CN107722612A - Graphene nylon composite powder powder material and preparation method thereof and the application in 3D printing - Google Patents
Graphene nylon composite powder powder material and preparation method thereof and the application in 3D printing Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a kind of graphene nylon composite powder powder material, raw material composition includes nylon and graphene, and the graphene is powdered graphene microchip, piece footpath≤100 micron, thickness≤30 micron；In gained graphene nylon composite powder powder material, graphene is present in nylon powder surface with sheet.Preparation method is：Graphene ultrasonic disperse is first obtained into graphene dispersing solution in organic solvent A；It is placed in after nylon is mixed with organic solvent B again in autoclave, is warming up to nylon for the first time and is completely dissolved, is cooled after releasing high pressure and obtain nylon micron particles suspension；Finally graphene dispersing solution is mixed with nylon micron particles suspension, post-processed again after heating response.There is high heat conduction, electric conductivity using the graphene nylon composite powder powder material as the product that raw material is prepared through laser sintering technology, and have excellent impact property concurrently.
Description
Technical field
The present invention relates to nylon composite materials and its preparation field, and in particular to a kind of graphene nylon composite powder powder material
And preparation method thereof and the application in 3D printing.
Background technology
Increases material manufacturing technology is (also referred to as " 3D printing ") to be based on Computerized three-dimensional CAD model, by the way of successively accumulating
The method for directly manufacturing three dimensional physical entity.Increases material manufacturing technology can produce any multiple fast precise in an equipment
The parts of miscellaneous shape and structure, so as to realize " freely manufacturing ".Wherein, laser sintering technology use polymer material and engineering for
Raw material, it is not necessary to which supporting construction can directly manufacture 3 D complex structure, solve conventional fabrication processes and be difficult to or even can not process
Manufacture problem.At present, it with high polymer material is most widely used 3D printing material at present to be available for 3D printing in the world, including
PA12, PEEK etc. are no more than 30 kinds, compared with up to ten thousand kinds of injection molding high polymer materials, far can not also reach commercial Application
It is horizontal.
Polyamide is commonly called as nylon (Nylon), due to its unique low-gravity, high-tensile, wear-resisting, self lubricity is good,
Impact flexibility is excellent, has the hard and soft performance having both, and copper and alloy can be replaced to be used to make wear part, drive mechanism part extensively
Deng wear resistant pieces.But the mechanical performance of 3D printing nylon material is perfect not enough, particularly toughness and elongation at break is obvious
Less than traditional injection moulding part.In addition, the nylon powder material used at present has larger cubical contraction, part is laser sintered
During be particularly easy to warpage, this further results in the needs that its combination property is difficult to meet engineer applied.In order to improve nylon
Material mechanical property and geometrical property under low temperature and dry condition, it usually needs add various modifying agent.
Graphene is to be currently known intensity highest material, and its intensity is about 100 times of structural steel.Meanwhile graphene is also
With the in light weight, characteristic such as pliability is good, can be manufactured using the direct processing graphite alkene composite of 3D printing technique is had
High intensity, parts or product in light weight and all good pliability.In addition, one of most important property of graphene is just
It is its unique carrier properties and the dirac fermion attribute of massless, this assigns its excellent heat conduction and electric conductivity.
At present, have tried to prepare laser sintered graphene composite nylon powder using liquid-phase coprecipitation, be specifically
Graphene powder and nylon are added in organic solvent, pressurized, heating, nylon dissolves and cooled after being well mixed with graphene
Out-phase crystallizes, and obtains graphene enhancement type nylon 3D printing powder body material.The powder body material that this preparation method obtains needs graphite
Alkene is dispersed in nylon matrix and is well bonded with nylon matrix, to reach the effect above, it is necessary to using single
Layer graphene.It is expensive and the preparation technology of single-layer graphene is complicated, it is difficult to should on heat conduction, conduction and large parts
With.Multi-layer graphene increases to tens to namely about tens nanometers of hundreds of layers or so to hundreds of nano thickness or so in the number of plies,
Its property and general graphite by above-mentioned liquid-phase coprecipitation method already close to will be difficult to obtain expected enhancing effect.
In addition, be the surface accuracy and mechanical property for ensureing 3D printing component, dusty material particle diameter used need 20~120 microns it
Between, preferably 45 microns.And individual layer deflocculated graphite alkene stable dimensions are maximum reachable 20 microns, about tens nanometers of multi-layer graphene
To hundreds of nano thickness or so, and usual hundreds of microns of diameter.Due to the heterogeneous nucleating effect of graphene particles, pass through above-mentioned liquid
Graphene composite nylon powder prepared by phase coprecipitation does not simply fail to meet laser sintering system generally more than microns up to a hundred
Requirement, and 3D printing component surface is coarse, it is also necessary to largely post-processes work.
Therefore, the inexpensive graphene composite nylon 3D of suitable heat conduction, conduction and the application of large-size components field is developed
Print powder, it will promote being widely popularized with graphene composite material in Aero-Space, automobile, semiconductor for increases material manufacturing technology
With the application in terms of advanced manufacturing industry.
The content of the invention
To overcome the shortcomings of existing 3D printing graphene/nylon composite granule in terms of performance and cost, the present invention carries
A kind of graphene nylon composite powder powder material and preparation method thereof is supplied, this method does not have special want to the lamellar structure of graphene
Ask, significantly reduce manufacturing cost；The production prepared using the graphene nylon composite powder powder material as raw material through laser sintering technology
Product have high heat conduction, electric conductivity, and have excellent impact property concurrently.
Concrete technical scheme is as follows：
A kind of graphene nylon composite powder powder material, raw material composition include nylon and graphene, and described graphene is powder
The graphene microchip of last shape, piece footpath≤100 micron, thickness≤30 micron；
In the graphene nylon composite powder powder material, graphene is present in nylon powder surface with sheet.
Preferably, in terms of raw material gross mass, the mass fraction of the graphene is 0.1~5%.
Described graphene can be as the mechanical stripping method known to those skilled in the art, oxidation-reduction method, SiC epitaxial growths
The methods of method, chemical vapour deposition technique (CVD), obtains.Preferably, described graphene is selected from pure graphene microchip, oxidation stone
At least one of black alkene microplate, organically-modified graphene microchip.
Because the graphene chemical stability of complete structure is high, the inert state in surface.Can be by organic to graphene
It is modified further to improve graphene and the interaction on nylon particles surface.Organically-modified graphene microchip bag of the present invention
Include the organic functional graphene that surface obtains through the small molecule of silanization, amidatioon, absorption containing aromatic structure and polymer
Microplate.
Preferably, described nylon in nylon-6, nylon -66, nylon-610, nylon 11, nylon 12 at least
It is a kind of.Described nylon also includes the thermoplastic copolymer being made up of at least two in above-mentioned nylon.
Preferably, raw material composition also includes antitack agent, further preferred amide-type antitack agent.
The invention discloses the preparation method of described graphene nylon composite powder powder material, step are as follows：
(1) graphene ultrasonic disperse is obtained into graphene dispersing solution in organic solvent A；
(2) it is placed in after mixing nylon, the alternative antitack agent added with organic solvent B in autoclave, for the first time
Be warming up to 150~230 DEG C until nylon be completely dissolved, release high pressure after, be cooled to 60~90 DEG C, obtain nylon micron particles and hang
Supernatant liquid；
(3) graphene dispersing solution prepared by step (1) is mixed with nylon micron particles suspension prepared by step (2)
Mixed liquor, 120~150 DEG C are warming up to again, it is post-treated again after reaction to obtain described graphene nylon composite powder powder material.
The graphene nylon composite powder powder material that the present invention is prepared, with using liquid phase coprecipitation legal system in the prior art
Standby graphene nylon composite powder body phase ratio, exist 2 points it is dramatically different：
1st, structure is different：The graphene composite nylon powder that liquid-phase coprecipitation is prepared, graphene is to be uniformly distributed
Inside nylon matrix, and the product that the present invention is prepared, graphene are uniformly wrapped on nylon powder surface with sheet.
2nd, raw material is different：Liquid-phase coprecipitation has special requirement to the lamellar structure of raw graphite alkene, its piece thickness
Degree must not have particular/special requirement, even piece thickness below hundreds of nanometers, and in the present invention for the lamellar structure of graphene
Degree reach 100 microns of graphene microchip also can guarantee that composite and the product members being prepared have good heat conduction,
The physical properties such as conduction.
Preferably, in step (1), described organic solvent A is selected from ethanol, ethylene glycol, normal propyl alcohol, isopropanol, positive fourth
At least one of alcohol, acetonitrile, formic acid, N,N-dimethylformamide；
The mass percent concentration of described graphene dispersing solution is 20~65%.
In the present invention, the dissolving of nylon raw material is crucial in step (2).Normally, nylon-type condensation polymer due to compared with
High crystallinity, it is difficult to dissolve at normal temperatures.Usually, only sulfuric acid, phenol solvent, chlorinated solvents and minority is containing fluorous solvent
It can be allowed to be completely dissolved.In the present invention, the course of dissolution of nylon is carried out in autoclave, with a high speed in course of dissolution
Stirring, the temperature of course of dissolution, time need to carry out accommodation according to the nylon species specifically used.
Preferably, in step (2), described organic solvent B is selected from ethanol, ethylene glycol, normal propyl alcohol, isopropanol, positive fourth
At least one of alcohol, acetonitrile, formic acid, N,N-dimethylformamide.
To prevent superfines from bonding caking, antitack agent is optionally added, if addition antitack agent, depending on particle diameter
Size.Little particle nylon powder is needed when generally showing that required precision is higher to 3D printing component, but because surface energy is larger
It is easy to reunite, and bulky grain nylon powder resistance to bond is preferable.Preferably, addition antitack agent is suggested when D50 is less than 50 microns.As
It is preferred that described antitack agent in oleamide, erucyl amide, ethanol bis-stearamides, the double lauramides of ethanol at least
It is a kind of.The dosage of antitack agent is usually the 0.1~1% of nylon quality.
Temperature-fall period in step (2) is for ensureing that prepared graphene nylon composite powder powder material has excellent property
There can be key effect.Because nylon solution is in hypersaturated state, if cooling rate is too fast, reactor temperature is uneven,
Cause cooler regions nylon nucleation and crystallization first, secondary nucleation, particle diameter distribution inequality or particle fast growth can then occur；Such as
Fruit cooling rate is excessively slow, and in some temperature fast nucleation occurs for nylon, so as to form a large amount of little particles, it is difficult to meet that 3D printing is set
Standby demand.Preferably, the speed of cooling of the present invention is 4~10 DEG C/min, using the rate of temperature fall, it is ensured that adding
Enter to be formed before graphene the spherical nylon particles suspension of 10~120 micro-meter scales.Found through experiment, above-mentioned rate of temperature fall can be protected
Nylon powder prepared by card has optimal powder fluidity and print component mechanical property in post laser sinter molding process.
In step (3), described post processing includes separation of solid and liquid and drying process, separation of solid and liquid can use centrifugation, filtering,
The separation methods well known to those skilled in the art such as heating volatilization, vacuum distillation.
Should in 3D printing the invention also discloses the graphene nylon composite powder powder material being prepared by the above method
With described 3D printing uses Selective Laser Sintering.
Compared with prior art, the invention has the advantages that：
(1) graphene composite nylon material of the invention is micro- by the graphene in nylon powder surface doping low cost
Piece, so as to form uniform graphene network in 3D printing component, be advantageous to improve the mechanical strength of 3D printing nylon member
And physical property, particularly under conditions of single-layer graphene is not used, you can it is special to obtain higher impact strength, resistance type
Property and excellent thermal conductivity.Advantageously account for serious caused by being concentrated due to laser sintering and moulding process thermal stress stick up
Bent metaboly, and improve the toughness and application field of printout.
(2) graphene compound xylanase preparation method of the invention, employs Two Liquid Phases synthetic method, graphene is main
Nylon powder particle surface is distributed in, not only the particle diameter distribution of nylon powder is also solved because graphene is nucleated than more uniform
The problem of effect causes nylon material crystallinity to reduce, size is difficult to meet 3D printing requirement.
(3) preparation method of the invention does not need graphene dispersed in nylon matrix, thus no matter mono-layer graphite
Alkene or big size graphene particle, the powder body material for meeting 3D printing can be obtained by this method, can be greatly lowered
Cost is prepared, and it is environmentally friendly.
Brief description of the drawings
Fig. 1 is the SEM figures for the nylon powder for not adding graphene that embodiment 1 is prepared；
Fig. 2 is the SEM figures for the graphene nylon composite powder powder material that embodiment 1 is prepared.
Embodiment
For the purpose, technical scheme and advantage that the present invention is furture elucidated, below in conjunction with specific embodiment, the present invention is made
It is further to describe in detail, but protection domain not thereby limiting the invention.
Embodiment 1
(1) by about 40 μm of diameter, about 25 μm of high purity graphite alkene microplates of thickness dry 24h in 200 DEG C of baking ovens, take 1g to dry
Graphene microchip afterwards is dispersed in 1min in 100g isopropanols with ultrasonoscope (power 900w, frequency 2.45GHz), and graphite is made
Alkene dispersion liquid.
(2) by the particle of 90g nylon 12 and 900g ethanol and ethene-stearic bicine diester amine blends (ethene-bis-stearamides matter
Fraction is measured 1%) to add in autoclave, nitrogen is passed through and is forced into 1MPa, and high-speed stirred (630rpm).Temperature is risen to
145 DEG C, insulation 1h to nylon 12 is completely dissolved.High pressure is released after being completely dissolved, 68 are cooled the temperature to 4 DEG C/min speed
DEG C, the nylon micron particles suspension of 35~72 micro-meter scales is obtained, shown in SEM figures as accompanying drawing 1.
(3) graphene dispersing solution is added and be placed in the nylon micron particles suspension in autoclave, be warming up to 140
DEG C, 1MPa is forced into, after constant speed stirs 1h, is down to normal temperature and pressure (i.e. 101kPa).Powder point will be separated out by vacuum filter
From, it is thorough in 100 DEG C of vacuum drying ovens after ethanol wash to dry 10h, obtain the enhancing of the micron graphite alkene of particle size 42~98
Nylon composite powder, shown in SEM figures as accompanying drawing 2.
In the graphene nylon composite powder powder material that the present embodiment is prepared, the graphene microchip of greater particle size passes through
140 DEG C of heat treatments, uniform adsorption are prevented during 3D printing powdering due to stone in the preformed powder surface of nylon 12
Black alkene is different from nylon particles proportion and split-phase occurs, and is also beneficial to improve printer powdering speed.
Comparative example 1
The preparation method that this comparative example is co-precipitated using graphene and nylon material, to improve graphene microchip and nylon base
The adhesion of body specifically includes following steps, it is necessary to graphene oxide is made in initial oxidation：
(1) about 40 μm of 1.0g diameters, the high purity graphite alkene microplate of about 25 μm of thickness are immersed in 69% concentrated nitric acid solution, risen
Temperature carries out surface chemistry to 83 DEG C and pre-processes 3h.Then platelet is embathed into 2h with deionized water, and dried in 200 DEG C of baking ovens
24h is subsequently added to obtain in the ethanol solution of OTAC modified oxidized to remove the acid of residual and water
Graphene microchip；
(2) modified graphene oxide microplate, the particle of 90g nylon 12 and 900g ethanol and ethene-bis-stearamides are mixed
Thing (ethene-bis-stearamides mass fraction is 1%) is added in autoclave together, is passed through nitrogen and is forced into 1MPa, and high
Speed stirring (630rpm).Temperature is risen to 145 DEG C, insulation 1h to nylon 12 is completely dissolved.High pressure, temperature are released after being completely dissolved
It is down to 68 DEG C of formation nylon powder suspensions.
(3) powder will be separated out by vacuum filter to separate, thoroughly dried in 100 DEG C of vacuum drying ovens after ethanol wash
10h, obtain graphene enhancing nylon composite powder.
In graphene oxide enhancing nylon material obtained by this comparative example, graphene oxide is evenly distributed in nylon matrix,
And form chemical bond with nylon.
Comparative example 2
The preparation method that this comparative example is mixed using graphene and nylon powder material mechanical, specifically includes following steps：
(1) by the particle of 90g nylon 12 and 900g ethanol and ethene-stearic bicine diester amine blends (ethene-bis-stearamides matter
Amount fraction is forced into 1MPa, and high-speed stirred (630rpm) to be passed through nitrogen in 1%) addition autoclave.Temperature is risen to
145 DEG C, insulation 1h to nylon 12 is completely dissolved.High pressure is released after being completely dissolved, temperature is down to 68 DEG C and forms the suspension of nylon powder
Liquid.
(2) powder will be separated out by vacuum filter to separate, thoroughly dried in 100 DEG C of vacuum drying ovens after ethanol wash
10h.Nylon powder of the diameter less than 100 μm is obtained finally by screening.
(3) by about 40 μm of 1.0g diameters, the high purity graphite alkene microplate that about 25 μm of thickness and nylon powder mechanical mixture, obtain
The composite powder of graphene composite nylon 12.
In graphene oxide enhancing nylon material obtained by this comparative example, graphene oxide is evenly mixed in one with nylon particles
Rise, but between without chemically or physically combining.
Embodiment 1, comparative example 1 and the powder body material of 2 gained graphene composite nylon of comparative example 12 are used for selective laser
Sintering system, diameter of particle and manufactured properties of product are as shown in table 1.
Table 1
As shown in Table 1, the material particle size of graphene composite nylon 12 prepared by the embodiment of the present invention 1 is smaller, strong in impact
All significantly improved in degree, thermal conductivity and electric conductivity these three performance indications than traditional co-precipitation method, wherein, impact strength, which improves, to be reached
39.2%, thermal conductivity improves 1.9 times, and conductance is improved up to 3 orders of magnitude.And the mechanical mixing shown in comparative example 3, no matter mechanicalness
Energy or thermal conductivity are both more above-mentioned low.This explanation present invention on powder granule surface by adding a small amount of graphene
Particle just can reach preferable effect.
Embodiment 2
Preparation technology is identical with embodiment 1, the diameter about 130 of high purity graphite alkene microplate used by differing only in
μm, about 102 μm of thickness.Obtain the graphene enhancing nylon composite powder of 135~170 micro-meter scales.
Graphene enhancing nylon powder material granule is larger obtained by the present embodiment, during laser sintered powdering performance compared with
It is good, but printout surface has larger roughness, and tensile strength is slightly less than example 1, can reach 50.7MPa.But Z-direction thermal conductivity
It is close with embodiment 1 for 0.92W/m K, Z-direction conductance 1.68E-07S/Cm, illustrate that the graphene that the present embodiment uses is micro-
Piece can be covered in particle surface and effective thermal conductivity network can be formed in 3D printing component.
Embodiment 3
Preparation technology is identical with embodiment 1, and it is 10 DEG C/min to differ only in the rate of temperature fall in step (2).
Graphene to 75~140 micro-meter scales strengthens nylon composite powder.
Graphene obtained by the present embodiment strengthens nylon powder body material through laser sintered obtained printout, and mechanical property is with leading
The printout that electricity, heat conductivility are prepared in embodiment 1 is suitable.
Found through experiment, further improve rate of temperature fall, gained graphene enhancing nylon powder material granule is larger, and
Distribution of particles is in polydispersion state, causes that laser sintered component hole is on the high side, and corner substantially deforms, and tensile strength is significantly lower than real
Example 1.
Embodiment 4
Preparation technology is identical with embodiment 1, and it is 2 DEG C/min to differ only in the rate of temperature fall in step (2).Obtain
The graphene enhancing nylon composite powder of 10~60 micro-meter scales.
Graphene enhancing nylon powder material particle size substantially reduces obtained by the present embodiment, cause between particle viscosity compared with
Greatly, laser sintered process powdering is lumpd on a small quantity, printout tensile strength 42.1Mpa.Printout hole is more.Further reduce drop
Warm speed, it is little to performance impact but time-consuming longer.
Embodiment 5
(1) carboxylated graphene microchip is dried into 24h to remove absorption water in 200 DEG C of baking ovens, obtains graphene microchip
About 3 μm of diameter, about 27 μm of thickness.0.1g graphene microchips ultrasonoscope (power 900w, frequency 5.8GHz) is taken to be dispersed in
1min in 100g isopropanols, graphene dispersing solution is made.
(2) particle of 99.9g nylon 6 and 1000g ethylene glycol are added in reactor, is passed through argon pressurization to 1MPa, and it is high
Speed stirring (650rpm).Temperature is risen to 220 DEG C, insulation 4.5h to nylon 6 is completely dissolved.High pressure is released after being completely dissolved, temperature
Degree is down to 68 DEG C of addition graphene dispersing solutions, obtains mixed liquor.
(3) autoclave is warming up to 150 DEG C, is forced into 1MPa, after constant speed stirs 1h, is down to normal temperature and pressure (i.e.
101kPa).Powder will be separated out by vacuum filter to separate, and thoroughly be dried in 100 DEG C of vacuum drying ovens after ethanol wash
10h.Nano composite powder of the diameter less than 100 μm is obtained finally by screening.
Embodiment 6
(1) graphene dispersing solution preparation method is same as Example 1.Graphene microchip in the present embodiment is N doping graphite
Alkene.
(2) by the particle of 45g nylon 6, the particle of 45g nylon 12,1000gN, dinethylformamide and the double lauroyl of 9g ethanol
Amine is added in reactor, is passed through nitrogen and is forced into 1MPa, and high-speed stirred (650rpm).Temperature is risen to 210 DEG C, is incubated 4.5h
It is completely dissolved to nylon.High pressure is released after being completely dissolved, temperature is down to 60 DEG C of addition graphene dispersing solutions, obtains mixed liquor.This
Step pays attention to recycling N,N-dimethylformamide solvent.
(3) autoclave is warming up to 130 DEG C, after constant speed stirs 1h, is down to normal temperature and pressure.Will by vacuum filter
Powder separation is separated out, thoroughly dries 10h in 100 DEG C of vacuum drying ovens after ethanol wash.It is small that diameter is obtained finally by screening
In 50~100um nano composite powder.
Embodiment 7
(1) it is 1 by mass ratio：1 high purity graphite alkene microplate immerses 69% concentrated nitric acid solution with nitrogen-doped graphene microplate
In, it is warming up to 83 DEG C and carries out surface chemistry pretreatment 3h.Then platelet is embathed into 2h with deionized water, and in 200 DEG C of baking ovens
24h is dried to remove the acid of residual and water.Obtain about 3 μm of graphene microchip diameter, about 25 μm of thickness.Take 1g microplate ultrasonic waves
Instrument (power 900w, frequency 2.45GHz) is dispersed in 1min in 100g isopropanols, and graphene dispersing solution is made.
(2) by 19g nylon66 fiber particles, 100g formic acid and DMF mixture (mixed proportion 4:1) add
Enter in autoclave, high-speed stirred (650rpm) under condition of normal pressure.Temperature is risen to 255 DEG C, insulation 4.5h is complete to nylon66 fiber
Fully dissolved.It is completely dissolved rear temperature and is down to 60 DEG C of addition graphene dispersing solutions, obtains mixed liquor.This step pays attention to recycling N-
Solvent dimethylformamide.
(3) autoclave is warming up to 130 DEG C, after constant speed stirs 1h, is down to normal temperature and pressure.Will by vacuum filter
Powder separation is separated out, thoroughly dries 10h in 100 DEG C of vacuum drying ovens after ethanol wash.It is small that diameter is obtained finally by screening
In 50~100um nano composite powder.
The foregoing is only a specific embodiment of the invention, does not form the limitation to the scope of this patent, any
Those familiar with the art can readily occur in change or replacement, should contain in the technical scope that the present invention discloses
Cover within protection scope of the present invention.
Claims (10)
1. a kind of graphene nylon composite powder powder material, raw material composition includes nylon and graphene, it is characterised in that described stone
Black alkene is powdered graphene microchip, piece footpath≤100 micron, thickness≤30 micron；
In the graphene nylon composite powder powder material, graphene is present in nylon powder surface with sheet.
2. graphene nylon composite powder powder material according to claim 1, it is characterised in that in terms of raw material gross mass, institute
The mass fraction for stating graphene is 0.1~5%.
3. graphene nylon composite powder powder material according to claim 2, it is characterised in that described graphene is selected from pure
At least one of graphene microchip, graphene oxide microplate, organically-modified graphene microchip.
4. graphene nylon composite powder powder material according to claim 1, it is characterised in that described nylon is selected from Buddhist nun
At least one of dragon -6, nylon -66, nylon-610, nylon 11, nylon 12.
5. graphene nylon composite powder powder material according to claim 1, it is characterised in that raw material composition also includes anti-sticking
Agent.
6. a kind of preparation method of graphene nylon composite powder powder material according to Claims 1 to 5 any claim,
Characterized in that, step is as follows：
(1) graphene ultrasonic disperse is obtained into graphene dispersing solution in organic solvent A；
(2) it is placed in after mixing nylon, the alternative antitack agent added with organic solvent B in autoclave, first heating
To 150~230 DEG C until nylon is completely dissolved, after releasing high pressure, 60~90 DEG C are cooled to, obtains the suspension of nylon micron particles
Liquid；
(3) graphene dispersing solution prepared by step (1) is mixed and must mixed with nylon micron particles suspension prepared by step (2)
Liquid, 120~150 DEG C are warming up to again, it is post-treated again after reaction to obtain described graphene nylon composite powder powder material.
7. the preparation method of graphene nylon composite powder powder material according to claim 6, it is characterised in that step (1)
In, described organic solvent A is selected from ethanol, ethylene glycol, normal propyl alcohol, isopropanol, n-butanol, acetonitrile, formic acid, N, N- dimethyl methyls
At least one of acid amides；
The mass percent concentration of described graphene dispersing solution is 20~65%.
8. the preparation method of graphene nylon composite powder powder material according to claim 6, it is characterised in that step (2)
In, described organic solvent B is selected from ethanol, ethylene glycol, normal propyl alcohol, isopropanol, n-butanol, acetonitrile, formic acid, N, N- dimethyl methyls
At least one of acid amides；
Described antitack agent in oleamide, erucyl amide, ethanol bis-stearamides, the double lauramides of ethanol at least one
Kind.
9. the preparation method of graphene nylon composite powder powder material according to claim 6, it is characterised in that step (2)
In, the speed of the cooling is 4~10 DEG C/min.
10. a kind of graphene nylon composite powder powder material according to Claims 1 to 5 any claim is in 3D printing
Using, it is characterised in that described 3D printing uses Selective Laser Sintering.
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