CN105860431A - Polyether ether ketone/multi-walled carbon nanotube composite powder material used for selective laser sintering technology, and preparation method thereof - Google Patents
Polyether ether ketone/multi-walled carbon nanotube composite powder material used for selective laser sintering technology, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a polyether ether ketone/multi-walled carbon nanotube composite powder material used for a selective laser sintering technology. Raw materials of the composite powder material mainly comprise modified polyether ether ketone and modified carbon nanotubes, wherein the modified polyether ether ketone is obtained through modifying polyether ether ketone with an antioxidant, and the modified carbon nanotubes are obtained through modifying carbon nanotubes with a surfactant. The polyether ether ketone/multi-walled carbon nanotube composite powder reserves the original high temperature resistance of the polyether ether ketone, has better particle size regularity than polyether ether ketone powder, and has higher apparent density than the polyether ether ketone powder, so requirements of the selective laser sintering technology for powder forming are met, the mechanical performances and the thermal performances of the composite powder material are obviously improved under a small use amount of the multi-walled carbon nanotubes, the application of the composite powder material in the high temperature resisting field is widened, and the high-strength and high-heat resistance powder material is provided for the selective laser sintering technology.
Description
Technical field
Present invention relates particularly to a kind of polyether-ether-ketone for Selective Laser Sintering/multi-walled carbon nano-tubes composite powder material and
Its preparation method.
Background technology
Selective laser sintering (SLS) technology is that the 3D that a kind of iraser carrys out sintered powder material molding as thermal source beats
Print technology.The polymer material and engineering being currently used for SLS technology mainly has the non-crystalline type polymer with polystyrene as representative
Dusty material and the Crystalline plastics dusty material with nylon 12 as representative.Polystyrene based powdered material sinter molding part
Mechanical strength is far below its bulk strength, is mainly used in making model and full form casting process；Nylon 12 based powdered material sinters
The mechanical strength of profiled member is close to the bulk strength of nylon 12, and hot strength reaches 40～50MPa, is current Physical Mechanical
Can a best family macromolecule sintered powder material.Along with the development of SLS technology, an urgent demand exploitation is more excellent than nylon 12 performance
Sintered powder material, to adapt to the fields such as Aero-Space to product high intensity, high heat-resisting requirement.Polyether-ether-ketone
(PEEK) being the polymer of a kind of heat-resisting crystal type, have the most excellent strength and stiffness, fatigue performance is excellent；
Chemical stability is good, and oil resistant is acidproof corrosion-resistant, and in conventional chemical reagent, only concentrated sulphuric acid can destroy its structure；Polyethers ether
Ketone resin has excellent sliding properties, anti-flammability and radiation resistance；Also there is good biocompatibility.It is usually used in automobile work
Industry, electrical equipment industry, medical apparatus and instruments and aerospace field.Polyether-ether-ketone is can further improve as reinforcing agent using CNT
Physical and mechanical properties.Polyether-ether-ketone and CNT are combined the sintered powder material being prepared as being suitable for SLS technique, can
There is the combination property being much better than nylon 12, the most emerging have be applicable to the material of SLS forming technique the most excellent
Gesture.
It is about 50 μm that dusty material required by SLS technology needs have mean diameter, and powder regularity is high, good fluidity
Etc. feature.The most conventional method preparing polymeric powder sintered material mainly has low-temperature grinding method and solvent precipitation.But
Low-temperature grinding method needs specific deep freeze refrigeration plant, and investment is many, and energy expenditure is big, and material needs repeatedly to pulverize can be only achieved to compare reason
The Particle size requirements (such as Merlon, polystyrene etc.) thought, and the powder morphology prepared is the most irregular；Solvent precipitation one
As use the organic solvent such as ethanol to use autoclave to prepare dusty material (such as nylon 11, nylon 12 etc.), due to poly-
Ether ether ketone cannot be dissolved in the solvent in addition to concentrated sulphuric acid, and therefore, solvent precipitation is not easy to implement.Exist between CNT
Stronger Van der Waals force so that it is be susceptible to reunite, it is difficult to be dispersed in polymeric matrix, meanwhile, CNT and polymer
The binding ability of matrix is more weak, easy and matrix generation Relative sliding when by shearing force, thus affects the mechanics of composite
Performance.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides a kind of for selective laser
The preparation method of the polyether-ether-ketone of sintering technology/multi-walled carbon nano-tubes composite powder material, improves polyether-ether-ketone powder regularity
Low, the shortcoming of poor fluidity, and multi-walled carbon nano-tubes is due to cause and not enough the asking of Interface adhesive strength between matrix of reuniting
Topic, meets the Selective Laser Sintering requirement to dusty material.
A kind of polyether-ether-ketone for Selective Laser Sintering/multi-walled carbon nano-tubes composite powder material, its raw material mainly wraps
Including modified polyetheretherketonefiber and modified carbon nano-tube, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification institute
, described modified carbon nano-tube is to use surfactant to carbon nano-tube modification gained.
By such scheme, described composite powder material is by mass percentage: multi-walled carbon nano-tubes content of powder is 0.1～10
Wt%.
By such scheme, the particle diameter of described polyether-ether-ketone powder is 10～100 μm, mean diameter 40～60 μm.
By such scheme, the external diameter of described multi-walled carbon nano-tubes is 5～30nm, a length of 10～30 μm, and purity is more than 95%.
SWCN price is high, and draw ratio is more than multi-walled carbon nano-tubes, and agglomeration is more serious, it is not easy to dispersion；Many walls carbon
Nanotube surface roughness is big, can improve and the Interface adhesive strength of polyether-ether-ketone matrix.
By such scheme, in described antioxidant, primary antioxidant is Hinered phenols antioxidant, selected from antioxidant 1098, antioxidant
1076, antioxidant hp136, antioxidant 2921T, one or more in antioxidant 1010；Or described antioxidant is auxiliary
Aid anti-oxidants, is selected from as the one or several in phosphite ester kind antioxidant (such as antioxidant 168) or monothioester kind antioxidant
Kind.
By such scheme, described surfactant is anionic surfactant so lauryl sulfate, DBSA
In sodium one or more；One or more in nonionic surfactant Polyethylene Glycol, tetramethylolmethane.
The preparation method of polyether-ether-ketone of the present invention/multi-walled carbon nano-tubes composite powder material, comprises the steps:
(1) choose raw material by following mass percent: polyether-ether-ketone 90～99.9%, multi-walled carbon nano-tubes 0.1～10%, standby
With；
(2) respectively polyether-ether-ketone, multi-walled carbon nano-tubes are modified process and obtain modified polyetheretherketonefiber and modification many walls carbon is received
Mitron, through dry, ball milling after the two being mixed, i.e. can get polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material.
By such scheme, the preparation method of described modified polyetheretherketonefiber is: carry out heat with antioxidant after being mixed homogeneously by polyether-ether-ketone
Process, infiltrate with organic solvent after ball milling, standby.Wherein, described antioxidant consumption is 0.1～1.5wt%；Described heat treatment
Temperature be 220-260 DEG C, the time is 1-2 hour；The time of described ball milling is 10-20min, and ball milling speed is
480～500r/min, ball milling ball is zirconia ceramics ball, a diameter of 5mm～15mm；Described organic solvent be ethanol or water or
Acetone etc., every 100g polyether-ether-ketone powder consumption of organic solvent is 50～70ml.
By such scheme, the preparation method of described modified multiwalled carbon nanotube is: infiltrate multi-walled carbon nano-tubes at surfactant
Aqueous solution is uniformly dispersed, obtains modified multiwalled carbon nanotube.Wherein, the mass concentration of described aqueous surfactant solution is
1～10mg/ml；Multi-walled carbon nano-tubes quality is 0.1～10g:100ml with the volume ratio of aqueous surfactant solution；Described dispersion
Can be by mechanical agitation and or ultrasonic disperse process.The preferred 20-40min of sonication treatment time, processes 3～5 times repeatedly.
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material that the present invention proposes is polyether-ether-ketone powder is carried out physical treatment
Surface modification with multi-walled carbon nano-tubes.By exceeding 70 DEG C of heat treatments carried out above of polyether-ether-ketone glass transition temperature,
Accelerate the motion of macromolecular chain segment, prevent polyether-ether-ketone oxidation at high temperature by adding primary antioxidant with auxiliary antioxidant,
Improved mobility and the regularity of powder afterwards by physics ball milling, thus be satisfied with selective laser sintering technique to powder
Requirement；By adding surfactant and carrying out ultrasonic disperse and improve agglomeration and and the matrix material of multi-walled carbon nano-tubes
Interface adhesive strength, is finally effectively improved mechanical strength and the heat resistance of composite powder material.
Compared with prior art.The invention have the benefit that
1. the present invention uses heat treatment and physics ball milling to improve mobility and the regularity of polyether-ether-ketone powder, lower than conventional physics
Temperature pulverizes lower to the requirement of equipment, simultaneously the most also will not because of chemical graft active group and to reduce the mechanics of polyether-ether-ketone strong
Degree and heat resistance；
2. in the present invention, the agglomeration of multi-walled carbon nano-tubes significantly improves, and improves the surface activity of multi-walled carbon nano-tubes, and
And there is preferable Interface adhesive strength between polyether-ether-ketone matrix.
3, polyether-ether-ketone prepared by the present invention/multi-walled carbon nano-tubes composite powder material, effectively improves commercially available polyether-ether-ketone powder
End particle regularity is poor, apparent density is the highest shortcoming, and multi-walled carbon nano-tubes cause due to reunion and interface between matrix
The problem that binding ability is the strongest, and under conditions of multi-walled carbon nano-tubes consumption is little, hence it is evident that improve composite powder material
Mechanical property and hot property, widened its application in high temperature resistant field, provides high intensity for Selective Laser Sintering high
The dusty material of thermostability.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office
It is limited to the following examples.
The particle diameter of the polyether-ether-ketone powder employed in following embodiment is 10～100 μm, mean diameter 40～60 μm；Many walls carbon
The external diameter of nanotube is 5～30nm, a length of 10～30 μm, and purity is more than 95%.
Polyether-ether-ketone of the present invention/multi-walled carbon nano-tubes composite powder material utilizes mould pressing process to be processed into test block.Described
Mould pressing process condition is: is put into by composite powder material in 200 DEG C of hot presses and preheats, is heated to when 220～250 DEG C being forced into
4～6MPa；It is heated to when 260～280 DEG C bleeding off pressure preheating 1min, repressurization to 6～8MPa；It is heated to 290～310 DEG C to bleed off pressure again
Preheating 1min, repressurization to 8～10MPa；Continuing to heat up, processing temperature maintains 355～365 DEG C, and pressure is
8～12MPa, the dwell time is 10～15min.
Embodiment 1
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, its raw material mainly includes modified polyetheretherketonefiber and modified carbon nano tube
Pipe, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification gained, and described modified carbon nano-tube is to use
Surfactant is to carbon nano-tube modification gained.
(1) preparation of modified polyetheretherketonefiber
It is placed in chamber type electric resistance furnace after 99g polyether-ether-ketone powder is mixed homogeneously with 1g antioxidant hp136, at 220 DEG C
Under the conditions of heat treatment 2 hours, after natural cooling, utilize ball mill to carry out physics ball milling 10min, afterwards by the anhydrous second of 50ml
Alcohol infiltrates, and i.e. obtains modified polyetheretherketonefiber, standby.
(2) preparation of modified multiwalled carbon nanotube
Using sodium lauryl sulphate as surfactant, 0.25g surfactant is joined the deionization of 60 DEG C of 100ml
In water, 0.25g multi-walled carbon nano-tubes, to being completely dissolved, is then infiltrated in aqueous surfactant solution, by machinery by stirring
Stirring and ultrasonic disperse process, and each sonication treatment time is 30min, repeatedly process 5 times, prepare modified multi-wall carbon nano-tube
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
By above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube mix and blend, until modified polyetheretherketonefiber surface is many without obvious modification
Wall carbon nano tube separates out, and puts into afterwards in 80 DEG C of vacuum drying ovens and is dried 48 hours；Dried composite powder is placed in ball
Ball milling 10min in grinding machine, prepares the polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of mix homogeneously.
Performance test: utilize hot press that the polyether-ether-ketone of the present embodiment/multi-walled carbon nano-tubes composite powder material is processed into test
Part.Concrete mould pressing process is: is placed in mould by composite powder, puts in 200 DEG C of hot presses and preheat, when being heated to 250 DEG C
Being forced into 6MPa, bleed off pressure preheating 1min during to 280 DEG C, repressurization, to 8MPa, is heated to 310 DEG C and bleeds off pressure preheating again
1min, repressurization to 10MPa, continue to heat up, processing temperature maintains 357 DEG C, and pressure is 10MPa, and the dwell time is
10min。
Embodiment 2
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, its raw material mainly includes modified polyetheretherketonefiber and modified carbon nano tube
Pipe, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification gained, and described modified carbon nano-tube is to use
Surfactant is to carbon nano-tube modification gained.
(1) preparation of modified polyetheretherketonefiber
It is placed in chamber type electric resistance furnace after 99g polyether-ether-ketone powder is mixed homogeneously with 1g antioxidant hp136, at 240 DEG C
Under the conditions of heat treatment 2 hours, after natural cooling, utilize ball mill to carry out physics ball milling 10min, afterwards by the anhydrous second of 50ml
Alcohol infiltrates, and i.e. obtains modified polyetheretherketonefiber, standby.
(2) preparation of modified multiwalled carbon nanotube
Using sodium lauryl sulphate as surfactant, 0.25g surfactant is joined 100ml, the deionization of 60 DEG C
In water, 0.25g multi-walled carbon nano-tubes, to being completely dissolved, is then infiltrated in aqueous surfactant solution, by machinery by stirring
Stirring and ultrasonic disperse process, and each sonication treatment time is 30min, repeatedly process 5 times, prepare modified multi-wall carbon nano-tube
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
By above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube mix and blend, until modified polyetheretherketonefiber surface is many without obvious modification
Wall carbon nano tube separates out, and puts into afterwards in 80 DEG C of vacuum drying ovens and is dried 48 hours；Dried composite powder is placed in ball
Ball milling 10min in grinding machine, prepares the polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of mix homogeneously.
Performance test: utilize hot press that the polyether-ether-ketone of the present embodiment/multi-walled carbon nano-tubes composite powder material is processed into test
Part.Concrete mould pressing process is: is placed in mould by composite powder, puts in 200 DEG C of hot presses and preheat, when being heated to 250 DEG C
Being forced into 6MPa, bleed off pressure preheating 1min during to 280 DEG C, repressurization, to 8MPa, is heated to 310 DEG C and bleeds off pressure preheating again
1min, repressurization to 10MPa, continue to heat up, processing temperature maintains 357 DEG C, and pressure is 10MPa, and the dwell time is
10min。
Embodiment 3
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, its raw material mainly includes modified polyetheretherketonefiber and modified carbon nano tube
Pipe, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification gained, and described modified carbon nano-tube is to use
Surfactant is to carbon nano-tube modification gained.
(1) preparation of modified polyetheretherketonefiber
It is placed in chamber type electric resistance furnace after 99g polyether-ether-ketone powder is mixed homogeneously with 1g antioxidant hp136, at 260 DEG C
Under the conditions of heat treatment 2 hours, after natural cooling, utilize ball mill to carry out physics ball milling 10min, afterwards by the anhydrous second of 50ml
Alcohol infiltrates, and i.e. obtains modified polyetheretherketonefiber, standby.
(2) preparation of modified multiwalled carbon nanotube
Using sodium lauryl sulphate as surfactant, 0.25g surfactant is joined 100ml, the deionization of 60 DEG C
In water, 0.25g multi-walled carbon nano-tubes, to being completely dissolved, is then infiltrated in aqueous surfactant solution, by machinery by stirring
Stirring and ultrasonic disperse process, and each sonication treatment time is 30min, repeatedly process 5 times, prepare modified multi-wall carbon nano-tube
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
By above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube mix and blend, until modified polyetheretherketonefiber surface is many without obvious modification
Wall carbon nano tube separates out, and puts into afterwards in 80 DEG C of vacuum drying ovens and is dried 48 hours；Dried composite powder is placed in ball
Ball milling 10min in grinding machine, prepares the polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of mix homogeneously.
Performance test: utilize hot press that the polyether-ether-ketone of the present embodiment/multi-walled carbon nano-tubes composite powder material is processed into test
Part.Concrete mould pressing process is: is placed in mould by composite powder, puts in 200 DEG C of hot presses and preheat, when being heated to 250 DEG C
Being forced into 6MPa, bleed off pressure preheating 1min during to 280 DEG C, repressurization, to 8MPa, is heated to 310 DEG C and bleeds off pressure preheating again
1min, repressurization to 10MPa, continue to heat up, processing temperature maintains 357 DEG C, and pressure is 10MPa, and the dwell time is
10min。
Embodiment 4
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, its raw material mainly includes modified polyetheretherketonefiber and modified carbon nano tube
Pipe, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification gained, and described modified carbon nano-tube is to use
Surfactant is to carbon nano-tube modification gained.
(1) preparation of modified polyetheretherketonefiber
It is placed on box resistance after being mixed homogeneously with 1g antioxidant 1010 and 0.5g irgasfos 168 by 98.5g polyether-ether-ketone powder
In stove, heat treatment 1 hour under conditions of 240 DEG C, after natural cooling, utilize ball mill to carry out physics ball milling 20min, it
Infiltrate with 60ml acetone afterwards, i.e. obtain modified polyetheretherketonefiber, standby.
(2) preparation of modified multiwalled carbon nanotube
Using sodium lauryl sulphate as surfactant, 3g surfactant is joined 100ml, the deionized water of 60 DEG C
In, 6g multi-walled carbon nano-tubes, to being completely dissolved, is then infiltrated in aqueous surfactant solution, passes through mechanical agitation by stirring
Processing with ultrasonic disperse, each sonication treatment time is 30min, repeatedly processes 5 times, prepares modified multiwalled carbon nanotube.
(3) preparation of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
By above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube mix and blend, until modified polyetheretherketonefiber surface is many without obvious modification
Wall carbon nano tube separates out, and puts into afterwards in 80 DEG C of vacuum drying ovens and is dried 48 hours；Dried composite powder is placed in ball
Ball milling 10min in grinding machine, prepares the polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of mix homogeneously.
Performance test: utilize hot press that the polyether-ether-ketone of the present embodiment/multi-walled carbon nano-tubes composite powder material is processed into test
Part.Concrete mould pressing process is: is placed in mould by composite powder, puts in 200 DEG C of hot presses and preheat, when being heated to 250 DEG C
Being forced into 6MPa, bleed off pressure preheating 1min during to 280 DEG C, repressurization, to 8MPa, is heated to 310 DEG C and bleeds off pressure preheating again
1min, repressurization to 10MPa, continue to heat up, processing temperature maintains 357 DEG C, and pressure is 10MPa, and the dwell time is
10min。
Embodiment 5
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, its raw material mainly includes modified polyetheretherketonefiber and modified carbon nano tube
Pipe, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification gained, and described modified carbon nano-tube is to use
Surfactant is to carbon nano-tube modification gained.
(1) preparation of modified polyetheretherketonefiber
It is placed on box resistance after being mixed homogeneously with 0.5g antioxidant 1010 and 0.5g irgasfos 168 by 99g polyether-ether-ketone powder
In stove, heat treatment 2 hours under conditions of 260 DEG C, after natural cooling, utilize ball mill to carry out physics ball milling 10min, it
Infiltrate with 65ml dehydrated alcohol afterwards, i.e. obtain modified polyetheretherketonefiber, standby.
(2) preparation of modified multiwalled carbon nanotube
Using dodecylbenzene sodium sulfonate as surfactant, 1.00g surfactant is joined 100ml, 60 DEG C go from
In sub-water, 1.00g multi-walled carbon nano-tubes, to being completely dissolved, is then infiltrated in aqueous surfactant solution, passes through machine by stirring
Tool stirring and ultrasonic disperse process, and each sonication treatment time is 30min, repeatedly process 5 times, prepare modified multi-wall carbon nano-tube
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
By above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube mix and blend, until modified polyetheretherketonefiber surface is many without obvious modification
Wall carbon nano tube separates out, and puts into afterwards in 80 DEG C of vacuum drying ovens and is dried 48 hours；Dried composite powder is placed in ball
Ball milling 10min in grinding machine, prepares the polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of mix homogeneously.
Performance test: utilize hot press that the polyether-ether-ketone of the present embodiment/multi-walled carbon nano-tubes composite powder material is processed into test
Part.Concrete mould pressing process is: is placed in mould by composite powder, puts in 200 DEG C of hot presses and preheat, when being heated to 250 DEG C
Being forced into 6MPa, bleed off pressure preheating 1min during to 280 DEG C, repressurization, to 8MPa, is heated to 310 DEG C and bleeds off pressure preheating again
1min, repressurization to 10MPa, continue to heat up, processing temperature maintains 357 DEG C, and pressure is 10MPa, and the dwell time is
10min。
Embodiment 6
Polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, its raw material mainly includes modified polyetheretherketonefiber and modified carbon nano tube
Pipe, wherein said modified polyetheretherketonefiber is to use antioxidant to polyether-ether-ketone modification gained, and described modified carbon nano-tube is to use
Surfactant is to carbon nano-tube modification gained.
(1) preparation of modified polyetheretherketonefiber
It is placed on box resistance after being mixed homogeneously with 0.5g antioxidant 1010 and 0.5g irgasfos 168 by 99g polyether-ether-ketone powder
In stove, heat treatment 2 hours under conditions of 260 DEG C, after natural cooling, utilize ball mill to carry out physics ball milling 10min, it
Infiltrate with 50ml dehydrated alcohol afterwards, i.e. obtain modified polyetheretherketonefiber, standby.
(2) preparation of modified multiwalled carbon nanotube
Using dodecylbenzene sodium sulfonate as surfactant, 1g surfactant is joined 100ml, the deionization of 60 DEG C
In water, 4.00g multi-walled carbon nano-tubes, to being completely dissolved, is then infiltrated in aqueous surfactant solution, by machinery by stirring
Stirring and ultrasonic disperse process, and each sonication treatment time is 30min, repeatedly process 5 times, prepare modified multi-wall carbon nano-tube
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
By above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube mix and blend, until modified polyetheretherketonefiber surface is many without obvious modification
Wall carbon nano tube separates out, and puts into afterwards in 80 DEG C of vacuum drying ovens and is dried 48 hours；Dried composite powder is placed in ball
Ball milling 10min in grinding machine, prepares the polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of mix homogeneously.
Performance test: utilize hot press that the polyether-ether-ketone of the present embodiment/multi-walled carbon nano-tubes composite powder material is processed into test
Part.Concrete mould pressing process is: is placed in mould by composite powder, puts in 200 DEG C of hot presses and preheat, when being heated to 250 DEG C
Being forced into 6MPa, bleed off pressure preheating 1min during to 280 DEG C, repressurization, to 8MPa, is heated to 310 DEG C and bleeds off pressure preheating again
1min, repressurization to 10MPa, continue to heat up, processing temperature maintains 357 DEG C, and pressure is 10MPa, and the dwell time is
10min。
The actual measurement mechanical property parameters of embodiment 1-6 is as shown in table 1.
Table 1
Can be concluded that by mechanical experimental results
Embodiment 1～6 is compared with blank group (pure polyether-ether-ketone), and mechanical property is all obviously improved, hot strength maximum lift
20.5%, impact strength maximum lift 32.1%, bending strength improves 10.6%, bending modulus maximum lift 2.3%
Vicat softening point maximum improves 8.5 DEG C.
Gained polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material of the present invention is sintered on Selective Laser Sintering
Experiment, at a temperature of the preheating of 320 DEG C, paving powder functional, scanning speed be 1000mm/s, sweep span be
0.2mm, laser power be 15w process conditions under sinterable molding, it was demonstrated that composite powder material of the present invention may be used for
Selective Laser Sintering.
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of conceiving without departing from the invention, it is also possible to making some modifications and variations, these broadly fall into the protection model of the present invention
Enclose.
Claims (10)
1. polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material is answering of the raw material as selective laser sintering and moulding technology
With.
2. polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, it is characterised in that raw material mainly includes modified polyetheretherketonefiber and changes
Property CNT, wherein said modified polyetheretherketonefiber be use antioxidant to polyether-ether-ketone modification gained, described modified carbon nano tube
Pipe is to use surfactant to carbon nano-tube modification gained.
Polyether-ether-ketone the most according to claim 2/multi-walled carbon nano-tubes composite powder material, it is characterised in that described compound
In dusty material by mass percentage: multi-walled carbon nano-tubes content of powder is 0.1～10wt%.
Polyether-ether-ketone the most according to claim 2/multi-walled carbon nano-tubes composite powder material, it is characterised in that described polyethers
The mean diameter of ether ketone powder is 10～100 μm；The external diameter of described multi-walled carbon nano-tubes is 5～30nm, a length of
10～30um, purity is more than 95%.
Polyether-ether-ketone the most according to claim 2/multi-walled carbon nano-tubes composite powder material, it is characterised in that described is anti-
Oxygen agent one or several in Hinered phenols antioxidant or monothioester class auxiliary antioxidant, phosphorous acid esters auxiliary antioxidant
Kind；Described surfactant is a kind of or several in anionic surfactant so lauryl sulfate, dodecylbenzene sodium sulfonate
Kind；One in nonionic surfactant Polyethylene Glycol, tetramethylolmethane and several.
6. the preparation method of polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material, it is characterised in that comprise the steps:
(1) choose raw material by following mass percent: polyether-ether-ketone 90～99.9%, multi-walled carbon nano-tubes 0.1～10%, standby
With；
(2) respectively polyether-ether-ketone, multi-walled carbon nano-tubes are modified process and obtain modified polyetheretherketonefiber and modification many walls carbon is received
Mitron, mixes the two, is then passed through being dried, ball milling, i.e. can get polyether-ether-ketone/multi-walled carbon nano-tubes composite powder material
Material.
The preparation method of polyether-ether-ketone the most according to claim 6/multi-walled carbon nano-tubes composite powder material, its feature exists
Preparation method in described modified polyetheretherketonefiber is: carry out heat treatment with antioxidant after being mixed homogeneously by polyether-ether-ketone, after ball milling
Infiltrate with organic solvent, standby；Described antioxidant consumption is the 0.1～1.5wt% of polyether-ether-ketone quality.
The preparation method of polyether-ether-ketone the most according to claim 7/multi-walled carbon nano-tubes composite powder material, its feature exists
Temperature in described heat treatment is 220～260 DEG C, and the time is 1～2 hour；The time of described ball milling is 10～20min；Described
Organic solvent is that consumption of organic solvent is 50～70ml needed for ethanol or water or acetone, every 100g polyether-ether-ketone powder.
The preparation method of polyether-ether-ketone the most according to claim 6/multi-walled carbon nano-tubes composite powder material, its feature exists
Preparation method in described modified multiwalled carbon nanotube is: multi-walled carbon nano-tubes infiltration fully divided in aqueous surfactant solution
Dissipate uniformly, obtain modified multiwalled carbon nanotube.
The preparation method of polyether-ether-ketone the most according to claim 9/multi-walled carbon nano-tubes composite powder material, its feature
The mass concentration being described aqueous surfactant solution is 1～10mg/ml；Multi-walled carbon nano-tubes quality and surfactant water
The volume ratio of solution is 0.1～10g:100ml.
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