CN106146864A - Graphene/polypropylene composite materials dusty material and preparation method for SLS - Google Patents
Graphene/polypropylene composite materials dusty material and preparation method for SLS Download PDFInfo
- Publication number
- CN106146864A CN106146864A CN201610859919.5A CN201610859919A CN106146864A CN 106146864 A CN106146864 A CN 106146864A CN 201610859919 A CN201610859919 A CN 201610859919A CN 106146864 A CN106146864 A CN 106146864A
- Authority
- CN
- China
- Prior art keywords
- graphene
- sls
- polypropylene
- composite materials
- supersound process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Abstract
The invention provides a kind of Graphene for SLS/polypropylene composite materials dusty material and preparation method, the preparation method of described composite powder material includes that the oxidation of Graphene is with surface-functionalized, then surface-functionalized graphene uniform is disperseed in aqueous, add polypropylene powder, it is stirred vigorously, rotary heating evaporates, and drying grinding is sieved and obtained composite powder material.The present invention uses the method for solution dispersion to be disperseed in the solution by graphene uniform, graphene uniform is dispersed in macromolecule matrix polypropylene during later stage solution evaporation again, the composite form preparing gained is uniform, size is suitable, good fluidity, the paving powder of beneficially SLS technology and laser sintered process.
Description
Technical field
The invention belongs to macromolecule material preparation area, more particularly, to a kind of Graphene/polypropylene for SLS
Composite powder material and preparation method.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) is a kind of increasing material manufacturing technology
(Additive Manufacturing, AM), it is by means of computer aided design and manufacture, uses Layered manufacturing superposition former
Reason, is Three-dimensional Entity Components by pressed powder direct forming.It is extensive that this technology has suitable material, it is not necessary to supports and shapes essence
Degree advantages of higher, is widely used in the numerous areas such as space flight and aviation, auto industry.Generally, SLS is special without the shaping of extraneous driving force
Point determines and also can there are some holes inside its drip molding, causes its mechanical property (such as intensity, toughness and fatigue durability etc.)
The most traditional molded item.At present, make composite by adding Nano filling, macromolecule matrix can be made by force
The aspects such as degree, fatigue performance keep toughness not decline while being increased dramatically, thus become raising SLS drip molding performance
Main path.
Polypropylene (Polypropylene.PP) is a kind of thermoplastic resin prepared by propylene polymerization, is the current world
On be most widely used, one of resin that increase of production is the fastest.PP has low-density, high-melting-point, price is low, mechanical performance is superior
And the feature such as chemical stability is good, it is indispensable base stock in fields such as electronics, electrical equipment, automobiles.But, polypropylene
SLS product cannot meet the high-tech area that performance requirement is high, need to strengthen part performance by adding Nano filling.Stone
Ink alkene (Graphene) is the two-dimensional material that the carbon atomic layer connected with SP2 hydridization is constituted, and its thickness is only an atomic layer
Thickness, its mechanical property (hot strength is up to 130GPa) with excellence and thermal property (thermal conductivity reaches 5300W/m k).
By adding a small amount of Graphene, it is possible to improve mechanical property and the thermal property of polypropylene SLS product.
But, presently disclosed data mainly has following methods can be used for prepare SLS polypropylene composite materials powder: 1) machine
Tool mixing method (application number 201410129572.X), i.e. by by polymeric powder and Nano filling at ball milling, three-dimensional kneader
Or other mixing apparatus carry out mechanical mixture.The method has that technique is simple, low cost and other advantages, but cannot be by Nano filling
It is evenly dispersed in macromolecule matrix；2)+low-temperature grinding method (application number 201410544610.8) is melt extruded, will high score
Sub-granule mixes according to a certain percentage with Nano filling, and through twin-screw extrusion, pelletize is pulverized the most at low temperatures.The method energy
Enough nano material is dispersed in macromolecule matrix, but obtained composite powder pattern is irregular, affects SLS product
Performance.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of for selective laser sintering technology
(SLS) Graphene/polypropylene composite materials dusty material and preparation method thereof, it uses solution blending evaporation Graphene is equal
Being dispersed in polypropylene matrix, the composite powder material of preparation has good mobility, suitable particle diameter and particle diameter and divides evenly
Cloth, excellent sintering character, it is adaptable to selective laser sintering technique, the performance of product also gets a promotion, and solves the most poly-third
The technical problem that alkene SLS part performance is the highest.
For achieving the above object, according to one aspect of the present invention, it is proposed that a kind of Graphene/polypropylene for SLS
The preparation method of composite powder material, comprises the steps:
(1) graphite flake is added in the mixed solution of concentrated sulphuric acid and nitric acid, after stirring 16h, use deionized water cyclic washing
Solution, to neutral, be then placed at a temperature of 100 DEG C and be dried under vacuum to constant weight by solution, then at 1050 DEG C after heat treatment 15s
Obtain expanded graphite, described expanded graphite is put in the ethanol water of 70vol%, after supersound process 8h, filter and 100
It is vacuum dried at DEG C, obtains graphene oxide；
(2) being dispersed in ethanol water by the graphene oxide obtained in step (1), supersound process is also acutely stirred
Mix, be slowly added to silane coupler, and at 70-80 DEG C, keep 20-28h, then sucking filtration, washing, be vacuum dried at 60 DEG C
To constant weight, obtain functionalization graphene；
(3) functionalization graphene obtained in surfactant and step (2) is added to ethanol water, ultrasonic place
Manage and be stirred vigorously and obtain uniform dispersion liquid；
(4) choose the particle diameter polypropylene powder in 10～150 μm, while being stirred vigorously, polypropylene powder is gradually added
Entering to the uniform dispersion obtained by step (3), supersound process is also stirred vigorously 24h and obtains required dispersion liquid；
(5) the required dispersion liquid rotary evaporation in a heated condition that finally will be obtained by step (4), dries and ground
Sieve obtains described Graphene/polypropylene composite materials dusty material.
As it is further preferred that in step (1) described mixed solution the volume ratio of concentrated sulphuric acid and nitric acid be 4:1；Step
(1) in, the concrete technology of supersound process is by solution ultrasonic 8h under the frequency of 50HZ.
As it is further preferred that supersound process being stirred vigorously in step (2) specifically comprises the processes of: in the frequency of 50HZ
Lower supersound process 40-60min also stirs under the rotating speed of 300-600r/min, and preferably sonication treatment time is 50min, and stirring turns
Speed is 450r/min；The addition speed of silane coupler is that to be preferably added to speed be 4g/s to 2-6g/s；Preferably keep at 75 DEG C
24h。
As it is further preferred that described silane coupler is gamma-aminopropyl-triethoxy-silane, 3-aminopropyl trimethoxy
Base silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane,
γ-methacryloxypropyl trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-
(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, one in N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane or
Multiple.
As it is further preferred that the mass ratio of silane coupler described in step (2) and graphene oxide is 4:1.
As it is further preferred that in step (2) and (3), the concentration of described ethanol water be 10vol%～
100vol%.
As it is further preferred that in step (3) mass ratio of surfactant and functionalization graphene be 0.5～0.8；
Supersound process the concrete technology being stirred vigorously are supersound process 40-60min at 300-600r/min under the frequency of 50HZ
Rotating speed under stir；Described surfactant is one or both in dodecyl sodium sulfate, dodecylbenzene sodium sulfonate
Mixture.
As it is further preferred that in step (4) particle diameter of polypropylene powder be preferably 20 μm-70 μm, particle surface is
Spherical or subsphaeroidal；It is 2-6g/s that described polypropylene powder adds the speed of uniform dispersion；Supersound process is also stirred vigorously
Concrete technology be that supersound process the rotating speed at 300-600r/min are stirred vigorously 24h under the frequency of 50HZ.
As it is further preferred that rotary evaporation in a heated condition in described step (5), dry and grind to sieve and obtain
The concrete technique of described Graphene/polypropylene composite materials dusty material is 80 DEG C, stirring evaporation under conditions of 300-600r/min,
Dry to constant weight and grind, finally crossing 300 eye mesh screens and obtain composite powder material..
It is another aspect of this invention to provide that provide a kind of Graphene/polypropylene for SLS prepared by described method
Composite powder material, described composite powder material includes polypropylene, functionalization graphene and surfactant, the weight of each component
Percentage ratio is: polypropylene 89.2～99.25%, functionalization graphene 0.5～6%, surfactant 0.25～4.8%.
In general, selective laser sintering Graphene/polypropylene high molecular nanometer composite powder material that the present invention provides
The preparation method of material, it is possible to graphene uniform is dispersed in polypropylene macromolecule matrix, the most powder sintered not affecting
On the premise of performance so that it is the performance (such as intensity, toughness, fatigue durability, wearability, heat conductivity, heat conductivity etc.) of SLS drip molding
It is greatly improved, compared with at present conventional mechanical mixing, deep cooling crush method etc., has a following beneficial effect:
(1) Graphene used has been carried out surface-functionalized by the present invention so that produce between Graphene and polypropylene matrix
Give birth to higher interfacial adhesion strength, it is possible to make final SLS product mechanical property be significantly improved, the dusty material prepared
Form is uniform, particle diameter is suitable, good fluidity, is highly suitable for SLS technology, the SLS initial blank of shaping possess degree of precision,
Intensity and toughness.
(2) graphene uniform is disperseed in the solution by the present invention initially with the method for solution dispersion, then at later stage solution
Being dispersed in by graphene uniform in macromolecule matrix polypropylene during volatilization, preferable dispersibility determines higher shaping
Part performance.
(3) present invention does not change pattern and the sintering character of polypropylene PP starting powder, is suitable for SLS and shapes high performance poly-
Propylene part.
(4) present invention uses ethanol water to be solvent, will not work the mischief environment and human body, greatly reduce material
To human body and the harmfulness of environment, there is the advantages such as technique is simple, the cycle is short, low cost, environmental protection.
Accompanying drawing explanation
Fig. 1 is virgin pp dusty material microscopic appearance figure；
Fig. 2 is Graphene/polypropylene composite materials dusty material microscopic appearance figure prepared by the present invention；
Fig. 3 is the FB(flow block) of preparation method of the present invention.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, right
The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and
It is not used in the restriction present invention.If additionally, technical characteristic involved in each embodiment of invention described below
The conflict of not constituting each other just can be mutually combined.
A kind of preparation method of the selective laser sintering Graphene/polypropylene nano composite powder material of the present invention, its
By means of surfactant, use supersound process by graphene dispersion in water, while being stirred vigorously solution, by PP powder by
During gradually trace adds solution, and carry out heating volatilization, finally the powder aggregates of acquisition is pulverized, be dried and sieve, answered
Closing dusty material, it comprises the following steps:
(1) graphite flake is added in concentrated sulphuric acid and nitric acid mixed solution, after stirring 16h, molten with deionized water cyclic washing
Solution, to neutral, be then placed at a temperature of 100 DEG C and be dried under vacuum to constant weight by liquid, and heat treatment 15s at 1050 DEG C obtains swollen
Swollen graphite, puts in the ethanol water of 70vol% by expanded graphite, under the frequency of 50HZ after supersound process 8h, filters also
It is vacuum dried at 100 DEG C, obtains product graphene oxide GO.
Preferably, concentrated sulfuric acid solution and salpeter solution volume ratio are 4:1, and the solution of this ratio is more beneficial for the oxygen of graphite flake
Change.
(2) the graphene oxide GO obtained in step (1) is dispersed in ethanol water, under the frequency of 50HZ
Supersound process 40-60min also stirs under the rotating speed of 300-600r/min, is slowly added to silane coupler with the speed of 2-6g/s
To above-mentioned solution, keeping 20-28h, sucking filtration at 70-80 DEG C, washing is to neutral, and 60 DEG C are dried under vacuum to constant weight, obtain product
Functionalization graphene FGO, the surface of this functionalization graphene FGO is connected to-O (C2H5) group, this group is conducive to Graphene poly-
Dispersion in polypropylene matrix and the interface cohesion with polypropylene powder.
Employing ultrasonic vibration the method being stirred vigorously can make graphene oxide GO be uniformly dispersed, fully with silane coupled
Agent is reacted, and makes graphene oxide form covalent bond with silane coupler and is connected.
Preferably, solution stirs under the rotating speed of 450r/min, and it is 4g/s that silane coupler adds speed.Add silane even
After connection agent, 24h, beneficially graphene oxide is kept to access-O (C at 75 DEG C2H5) group.
Preferably, silane coupler is gamma-aminopropyl-triethoxy-silane (KH550), 3-aminopropyl trimethoxysilane
(KH551), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), γ-(2,3-epoxy the third oxygen) propyl group trimethoxy
Base silane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), N-(β-aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane (KH602), N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane (KH791), N-(β-ammonia second
Base) one or compounding in-gamma-aminopropyl-triethoxy-silane (KH901).Silane coupler with graphene oxide mass ratio is
4:1, beneficially graphene oxide connect group.The concentration of ethanol water is 10vol%～100vol%, at this strength solution
Under be more beneficial for the generation of functionalization graphene.
(3) the functionalization graphene FGO obtained in step (2) and surfactant are added to ethanol water,
Supersound process 40-60min be stirred vigorously under the rotating speed of 300-600r/min and obtain uniform dispersion liquid under the frequency of 50HZ.
Preferably, sonication treatment time is 50min, and the rotating speed of stirring is 450r/min.
Preferably, the concentration of ethanol water is 10vol%～100vol%, and surfactant is dodecyl sodium sulfate
(SDS) one or both the mixture, in dodecylbenzene sodium sulfonate (SDBS), surfactant and functionalization graphene
Mass ratio is 0.5～0.8, disperses in the solution with being conducive to graphene uniform under this mass ratio.
(4) particle diameter polypropylene PP powder in 10～150 μm is chosen, under the rotating speed of 300-600r/min while stirring
Preferred PP powder is added to the uniform dispersion obtained by step (3) with the speed gradually trace of 2-6g/s, at 50HZ
Frequency under supersound process be stirred vigorously 24h at the rotating speed of 300-600r/min.
Wherein, polypropylene is the powder with appropriate particle size and granule-morphology, and the particle diameter of PP is preferably 20 μm-70 μm,
Grain surface is spherical or subsphaeroidal, beneficially composite powder material SLS thermal sintering.Preferably, when adding PP powder, stirring
Rotating speed be 450r/min, PP powder add speed be 4g/s.
(5) last, the dispersion liquid rotary evaporation in a heated condition that will be obtained by step (4), dry and grind and sieve
To composite powder material.Concrete, dispersion liquid evaporates under the rotating speed stirring condition of 80 DEG C and 300-600r/min, dries extremely
Constant weight ground 300 mesh sieves obtain composite powder material.
Preferably, speed of agitator is 450r/mi；Graphene content in the composite is 0.5wt%-6wt%, this
The agglomeration that the Graphene of content/polypropylene composite materials powder avoids too much filler and produces, it is ensured that composite powder material
Performance.
Present invention also offers a kind of Graphene for SLS technology/polypropylene composite materials dusty material, wherein, Graphene
Material is dispersed in the surface of polypropylene matrix, and composite is powder, uniform particle sizes, good sphericity, utilizes laser to select
District's thermal sintering manufactures personalization, complicated part, and Graphene content in the composite is 0.5wt%-6wt%.
It is below embodiment:
Example 1:(Graphene mass fraction is the Graphene/polypropylene composite materials powder of 0.5wt%)
(1) 1g graphite flake is added in concentrated sulphuric acid and nitric acid mixed solution, after stirring 16h, use deionized water cyclic washing
Solution, to neutral, be then placed in vacuum drying constant weight, heat treatment 15s at 1050 DEG C at a temperature of 100 DEG C, obtain swollen by solution
Swollen graphite, puts in the ethanol water of 70vol% by expanded graphite, under the frequency of 50HZ after supersound process 8h, filters also
At 100 DEG C, it is dried under vacuum to constant weight, obtains product graphene oxide GO.
(2) take out the graphene oxide GO obtained in 0.1g step (1), be dispersed in 20vol% ethanol water,
Supersound process being stirred vigorously under the rotating speed of 450r/min under the frequency of 50HZ, is slowly added to 0.4g with the speed of 4g/s
Gamma-aminopropyl-triethoxy-silane (KH550) arrives above-mentioned solution, keeps 24h, sucking filtration at 75 DEG C, and washing is to neutral, and 60 DEG C true
Sky is dried to constant weight, obtains product functionalization graphene FGO.
(3) take out functionalization graphene FGO and 0.05gSDBS obtained in 0.1g step (2) to add to 500mL
In 10vol% ethanol water, supersound process 50min being stirred vigorously under the rotating speed of 350r/min under the frequency of 50HZ
To uniform dispersion liquid.
(4) the 20g particle diameter polypropylene PP powder in 70 μm is chosen, will while being stirred vigorously under the rotating speed of 450r/min
PP powder adds to the uniform dispersion obtained by step (3) with the speed gradually trace of 4g/s, super under the frequency of 50HZ
Sonication is also stirred vigorously 24h at the rotating speed of 450r/min.
(5) last, the dispersion liquid that will be obtained by step (4) evaporates under the rotating speed stirring condition of 80 DEG C and 450/min,
Drying to constant weight ground 300 mesh sieves obtains composite powder material.
Example 2:(Graphene mass fraction is the Graphene/polypropylene composite materials powder of 6wt%)
(1) 50g graphite flake is added in concentrated sulphuric acid and nitric acid mixed solution, after stirring 16h, use deionized water cyclic washing
Solution, to neutral, be then placed in vacuum drying constant weight, heat treatment 15s at 1050 DEG C at a temperature of 100 DEG C, obtain swollen by solution
Swollen graphite, puts in the ethanol water of 70vol% by expanded graphite, under the frequency of 50HZ after supersound process 8h, filters also
At 100 DEG C, it is dried under vacuum to constant weight, obtains product graphene oxide GO.
(2) take out the graphene oxide GO obtained in 30g step (1), be dispersed in 10vol% ethanol water,
Supersound process being stirred vigorously under the rotating speed of 300r/min under the frequency of 50HZ, is slowly added to 120g with the speed of 2g/s
N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane (KH901) arrives above-mentioned solution, keeps 20h, sucking filtration, washing at 80 DEG C
To neutral, 60 DEG C are dried under vacuum to constant weight, obtain product functionalization graphene FGO.
(3) take out functionalization graphene FGO and 20gSDBS obtained in 30g step (2) to add to 100L 100vol%
In ethanol water, under the frequency of 50HZ, supersound process 60min being stirred vigorously under the rotating speed of 300r/min obtains uniformly
Dispersion liquid.
(4) the 500g particle diameter polypropylene PP powder in 20 μm is chosen, while being stirred vigorously under the rotating speed of 300r/min
PP powder is added to the uniform dispersion obtained by step (3) with the speed gradually trace of 2g/s, under the frequency of 50HZ
Supersound process is also stirred vigorously 24h at the rotating speed of 300r/min.
(5) last, the dispersion liquid that will be obtained by step (4) steams under the rotating speed stirring condition of 80 DEG C and 300r/min
Sending out, drying to constant weight ground 300 mesh sieves obtains composite powder material.
Example 3:(Graphene mass fraction is the Graphene/polypropylene composite materials powder of 5wt%)
(1) 3g graphite flake is added in concentrated sulphuric acid and nitric acid mixed solution, after stirring 16h, use deionized water cyclic washing
Solution, to neutral, be then placed in vacuum drying constant weight, heat treatment 15s at 1050 DEG C at a temperature of 100 DEG C, obtain swollen by solution
Swollen graphite, puts in the ethanol water of 70vol% by expanded graphite, under the frequency of 50HZ after supersound process 8h, filters also
At 100 DEG C, it is dried under vacuum to constant weight, obtains product graphene oxide GO.
(2) take out the graphene oxide GO obtained in 2g step (1), be dispersed in 100vol% ethanol water,
Supersound process being stirred vigorously under the rotating speed of 600r/min under the frequency of 50HZ, is slowly added to 8g 3-with the speed of 6g/s
Aminopropyl trimethoxysilane (KH551) arrives above-mentioned solution, keeps 28h, sucking filtration at 70 DEG C, and washing is to neutrality, 60 DEG C of vacuum
It is dried to constant weight, obtains product functionalization graphene FGO.
(3) take out functionalization graphene FGO and 1.6gSDS obtained in 2g step (2) and 0.8gSDBS to add to 8L
In 80vol% ethanol water, surpass under the frequency of 50HZ supersound process 60min and be stirred vigorously under the rotating speed of 600r/min
Obtain uniform dispersion liquid.
(4) the 38g particle diameter polypropylene PP powder in 150 μm is chosen, while being stirred vigorously under the rotating speed of 600r/min
PP powder is added to the uniform dispersion obtained by step (3) with the speed gradually trace of 6g/s, under the frequency of 50HZ
Supersound process is also stirred vigorously 24h at the rotating speed of 600r/min.
(5) last, the dispersion liquid that will be obtained by step (4) steams under the rotating speed stirring condition of 80 DEG C and 600r/min
Sending out, drying to constant weight ground 300 mesh sieves obtains composite powder material.
Example 4:(Graphene mass fraction is the Graphene/polypropylene composite materials powder of 1wt%)
(1) 15g graphite flake is added in concentrated sulphuric acid and nitric acid mixed solution, after stirring 16h, use deionized water cyclic washing
Solution, to neutral, be then placed in vacuum drying constant weight, heat treatment 15s at 1050 DEG C at a temperature of 100 DEG C, obtain swollen by solution
Swollen graphite, puts in the ethanol water of 70vol% by expanded graphite, under the frequency of 50HZ after supersound process 8h, filters also
At 100 DEG C, it is dried under vacuum to constant weight, obtains product graphene oxide GO.
(2) take out the graphene oxide GO obtained in 10g step (1), be dispersed in 60vol% ethanol water,
Supersound process is also stirred vigorously, and is slowly added to 20g KH550,10g KH602 and 10g KH791 to above-mentioned molten with the speed of 5g/s
Liquid, 75 DEG C keep 24h, sucking filtration, and washing, 60 DEG C are dried under vacuum to constant weight, obtain product functionalization graphene FGO.
Take out the graphene oxide GO obtained in 10g step (1), be dispersed in 10vol% ethanol water,
Supersound process being stirred vigorously under the rotating speed of 500r/min under the frequency of 50HZ, is slowly added to 20g N-with the speed of 2g/s
(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane (KH901) and 20g N-(β-aminoethyl)-γ-aminopropyl trimethoxy silicon
Alkane (KH792) arrives above-mentioned solution, keeps 26h, sucking filtration at 76 DEG C, and washing is to neutral, and 60 DEG C are dried under vacuum to constant weight, are produced
Thing functionalization graphene FGO.
(3) take out functionalization graphene FGO and 5gSDBS obtained in 10g step (2) and 8gSDS to add to 45L
In 100vol% ethanol water, supersound process 60min being stirred vigorously under the rotating speed of 500r/min under the frequency of 50HZ
Obtain uniform dispersion liquid.
(4) the 1kg particle diameter polypropylene PP powder in 10 μm is chosen, will while being stirred vigorously under the rotating speed of 500r/min
PP powder adds to the uniform dispersion obtained by step (3) with the speed gradually trace of 5g/s, super under the frequency of 50HZ
Sonication is also stirred vigorously 24h at the rotating speed of 500r/min.
(5) last, the dispersion liquid that will be obtained by step (4) steams under the rotating speed stirring condition of 80 DEG C and 500r/min
Sending out, drying to constant weight ground 300 mesh sieves obtains composite powder material.
Powder embodiment 1-4 prepared utilizes identical SLS preparation technology to prepare product, the properties result of product
It is shown in Table 1, wherein also add the comparative example that Graphene content is 0.By table 1, use dusty material prepared by the present invention
Being applicable to SLS technology, dusty material flowing property prepared by the present invention is good, and the SLS initial blank of shaping possesses higher intensity
And toughness, the good mechanical performance of product.
Table 1SLS product mechanical property contrast table
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, all should comprise
Within protection scope of the present invention.
Claims (10)
1. the preparation method for the Graphene/polypropylene composite materials dusty material of SLS, it is characterised in that include walking as follows
Rapid:
(1) graphite flake is added in the mixed solution of concentrated sulphuric acid and nitric acid, after stirring 16h, with deionized water cyclic washing solution
To neutral, then solution be placed at a temperature of 100 DEG C and be dried under vacuum to constant weight, then obtain after heat treatment 15s at 1050 DEG C
Expanded graphite, puts in the ethanol water of 70vol% by described expanded graphite, after supersound process 8h, filters and at 100 DEG C
Vacuum drying, obtains graphene oxide；
(2) being dispersed in ethanol water by the graphene oxide obtained in step (1), supersound process is also stirred vigorously,
It is slowly added to silane coupler, and at 70-80 DEG C, keeps 20-28h, then sucking filtration, washing, at 60 DEG C, be dried under vacuum to perseverance
Weight, obtains functionalization graphene；
(3) being added to ethanol water by the functionalization graphene obtained in surfactant and step (2), supersound process is also
It is stirred vigorously and obtains uniform dispersion liquid；
(4) choose the particle diameter polypropylene powder in 10～150 μm, while being stirred vigorously, polypropylene powder is gradually added into
In the uniform dispersion obtained by step (3), supersound process is also stirred vigorously 24h and obtains required dispersion liquid；
(5) the required dispersion liquid rotary evaporation in a heated condition that finally will be obtained by step (4), dries and grinds and sieve
To described Graphene/polypropylene composite materials dusty material.
2. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 1, its feature exists
In, in step (1) described mixed solution, the volume ratio of concentrated sulphuric acid and nitric acid is 4:1；The concrete technology of supersound process in step (1)
For by solution ultrasonic 8h under the frequency of 50HZ.
3. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 1 or 2, its feature
It is, supersound process being stirred vigorously in step (2) specifically comprises the processes of: supersound process 40-60min is also under the frequency of 50HZ
Stirring under the rotating speed of 300-600r/min, preferably sonication treatment time is 50min, and speed of agitator is 450r/min；Silane is even
The addition speed of connection agent is 2-6g/s, and being preferably added to speed is 4g/s；At 75 DEG C, preferably keep 24h.
4. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 3, its feature exists
In, described silane coupler is gamma-aminopropyl-triethoxy-silane, 3-aminopropyl trimethoxysilane, N-(β-aminoethyl)-
γ-aminopropyltrimethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl
Trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl three
Ethoxysilane, one or more in N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane.
5. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 4, its feature exists
In, silane coupler described in step (2) is 4:1 with the mass ratio of graphene oxide.
6. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 5, its feature exists
In, in step (2) and (3), the concentration of described ethanol water is 10vol%～100vol%.
7. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 6, its feature exists
In, in step (3), the mass ratio of surfactant and functionalization graphene is 0.5～0.8；Supersound process the tool being stirred vigorously
Body technology is supersound process 40-60min stirring under the rotating speed of 300-600r/min under the frequency of 50HZ；Live in described surface
Property agent is one or both the mixture in dodecyl sodium sulfate, dodecylbenzene sodium sulfonate.
8. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 7, its feature exists
In, in step (4), the particle diameter of polypropylene powder is preferably 20 μm-70 μm, and particle surface is spherical or subsphaeroidal；Described poly-third
It is 2-6g/s that alkene powder adds the speed of uniform dispersion；Supersound process the concrete technology being stirred vigorously are the frequency at 50HZ
Lower supersound process is also stirred vigorously 24h at the rotating speed of 300-600r/min.
9. the preparation method of the Graphene/polypropylene composite materials dusty material for SLS as claimed in claim 8, its feature exists
In, rotary evaporation in a heated condition in described step (5), dry and grind to sieve and obtain described Graphene/polypropylene composite materials
The concrete technique of dusty material is: 80 DEG C, stirring evaporation under conditions of 300-600r/min, dries to constant weight and grinds,
Rear mistake 300 eye mesh screen obtains composite powder material.
10. the Graphene for SLS prepared by method described in any one of claim 1-9/polypropylene composite materials powder material
Material, it is characterised in that described composite powder material includes polypropylene, functionalization graphene and surfactant, the weight of each component
Amount percentage ratio is: polypropylene 89.2～99.25%, functionalization graphene 0.5～6%, surfactant 0.25～4.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610859919.5A CN106146864B (en) | 2016-09-27 | 2016-09-27 | Graphene/polypropylene composite materials dusty material and preparation method for SLS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610859919.5A CN106146864B (en) | 2016-09-27 | 2016-09-27 | Graphene/polypropylene composite materials dusty material and preparation method for SLS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106146864A true CN106146864A (en) | 2016-11-23 |
| CN106146864B CN106146864B (en) | 2018-09-28 |
Family
ID=57341501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610859919.5A Active CN106146864B (en) | 2016-09-27 | 2016-09-27 | Graphene/polypropylene composite materials dusty material and preparation method for SLS |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106146864B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106670476A (en) * | 2016-12-30 | 2017-05-17 | 尹宗杰 | Graphene-nonmetal-metal composite material for 3D printing, preparation method and application |
| CN106829945A (en) * | 2016-12-30 | 2017-06-13 | 广州锋尚电器有限公司 | A kind of layer type casting moulding Graphene nonmetallic composite and preparation method |
| CN108976608A (en) * | 2018-08-10 | 2018-12-11 | 福建工程学院 | Modified tossa/PP composite material of a kind of graphene and preparation method thereof |
| US20220134642A1 (en) * | 2020-11-03 | 2022-05-05 | Eos Of North America, Inc. | Pretreated Material for Laser Sintering |
-
2016
- 2016-09-27 CN CN201610859919.5A patent/CN106146864B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106670476A (en) * | 2016-12-30 | 2017-05-17 | 尹宗杰 | Graphene-nonmetal-metal composite material for 3D printing, preparation method and application |
| CN106829945A (en) * | 2016-12-30 | 2017-06-13 | 广州锋尚电器有限公司 | A kind of layer type casting moulding Graphene nonmetallic composite and preparation method |
| CN106670476B (en) * | 2016-12-30 | 2019-12-03 | 尹宗杰 | 3D printing graphene-nonmetallic-metallic composite, preparation method and application |
| CN106829945B (en) * | 2016-12-30 | 2019-12-03 | 广州锋尚电器有限公司 | A kind of layer of type casting moulding graphene-nonmetallic composite and preparation method |
| CN108976608A (en) * | 2018-08-10 | 2018-12-11 | 福建工程学院 | Modified tossa/PP composite material of a kind of graphene and preparation method thereof |
| US20220134642A1 (en) * | 2020-11-03 | 2022-05-05 | Eos Of North America, Inc. | Pretreated Material for Laser Sintering |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106146864B (en) | 2018-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106146864A (en) | Graphene/polypropylene composite materials dusty material and preparation method for SLS | |
| CN110054864B (en) | High-thermal-conductivity composite filler and preparation method of polymer-based composite material thereof | |
| CN102786815B (en) | Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material | |
| CN105669208A (en) | Phenolic resin coated ceramic powder for laser 3D printing and preparation method thereof | |
| CN106189088B (en) | A kind of preparation method of carbon nanotube-graphene oxide hybrid reinforced composite material | |
| CN104774573B (en) | A kind of high-performance conductive silver paste of containing graphene and preparation method thereof | |
| CN101629057A (en) | Nano conductive adhesive and preparation method thereof | |
| CN103756252B (en) | A kind of thermosetting resin base heat-conductive composite material and its preparation method and application | |
| CN101891942B (en) | Method for preparing nanocomposite hybrid multi-dimension material | |
| CN102876272B (en) | Heat-conduction binding material and preparation method thereof | |
| CN104151775A (en) | Preparation method of three-dimensional cross-linked graphene foam structure reinforced resin composite material | |
| CN105504749B (en) | A kind of 3D printing polycarbonate composite material and preparation method thereof | |
| CN104109343A (en) | High-flowability plastic composite powder material and preparation method thereof | |
| Jouyandeh et al. | Epoxy coatings physically cured with hydroxyl-contained silica nanospheres and halloysite nanotubes | |
| CN106589588A (en) | Flame-retardant enhanced-type polypropylene composite material and preparing method thereof | |
| CN103080265A (en) | High performance die attach adhesives (DAAs) nanomaterials for high brightness LED | |
| CN112537921B (en) | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof | |
| CN106633626B (en) | Graphene/polyether-ether-ketone composite powder material and preparation method for SLS | |
| CN105176081A (en) | Preparation method for flame-retardant heat-resistant antenna radome base material | |
| Wang et al. | A high-performance thermally conductive and electrically insulating silver@ siloxane/graphene/epoxy composites at low filler content: Fabrication, mechanism study of insulation and thermal conductivity enhancement | |
| CN110982255B (en) | Long-carbon-chain polyamide/carbon nanotube composite material, preparation method thereof and application thereof in FDM | |
| CN105153639A (en) | Carbon nano-tube microsphere/glass fiber synergistically-reinforced epoxy composite material preparation method | |
| CN102504609A (en) | Method for processing surface of hollow glass microsphere | |
| CN101891936B (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN109897341B (en) | Composite material of modified graphene reinforced epoxy resin and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |