CN109111682A - A kind of preparation process of polyether-ether-ketone base modified nano composite material - Google Patents
A kind of preparation process of polyether-ether-ketone base modified nano composite material Download PDFInfo
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Abstract
The present invention discloses a kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps: (1) graphene and carbon nano tube dispersion liquid preparation；(2) nano-silicon nitride and the preparation of nanometer Al-Doped ZnO dispersion liquid；(3) preparation of polyether-ether-ketone mixture；(4) preparation of polyether-ether-ketone base modified nano composite material: the nano-filled material of the method for the present invention passes through high speed dispersion after ultrasonic grinding, again with polymer spray adhesion, then melting mixing, last extruding pelletization, obtain novel self-lubricating thermal conductivity Wear-resistant, high-temperature resistant polyether-ether-ketone base modified nano composite material, the crystallization temperature of the composite material improves 12 DEG C than pure polyether-ether-ketone, increase the high temperature resistant of material, abrasion-resistant ability, enhance self-lubricating property and conductive and heat-conductive ability, improve the extrusion processability of PEEK material, mechanical performance is high, good toughness, it is a kind of energy composite polymeric materials of excellent combination property, and preparation process is simple, cost is relatively low.
Description
Technical field
The present invention relates to field of compound material technologies, refer in particular to a kind of system of polyether-ether-ketone base modified nano composite material
Standby technique.
Background technique
Polyether-ether-ketone (PEEK) is that aromatic ketone and phenol are obtained by nucleophilic polycondensation, the weight in main chain containing ketonic bond and ehter bond
The high polymer of multiple unit, is a kind of thermoplastic special engineering plastic of all aromatic hemicrystalline, has high temperature resistant, chemically-resistant
The excellent properties such as burn into radiation hardness, high intensity, insulating properties stabilization, high-fracture toughness, easy processing, in machinery, medical treatment, nuclear power, stone
It is used widely in the fields such as oiling work, aerospace, electronic information.But its glass transition temperature is lower, thermal deformation temperature
Spend relatively low, processing difficulties, preparation cost is higher, and pure PEEK resin, which is still difficult to meet different use condition and use, to be wanted
It asks.Therefore, by PEEK resin is modified prepare excellent combination property composite material it is imperative.At present to PEEK
Modification have the methods of fiber-reinforced modified, blending and modifying, filling-modified, mechanical property, the heat of PEEK can be further enhanced
Performance and frictional behaviour reduce material cost, expand the scope of application of material.
Graphene is optimal two-dimension nano materials now, one-dimensional carbon nano material subject to carbon nanotube (CNTs), all
It can be with great specific surface area, excellent structural stability, high conductivity and outstanding mechanical performance, between them
Generate synergistic effect, the physical and chemical performance of material is remarkably improved when carrying out composite modified to polymer, allow composite material more
It is able to satisfy special requirement.
Nano-silicon nitride (nano-Si3N4) nano-silicon nitride is a kind of ceramic powder haveing excellent performance, there are silicon on surface
The groups such as nitrogen, silanamines, silanol, high mechanical strength, resistance to chemical corrosion is good, and especially elevated temperature strength is big, and has certainly
Lubricant effect.Pass through nano-Si3N4Modification can make thermal property, mechanical property, crystal property, frictional behaviour, the electricity of polymer
Performance etc. obtains larger raising.Due to nano-Si3N4It is atomic crystal, there is shortrange order, partial size is small, and surface can be high, right
The crystallization behavior of hypocrystalline polyether-ether-ketone can be generated and be significantly affected, and play the role of strong nucleating agent, improve crystallinity, improve material
Mechanical property, heating conduction and the crocking resistance of material.
Thermally conductive, conductive, abrasion-resistant polymers composite material has broad application prospects in terms of industrial production and military project,
Daily life and civilian aspect all have great application value.Conductive polyetheretherketonematerials materials currently on the market mostly use carbon fiber
Tie up modification, add the filling of a large amount of conductive material, mechanical strength and toughness are all deteriorated, temperature tolerance, lubricity, thermal conductivity and
Mechanical property etc. is unable to satisfy the application requirement of special dimension.The polyether-ether-ketone product of current developed wear-resisting series is universal
In the presence of easily losing powder, lubricate the problems such as inadequate.
107090158 A of Chinese invention patent application publication No. CN discloses a kind of wear-resisting polyetheretherketonematerials materials and its system
Preparation Method, method are:
(1) in N2Under protection, high temperature coupling agent is dissolved in organic solvent in the ratio of 1g:30-50 mL, nanometer is then added
Tungsten disulfide, glass fibre and nanometer powder, stirring, are heated to reflux temperature, are 60:1- by the volume ratio of organic solvent and water
Water is added in the ratio of 80:1, continues to be heated to reflux 2-4 hours, composite granule is obtained after suction filtration；
(2) it will be dried away at 100-120 DEG C in vacuum drying oven after above-mentioned composite granule organic solvent washing organic molten
Agent；
(3) powder of composite granule and polyether-ether-ketone after drying is mixed, is premixed in high-speed mixer machine uniformly, with double spiral shells
Bar extruder extruding pelletization, obtains wear-resisting polyetheretherketonematerials materials.The parts by weight of each component are as follows: 1-3 parts of nano tungsten disulfide, gather
97-99 parts of ether ether ketone, 0.2-0.5 parts of high temperature coupling agent, 10-15 parts of glass fibre, 15-25 parts of nanometer powder.
The above method is that after organic solvent mixes then directly and polyether-ether-ketone blending re-dry is squeezed by functional stuffing
It is granulated to obtain target product out, in the above-mentioned methods, high temperature coupling agent cannot sufficiently modify powder, make powder meeting in matrix resin
Generating to reunite causes dispersion uneven.The wear-resisting polyetheretherketonematerials materials self-lubricating capacities prepared in the above method are poor, wear-resisting energy
Power is limited.The present invention is directly sprayed using the dispersion liquid of coupling agent modified modification nano functional filler preparation and matrix resin is added,
Not only it had enhanced the function of nanoparticle but also had promoted evenly dispersed, and and nanoparticle and matrix tree had been allowed by the effect of the bridge chain of coupling agent
Rouge surface combines, and allows the polyether-ether-ketone base modified nano composite material of preparation to have comprehensive and excellent comprehensive performance, allows material
The test that harsh use environment can be coped with extends the service life of material and expands use scope.
It is multiple that 103087468 A of Chinese invention patent application publication No. CN discloses a kind of high heat resistance, high abrasion polyether-ether-ketone
Condensation material and its preparation process, method are:
(1) surface treatment of carbon-graphite fiber；
(2) surface treatment of PEEK；
(3) 20~85 parts of PEEK resin, PTFE5~30 part；1~3 part of coupling agent；1~3 part of other processing aids；In proportion
It weighs raw material and to put into high-speed mixer and mixing uniform, add in double screw extruder；
(4) mouth is added from profession in 10~50 parts of carbon-graphite fiber after surface treatment to be added, each component is kneaded, is squeezed
Out, cooling, pelletizing, obtains cylindrical pellet product.
With polyether-ether-ketone (PEEK), carbon-graphite fiber and polytetrafluoroethylene (PTFE) (PTFE) for primary raw material in the above method,
Add suitable coupling agent and other processing aids preparation polyether-ether-ketone composite material, preparation cost is higher, mechanical property and
Heat distortion temperature reduces.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of polyether-ether-ketone bases
The preparation process of modified nano composite material can effectively solve existing polyether-ether-ketone composite material preparation cost height and power
Learn performance and the low problem of heat distortion temperature.
To achieve the above object, the present invention is using following technical solution:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) graphene and carbon nano tube dispersion liquid preparation:
Graphene oxide dry powder, the processed multi-walled carbon nanotube of nitration mixture and high temperature coupling agent are added in NMP, at room temperature,
50-80 min is stirred in dispersion emulsifying machine with 1000 rpm mixing speeds, then ultrasonic disperse 1-3 h, forms stable GO
+ WCNTs dispersion liquid；
(2) nano-silicon nitride and the preparation of nanometer Al-Doped ZnO dispersion liquid:
Nano-silicon nitride keeps the temperature 2-3 h at 200 DEG C, is washed after cooling with dehydrated alcohol, dries；Nano-silicon nitride is added to
The volume ratio of ethanol solution, ethyl alcohol and water is 8:1, then addition nanometer Al-Doped ZnO and high temperature coupling agent, Al mix into solution
Miscellaneous amount is 1-2wt%, with 1000-2500rpm high speed shearing emulsification 60-90 min, then the ultrasound 30-90 min in 30 DEG C of water-baths,
Form stable Si3N4+ ZnO dispersion liquid；
(3) preparation of polyether-ether-ketone mixture:
The polyether-ether-ketone powder of melt index 25g/10min is added in high speed mixer, is stirred with the speed of 800-1200rpm
It mixes lower respectively by GO+WCNTs dispersion liquid and Si3N4+ ZnO dispersion liquid is added in polyether-ether-ketone powder simultaneously by the way of spray,
Continue high-speed stirred 30-90 min after adding, organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixture；
(4) preparation of polyether-ether-ketone base modified nano composite material:
Above-mentioned polyether-ether-ketone mixture, nano graphite powder, the graphite fibre that is chopped sufficiently are premixed in high speed mixer, using double
Screw extruder carries out melt blending and extruding pelletization: processing temperature is 360 DEG C, screw speed 40-80rpm, feed screw
Revolving speed 10-40 rpm, pelleter revolving speed 200-400rpm.
As a preferred embodiment, the GO+WCNTs dispersion liquid and Si3N4First to functional stuffing when prepared by+ZnO dispersion liquid
It is modified that the nanoparticle of powder carries out surface, then with high temperature coupling agent functional modification.
As a preferred embodiment, it is calculated by each component and 100.0wt%, 70~90 wt % of polyether-ether-ketone powder receives
Rice 10~30wt% of graphite powder, nanometer 5~40wt% of Al-Doped ZnO, be chopped 5~20wt% of graphite fibre, and nano-silicon nitride 1~
5wt%, 0.1~2wt% of graphene oxide, 0.1~2wt% of multi-walled carbon nanotube.
As a preferred embodiment, the high temperature coupling agent is silane coupling agent or titanate coupling agent.
As a preferred embodiment, the dosage of the high temperature coupling agent is 0.2-5 wt% of powder.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal
Known to:
The nano-filled material of the method for the present invention passes through high speed dispersion after ultrasonic grinding, then with polymer spray adhesion, then melting is mixed
Refining, last extruding pelletization obtain novel self-lubricating thermal conductivity Wear-resistant, high-temperature resistant polyether-ether-ketone base modified nano composite material,
The crystallization temperature of the composite material improves 12 DEG C than pure polyether-ether-ketone, increases high temperature resistant, the abrasion-resistant ability of material, enhances
Self-lubricating property and conductive and heat-conductive ability improve the extrusion processability of PEEK material, and mechanical performance is high, good toughness, are a kind of
The energy composite polymeric materials of excellent combination property, and preparation process is simple, cost is relatively low, and it is environmental-friendly, it is volume production and application
It lays a good foundation, there is good potential using value.
Detailed description of the invention
Fig. 1 is preparation flow schematic diagram of the invention.
Specific embodiment
Present invention discloses a kind of preparation processes of polyether-ether-ketone base modified nano composite material, include following steps:
(1) graphene and carbon nano tube dispersion liquid preparation:
Graphene oxide (GO) dry powder, the processed multi-walled carbon nanotube of nitration mixture (WCNTs) and high temperature coupling agent are added to NMP
In (N-Methyl pyrrolidone), at room temperature, 50-80 min is stirred in dispersion emulsifying machine with 1000 rpm mixing speeds, then
Ultrasonic disperse 1-3 h forms stable GO+WCNTs dispersion liquid.
(2) nano-silicon nitride and the preparation of nanometer Al-Doped ZnO dispersion liquid:
Nano-silicon nitride keeps the temperature 2-3 h at 200 DEG C, is washed after cooling with dehydrated alcohol, dries；Nano-silicon nitride is added to
The volume ratio of ethanol solution, ethyl alcohol and water is 8:1, then addition nanometer Al-Doped ZnO and high temperature coupling agent, Al mix into solution
Miscellaneous amount is 1-2wt%, with 1000-2500rpm high speed shearing emulsification 60-90 min, then the ultrasound 30-90 min in 30 DEG C of water-baths,
Form stable Si3N4+ ZnO dispersion liquid.
(3) preparation of polyether-ether-ketone mixture:
The polyether-ether-ketone powder of melt index 25g/10min is added in high speed mixer, is stirred with the speed of 800-1200rpm
It mixes lower respectively by GO+WCNTs dispersion liquid and Si3N4+ ZnO dispersion liquid is added in polyether-ether-ketone powder simultaneously by the way of spray,
Continue high-speed stirred 30-90 min after adding, organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixture.It is functional
Filler is come into full contact with polyether-ether-ketone powder by the way of dispersion liquid spray and is uniformly mixed, and nanoparticle passes through small-size effect
It is acted in conjunction with polyether-ether-ketone powder with the bridge chain of coupling agent, enhances the modified effect of nanoparticle.
(4) preparation of polyether-ether-ketone base modified nano composite material:
Above-mentioned polyether-ether-ketone mixture, nano graphite powder, the graphite fibre that is chopped sufficiently are premixed in high speed mixer, using double
Screw extruder carries out melt blending and extruding pelletization: processing temperature is 360 DEG C, screw speed 40-80rpm, feed screw
Revolving speed 10-40 rpm, pelleter revolving speed 200-400rpm.It is squeezed out after polyether-ether-ketone matrix and filler in an extruder melt blending
It is granulated, it is therefore prevented that the reunion again of nanoparticle, to prepare the composite material of excellent combination property.
The GO+WCNTs dispersion liquid and Si3N4+ ZnO dispersion liquid prepare when first to the nanoparticle of functional stuffing powder into
Row surface is modified, then uses high temperature coupling agent functional modification, increases the interface binding power of nanoparticle and polymer, raising particle
Dispersibility, re-ultrasonic dispersion after high speed shearing emulsification forms stable dispersion.
It is calculated by each component and 100.0wt%, polyether-ether-ketone powder 70~90 wt %, 10~30wt% of nano graphite powder,
Nanometer 5~40wt% of Al-Doped ZnO, be chopped 5~20wt% of graphite fibre, 1~5wt% of nano-silicon nitride, and graphene oxide 0.1~
2wt%, 0.1~2wt% of multi-walled carbon nanotube.
The high temperature coupling agent is silane coupling agent or titanate coupling agent, and the dosage of the high temperature coupling agent is powder
0.2 -5 wt%。
With multiple embodiments, invention is further described in detail below:
Embodiment 1:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) 10 g GO dry powder, the processed WCNTs of 10 g nitration mixture and high temperature silane coupling agent are added in 1000mL NMP,
At 25 DEG C, with 1000rpm mixing speed in 60 min of dispersion emulsifying machine high speed shear agitation, then 2 h of ultrasonic disperse, matches
It is spare that stable GO+WCNTs dispersion liquid is made.
(2) nano-silicon nitride is kept the temperature at 200 DEG C 3 h, is washed after cooling with dehydrated alcohol, 130 g is weighed after drying
It is added to 500mL ethanol solution (ethyl alcohol: water=8:1, V/V), then (the Al doping of 150g nanometers of Al-Doped ZnOs is added into solution
Amount is 2wt%) and high temperature coupling agent, 90 min of 2000rpm high speed shearing emulsification, then in 30 DEG C of 60 min of water bath sonicator, formed
Stable Si3N4+ ZnO dispersion liquid is spare.
(3) the polyether-ether-ketone powder for weighing 3800 g melt index 25g/10min is added in high speed mixer, and 1000
Rpm stirring lower GO+WCNTs dispersion liquid and Si respectively3N4Polyether-ether-ketone powder is added in+ZnO dispersion liquid simultaneously by the way of spray
In, 1200 rpm continue 60 min of high-speed stirred after adding, and organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixing
Material.
(4) above-mentioned polyether-ether-ketone mixture, 500g nano graphite powder, 400g are chopped graphite fibre in high speed mixer
It is blended with the revolving speed of 1500 rpm, time 20min is blended, blend composition is added twin-screw extrude into carry out melt blending
And extrusion, it crosses water cooling granulation and obtains target product.Processing temperature is 360 DEG C, and screw speed is 60 rpm, feed screw revolving speed
30 rpm, pelleter revolving speed 300rpm.
Embodiment 2:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) 12 g GO dry powder, the processed WCNTs of 14 g nitration mixture and high temperature silane coupling agent are added in 980mL NMP,
At 25 DEG C, with 1000rpm mixing speed in 50 min of dispersion emulsifying machine high speed shear agitation, then 1 h of ultrasonic disperse, matches
It is spare that stable GO+WCNTs dispersion liquid is made.
(2) nano-silicon nitride is kept the temperature at 200 DEG C 2 h, is washed after cooling with dehydrated alcohol, 135 g is weighed after drying
It is added to 520mL ethanol solution (ethyl alcohol: water=8:1, V/V), then (the Al doping of 160g nanometers of Al-Doped ZnOs is added into solution
Amount is 1wt%) and high temperature coupling agent, 60 min of 1000rpm high speed shearing emulsification, then in 30 DEG C of 60 min of water bath sonicator, formed
Stable Si3N4+ ZnO dispersion liquid is spare.
(3) the polyether-ether-ketone powder for weighing 3900 g melt index 25g/10min is added in high speed mixer, and 1000
Rpm stirring lower GO+WCNTs dispersion liquid and Si respectively3N4Polyether-ether-ketone powder is added in+ZnO dispersion liquid simultaneously by the way of spray
In, 1100 rpm continue 40 min of high-speed stirred after adding, and organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixing
Material.
(4) above-mentioned polyether-ether-ketone mixture, 520g nano graphite powder, 410g are chopped graphite fibre in high speed mixer
It is blended with the revolving speed of 1500 rpm, time 20min is blended, blend composition is added twin-screw extrude into carry out melt blending
And extrusion, it crosses water cooling granulation and obtains target product.Processing temperature is 360 DEG C, and screw speed is 40 rpm, feed screw revolving speed
10 rpm, pelleter revolving speed 200rpm.
Embodiment 3:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) 15 g GO dry powder, the processed WCNTs of 13 g nitration mixture and high temperature silane coupling agent are added in 1100mL NMP,
At 25 DEG C, with 1000rpm mixing speed in 70 min of dispersion emulsifying machine high speed shear agitation, then 1.5 h of ultrasonic disperse,
It is spare to be configured to stable GO+WCNTs dispersion liquid.
(2) nano-silicon nitride is kept the temperature at 200 DEG C 2.2h, is washed after cooling with dehydrated alcohol, 140 g is weighed after drying
It is added to 550mL ethanol solution (ethyl alcohol: water=8:1, V/V), then (the Al doping of 160g nanometers of Al-Doped ZnOs is added into solution
Amount is 1.5wt%) and high temperature coupling agent, 70 min of 2000rpm high speed shearing emulsification, then in 30 DEG C of 30 min of water bath sonicator, shape
At stable Si3N4+ ZnO dispersion liquid is spare.
(3) the polyether-ether-ketone powder for weighing 3900 g melt index 25g/10min is added in high speed mixer, and 800
Rpm stirring lower GO+WCNTs dispersion liquid and Si respectively3N4Polyether-ether-ketone powder is added in+ZnO dispersion liquid simultaneously by the way of spray
In, 1300 rpm continue 30 min of high-speed stirred after adding, and organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixing
Material.
(4) above-mentioned polyether-ether-ketone mixture, 550g nano graphite powder, 430g are chopped graphite fibre in high speed mixer
It is blended with the revolving speed of 1500 rpm, time 20min is blended, blend composition is added twin-screw extrude into carry out melt blending
And extrusion, it crosses water cooling granulation and obtains target product.Processing temperature is 360 DEG C, and screw speed is 50 rpm, feed screw revolving speed
15 rpm, pelleter revolving speed 250rpm.
Embodiment 4:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) 12 g GO dry powder, the processed WCNTs of 14 g nitration mixture and high temperature silane coupling agent are added in 980mL NMP,
At 25 DEG C, with 1000rpm mixing speed in 60 min of dispersion emulsifying machine high speed shear agitation, then 2 h of ultrasonic disperse, matches
It is spare that stable GO+WCNTs dispersion liquid is made.
(2) nano-silicon nitride is kept the temperature at 200 DEG C 2.3 h, is washed after cooling with dehydrated alcohol, 132 is weighed after drying
G is added to 530mL ethanol solution (ethyl alcohol: water=8:1, V/V), then (Al mixes 155g nanometers of Al-Doped ZnOs of addition into solution
Miscellaneous amount is 2wt%) and high temperature coupling agent, 80 min of 1500rpm high speed shearing emulsification, then in 30 DEG C of 70 min of water bath sonicator, shape
At stable Si3N4+ ZnO dispersion liquid is spare.
(3) the polyether-ether-ketone powder for weighing 3850 g melt index 25g/10min is added in high speed mixer, and 1100
Rpm stirring lower GO+WCNTs dispersion liquid and Si respectively3N4Polyether-ether-ketone powder is added in+ZnO dispersion liquid simultaneously by the way of spray
In, 1200 rpm continue 50 min of high-speed stirred after adding, and organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixing
Material.
(4) above-mentioned polyether-ether-ketone mixture, 558g nano graphite powder, 425g are chopped graphite fibre in high speed mixer
It is blended with the revolving speed of 1500 rpm, time 20min is blended, blend composition is added twin-screw extrude into carry out melt blending
And extrusion, it crosses water cooling granulation and obtains target product.Processing temperature is 360 DEG C, and screw speed is 60 rpm, feed screw revolving speed
25rpm, pelleter revolving speed 300rpm.
Embodiment 5:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) 16 g GO dry powder, the processed WCNTs of 13 g nitration mixture and high temperature silane coupling agent are added in 1200mL NMP,
At 25 DEG C, with 1000rpm mixing speed in 75 min of dispersion emulsifying machine high speed shear agitation, then 2.5 h of ultrasonic disperse,
It is spare to be configured to stable GO+WCNTs dispersion liquid.
(2) nano-silicon nitride is kept the temperature at 200 DEG C 2.8 h, is washed after cooling with dehydrated alcohol, 140 is weighed after drying
G is added to 580mL ethanol solution (ethyl alcohol: water=8:1, V/V), then (Al mixes 160g nanometers of Al-Doped ZnOs of addition into solution
Miscellaneous amount is 1.6wt%) and high temperature coupling agent, 90 min of 2200rpm high speed shearing emulsification, then in 30 DEG C of 50 min of water bath sonicator,
Form stable Si3N4+ ZnO dispersion liquid is spare.
(3) the polyether-ether-ketone powder for weighing 4000 g melt index 25g/10min is added in high speed mixer, and 1200
Rpm stirring lower GO+WCNTs dispersion liquid and Si respectively3N4Polyether-ether-ketone powder is added in+ZnO dispersion liquid simultaneously by the way of spray
In, 1300 rpm continue 78 min of high-speed stirred after adding, and organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixing
Material.
(4) above-mentioned polyether-ether-ketone mixture, 530g nano graphite powder, 440g are chopped graphite fibre in high speed mixer
It is blended with the revolving speed of 1500 rpm, time 20min is blended, blend composition is added twin-screw extrude into carry out melt blending
And extrusion, it crosses water cooling granulation and obtains target product.Processing temperature is 360 DEG C, and screw speed is 70 rpm, feed screw revolving speed
30 rpm, pelleter revolving speed 350rpm.
Embodiment 6:
A kind of preparation process of polyether-ether-ketone base modified nano composite material, includes following steps:
(1) 18 g GO dry powder, the processed WCNTs of 16 g nitration mixture and high temperature silane coupling agent are added in 1250mL NMP,
At 25 DEG C, with 1000rpm mixing speed in 80 min of dispersion emulsifying machine high speed shear agitation, then 3 h of ultrasonic disperse, matches
It is spare that stable GO+WCNTs dispersion liquid is made.
(2) nano-silicon nitride is kept the temperature at 200 DEG C 3 h, is washed after cooling with dehydrated alcohol, 140 g is weighed after drying
It is added to 580mL ethanol solution (ethyl alcohol: water=8:1, V/V), then (the Al doping of 160g nanometers of Al-Doped ZnOs is added into solution
Amount is 1.3wt%) and high temperature coupling agent, 78 min of 2500rpm high speed shearing emulsification, then in 30 DEG C of 90 min of water bath sonicator, shape
At stable Si3N4+ ZnO dispersion liquid is spare.
(3) the polyether-ether-ketone powder for weighing 3900 g melt index 25g/10min is added in high speed mixer, and 900
Rpm stirring lower GO+WCNTs dispersion liquid and Si respectively3N4Polyether-ether-ketone powder is added in+ZnO dispersion liquid simultaneously by the way of spray
In, 1250 rpm continue 90 min of high-speed stirred after adding, and organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixing
Material.
(4) above-mentioned polyether-ether-ketone mixture, 550g nano graphite powder, 460g are chopped graphite fibre in high speed mixer
It is blended with the revolving speed of 1500 rpm, time 20min is blended, blend composition is added twin-screw extrude into carry out melt blending
And extrusion, it crosses water cooling granulation and obtains target product.Processing temperature is 360 DEG C, and screw speed is 80 rpm, feed screw revolving speed
40 rpm, pelleter revolving speed 400rpm.
The pellet of polyether-ether-ketone base modified nano composite material prepared in above-mentioned each embodiment is placed in air blast to do
150 DEG C of 3 h of drying are being crossed in dry case, batten needed for being then molded into test using extra large day injection molding machine, injecting condition: barrel temperature
Degree 360 DEG C, injection pressure 800MPa, 3 min of dwell time, cooling time 2S, the batten of injection molding is in 200 DEG C of 4 h of constant temperature
It is heat-treated, cooled to room temperature carries out the performance test of mechanics, calorifics, electricity and tribology, and mechanical performance is omnipotent
Testing machine tests (23 ± 1 DEG C) by ASTM standard, the molded specimens 28-30mm of heating conduction, thickness 20-4mm, and use is thermally conductive
Coefficient measuring instrument test, the test condition of frictional behaviour are as follows: load 100Kg, 200 rpm of linear velocity, testing time are continuous
1h.Test result is as follows table:
As seen from the above table, polyether-ether-ketone base modified nano composite material prepared by the present invention has excellent comprehensive performance, larger
Degree improves the various aspects of performance such as mechanics, calorifics, electricity and the tribology of material, and the composite material is especially suitable for particular/special requirement
High quality is wear-resisting, the processing of heat-resisting, conductive, antistatic part, such as unlubricated bearing, high gear, engine.
Design focal point of the invention is: the nano-filled material of the method for the present invention pass through ultrasonic grinding after high speed dispersion, then with
Polymer spray adhesion, then melting mixing, last extruding pelletization, it is poly- to obtain novel self-lubricating thermal conductivity Wear-resistant, high-temperature resistant
The crystallization temperature of ether ether ketone base modified nano composite material, the composite material improves 12 DEG C than pure polyether-ether-ketone, increases material
High temperature resistant, abrasion-resistant ability, enhance self-lubricating property and conductive and heat-conductive ability, improve PEEK material extrusion processing
Property, mechanical performance is high, and good toughness is a kind of energy composite polymeric materials of excellent combination property, and preparation process is simple, cost
It is lower, it is environmental-friendly, it lays a good foundation for volume production and application, there is good potential using value.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any subtle modifications, equivalent variations and modifications to the above embodiments according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (5)
1. a kind of preparation process of polyether-ether-ketone base modified nano composite material, it is characterised in that: include following steps:
(1) graphene and carbon nano tube dispersion liquid preparation:
Graphene oxide dry powder, the processed multi-walled carbon nanotube of nitration mixture and high temperature coupling agent are added in NMP, at room temperature,
50-80 min is stirred in dispersion emulsifying machine with 1000 rpm mixing speeds, then ultrasonic disperse 1-3 h, forms stable GO
+ WCNTs dispersion liquid；
(2) nano-silicon nitride and the preparation of nanometer Al-Doped ZnO dispersion liquid:
Nano-silicon nitride keeps the temperature 2-3 h at 200 DEG C, is washed after cooling with dehydrated alcohol, dries；Nano-silicon nitride is added to
The volume ratio of ethanol solution, ethyl alcohol and water is 8:1, then addition nanometer Al-Doped ZnO and high temperature coupling agent, Al mix into solution
Miscellaneous amount is 1-2wt%, with 1000-2500rpm high speed shearing emulsification 60-90 min, then the ultrasound 30-90 min in 30 DEG C of water-baths,
Form stable Si3N4+ ZnO dispersion liquid；
(3) preparation of polyether-ether-ketone mixture:
The polyether-ether-ketone powder of melt index 25g/10min is added in high speed mixer, is stirred with the speed of 800-1200rpm
It mixes lower respectively by GO+WCNTs dispersion liquid and Si3N4+ ZnO dispersion liquid is added in polyether-ether-ketone powder simultaneously by the way of spray,
Continue high-speed stirred 30-90 min after adding, organic solvent is removed at 250 DEG C and obtains polyether-ether-ketone mixture；
(4) preparation of polyether-ether-ketone base modified nano composite material:
Above-mentioned polyether-ether-ketone mixture, nano graphite powder, the graphite fibre that is chopped sufficiently are premixed in high speed mixer, using double
Screw extruder carries out melt blending and extruding pelletization: processing temperature is 360 DEG C, screw speed 40-80rpm, feed screw
Revolving speed 10-40 rpm, pelleter revolving speed 200-400rpm.
2. a kind of preparation process of polyether-ether-ketone base modified nano composite material according to claim 1, it is characterised in that:
The GO+WCNTs dispersion liquid and Si3N4First surface is carried out to the nanoparticle of functional stuffing powder when prepared by+ZnO dispersion liquid to change
Property, then with high temperature coupling agent functional modification.
3. a kind of preparation process of polyether-ether-ketone base modified nano composite material according to claim 1, it is characterised in that:
It is calculated by each component and 100.0wt%, polyether-ether-ketone powder 70~90 wt %, 10~30wt% of nano graphite powder, nanometer mixes aluminium
5~40wt% of zinc oxide, be chopped 5~20wt% of graphite fibre, 1~5wt% of nano-silicon nitride, graphene oxide 0.1~2wt%, more
0.1~2wt% of wall carbon nano tube.
4. a kind of preparation process of polyether-ether-ketone base modified nano composite material according to claim 1, it is characterised in that:
The high temperature coupling agent is silane coupling agent or titanate coupling agent.
5. a kind of preparation process of polyether-ether-ketone base modified nano composite material according to claim 1, it is characterised in that:
The dosage of the high temperature coupling agent is 0.2-5 wt% of powder.
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