industry.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and having in below (eg embodiment)
Can be combined with each other between each technical characteristic of body description, thus constituting new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description
Fig. 1 is scanning electron micrograph, and wherein a is polyethylene powder body；B is stratiform hexagonal boron nitride powder.
The scanning electron microscopy of the boron nitride enhanced polyethylene composite that Fig. 2 is 50% for boron nitride volume fraction shines
Piece, wherein a are the scanning electron micrograph of the section arrangement orientation parallel to hot pressing direction；B is perpendicular to hot pressing direction
The scanning electron micrograph of section arrangement orientation.
Fig. 3 is different volumes fraction boron nitride to boron nitride enhanced polyethylene heat conductivity (thermal
Conductivity, tc) influence curve.It can be seen that with the rising of boron nitride volume fraction, this composite
Thermal conductivity also constantly rise, when volume fraction be 60% when, x-y direction thermal conductivity is up to 37w/m k.
Fig. 4 is the influence curve to boron nitride enhanced polyethylene composite anti-bending strength for the different volumes fraction boron nitride.
It can be seen that with the rising of volume fraction, the bending strength of this composite constantly declines, even so, working as nitrogen
When changing boron volume fraction for 60%, bending strength also can reach 11.6mpa.
The scanning electron of boron nitride/composite polyethylene material that Fig. 5 is 50% for boron nitride volume fraction in comparative example 2 shines
Piece, wherein a are the scanning electron photo of the section arrangement parallel to hot pressing direction, and b is the section arrangement perpendicular to hot pressing direction
Scanning electron photo.
Specific embodiment
The present inventor, through extensively and in depth studying, finds to fill out as heat conduction using high heat conduction sheet boron nitride powder
Fill reinforcing material, after uniformly mixing through double center mixing dispersion machines with polymer powder, through swinging vibration control high heat conduction piece
The arrangement of layer boron nitride powder, then carries out Thermocompressed sintering and forming through vacuum hotpressing, obtains highly directional boron nitride and strengthens polymerization
Thing based composites.Mechanical mixture improves powder body dispersing uniformity in composite, and swinging oscillation crosswise improves this and is combined
The conforming arrangement of lamella boron nitride powder in material, vacuum hotpressing improves the relative density of composite.Additionally, the present invention
Composite material interface bond strength suitable, there is preferably bending strength, hot property is excellent, heat conductivity is good, wear-resisting it is easy to plus
Work becomes complicated shape, and preparation method is simple, easy to control.On this basis, the present inventor completes the present invention.
Boron nitride powder
As used herein, the boron nitride powder that the present invention adopts is to belong to micrometer laminar (also referred to as sheet) six side nitridation
Boron powder body.
A size of 50 microns～400 microns of stratiform hexagonal boron nitride powder preferred planar；Preferably 10 microns～300 is micro-
Rice.
In the present invention, described planar dimension refers to powder body and naturally tiles open the average diameter size in back plane direction.
The thickness of stratiform hexagonal boron nitride powder is 0.1-10 micron, preferably 0.1-8 micron or 0.1-5 micron.
Polymer powder
The polymer powder of the present invention has no particular limits, and the preparation method using the present invention can be with boron nitride hot pressing
Polymer be suitable for the present invention.
For example, described polymer is polyethylene, polypropylene, nylon, polyimides, polyphenylene sulfide.Another preferred
In example, described polymer is polyethylene.Described polyethylene include ldpe (Low Density Polyethylene or claim polyethylene from high pressure process),
Lldpe (linear low density of polyethylene), mdpe (medium density polyethylene), hdpe (high density polyethylene (HDPE)), uhmwpe (supra polymer
Weight northylen) and various ethylene copolymer.
In the present invention, polymer powder is granulated polymer powder.In another preference, the grain of polymer powder
Footpath is no more than 300 microns.It is preferred that the particle diameter of described polymer powder is no more than 100 microns, more preferably micro- for 1～75
Rice.
Boron nitride strengthens polymer matrix composite and preparation method thereof
The boron nitride of the present invention strengthens polymer matrix composite and includes boron nitride and two kinds of ingredients of polymer, passes through
The stratiform aligning hexagonal boron nitride powder and polymer powder hot pressed sintering are obtained the composite of the present invention.
The present invention is used as conductive filler reinforcing material by adding high heat conduction big particle diameter lamella boron nitride powder material, obtains
Composite have in terms of hot property and be significantly increased.
In another preference, boron nitride quality accounts for the 40%-95% of composite gross mass, preferably 40-90%, more
Good for 50-85%.
This composite has that intensity is suitable, wear-resisting, the excellent performance such as thermal diffusivity is good.In the neck such as Electronic Packaging, radiating
Domain has a wide range of applications.
The preparation method of the composite of the present invention, comprises the following steps:
A) in the presence of double center mixing dispersion machines, mixing stratiform hexagonal boron nitride powder and polymer powder so that
Described polymer powder uniform adhesion obtains mixture on described boron nitride powder surface；
B) mixture that vibrating step a) obtains on swinging vibration table is so that sheet boron nitride powder realizes lamella
The preferential arrangement in direction；
C) mixture through step b) oscillation crosswise for the vacuum hotpressing, obtains described composite.
In another preference, described polymer is polyethylene, polypropylene, nylon, polyimides, polyphenylene sulfide.
In another preference, described be blended in double center mixing dispersion machines in the presence of carry out.Mixing rate is 1000
～2000 revs/min, incorporation time is 30～120s.In another preference, mixing rate is 1200 revs/min, during mixing
Between be 30～60s.
In another preference, described mixed powder is carried out on swinging vibration table, provides lamella boron nitride powder to arrange
The concordance of row.The rotary speed of described oscillation crosswise, also referred to as frequency of vibration, are 40～200 revs/min.Preferably 60～190
Rev/min, more preferably 60～180 revs/min.In another preference, the time of vibration of described oscillation crosswise is 5～100 points
Clock, preferably 5～80 or 10～60 minutes.
In another preference, described vacuum hotpressing is under vacuum, and the mixture through step b) oscillation crosswise is warmed up to
100～400 DEG C are pressurizeed, and pressure is 10～80mpa (preferably 10～50mpa, more preferably 10～30mpa), the dwell time
For 10～60min (preferably 20～60min, more preferably 20～30min).In another preference, the vacuum of described vacuum
≤200pa.
In another preference, described prepares boron nitride/composite polyethylene material warming temperature for 100～200 DEG C (relatively
Good is 130～180 degrees Celsius, more preferably 140～160 degrees Celsius).
In another preference, described prepares boron nitride/PP composite material warming temperature for 100～200 DEG C (relatively
Good is 150～180 degrees Celsius, more preferably 160～180 degrees Celsius).
In another preference, described prepares boron nitride/nylon composite materials warming temperature for 200～300 DEG C (preferably
For 250～280 degrees Celsius, more preferably 255～270 degrees Celsius).
In another preference, described boron nitride/composite polyimide material warming temperature of preparing is 300～400 DEG C
(preferably 350～380 degrees Celsius, more preferably 350～370 degrees Celsius).
In another preference, described boron nitride/polyphenyl thioether composite material warming temperature of preparing is 200～300 DEG C
(preferably 250～300 degrees Celsius, more preferably 290～300 degrees Celsius).
In another preference, the preparation method of the present invention comprises the following steps:
A () weighs the boron nitride that mass ratio is 1:1～5:1 and polyethylene powder body, boron nitride powder and polyethylene powder body exist
Carry out mixed at high speed uniformly so that polyethylene powder body uniform adhesion is on boron nitride micro-powder surface in double center mixing dispersion machines
Improve polyethylene distributing homogeneity in the composite；
Preferably, calculate by this mixture cumulative volume, the volume of layered hexagonal boron nitride powder accounts for layered six
The 30～60% of the cumulative volume of the mixture of square boron nitride powder and polymer powder, preferably 40～60%, more preferably 50～
60%.
B () puts into mixture in mould, be subsequently placed on swinging vibration table and carry out powder body vibration arrangement, improve nitridation
Boron micron sheet direction arrangement concordance；The time range of vibration is between 10～60min；
Vibration rotary speed and time of vibration according to powder body and its filling volume depending on, preferably vibration rotary speed be 40～
200 (revs/min), time of vibration is 10～60min；
C mould is put in the middle of vacuum hotpressing furnace apparatus by (), sample is warmed up to 100～200 by hot pressing under vacuum atmosphere
During temperature range, pressurizeed, be then incubated 10～60min, be finally cooled to demoulding sampling after room temperature, obtain boron nitride and strengthen
Composite polyethylene material.
Preferably, described true temp is 130～180 DEG C, preferably 140～160 DEG C；
The dwell time of described vacuum hotpressing is 10～60min；Preferably 20～30min；
The pressure of described vacuum hotpressing is 10～50mpa；Preferably 10～30mpa.
Sheet hexagonal boron nitride has its special structure, has high heat conduction in boron nitride lamella direction (x-y plane),
There is certain particle diameter difference, polymer powder such as polyethylene powder between lamella boron nitride and polymer powder such as polyethylene powder body
Body also has certain viscosity, is coated on greatly small particle polymer powder such as polyethylene powder body by physics mode high speed batch mixing
The surface of particle splat boron nitride, thus improve polymer powder such as polyethylene powder body to strengthen polymer matrix composite wood in boron nitride
Even distribution in material；By controlling mixing velocity and time, that is, ensure mixing uniformity, ensure that boron nitride powder will not again
Because of too fast rotating speed rupture.
The present invention passes through the method using vacuum hot pressing formation, with sheet boron nitride powder as particle filled composite, and poly-
Compound powder body such as polyethylene powder body is combined, on the one hand due to the sliding of hexagonal boron nitride piece interlayer and this temperature in hot pressing
The melting deformation of the lower polymer powder such as polyethylene powder body of degree makes the mechanical snap of interface cohesion between boron nitride and polymer
Effect is more obvious；On the other hand due to the big particle diameter of lamella boron nitride powder, be conducive to the preferentially fixed of sheet boron nitride powder
To arrangement, in the preparation process therefore strengthening polymer matrix composite in boron nitride, primary concern is that the particle diameter chi of boron nitride
The very little preferential arrangement problem with boron nitride powder.Make full use of the high-termal conductivity in boron nitride lamella direction (x-y plane) so that piece
Layer boron nitride powder obtains oriented preferentially in composite preparation process.So preparation high heat conduction boron nitride is increased
Strength polymer composite is just particularly important.The present inventor, through extensively and profoundly studying, finds to vibrate by swinging
Arrangement can effectively improve the oriented alignment of sheet boron nitride.
Additionally, being conducive under vacuum fully connecing between hexagonal boron nitride and polymer powder such as polyethylene powder body
Touch, reduce the inside and form pore, advantageously form the high boron nitride of relative density and strengthen polymer matrix composite.
Boron nitride powder strengthens polymer such as composite polyethylene material heat as the boron nitride that packing material prepares and becomes
Shape temperature is high, molding shrinkage is low, can be used for making the excellent heat pipe of fine heat-resisting performance, resistance to chemical corrosion, heat conduction
The aspects such as the solar water heater of excellent performance have very big prospect.And these performances of composite can also be applied to
In the processing heat consumption assembly of microelectronics industry.
The preparation method of composite of the present invention, improves powder using double center mixing dispersion machine plant equipment mixed powders
Uniformity between body；Improve the concordance arrangement of boron nitride powder using the use of swinging vibration table；Under vacuum condition
Hot-forming, improve the relative density of composite.Boron nitride strengthen polymer such as composite polyethylene material, edge perpendicular to
Hot pressing direction (i.e. the x-y direction of sample) highest heat conductivity (total heat-transfer capability) reaches 37w/m k, have certain intensity and
It is easily processed into complicated shape, and solves that high-molecular polythene material thermal conductivity is low, molding cycle is long, need prolonged curing asking
Topic.
The features described above that the present invention mentions, or the feature that embodiment is mentioned can be in any combination.Disclosed in this case description
All features can be used in combination with any combinations thing form, each feature disclosed in description, can any provide identical, equal
Deng or similar purpose alternative characteristics replace.Therefore removing has special instruction, and disclosed feature is only impartial or similar features
General example.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part or according to the condition proposed by manufacturer.Unless otherwise defined, literary composition used in all specialty with scientific words with this
Same meaning familiar to field skilled person institute.Additionally, any method similar or impartial to described content and material all may be used
It is applied in the inventive method.Preferable implementation described in literary composition is only presented a demonstration with material and is used.
Universal method
(1) thermal conductivity
Test by gb/t 14452-93 standard.
(2) bending strength and bending moduluses
Test by gb/t 14452-93 standard.
Specimen types are specimen size (mm): (50 ± 2) (length) × (10 ± 0.2) × (10 ± 0.2)
Embodiment 1 boron nitride strengthens the preparation of polymer matrix composite 1
A: measure following components by volumes below proportioning:
Boron nitride powder 40vol%
Polyethylene powder body 60vol%
B: stir 30s by putting in double center mixing dispersion machines after described powder body mixing, revolution controls in 1200rpm.
The mixture obtaining is put in accurate compacting tool set, on swinging vibration table uniformly after vibration 30min, the turning of oscillation crosswise
Speed is 162rpm.
C: by the sample in step b with die assembly good after, put in vacuum hotpressing stove, be evacuated to vacuum extremely
Below 200pa, heating rate is warming up to 150 DEG C for 8 DEG C/min, carries out hot pressing, and pressure size is 20mpa, pressurize 20min, so
After cool to room temperature with the furnace.
The sample that high-temperature process is crossed is cooled to after room temperature and takes out demoulding acquisition boron nitride enhancing polymer matrix composite.
The thermal conductivity (with being defined of highest aspect) of determination sample is as 26.32w/m.k.Bending strength is 26.12mpa.Close
Spend for 1.475g/cm3, vertical direction thermal diffusion coefficient is 12.220mm2/ s, parallel direction thermal diffusion coefficient is 2.386mm2/s.
In the present embodiment, described polyethylene powder body is uhmwpe ultra-high molecular weight polyethylene, and grain diameter size exists
50～75 microns, boron nitride powder is sheet six side's powder body, and powder body planar dimension size is 10-500 micron, and thickness is in 0.1-
10 microns.The scanning electron micrograph of polyethylene powder body and sheet hexagonal boron nitride powder is as shown in Figure 1.
Embodiment 2 boron nitride strengthens the preparation of polymer matrix composite 2
With embodiment 1, difference is: boron nitride powder volume fraction is 30vol.%.
As 8.78w/m.k, bending strength is 32mpa to the thermal conductivity (with being defined of highest aspect) of determination sample.
Density is 1.345g/cm3, vertical direction thermal diffusion coefficient is 4.049mm2/ s, parallel direction thermal diffusion coefficient is
1.707mm2/s.
Embodiment 3 boron nitride strengthens the preparation of polymer matrix composite 3
With embodiment 1, difference is: boron nitride powder volume fraction is 50vol.%.
Fig. 2 be boron nitride/composite polyethylene material scanning electron photo it can be seen that polyethylene is uniformly dispersed, big particle diameter
Boron nitride powder in the composite be easier each other carrying out put up a bridge connect, x-y and z direction keep preferred orientation.
After swinging vibration table, boron nitride is preferentially arranged effectively, specifically, refers to most of sheet boron nitride powder and totally becomes
Want, in towards the tiling of x-y direction, between lamella, to be interconnected to form heat transfer path.
As 31.25w/m.k, bending strength is 18mpa to the thermal conductivity (with being defined of highest aspect) of determination sample.
Density is 1.603g/cm3, vertical direction thermal diffusion coefficient is 14.605mm2/ s, parallel direction thermal diffusion coefficient is
5.97mm2/s.
Embodiment 4 boron nitride strengthens the preparation of polymer matrix composite 4
With embodiment 1, difference is: boron nitride powder volume fraction is 60vol.%.
As 37.31w/m.k, bending strength is 12mpa to the thermal conductivity (with being defined of highest aspect) of determination sample.
Density is 1.732g/cm3, vertical direction thermal diffusion coefficient is 17.548mm2/ s, parallel direction thermal diffusion coefficient is
5.126mm2/s.
Fig. 3 and Fig. 4 different volumes fraction boron nitride is to boron nitride enhanced polyethylene heat conductivity (thermal
Conductivity, tc) and anti-bending strength influence curve.It can be seen that with the rising of boron nitride volume fraction,
The thermal conductivity of this composite also constantly rises, and when volume fraction is 60%, x-y direction thermal conductivity is up to 37w/m k.This
The outer rising with volume fraction, the bending strength of this composite constantly declines, even so, when boron nitride volume fraction is
When 60%, bending strength also can reach 11.6mpa.
Embodiment 5 boron nitride strengthens the preparation of polymer matrix composite
A: measure following components by volumes below proportioning:
Boron nitride powder 60vol%
Nylon -66 powder body 40vol%
B: stir 30s by putting in double center mixing dispersion machines after described powder body mixing, revolution controls in 1300rpm.
The mixture obtaining is put in accurate compacting tool set, on swinging vibration table uniformly after vibration 30min, the turning of oscillation crosswise
Speed is 170rpm.
C: by the sample in step b with die assembly good after, put in vacuum hotpressing stove, be evacuated to vacuum extremely
Below 200pa, heating rate is warming up to 268 DEG C for 8 DEG C/min, carries out hot pressing, and pressure size is 20mpa, pressurize 20min, so
After cool to room temperature with the furnace.
The sample that high-temperature process is crossed is cooled to after room temperature and takes out demoulding acquisition boron nitride enhancing polymer matrix composite.
The thermal conductivity (with being defined of highest aspect) of determination sample is as 25.4536w/m.k.Bending strength is 21.3mpa.Close
Spend for 1.969g/cm3, vertical direction thermal diffusion coefficient is 11.633mm2/ s, parallel direction thermal diffusion coefficient is 2.292mm2/s.
In the present embodiment, described polymer powder be nylon -66 powder body, grain diameter size at 50～75 microns,
Boron nitride powder is sheet six side's powder body, and powder body planar dimension size is 10-500 micron, and thickness is in 0.1-10 micron.
Embodiment 6 boron nitride strengthens the preparation of polymer matrix composite
A: measure following components by volumes below proportioning:
Boron nitride powder 60vol%
Polyimides powder body 40vol%
B: stir 30s by putting in double center mixing dispersion machines after described powder body mixing, revolution controls in 1300rpm.
The mixture obtaining is put in accurate compacting tool set, on swinging vibration table uniformly after vibration 30min, the turning of oscillation crosswise
Speed is 170rpm.
C: by the sample in step b with die assembly good after, put in vacuum hotpressing stove, be evacuated to vacuum extremely
Below 200pa, heating rate is warming up to 360 DEG C for 8 DEG C/min, carries out hot pressing, and pressure size is 20mpa, pressurize 20min, so
After cool to room temperature with the furnace.
The sample that high-temperature process is crossed is cooled to after room temperature and takes out demoulding acquisition boron nitride enhancing polymer matrix composite.
The thermal conductivity (with being defined of highest aspect) of determination sample is as 22.745w/m.k.Bending strength is 20.2mpa.Close
Spend for 1.977g/cm3, vertical direction thermal diffusion coefficient is 11.932mm2/ s, parallel direction thermal diffusion coefficient is 2.386mm2/s.
In the present embodiment, described polymer powder be polyimides powder body, grain diameter size at 50～75 microns,
Boron nitride powder is sheet six side's powder body, and powder body planar dimension size is 10-500 micron, and thickness is in 0.1-10 micron.
Embodiment 7 boron nitride strengthens the preparation of polymer matrix composite
A: measure following components by volumes below proportioning:
Boron nitride powder 60vol%
Polyphenylene sulfide powder body 40vol%
B: stir 30s by putting in double center mixing dispersion machines after described powder body mixing, revolution controls in 1250rpm.
The mixture obtaining is put in accurate compacting tool set, on swinging vibration table uniformly after vibration 30min, the turning of oscillation crosswise
Speed is 165rpm.
C: by the sample in step b with die assembly good after, put in vacuum hotpressing stove, be evacuated to vacuum extremely
Below 200pa, heating rate is warming up to 295 DEG C for 8 DEG C/min, carries out hot pressing, and pressure size is 20mpa, pressurize 20min, so
After cool to room temperature with the furnace.
The sample that high-temperature process is crossed is cooled to after room temperature and takes out demoulding acquisition boron nitride enhancing polymer matrix composite.
The thermal conductivity (with being defined of highest aspect) of determination sample is as 12.16w/m.k.Bending strength is 26.12mpa.Close
Spend for 1.993g/cm3, vertical direction thermal diffusion coefficient is 8.311mm2/ s, parallel direction thermal diffusion coefficient is 2.386mm2/s.
In the present embodiment, described polymer powder be polyphenylene sulfide powder body, grain diameter size at 50～75 microns,
Boron nitride powder is sheet six side's powder body, and powder body planar dimension size is 10-500 micron, and thickness is in 0.1-10 micron.
Embodiment 8 boron nitride strengthens the preparation of polymer matrix composite
A: measure following components by volumes below proportioning:
Boron nitride powder 60vol%
Polypropylene powder body 40vol%
B: stir 30s by putting in double center mixing dispersion machines after described powder body mixing, revolution controls in 1300rpm.
The mixture obtaining is put in accurate compacting tool set, on swinging vibration table uniformly after vibration 35min, the turning of oscillation crosswise
Speed is 164rpm.
C: by the sample in step b with die assembly good after, put in vacuum hotpressing stove, be evacuated to vacuum extremely
Below 200pa, heating rate is warming up to 165 DEG C for 9 DEG C/min, carries out hot pressing, and pressure size is 20mpa, pressurize 20min, so
After cool to room temperature with the furnace.
The sample that high-temperature process is crossed is cooled to after room temperature and takes out demoulding acquisition boron nitride enhancing polymer matrix composite.
The thermal conductivity (with being defined of highest aspect) of determination sample is as 22.32w/m.k.Bending strength is 22.3mpa.Density
For 2.0542g/cm3, vertical direction thermal diffusion coefficient is 12.341mm2/ s, parallel direction thermal diffusion coefficient is 2.253mm2/s.
In the present embodiment, described polymer powder be polypropylene powder body, grain diameter size at 50～75 microns, nitrogen
Change boron powder body is sheet six side's powder body, and powder body planar dimension size is 10-500 micron, and thickness is in 0.1-10 micron.
The preparation of the pure composite polyethylene material of comparative example 1
Substantially with embodiment 1, difference is step: polyethylene powder body volume fraction is 100vol.%.
As 0.42w/m.k, bending strength is 14mpa to the thermal conductivity (with being defined of highest aspect) of determination sample.
Comparative example 2 boron nitride strengthens the preparation of polymer matrix composite
A: measure following components by volumes below proportioning:
Boron nitride powder 50vol.%
Polyethylene powder body 50vol.%
B: stir 30s by putting in double center mixing dispersion machines after described powder body mixing, revolution controls in 1200rpm.
The mixture obtaining is put in accurate compacting tool set, on a vibration table uniformly after vibration 30min, the rotary speed of oscillation crosswise is
160rpm.
C: by the sample in step b with die assembly good after, put in vacuum hotpressing stove, be evacuated to vacuum extremely
Below 200pa, heating rate is warming up to 152 DEG C for 8 DEG C/min, carries out hot pressing, and pressure size is 20mpa, pressurize 20min, so
After cool to room temperature with the furnace.The sample that high-temperature process is crossed takes out the demoulding and obtains boron nitride enhancing polymer matrix complex.Measure
As 9.399w/m.k, bending strength is 8.53mpa to the thermal conductivity (with being defined of highest aspect) of sample.
In this example, described polyvinyl resin is uhmwpe ultra-high molecular weight polyethylene, grain diameter size 150～
200 microns, this boron nitride powder is the powder body of sheet, and, in 10-50 micron, thickness is in 0.1-10 micron for powder body size.
Fig. 5 is boron nitride/composite polyethylene material scanning electron photo.As can be seen that the boron nitride powder of small particle with
Preferably can preferentially arrange after polyethylene mixing, but it is inconsistent to there is a part of hexagonal boron nitride powder arrangement.
As can be seen that the boron nitride obtaining in the present invention strengthens polymer matrix composite wood from embodiment 1-8 and comparative example
Material has good mechanical performance and processing characteristics, also possesses good hot property, when the volume ratio of boron nitride and polyethylene is
When 1:1, various Performance comparision are comprehensive.
The all documents referring in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, those skilled in the art can
To make various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. a kind of boron nitride strengthen polymer matrix composite preparation method it is characterised in that described preparation method include with
Lower step:
A) in the presence of double center mixing dispersion machines, mixing stratiform hexagonal boron nitride powder and polymer powder are mixed
Thing；
B) mixture that vibrating step a) obtains on swinging vibration table；
C) mixture that vacuum hotpressing is vibrated through step b), obtains described composite.
2. preparation method as claimed in claim 1 is it is characterised in that the planar dimension of layered hexagonal boron nitride powder is
10～500 microns, thickness is 0.1～10 micron.
3. preparation method as claimed in claim 1 it is characterised in that described polymer be polyethylene, polypropylene, nylon, poly-
Acid imide or polyphenylene sulfide.
4. preparation method as claimed in claim 1 is it is characterised in that planar dimension≤300 micron of described polymer powder.
5. preparation method as claimed in claim 1 it is characterised in that the volume of layered hexagonal boron nitride powder account for described
The 30～60% of the cumulative volume of the mixture of stratiform hexagonal boron nitride powder and polymer powder.
6. preparation method as claimed in claim 1 is it is characterised in that layered hexagonal boron nitride powder and described polymer
Mass ratio be 1:1～5:1.
7. preparation method as claimed in claim 1 it is characterised in that described pair of center mixing dispersion machine rotating speed be 1000～
2000rpm.
8. preparation method as claimed in claim 1 is it is characterised in that the time mixing in described step a) is 30～150 seconds.
9. preparation method as claimed in claim 1 it is characterised in that in described step b) frequency of vibration be 40～200 revs/min
Clock；And/or
In described step b), time of vibration is 5～100min.
10. preparation method as claimed in claim 1, it is characterised in that described vacuum hotpressing is under vacuum, will be shaken through step b)
Dynamic mixture is warmed up to 100～400 DEG C and is pressurizeed, and pressure is 10～80mpa, and the dwell time is 10～60min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107618123A (en) * | 2017-09-30 | 2018-01-23 | 华中科技大学 | A kind of preparation method and product of polyethylene crystalline flake graphite composite |
| CN109880129A (en) * | 2019-02-22 | 2019-06-14 | 黑龙江省科学院石油化学研究院 | The polyimide precursor gel and its preparation method and application of insulating heat-conductive and heat resistant poly acid imide lightweight labyrinth can be prepared |
| CN110452443A (en) * | 2019-08-27 | 2019-11-15 | 国网四川省电力公司电力科学研究院 | A kind of Cross-linked Polyethylene Composites and preparation method, application |
| CN111303521A (en) * | 2020-03-23 | 2020-06-19 | 华东交通大学 | Flexible high-thermal-conductivity polymer nano composite film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435971A (en) * | 2013-07-19 | 2013-12-11 | 天津学子电力设备科技有限公司 | Preparation method of high-heat-conduction epoxy resin for IGBT insulation substrate |
| CN103467919A (en) * | 2013-09-10 | 2013-12-25 | 天津道俊包装制品销售有限公司 | Thermally conductive and insulating polymer prepared from nano-boron nitride |
| CN105308111A (en) * | 2013-06-19 | 2016-02-03 | 3M创新有限公司 | Component parts produced by thermoplastic processing of polymer/boron nitride compounds, polymer/boron nitride compounds for producing such component parts and use thereof |
| CN105733065A (en) * | 2014-12-06 | 2016-07-06 | 哈尔滨理工大学 | Anisotropic heat-conducting polymer composite and preparation method thereof |
-
2016
- 2016-08-26 CN CN201610747049.2A patent/CN106366402B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105308111A (en) * | 2013-06-19 | 2016-02-03 | 3M创新有限公司 | Component parts produced by thermoplastic processing of polymer/boron nitride compounds, polymer/boron nitride compounds for producing such component parts and use thereof |
| CN103435971A (en) * | 2013-07-19 | 2013-12-11 | 天津学子电力设备科技有限公司 | Preparation method of high-heat-conduction epoxy resin for IGBT insulation substrate |
| CN103467919A (en) * | 2013-09-10 | 2013-12-25 | 天津道俊包装制品销售有限公司 | Thermally conductive and insulating polymer prepared from nano-boron nitride |
| CN105733065A (en) * | 2014-12-06 | 2016-07-06 | 哈尔滨理工大学 | Anisotropic heat-conducting polymer composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PENG-GANG REN ET. AL: "Synergistic effect of BN and MWCNT hybrid fillers on thermal conductivity and thermal stability of ultra-high-molecular-weight polyethylene composites with a segregated structure", 《JOURNAL OF POLYMER RESEARCH》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107618123A (en) * | 2017-09-30 | 2018-01-23 | 华中科技大学 | A kind of preparation method and product of polyethylene crystalline flake graphite composite |
| CN109880129A (en) * | 2019-02-22 | 2019-06-14 | 黑龙江省科学院石油化学研究院 | The polyimide precursor gel and its preparation method and application of insulating heat-conductive and heat resistant poly acid imide lightweight labyrinth can be prepared |
| CN109880129B (en) * | 2019-02-22 | 2021-10-08 | 黑龙江省科学院石油化学研究院 | Polyimide precursor gel capable of preparing insulating, heat-conducting and heat-resistant polyimide light complex structure and application |
| CN110452443A (en) * | 2019-08-27 | 2019-11-15 | 国网四川省电力公司电力科学研究院 | A kind of Cross-linked Polyethylene Composites and preparation method, application |
| CN111303521A (en) * | 2020-03-23 | 2020-06-19 | 华东交通大学 | Flexible high-thermal-conductivity polymer nano composite film and preparation method thereof |
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