CN105860431B - A kind of polyether-ether-ketone/multi-walled carbon nanotube composite powder material and preparation method thereof for Selective Laser Sintering - Google Patents
A kind of polyether-ether-ketone/multi-walled carbon nanotube composite powder material and preparation method thereof for Selective Laser Sintering Download PDFInfo
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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
- C08K9/00—Use of pretreated ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
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Abstract
The preparation method for polyether-ether-ketone/multi-walled carbon nanotube composite powder material that the present invention provides a kind of for Selective Laser Sintering, raw material includes mainly modified polyetheretherketonefiber and modified carbon nano-tube, the wherein described modified polyetheretherketonefiber is to be modified gained to polyether-ether-ketone using antioxidant, and the modified carbon nano-tube is using surfactant to obtained by carbon nano-tube modification.Polyether-ether-ketone provided by the invention/multi-walled carbon nanotube composite powder is while remaining polyether-ether-ketone original high temperature resistance, polyether-ether-ketone powder grain size regularity is improved to a certain extent, improve the apparent density of polyether-ether-ketone powder, to meet requirement of the Selective Laser Sintering to powder for molding, and under conditions of multi-walled carbon nanotube dosage is seldom, it has been obviously improved the mechanical property and hot property of composite powder material, its application in high temperature resistant field has been widened, the dusty material of high-intensity high heat-resistance is provided for Selective Laser Sintering.
Description
Technical field
Polyether-ether-ketone/multi-walled carbon nanotube composite powder that present invention relates particularly to a kind of for Selective Laser Sintering
Powder material and preparation method thereof.
Background technology
Selective laser sintering (SLS) technology is a kind of to be sintered the molding 3D of dusty material as heat source with infrared laser
Printing technique.Polymer material and engineering currently used for SLS technologies mainly has to be polymerize by the non-crystalline type of representative of polystyrene
Object dusty material and be the Crystalline plastics dusty material of representative with nylon 12.Polystyrene based powdered material sinter molding part
Mechanical strength be far below its bulk strength, be mainly used for making model and full form casting process；12 based powdered material of nylon is burnt
The mechanical strength of molded part is tied close to the bulk strength of nylon 12, tensile strength reaches 40~50MPa, is current Physical Mechanical
It can preferably a kind of polymeric powder agglomerated material.With the development of SLS technologies, an urgent demand is developed more preferably than 12 performance of nylon
Sintered powder material, to adapt to the fields such as aerospace to product high intensity, high heat-resisting requirement.Polyether-ether-ketone (PEEK) is one
The polymer of the heat-resisting crystal type of kind, has very excellent strength and stiffness, fatigue performance excellent；Chemical stability is good,
Oil resistant is acidproof corrosion-resistant, and in common chemical reagent, only the concentrated sulfuric acid can destroy its structure；Polyether-ether-ketone resin has excellent
Sliding properties, anti-flammability and radiation resistance；Also there is good biocompatibility.It is usually used in auto industry, electrical equipment industry, doctor
Treat instrument and aerospace field.It can further improve the Physical Mechanical of polyether-ether-ketone using carbon nanotube as reinforcing agent
Energy.Compound be prepared into of polyether-ether-ketone and carbon nanotube is suitable for the sintered powder materials of SLS techniques, can have and be much better than nylon
12 comprehensive performance, emerging in recent years has significant advantage suitable for the material of SLS forming techniques.
Dusty material required by SLS technologies needs with average grain diameter to be 50 μm or so, powder regularity height, mobility
The features such as good.The currently used method for preparing polymeric powder agglomerated material mainly has low-temperature grinding method and solvent precipitation.
But low-temperature grinding method needs specific deep freeze refrigeration plant, investment is more, and energy expenditure is big, and material, which needs repeatedly to crush, can be only achieved ratio
Comparatively ideal Particle size requirements (such as makrolon, polystyrene), and powder morphology obtained is very irregular；Solvent precipitation
Dusty material (such as nylon 11, nylon 12) is generally prepared using autoclave using organic solvents such as ethyl alcohol, due to poly-
Ether ether ketone can not be dissolved in the solvent in addition to the concentrated sulfuric acid, and therefore, solvent precipitation is not easy to implement.Exist between carbon nanotube
Stronger Van der Waals force makes it be easy to happen reunion, it is difficult to disperses in a polymer matrix, meanwhile, carbon nanotube and polymer
The binding ability of matrix is weaker, is easy to generate Relative sliding with matrix when by shearing force, to influence the power of composite material
Learn performance.
Invention content
The technical problem to be solved by the present invention is to provide a kind of for selecting in view of the deficiency of the prior art
The preparation method of the polyether-ether-ketone of selecting property laser sintering technology/multi-walled carbon nanotube composite powder material improves polyether-ether-ketone powder
The shortcomings that last regularity is low, poor fluidity and multi-walled carbon nanotube due to caused by reuniting between matrix interface bonding energy
Hypodynamic problem meets requirement of the Selective Laser Sintering to dusty material.
A kind of polyether-ether-ketone/multi-walled carbon nanotube composite powder material for Selective Laser Sintering, raw material
Include mainly modified polyetheretherketonefiber and modified carbon nano-tube, wherein the modified polyetheretherketonefiber is to use antioxidant to polyethers ether
Ketone is modified gained, and the modified carbon nano-tube is using surfactant to obtained by carbon nano-tube modification.
By said program, it is by mass percentage in the composite powder material：Multi-walled carbon nanotube content of powder is
0.1~10wt%.
By said program, the grain size of the polyether-ether-ketone powder is 10~100 μm, 40~60 μm of average grain diameter.
By said program, the outer diameter of the multi-walled carbon nanotube is 5~30nm, and length is 10~30 μm, and purity is more than
95%.Single-walled carbon nanotube price is high, and draw ratio is more than multi-walled carbon nanotube, and agglomeration is more serious, it is not easy to disperse；It is more
Wall carbon nano tube surface roughness is big, can improve the Interface adhesive strength with polyether-ether-ketone matrix.
By said program, primary antioxidant is Hinered phenols antioxidant in the antioxidant, selected from antioxidant 1098, antioxygen
Agent 1076, antioxidant hp136, antioxidant 2921T, one or more of antioxidant 1010；Or supplemented by the antioxidant
Aid anti-oxidants, it is phosphite ester kind antioxidant (such as antioxidant 168) or one kind or several in thioester antioxidant to be selected from
Kind.
By said program, the surfactant is anionic surfactant so lauryl sulfate, dodecyl
It is one or more of in benzene sulfonic acid sodium salt；One or more of nonionic surface active agent polyethylene glycol, pentaerythrite.
The preparation method of polyether-ether-ketone of the present invention/multi-walled carbon nanotube composite powder material, includes the following steps：
(1) the selection raw material based on following mass percent：Polyether-ether-ketone 90~99.9%, multi-walled carbon nanotube 0.1~
10%, it is spare；
(2) processing is modified to polyether-ether-ketone, multi-walled carbon nanotube respectively and obtains modified polyetheretherketonefiber and modified multi wall
Carbon nanotube, by drying, ball milling after the two is mixed, you can obtain polyether-ether-ketone/multi-walled carbon nanotube composite powder material.
By said program, the preparation method of the modified polyetheretherketonefiber is：After mixing by polyether-ether-ketone and antioxidant
It is heat-treated, is infiltrated with organic solvent after ball milling, it is spare.Wherein, the antioxidant dosage is 0.1~1.5wt%；It is described
The temperature of heat treatment is 220-260 DEG C, and the time is 1-2 hours；The time of the ball milling is 10-20min, ball milling speed 480
~500r/min, ball milling are zirconia ceramics ball, a diameter of 5mm~15mm with ball；The organic solvent is ethyl alcohol or water or third
Ketone etc. is 50~70ml per 100g polyether-ether-ketone powder consumption of organic solvent.
By said program, the preparation method of the modified multiwalled carbon nanotube is：Multi-walled carbon nanotube is infiltrated on surface
It is uniformly dispersed in aqueous surfactant solutions, obtains modified multiwalled carbon nanotube.Wherein, the quality of the aqueous surfactant solution
A concentration of 1~10mg/ml；Multi-walled carbon nanotube quality and the volume ratio of aqueous surfactant solution are 0.1~10g：100ml；
The dispersion can be handled by mechanical agitation and/or ultrasonic disperse.The preferred 20-40min of sonication treatment time, repeatedly handle 3~
5 times.
Polyether-ether-ketone proposed by the present invention/multi-walled carbon nanotube composite powder material is to carry out object to polyether-ether-ketone powder
The surface of reason processing and multi-walled carbon nanotube is modified.By being higher by 70 DEG C of polyether-ether-ketone glass transition temperature or more progress heat
Processing, accelerates the movement of macromolecular chain segment, and polyether-ether-ketone is prevented at high temperature by the way that primary antioxidant is added with auxiliary antioxidant
Oxidation, improve the mobility and regularity of powder by physics ball milling later, to be satisfied with selective laser sintering work
Requirement of the skill to powder；By be added surfactant and carry out ultrasonic disperse come improve the agglomeration of multi-walled carbon nanotube with
And with basis material Interface adhesive strength, finally effectively improve the mechanical strength and heat resistance of composite powder material.
Compared with prior art.Beneficial effects of the present invention are：
1. the present invention improves the mobility and regularity of polyether-ether-ketone powder using heat treatment and physics ball milling, than common
The requirement that physical low-temperature is crushed to equipment is lower, while will not reduce polyether-ether-ketone because of chemical graft active group
Mechanical strength and heat resistance；
2. the agglomeration of multi-walled carbon nanotube significantly improves in the present invention, the surface for improving multi-walled carbon nanotube is lived
Property, and have preferable Interface adhesive strength between polyether-ether-ketone matrix.
3, polyether-ether-ketone/multi-walled carbon nanotube composite powder material prepared by the present invention, effectively improves commercially available polyethers
The disadvantage and multi-walled carbon nanotube that ether ketone powder particle regularity is poor, apparent density is not high are due to caused and matrix of reuniting
Between the not strong problem of Interface adhesive strength, and under conditions of multi-walled carbon nanotube dosage is seldom, hence it is evident that improve compound
The mechanical property and hot property of dusty material have been widened its application in high temperature resistant field, have been carried for Selective Laser Sintering
The dusty material of high-intensity high heat-resistance is supplied.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
The grain size of polyether-ether-ketone powder employed in following embodiments is 10~100 μm, 40~60 μm of average grain diameter；It is more
The outer diameter of wall carbon nano tube is 5~30nm, and length is 10~30 μm, and purity is more than 95%.
Polyether-ether-ketone of the present invention/multi-walled carbon nanotube composite powder material is processed into test block using mould pressing process.
The mould pressing process condition is：Composite powder material is put into 200 DEG C of hot presses and is preheated, is heated to adding at 220~250 DEG C
It is depressed into 4~6MPa；It is heated to bleeding off pressure preheating 1min, repressurization to 6~8MPa at 260~280 DEG C；It is heated to 290~310 DEG C again
Bleed off pressure preheating 1min, repressurization to 8~10MPa；Continuing to heat up, processing temperature maintains 355~365 DEG C, and pressure is 8~
12MPa, dwell time are 10~15min.
Embodiment 1
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material, raw material include mainly modified polyetheretherketonefiber and carbon modified
Nanotube, wherein the modified polyetheretherketonefiber is to be modified gained, the modified carbon nano-tube to polyether-ether-ketone using antioxidant
It is to use surfactant to obtained by carbon nano-tube modification.
(1) preparation of modified polyetheretherketonefiber
99g polyether-ether-ketone powders and 1g antioxidant hp136 are placed in chamber type electric resistance furnace after mixing, at 220 DEG C
Under conditions of be heat-treated 2 hours, after natural cooling, using ball mill carry out physics ball milling 10min, later use 50ml absolute ethyl alcohols
Infiltration is spare to get to modified polyetheretherketonefiber.
(2) preparation of modified multiwalled carbon nanotube
Using lauryl sodium sulfate as surfactant, 0.25g surfactants are added to going for 60 DEG C of 100ml
It in ionized water, stirs to being completely dissolved, then passes through the infiltration of 0.25g multi-walled carbon nanotubes in aqueous surfactant solution
Mechanical agitation and ultrasonic disperse processing, each sonication treatment time are 30min, are handled 5 times repeatedly, and modified multi-wall carbon nano-tube is made
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nanotube composite powder material
Above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube are mixed, until modified polyetheretherketonefiber surface is without apparent
Modified multiwalled carbon nanotube is precipitated, and is put into later in 80 DEG C of vacuum drying chambers 48 hours dry；By dried composite powder
It is placed in ball milling 10min in ball mill, uniformly mixed polyether-ether-ketone/multi-walled carbon nanotube composite powder material is made.
Performance test：The polyether-ether-ketone of the present embodiment/multi-walled carbon nanotube composite powder material is processed using hot press
At test block.Specifically mould pressing process is：Composite powder is placed in mold, is put into 200 DEG C of hot presses and preheats, be heated to 250
DEG C when be forced into 6MPa, until 280 DEG C of whens bleed off pressure preheating 1min, repressurization to 8MPa is heated to 310 DEG C and bleeds off pressure preheating 1min again,
Repressurization continues to heat up to 10MPa, and processing temperature maintains 357 DEG C, pressure 10MPa, dwell time 10min.
Embodiment 2
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material, raw material include mainly modified polyetheretherketonefiber and carbon modified
Nanotube, wherein the modified polyetheretherketonefiber is to be modified gained, the modified carbon nano-tube to polyether-ether-ketone using antioxidant
It is to use surfactant to obtained by carbon nano-tube modification.
(1) preparation of modified polyetheretherketonefiber
99g polyether-ether-ketone powders and 1g antioxidant hp136 are placed in chamber type electric resistance furnace after mixing, at 240 DEG C
Under conditions of be heat-treated 2 hours, after natural cooling, using ball mill carry out physics ball milling 10min, later use 50ml absolute ethyl alcohols
Infiltration is spare to get to modified polyetheretherketonefiber.
(2) preparation of modified multiwalled carbon nanotube
Using lauryl sodium sulfate as surfactant, by 0.25g surfactants be added to 100ml, 60 DEG C go
It in ionized water, stirs to being completely dissolved, then passes through the infiltration of 0.25g multi-walled carbon nanotubes in aqueous surfactant solution
Mechanical agitation and ultrasonic disperse processing, each sonication treatment time are 30min, are handled 5 times repeatedly, and modified multi-wall carbon nano-tube is made
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nanotube composite powder material
Above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube are mixed, until modified polyetheretherketonefiber surface is without apparent
Modified multiwalled carbon nanotube is precipitated, and is put into later in 80 DEG C of vacuum drying chambers 48 hours dry；By dried composite powder
It is placed in ball milling 10min in ball mill, uniformly mixed polyether-ether-ketone/multi-walled carbon nanotube composite powder material is made.
Performance test：The polyether-ether-ketone of the present embodiment/multi-walled carbon nanotube composite powder material is processed using hot press
At test block.Specifically mould pressing process is：Composite powder is placed in mold, is put into 200 DEG C of hot presses and preheats, be heated to 250
DEG C when be forced into 6MPa, until 280 DEG C of whens bleed off pressure preheating 1min, repressurization to 8MPa is heated to 310 DEG C and bleeds off pressure preheating 1min again,
Repressurization continues to heat up to 10MPa, and processing temperature maintains 357 DEG C, pressure 10MPa, dwell time 10min.
Embodiment 3
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material, raw material include mainly modified polyetheretherketonefiber and carbon modified
Nanotube, wherein the modified polyetheretherketonefiber is to be modified gained, the modified carbon nano-tube to polyether-ether-ketone using antioxidant
It is to use surfactant to obtained by carbon nano-tube modification.
(1) preparation of modified polyetheretherketonefiber
99g polyether-ether-ketone powders and 1g antioxidant hp136 are placed in chamber type electric resistance furnace after mixing, at 260 DEG C
Under conditions of be heat-treated 2 hours, after natural cooling, using ball mill carry out physics ball milling 10min, later use 50ml absolute ethyl alcohols
Infiltration is spare to get to modified polyetheretherketonefiber.
(2) preparation of modified multiwalled carbon nanotube
Using lauryl sodium sulfate as surfactant, by 0.25g surfactants be added to 100ml, 60 DEG C go
It in ionized water, stirs to being completely dissolved, then passes through the infiltration of 0.25g multi-walled carbon nanotubes in aqueous surfactant solution
Mechanical agitation and ultrasonic disperse processing, each sonication treatment time are 30min, are handled 5 times repeatedly, and modified multi-wall carbon nano-tube is made
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nanotube composite powder material
Above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube are mixed, until modified polyetheretherketonefiber surface is without apparent
Modified multiwalled carbon nanotube is precipitated, and is put into later in 80 DEG C of vacuum drying chambers 48 hours dry；By dried composite powder
It is placed in ball milling 10min in ball mill, uniformly mixed polyether-ether-ketone/multi-walled carbon nanotube composite powder material is made.
Performance test：The polyether-ether-ketone of the present embodiment/multi-walled carbon nanotube composite powder material is processed using hot press
At test block.Specifically mould pressing process is：Composite powder is placed in mold, is put into 200 DEG C of hot presses and preheats, be heated to 250
DEG C when be forced into 6MPa, until 280 DEG C of whens bleed off pressure preheating 1min, repressurization to 8MPa is heated to 310 DEG C and bleeds off pressure preheating 1min again,
Repressurization continues to heat up to 10MPa, and processing temperature maintains 357 DEG C, pressure 10MPa, dwell time 10min.
Embodiment 4
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material, raw material include mainly modified polyetheretherketonefiber and carbon modified
Nanotube, wherein the modified polyetheretherketonefiber is to be modified gained, the modified carbon nano-tube to polyether-ether-ketone using antioxidant
It is to use surfactant to obtained by carbon nano-tube modification.
(1) preparation of modified polyetheretherketonefiber
98.5g polyether-ether-ketone powders are placed on 1g antioxidant 1010s and 0.5g irgasfos 168s after mixing box
It in resistance furnace, is heat-treated 1 hour under conditions of 240 DEG C, after natural cooling, physics ball milling 20min is carried out using ball mill, it
60ml acetone is used to infiltrate to get to modified polyetheretherketonefiber afterwards, it is spare.
(2) preparation of modified multiwalled carbon nanotube
Using lauryl sodium sulfate as surfactant, 3g surfactants are added to 100ml, 60 DEG C of deionization
It in water, stirs to being completely dissolved, the infiltration of 6g multi-walled carbon nanotubes is then passed through into mechanical agitation in aqueous surfactant solution
With ultrasonic disperse processing, each sonication treatment time is 30min, handles 5 times repeatedly, modified multiwalled carbon nanotube is made.
(3) preparation of polyether-ether-ketone/multi-walled carbon nanotube composite powder material
Above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube are mixed, until modified polyetheretherketonefiber surface is without apparent
Modified multiwalled carbon nanotube is precipitated, and is put into later in 80 DEG C of vacuum drying chambers 48 hours dry；By dried composite powder
It is placed in ball milling 10min in ball mill, uniformly mixed polyether-ether-ketone/multi-walled carbon nanotube composite powder material is made.
Performance test：The polyether-ether-ketone of the present embodiment/multi-walled carbon nanotube composite powder material is processed using hot press
At test block.Specifically mould pressing process is：Composite powder is placed in mold, is put into 200 DEG C of hot presses and preheats, be heated to 250
DEG C when be forced into 6MPa, until 280 DEG C of whens bleed off pressure preheating 1min, repressurization to 8MPa is heated to 310 DEG C and bleeds off pressure preheating 1min again,
Repressurization continues to heat up to 10MPa, and processing temperature maintains 357 DEG C, pressure 10MPa, dwell time 10min.
Embodiment 5
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material, raw material include mainly modified polyetheretherketonefiber and carbon modified
Nanotube, wherein the modified polyetheretherketonefiber is to be modified gained, the modified carbon nano-tube to polyether-ether-ketone using antioxidant
It is to use surfactant to obtained by carbon nano-tube modification.
(1) preparation of modified polyetheretherketonefiber
99g polyether-ether-ketone powders are placed on 0.5g antioxidant 1010s and 0.5g irgasfos 168s after mixing box
It in resistance furnace, is heat-treated 2 hours under conditions of 260 DEG C, after natural cooling, physics ball milling 10min is carried out using ball mill, it
65ml absolute ethyl alcohols are used to infiltrate to get to modified polyetheretherketonefiber afterwards, it is spare.
(2) preparation of modified multiwalled carbon nanotube
Using neopelex as surfactant, by 1.00g surfactants be added to 100ml, 60 DEG C
It in deionized water, stirs to being completely dissolved, then leads to the infiltration of 1.00g multi-walled carbon nanotubes in aqueous surfactant solution
Mechanical agitation and ultrasonic disperse processing are crossed, each sonication treatment time is 30min, is handled 5 times repeatedly, and modified multi wall carbon is made and receives
Mitron.
(3) preparation of polyether-ether-ketone/multi-walled carbon nanotube composite powder material
Above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube are mixed, until modified polyetheretherketonefiber surface is without apparent
Modified multiwalled carbon nanotube is precipitated, and is put into later in 80 DEG C of vacuum drying chambers 48 hours dry；By dried composite powder
It is placed in ball milling 10min in ball mill, uniformly mixed polyether-ether-ketone/multi-walled carbon nanotube composite powder material is made.
Performance test：The polyether-ether-ketone of the present embodiment/multi-walled carbon nanotube composite powder material is processed using hot press
At test block.Specifically mould pressing process is：Composite powder is placed in mold, is put into 200 DEG C of hot presses and preheats, be heated to 250
DEG C when be forced into 6MPa, until 280 DEG C of whens bleed off pressure preheating 1min, repressurization to 8MPa is heated to 310 DEG C and bleeds off pressure preheating 1min again,
Repressurization continues to heat up to 10MPa, and processing temperature maintains 357 DEG C, pressure 10MPa, dwell time 10min.
Embodiment 6
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material, raw material include mainly modified polyetheretherketonefiber and carbon modified
Nanotube, wherein the modified polyetheretherketonefiber is to be modified gained, the modified carbon nano-tube to polyether-ether-ketone using antioxidant
It is to use surfactant to obtained by carbon nano-tube modification.
(1) preparation of modified polyetheretherketonefiber
99g polyether-ether-ketone powders are placed on 0.5g antioxidant 1010s and 0.5g irgasfos 168s after mixing box
It in resistance furnace, is heat-treated 2 hours under conditions of 260 DEG C, after natural cooling, physics ball milling 10min is carried out using ball mill, it
50ml absolute ethyl alcohols are used to infiltrate to get to modified polyetheretherketonefiber afterwards, it is spare.
(2) preparation of modified multiwalled carbon nanotube
Using neopelex as surfactant, by 1g surfactants be added to 100ml, 60 DEG C go from
It in sub- water, stirs to being completely dissolved, the infiltration of 4.00g multi-walled carbon nanotubes is then passed through into machine in aqueous surfactant solution
Tool stirs and ultrasonic disperse processing, and each sonication treatment time is 30min, is handled 5 times repeatedly, and modified multi-wall carbon nano-tube is made
Pipe.
(3) preparation of polyether-ether-ketone/multi-walled carbon nanotube composite powder material
Above-mentioned modified polyetheretherketonefiber and modified carbon nano-tube are mixed, until modified polyetheretherketonefiber surface is without apparent
Modified multiwalled carbon nanotube is precipitated, and is put into later in 80 DEG C of vacuum drying chambers 48 hours dry；By dried composite powder
It is placed in ball milling 10min in ball mill, uniformly mixed polyether-ether-ketone/multi-walled carbon nanotube composite powder material is made.
Performance test：The polyether-ether-ketone of the present embodiment/multi-walled carbon nanotube composite powder material is processed using hot press
At test block.Specifically mould pressing process is：Composite powder is placed in mold, is put into 200 DEG C of hot presses and preheats, be heated to 250
DEG C when be forced into 6MPa, until 280 DEG C of whens bleed off pressure preheating 1min, repressurization to 8MPa is heated to 310 DEG C and bleeds off pressure preheating 1min again,
Repressurization continues to heat up to 10MPa, and processing temperature maintains 357 DEG C, pressure 10MPa, dwell time 10min.
The actual measurement mechanical property parameters of embodiment 1-6 are as shown in table 1.
Table 1
It can be obtained by mechanical experimental results to draw a conclusion：
Compared with blank group (pure polyether-ether-ketone), mechanical property is obviously improved Examples 1 to 6, and tensile strength is maximum
Improve 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.
Polyether-ether-ketone/multi-walled carbon nanotube composite powder material obtained by the present invention is enterprising in Selective Laser Sintering
Row sintering experiment, under 320 DEG C of preheating temperature, powdering is functional, sweep speed is 1000mm/s, sweep span is
Sinterable molding under 0.2mm, the process conditions that laser power is 15w, it was demonstrated that composite powder material of the present invention can be used for
Selective Laser Sintering.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (5)
1. polyether-ether-ketone/multi-walled carbon nanotube composite powder material alternatively answer by the raw material of property laser sintering and moulding technology
With, it is characterised in that the preparation method of polyether-ether-ketone/multi-walled carbon nanotube composite powder material includes the following steps：
（1）The selection raw material based on following mass percent：Polyether-ether-ketone 90 ~ 99.9%, multi-walled carbon nanotube 0.1 ~ 10 %, it is spare；
（2）Polyether-ether-ketone is heat-treated after mixing with antioxidant, the temperature of heat treatment is 220 ~ 260 DEG C, the time 1
It ~ 2 hours, is infiltrated with organic solvent after ball milling, it is spare to obtain modified polyetheretherketonefiber；The antioxidant dosage is polyether-ether-ketone matter
0.1 ~ 1.5wt% of amount；
Multi-walled carbon nanotube infiltration ultrasonic disperse in aqueous surfactant solution is uniform, obtain modified multiwalled carbon nanotube；
（3）Both modified polyetheretherketonefiber and modified multiwalled carbon nanotube mix, then by dry, ball milling, you can obtain polyethers
Ether ketone/multi-walled carbon nanotube composite powder material.
2. alternatively property is laser sintered for polyether-ether-ketone according to claim 1/multi-walled carbon nanotube composite powder material
The application of the raw material of forming technique, it is characterised in that the average grain diameter of the polyether-ether-ketone powder is 10 ~ 100 μm；The multi wall
The outer diameter of carbon nanotube is 5 ~ 30nm, and length is 10 ~ 30 μm, and purity is more than 95%.
3. alternatively property is laser sintered for polyether-ether-ketone according to claim 1/multi-walled carbon nanotube composite powder material
The application of the raw material of forming technique, it is characterised in that the antioxidant is selected from Hinered phenols antioxidant or thioesters assist
One or more of antioxidant, phosphorous acid esters auxiliary antioxidant；The surfactant is anionic surfactant
It is one or more of in lauryl sodium sulfate, neopelex；Nonionic surface active agent polyethylene glycol, Ji Wusi
One or more of alcohol.
4. alternatively property is laser sintered for polyether-ether-ketone according to claim 1/multi-walled carbon nanotube composite powder material
The application of the raw material of forming technique, it is characterised in that the time of the ball milling is 10 ~ 20min；The organic solvent be ethyl alcohol or
Acetone is 50 ~ 70mL per consumption of organic solvent needed for 100g polyether-ether-ketone powders.
5. alternatively property is laser sintered for polyether-ether-ketone according to claim 1/multi-walled carbon nanotube composite powder material
The application of the raw material of forming technique, it is characterised in that the mass concentration of the aqueous surfactant solution is 1 ~ 10mg/mL；It is more
Wall carbon nano tube quality and the volume ratio of aqueous surfactant solution are 0.1 ~ 10g：100mL.
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| CN109675116A (en) * | 2019-02-18 | 2019-04-26 | 永康市仁合五金制品有限公司 | A kind of preparation method of PEEK composite material joint prosthesis |
| CN110157149A (en) * | 2019-05-13 | 2019-08-23 | 西安交通大学 | A kind of polyetherether ketone composition and preparation method thereof for selective laser sintering |
| US20220135740A1 (en) * | 2020-11-05 | 2022-05-05 | The Texas A&M University System | Poly(aryl ether ketone) compositions containing carbon-based nanomaterials |
| CN114573894B (en) * | 2020-12-01 | 2024-03-01 | 中国石油天然气股份有限公司 | Carbon nano tube master batch and preparation method and application thereof |
| CN114437500B (en) * | 2021-12-22 | 2023-06-30 | 重庆交通大学绿色航空技术研究院 | Polyether-ether-ketone composite powder for laser selective sintering and preparation method thereof |
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