CN105713362B - A kind of composition for 3D printing, 3D printing material containing it and preparation method thereof, application and 3D printing equipment - Google Patents
A kind of composition for 3D printing, 3D printing material containing it and preparation method thereof, application and 3D printing equipment Download PDFInfo
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- CN105713362B CN105713362B CN201610230921.6A CN201610230921A CN105713362B CN 105713362 B CN105713362 B CN 105713362B CN 201610230921 A CN201610230921 A CN 201610230921A CN 105713362 B CN105713362 B CN 105713362B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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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
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- C—CHEMISTRY; METALLURGY
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of composition for 3D printing, 3D printing material containing it and preparation method thereof, application and 3D printing equipment, the composition for 3D printing of the rare earth doped element comprising following component：20~60 parts by weight of thermoplastic resin；40~80 amount part of alloy powder containing rare earth element.This is used for the composition of 3D printing since doped with rare-earth magnetic element, 3D printing material prepared therefrom can form permanent magnet after magnetizing, and has many potential applications.The preparation method simple process and low cost, it is safe.3D printing material prepared by method using the present invention can be filament, can be directly used for fused glass pellet 3D printing, shaping speed is fast.The product that preset shape can be formed by 3D printing, magnetizes after printing, by magnetizing, finally obtains the permanent magnet of complicated shape, to meet the application on some special occasions, while filling up this market vacancy.
Description
Technical field
The invention belongs to 3D printing field of material technology, specifically, more particularly, to a kind of combination for 3D printing
Object contains its 3D printing material and preparation method thereof, application and 3D printing equipment.
Background technology
Rapid shaping (Rapid Prototype, RP) technology be develop rapidly the 1990s one kind it is advanced
Manufacturing technology is a kind of key technology for serving manufacturing industry new product development.It is to promoting the products innovation of enterprise, shortening newly
Research and development of products period, raising product competitiveness etc. play positive impetus.The technology since the advent of the world, it is gradually each in the world
It is widely used in the manufacturing industry of state, and thus expedites the emergence of out an emerging technical field.3D printing technique is as one
The emerging rapid shaping technique of kind, is applied primarily to the necks such as product prototype, mold manufacturing and artistic creation, jewelry-making
Domain, some traditional fine-processing techniques for substituting these fields.In addition, 3D printing technique is also gradually applied to medicine, life
Wide space has been opened up in the fields such as object engineering, building, clothes for innovation.Currently, 3D printing molding mode includes mainly melting
Deposition modeling (Fused Deposition Modeling, FDM), selective laser sintering and moulding (Selective Laser
Sintering, SLS), Stereolithography (stereo lithography apparatus, SLA), laminated solid body molding
Technologies, wherein FDM such as (Laminated Object Manufacturing, LOM) are with fastest developing speed.
FDM refers to that Filamentous thermoplastic material is sent into nozzle by wire feeder, is heated to molten state in the showerhead, is squeezed through nozzle
Go out.The Filamentous thermoplastic material of molten state is extruded out, according to three-dimensional software individual-layer data control path squeeze and
Specified position coagulation forming, layer by layer deposition solidification, eventually forms entire three-dimensional objects.The operating environment of FDM is clean, safe,
It is simple for process, easily operated, and rubbish is not generated, therefore operation occasion has been widened significantly.Its raw materials is with spool silk
Form provides, and is easily portable and quick-replaceable.But at this stage there is defect substantially in FDM molding modes.When material is from height
Warm nozzle is relied solely on itself after squeezing out and is gravitationally deposited on the lower layer's material cooled down, while the receipts that rapid cooled generation is certain
Contracting, causes gap between layers larger, and interfacial bonding strength is small, finally so that product overall performance is poor, therefore current FDM
Application range is limited significantly, is concentrated mainly on craftwork and the industries such as hand is done.
Polycaprolactone (PCL) is the product of DICELL chemical industrial companies exploitation, and fusing point is 59-64 DEG C, and vitrifying turns
Temperature is -60 DEG C, and decomposition temperature is 200 DEG C, is rubbery state, better heat stability at room temperature.Meanwhile its strand ratio
It is more regular, there is flexible and processability well.Its protrude feature be have good biocompatibility, biological degradability with
And permeability, this keeps it extremely wide in the application of technical field of biological material, can be used as controlled release drug carrier, cell, tissue cultures
Pedestal etc..PCL is with nontoxic, melting temperature is relatively low, thermal stability is good, biodegradable and non-toxic pungent in melting process
The advantages that smell is released, especially meets the requirement of 3D printing material.
But the report for the 3D printing material developed at present using PCL as matrix is less.Chinese patent application
CN20141018367 discloses a kind of PCL materials and preparation method thereof for 3D printing.The patent is handed over by adding small molecule
Join the components such as agent, chain extender, melt blending is carried out by different ratio with PCL, to realize the effect of toughening and enhancing.But this is specially
Profit only considers how the mechanical property of raising PCL, does not open up its functional direction.
Invention content
The purpose of the present invention is to provide a kind of novel composition for 3D printing, the 3D printing material containing it and
Preparation method, application and 3D printing equipment, the 3D printing material are greatly expanded the application range of FDM.
To achieve the goals above, the present invention provides a kind of composition for 3D printing of rare earth doped element,
Including following component：
20~60 parts by weight of thermoplastic resin；And 40~80 parts by weight of alloy powder containing rare earth element.
Preferably, it is also comprised the following components in the composition：1~10 parts by weight of toughener.
Preferably, it is also comprised the following components in the composition：2~10 parts by weight of tackifier.
Preferably, it is also comprised the following components in the composition：0.5~1 parts by weight of antioxidant.
Preferably, it is also comprised the following components in the composition：0.5~1 parts by weight of surfactant.
Preferably, the dosage of the thermoplastic resin is 25~55 parts by weight, more preferable 25~45 parts by weight, such as can be with
It is 28 parts by weight, 30 parts by weight or 40 parts by weight.
Preferably, the dosage of the alloy powder containing rare earth element is 40~70 parts by weight, more preferable 45~65 weight
Part, such as can be 46 parts by weight, 58 parts by weight or 62 parts by weight.
Preferably, the dosage of the toughener is 3~5 parts by weight.
Preferably, the dosage of the tackifier is 7~9 parts by weight, more preferable 8~8.5 parts by weight.
Preferably, the composition may include following component：
40 parts by weight of thermoplastic resin, 46 parts by weight of alloy powder containing rare earth element, 5 parts by weight of toughener, tackifier
8.0 parts by weight, 0.5 parts by weight of 0.5 parts by weight of antioxidant and surfactant；Or
28 parts by weight of thermoplastic resin, 62 parts by weight of alloy powder containing rare earth element, 3 parts by weight of toughener, tackifier
8.2 parts by weight, 0.3 parts by weight of 0.5 parts by weight of antioxidant and surfactant；Or
30 parts by weight of thermoplastic resin, 58 parts by weight of alloy powder containing rare earth element, 3 parts by weight of toughener, tackifier
8.0 parts by weight, 0.5 parts by weight of 0.5 parts by weight of antioxidant and surfactant.
According to the present invention, the grain size of the thermoplastic resin is 100~1000 μm；Further preferably 200~500 μm.
Preferably, the number-average molecular weight of the thermoplastic resin is 30000~80000, preferably 40000~60000.Preferably, described
The melt index of thermoplastic resin is 10~40g/10 minutes (190 DEG C, 2.16kg)；It is preferred that 20~30g/10 minutes (190 DEG C,
2.16kg)。
Preferably, the thermoplastic resin be polycaprolactone (PCL), acrylonitrile-butadiene-styrene copolymer (ABS),
It is one or more in polylactic acid (PLA), makrolon (PC) and nylon (PA)；More preferably PCL.Specifically, the PCL can
Think Perstorp CapaTM6400, Perstorp CapaTM6500 or Perstorp CapaTM 6800。
According to the present invention, the alloy powder containing rare earth element is rare earth permanent-magnetic material powder；Such as can be
SmCo5、Sm2Co17、Nd2Fe14B and Sm2Fe17N3In it is one or more.
According to the present invention, the toughener is haloflex, styrene butadiene thermoplasticelastomer, ethyl vinyl acetate
It is one or more in vinyl ester copolymers, ethylene propylene diene rubber and ethylene-octene block copolymer.Optimal ethylene-acetic acid second
The mixture of enoate copolymer and haloflex.It is specifically as follows Dow POE 8411, Dupont EVA 260 or Dow POE
It is one or more in 8402.
According to the present invention, the tackifier are tackifying resin；The tackifying resin is C5Petropols, C9Petropols, hydrogen
Change one or more of aromatic petroleum resin, terpene resin and rosin resin；Preferably hydrogenated aromatic Petropols.
Preferably, the antioxidant is irgasfos 168 (can be purchased from Germany BASF), and antioxidant 1010 (can be purchased from moral
State BASF), antioxidant B215 (Switzerland's vapour bar can be purchased from) and one kind in antioxidant B225 (Switzerland's vapour bar can be purchased from) or
It is several；Preferably irgasfos 168 (Germany BASF can be purchased from).
Preferably, the surfactant is silane coupling agent, such as KH550 (can be purchased from Nanjing connection silication work),
One or more of KH570 (Nanjing connection silication work can be purchased from) and KH560 (Guangzhou Ou Ying chemical industry can be purchased from).
The present invention also provides a kind of material for 3D printing of rare earth doped element, raw material is above-mentioned composition.
According to the present invention, the material for 3D printing is the filament made from above-mentioned composition.
Preferably, a diameter of 0.5~5mm of the filament, more preferable 1.5~3.5mm, for example, can be 1.75mm or
3mm。
The present invention also provides a kind of preparation methods of above-mentioned material, include the following steps：
1) each component in the composition is mixed；It is preferred that being sufficiently mixed 5~30 minutes by high-speed mixer；
2) mixture obtained after mixing step 1) is made by double screw extruder fusion plastification, and by pelleter
Grain；Preferably, the temperature of the double screw extruder fusion plastification is 60~150 DEG C.
It is further preferred that the preparation method is further comprising the steps of：
3) the pellet wire drawing for obtaining step 2), obtains filament；It is preferred that passing through screw extruder wire drawing；It is further preferably logical
Cross single screw extrusion machine wire drawing.
Preferably, a diameter of 0.5~5mm of the filament, more preferable 1.5~3.5mm, for example, can be 1.75mm or
3mm。
Further include first by thermoplastic resin before the thermoplastic resin in the composition is mixed according to the present invention
Particle carries out the step of ball milling forms powder under liquid nitrogen environment.
Preferably, the grain size of the powder formed after the ball milling is 100~1000 μm；Further preferably 200~500 μ
m。
Further include by silane coupling agent point before the alloy powder containing rare earth element is mixed according to the present invention
The step being dispersed in the alloy powder containing rare earth element.The silane coupling agent is, for example, KH570.
The present invention also provides a kind of products, are beaten through 3D by the material for 3D printing of above-mentioned rare earth doped element
It prints.
According to the present invention, the product is by above-mentioned material through permanent magnet made from 3D printing.
According to the present invention, the product is embedded by plastic products of the above-mentioned material through permanent magnet made from 3D printing.
The 3D printing equipment based on FDM that the present invention also provides a kind of, for being printed to above-mentioned 3D printing material,
It includes：
Wire feeder, for Filamentous thermoplastic material to be sent into heating element；
Heating element, for receiving the Filamentous thermoplastic material that the wire feeder sends and being heated to melting
State；
Nozzle is connected with the heating element, for squeezing out the Filamentous thermoplastic material of the molten state；
Magnetic printing platform is arranged in the underface of the nozzle, and the material for being extruded for the nozzle provides magnetic
Power.
According to the present invention, pass through the magnetic printing platform so that extruded from the nozzle in whole printing process
The magnetic force given always by the magnetic printing platform of material, to avoid FDM printers in 3D printing to gravity item
The requirement of part.
According to the present invention, the equipment further includes spring clamping feature, for ensureing that the Filamentous thermoplastic material follows
The stepping of the wire feeder.Preferably, the spring clamping feature is oppositely arranged with the wire feeder.
Further include the thermal sleeve being arranged on the heating element top according to the present invention.Preferably, the thermal sleeve
Material be polytetrafluoroethylene (PTFE).
According to the present invention, the heating element is heating rod.
According to the present invention, the heating rod is two, respectively symmetrically is arranged and squeezes out channel in Filamentous thermoplastic material
Both sides.
According to the present invention, the magnetic printing platform built-in has rare-earth permanent magnet.
Preferably, the rare-earth permanent magnet is uniformly embedded at intervals in the magnetic printing platform interior.
According to the present invention, the magnetic printing platform is insulating materials；Preferably, the magnetic printing platform is wooden knot
Structure.
According to the present invention, the complete machine rack and internal guide rail of the 3D printing equipment are all made of nonferromugnetic material, to protect
Demonstrate,prove the Distribution of Magnetic Field of the position and rare-earth permanent magnet of magnetic printing platform.
Beneficial effects of the present invention：
Composition provided by the present invention for 3D printing is prepared therefrom due to doped with rare-earth magnetic element
3D printing material can form permanent magnet after magnetizing, and have many potential applications.The preparation method work of the 3D printing material
Skill is simple, at low cost, safe.3D printing material prepared by method using the present invention can be filament, can directly use
In fused glass pellet 3D printing, shaping speed is fast.The product that preset shape can be formed by 3D printing, fills after printing
Magnetic finally obtains the permanent magnet of complicated shape, to meet the application on some special occasions, while filling up this by magnetizing
One market vacancy.
In addition, the present invention has also carried out appropriate reconstruction to the printing base platform of the 3D printing equipment based on FDM, in nozzle
Lower section be arranged magnetic printing platform, such as using embed rare-earth permanent magnet plank.Present invention combination magnetic printing platform so that
In whole printing process, the magnetic force that the material of the molten state squeezed out from nozzle is given by print platform always can exempt from
Requirement except FDM 3D printings to gravity condition is realized and carries out 3D printing in irregular or non-horizontal surface, can also realize
3D printing is carried out under the space environment of zero-g and under the environment such as the ship that jolts, vehicle and the aircraft of Gravity changer, from
And the application range of FDM has been widened significantly.
Description of the drawings
Fig. 1 is the structural schematic diagram of the 3D printing equipment based on FDM of the present invention；
Fig. 2 is the electron microscope for 3D printing material of rare earth doped element in the embodiment of the present invention 1.
Specific implementation mode
As previously mentioned, the invention discloses a kind of composition for 3D printing of rare earth doped element, the composition packet
Include following component：20~60 parts by weight of thermoplastic resin；With 40~80 parts by weight of alloy powder containing rare earth element.
Wherein, by alloy powder of the introducing containing rare earth element into thermoplastic resin, 3D printing application environment has been widened,
By combining improved 3D printer, agravic 3D printing is realized.The alloy powder containing rare earth element is Rare-Earth Magnetic
Property powder, such as can be SmCo5、Sm2Co17、Nd2Fe14B、Sm2Fe17N3It is one or more.
The continuous phase for functioning as 3D printing material of the thermoplastic resin, for cohering rare-earth magnetic powder.Institute
The grain size for stating thermoplastic resin is 100~1000um.Within the above range by the size controlling of thermoplastic resin, mainly consider
Disperse evenly to rare-earth magnetic powder is made.Preferably, the grain size of the thermoplastic resin is 200~500um.The thermoplasticity
The number-average molecular weight of resin is 30000~80000, preferably 40000~60000.The present invention uses molecular weight within this range
Thermoplastic resin mainly consider requirement of the 3D printing to viscosity of material.The melt index of the thermoplastic resin be 10~
40g/10 minutes (190 DEG C, 2.16kg).It is preferred that 20~30g/10 minutes (190 DEG C, 2.16kg).
Thermoplastic resin of the present invention can be polycaprolactone (PCL), acrylonitrile-butadiene-styrene (ABS) copolymerization
It is one or more in object (ABS), polylactic acid (PLA), makrolon (PC) and nylon (PA).Preferably PCL.
Specifically, the PCL can be Perstorp CapaTM6400, Perstorp CapaTM6500, or
Perstorp CapaTM 6800。
According to the present invention, toughener can also be added in the composition.Used toughener is, for example, chlorinated polyethylene
Alkene, styrene butadiene thermoplasticelastomer, ethylene-vinyl acetate copolymer, ethylene propylene diene rubber and ethylene-octene are embedding
It is one or more in section copolymer.The mixture of optimal ethylene-vinyl acetate co-polymer and haloflex；It specifically can be with
For Dow POE 8411, Dupont EVA 260 or Dow POE 8402.Toughener can reduce crisp in material drawing process
Property, so that it is not allowed easy fracture.
According to the present invention, tackifier can also further be added in the composition, the purpose for adding tackifier is to pass through
Diffusion into the surface or internal diffusion moistening gluing of surfaces, adhesive strength improves between making material internal each component.The tackifier are excellent
It is selected as tackifying resin.Specifically, the tackifying resin can be C5Petropols, C9Petropols, hydrogenated aromatic oil tree
One or more of fat, terpene resin and rosin resin.Preferably hydrogenated aromatic Petropols.
Preferably, antioxidant can also further be added in the composition.The antioxidant is Germany's BASF antioxidant
168, German BASF antioxidant 1010s, Switzerland vapour bar antioxidant B215, Switzerland vapour bar antioxidant B225 one or more；It is preferred that
For German BASF irgasfos 168s.It can delay or inhibit the progress of thermoplastic polymer oxidation process by adding antioxidant, have
Help prevent its aging and extends its service life.
Preferably, surfactant can also further be added in the composition.Preferably, the surfactant is
Silane coupling agent, for example, Nanjing join silication work KH550, Nanjing join silication work KH570, one kind of Guangzhou Ou Ying chemical industry KH560 or
It is several.The surface energy of rareearth magnetic material can be reduced by adding surfactant, contributes to it in thermoplastic resin
Dispersion.
The present invention also provides a kind of material for 3D printing of rare earth doped element, raw material is above-mentioned composition.
Preferably, the material for 3D printing is the filament made from above-mentioned composition.A diameter of 0.5~5mm of the filament,
More preferable 1.5~3.5mm, such as can be 1.75mm or 3mm.
The present invention is preferred but is not limited to the material of above-mentioned shape, can be prepared not according to the requirement of 3D printer
The material of similar shape and structure.Such as the size of the material of the invention prepared can be the cylindrical linear of a diameter of 0.5~5mm
Structure.
The present invention also provides a kind of preparation methods of the material for 3D printing, include the following steps：
1) each component in the composition is mixed；It is preferred that being sufficiently mixed 5~30 minutes by high-speed mixer；
2) mixture obtained after mixing step 1) is made by double screw extruder fusion plastification, and by pelleter
Grain；Preferably, the temperature of the double screw extruder fusion plastification is 60~150 DEG C.
It is further preferred that the preparation method is further comprising the steps of：
3) the pellet wire drawing for obtaining step 2), obtains filament；It is preferred that passing through screw extruder wire drawing；It is further preferably logical
Cross single screw extrusion machine wire drawing.The preparation method simple process and low cost, it is safe.A diameter of the 0.5 of obtained filament~
5mm, more preferable 1.5~3.5mm, such as can be 1.75mm or 3mm.
Further include first by thermoplastic resin before the thermoplastic resin in the composition is mixed according to the present invention
Particle carries out the step of ball milling forms powder under liquid nitrogen environment.Thermoplastic resin particle ball is clayed into power in advance, purpose
It is that can evenly be mixed with Magnaglo.Using carrying out ball milling under liquid nitrogen environment, to avoid in mechanical milling process temperature increase
Lead to resin melting.
Preferably, the grain size of the powder formed after the ball milling is 100~1000 μm；Further preferably 200~500 μ
m。
Further include by surfactant, example before the alloy powder containing rare earth element is mixed according to the present invention
Step in the alloy powder containing rare earth element as described in being dispersed in silane coupling agent.The purpose is to reduce alloy powder surface
Energy.Preferably, the silane coupling agent is, for example, KH570.
The 3D printing equipment based on FDM that the present invention also provides a kind of, for being printed to above-mentioned 3D printing material,
As shown in Figure 1, the 3D printing equipment includes：Wire feeder 1, heating element 3, nozzle 4 and magnetic printing platform 5.Wire-feed motor
Structure 1 is used to Filamentous thermoplastic material being sent into heating element 3.Heating element 3 receives the Filamentous heat that wire feeder 1 is sent
Molten state is heated to after plastic material.
Preferably, further include spring clamping feature 7, be preferably oppositely arranged with the wire feeder 1, for ensureing filiform
Thermoplastic material follows the stepping of the wire feeder 1.
Preferably, 3D printing equipment further includes the thermal sleeve 2 being arranged on 3 top of heating element.The thermal sleeve 2
Material is polytetrafluoroethylene (PTFE).The heating element 3 can be heating rod.It is highly preferred that the heating rod is two, respectively symmetrically
The both sides that channel is squeezed out in Filamentous thermoplastic material are arranged in ground.
Nozzle 4 is connected with heating element 3, for squeezing out the Filamentous thermoplastic material of the molten state.Magnetic printing
Platform 5 is arranged in the underface of nozzle 4 so that the material extruded from nozzle 4 in whole printing process is always by described
The magnetic force that magnetic printing platform 5 is given, to avoid FDM printers in 3D printing to the requirement of gravity condition.
According to the present invention, the magnetic printing platform 5 is embedded with rare-earth permanent magnet 6.Preferably, the rare-earth permanent magnet 6
It is uniformly embedded at intervals inside the magnetic printing platform 5.
The magnetic printing platform 5 is insulating materials.Preferably, the magnetic printing platform 5 is wooden structures.FDM is whole
Machine rack and internal guide rail are all made of nonferromugnetic material.
According to the present invention, the spring clamping feature 7 is the matching component of wire feeder 1, for ensureing the filiform
Thermoplastic material follows the stepping of wire feeder 1.
The present invention carries out appropriate reconstruction by the printing base platform to the 3D printing equipment based on FDM, under nozzle
Side's setting magnetic printing platform so that in whole printing process, the material of the molten state squeezed out from nozzle always by
The magnetic force that print platform is given can exempt requirement of the FDM 3D printings to gravity condition, realize in irregular or non-horizontal surface
3D printing is carried out, can also be realized under the space environment of zero-g and the ship that jolts, vehicle and the aircraft of Gravity changer
3D printing is carried out under equal environment, to widen the application range of FDM significantly.
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
Embodiment 1
One, following weight is pressed：
Perstorp CapaTM6400 40 parts of (number-average molecular weight 37000)；
Sm2Fe17N346 parts of powder；
84115 parts of toughener Dow POE；
Tackifier C98 parts of Petropols (offer of Puyang Hengfeng petrochemical industry Co., Ltd)；
0.5 part of German BASF irgasfos 168s；
Nanjing joins 0.5 part of silication work KH570.
Two, preparation method
1) raw material weighs up in proportion；
2) by PCL pellets under liquid nitrogen environment ball milling 1 hour, obtain the powder of 200 μm or so of grain size；Simultaneously by silane idol
Connection agent KH570 is dispersed in Sm2Fe17N3In powder；
3) above-mentioned each component is put into high mixer high speed to stir 10 minutes, is sufficiently mixed；
4) mixture obtained after being sufficiently mixed in step 3) is put into plasticizing in HAAKE double screw extruders and squeezes out and make
It is granulated with pelleter, process conditions are as shown in table 1.
Table 1
| TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | N/r/ minutes |
| 70 | 75 | 85 | 90 | 90 | 80 | 7 | 50 |
5) grain made is put into single screw extrusion machine wire drawing and wound, a diameter of 1.75~2mm of the filament.This is thin
Silk can be directly used for 3D printing.The process conditions of single screw extrusion machine wire drawing are as shown in table 2.
Table 2
| One area/DEG C | 2nd area/DEG C | Die orifice/DEG C | Rotating speed n/r/min |
| 80 | 85 | 75 | 700 |
Embodiment 2
One, following weight is pressed：
Perstorp CapaTM6500 28 parts of (number-average molecular weight 50000)；
Nd2Fe1462 parts of B powder；
260 3 parts of toughener Dupont EVA；
C56.2 parts of Petropols (offer of Puyang Hengfeng petrochemical industry Co., Ltd)；
0.5 part of BASF irgasfos 168s；
Nanjing joins 0.3 part of silication work KH560
Two, preparation method
1) raw material is weighed up in proportion；
2) by PCL pellets under liquid nitrogen environment ball milling 1 hour, it is 200 μm or so of powder to obtain grain size；Simultaneously by silane
Coupling agent KH560 is dispersed in Nd2Fe14In B powder；
3) above-mentioned each component is put into high mixer high speed and stirs 10 minutes, is sufficiently mixed；
4) mixture obtained after being sufficiently mixed in step 3) is put into plasticizing in HAAKE double screw extruders and squeezes out and make
It is granulated with pelleter, process conditions such as table 3.
Table 3
| TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | n/r/min |
| 70 | 75 | 85 | 90 | 90 | 80 | 7 | 50 |
5) grain made is put into single screw extrusion machine wire drawing and wound, a diameter of 1.75~2mm of the filament.This is thin
Silk can be directly used for 3D printing.The process conditions of single screw extrusion machine wire drawing are as shown in table 4.
Table 4
Embodiment 3
One, following weight is pressed：
Perstorp CapaTM6800 30 parts of (number-average molecular weight 80000)；
SmCo558 parts of powder；
8,402 3 parts of Dow POE；
C98.0 parts of Petropols (offer of Puyang Hengfeng petrochemical industry Co., Ltd)；
0.5 part of BASF irgasfos 168s；
KH5600.5 parts of Guangzhou Ou Ying chemical industry
Two, preparation method
1) raw material is weighed up in proportion；
2) by PCL pellets under liquid nitrogen environment ball milling 1 hour, obtain the powder of 200 μm or so of grain size；Simultaneously by silane idol
Connection agent KH560 is dispersed in SmCo5Powder；
3) above-mentioned each component is put into high mixer high-speed stirred 10 minutes, repeats to mix；
4) mixture obtained after being sufficiently mixed in step 3) is put into plasticizing in HAAKE double screw extruders and squeezes out and make
It is granulated with pelleter, process conditions such as table 5：
Table 5
| TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | N/r/ minutes |
| 70 | 75 | 85 | 90 | 90 | 80 | 7 | 50 |
5) grain made is put into single screw extrusion machine wire drawing and wound, a diameter of 1.75~2mm of the filament.This is thin
Silk can be directly used for 3D printing.The process conditions of single screw extrusion machine wire drawing are as shown in table 6.
Table 6
Embodiment 4
One, following weight is pressed：
Perstorp CapaTM6800 35 parts of (number-average molecular weight 80000)；
SmCo565 parts of powder；
Two, preparation method
1) raw material is weighed up in proportion；
2) by PCL pellets under liquid nitrogen environment ball milling 1 hour, obtain the powder of 200 μm or so of grain size；
3) by PCL powder and SmCo5Powder is put into high mixer high-speed stirred 10 minutes, repeats to mix；
4) mixture obtained after being sufficiently mixed in step 3) is put into plasticizing in HAAKE double screw extruders and squeezes out and make
It is granulated with pelleter, process conditions such as table 7：
Table 7
| TS1/℃ | TS2/℃ | TS3/℃ | TS4/℃ | TS5/℃ | TS6/℃ | FR/% | N/r/ minutes |
| 70 | 75 | 85 | 90 | 90 | 80 | 7 | 50 |
5) grain made is put into single screw extrusion machine wire drawing and wound, a diameter of 1.75~2mm of the filament.This is thin
Silk can be directly used for 3D printing.The process conditions of single screw extrusion machine wire drawing are as shown in table 8.
Table 8
The performance test results for the modification PCL being prepared in the various embodiments described above are as follows：
Table 9
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (39)
1. a kind of composition for 3D printing, which is characterized in that it includes following component：25 ~ 55 parts by weight of thermoplastic resin；
And 40 ~ 70 parts by weight of alloy powder containing rare earth element；
Wherein, the grain size of the thermoplastic resin is 100 ~ 1000 μm；The thermoplastic resin is polycaprolactone；The thermoplasticity
The number-average molecular weight of resin is 30000 ~ 80000；At 190 DEG C, the melt index under the conditions of 2.16kg is the thermoplastic resin
10 ~ 40g/10 minutes.
2. composition according to claim 1, which is characterized in that also comprised the following components in the composition：Toughener 1
~ 10 parts by weight.
3. composition according to claim 1 or 2, which is characterized in that also comprised the following components in the composition：Thickening
2 ~ 10 parts by weight of agent.
4. composition according to claim 1 or 2, which is characterized in that also comprised the following components in the composition：Antioxygen
0.5 ~ 1 parts by weight of agent.
5. composition according to claim 1 or 2, which is characterized in that also comprised the following components in the composition：Surface
0.5 ~ 1 parts by weight of activating agent.
6. composition according to claim 1, which is characterized in that the dosage of the thermoplastic resin is 25 ~ 45 parts by weight.
7. composition according to claim 6, which is characterized in that the dosage of the thermoplastic resin is 28 parts by weight, 30
Parts by weight or 40 parts by weight.
8. composition according to claim 1, which is characterized in that the dosage of the alloy powder containing rare earth element is 45
~ 65 parts by weight.
9. composition according to claim 8, which is characterized in that the dosage of the alloy powder containing rare earth element is 46
Parts by weight, 58 parts by weight or 62 parts by weight.
10. composition according to claim 2, which is characterized in that the dosage of the toughener is 3 ~ 5 parts by weight.
11. composition according to claim 3, which is characterized in that the dosage of the tackifier is 7 ~ 9 parts by weight.
12. composition according to claim 11, which is characterized in that the dosage of the tackifier is 8 ~ 8.5 parts by weight.
13. composition according to claim 1, which is characterized in that the composition includes following component：
40 parts by weight of thermoplastic resin, 46 parts by weight of alloy powder containing rare earth element, 5 parts by weight of toughener, 8.0 weight of tackifier
Measure part, 0.5 parts by weight of 0.5 parts by weight of antioxidant and surfactant；Or
28 parts by weight of thermoplastic resin, 62 parts by weight of alloy powder containing rare earth element, 3 parts by weight of toughener, 8.2 weight of tackifier
Measure part, 0.3 parts by weight of 0.5 parts by weight of antioxidant and surfactant；Or
30 parts by weight of thermoplastic resin, 58 parts by weight of alloy powder containing rare earth element, 3 parts by weight of toughener, 8.0 weight of tackifier
Measure part, 0.5 parts by weight of 0.5 parts by weight of antioxidant and surfactant.
14. composition according to claim 1, which is characterized in that the grain size of the thermoplastic resin is 200 ~ 500 μm.
15. composition according to claim 1, which is characterized in that the number-average molecular weight of the thermoplastic resin is 40000
~60000；For the thermoplastic resin at 190 DEG C, the melt index under the conditions of 2.16kg is 20 ~ 30g/10 minutes.
16. composition according to claim 1, which is characterized in that the polycaprolactone is PerstorpCapaTM6400,
PerstorpCapaTM6500 or PerstorpCapaTM 6800。
17. composition according to claim 1, which is characterized in that the alloy powder containing rare earth element be rare earth forever
Magnetic material powder.
18. composition according to claim 17, which is characterized in that the rare earth permanent-magnetic material powder is SmCo5、
Sm2Co17、Nd2Fe14B and Sm2Fe17N3In it is one or more.
19. composition according to claim 2, which is characterized in that
The toughener is haloflex, styrene butadiene thermoplasticelastomer, ethylene-vinyl acetate copolymer, three
It is one or more in first EP rubbers and ethylene-octene block copolymer.
20. composition according to claim 19, which is characterized in that the toughener is copolymerized for ethylene-vinyl acetate
The mixture of object and haloflex.
21. composition according to claim 3, which is characterized in that the tackifier are tackifying resin；The tackifying resin
For C5Petropols, C9One or more of Petropols, hydrogenated aromatic Petropols, terpene resin and rosin resin.
22. composition according to claim 21, which is characterized in that the tackifier are hydrogenated aromatic Petropols.
23. composition according to claim 4, which is characterized in that the antioxidant be irgasfos 168, antioxidant 1010,
One or more of antioxidant B215 and antioxidant B225.
24. composition according to claim 23, which is characterized in that the antioxidant is irgasfos 168.
25. composition according to claim 5, which is characterized in that the surfactant is silane coupling agent.
26. composition according to claim 25, which is characterized in that the surfactant be KH550, KH570 and
One or more of KH560.
27. a kind of material for 3D printing of rare earth doped element, raw material is used for claim 1-26 any one of them
In the composition of 3D printing.
28. material according to claim 27, which is characterized in that the material for 3D printing is by above-mentioned composition
Filament obtained.
29. material according to claim 28, which is characterized in that a diameter of 0.5 ~ 5mm of the filament.
30. material according to claim 29, which is characterized in that a diameter of 1.5 ~ 3.5mm of the filament.
31. material according to claim 30, which is characterized in that the diameter of the filament is 1.75mm or 3mm.
32. a kind of preparation method of the material for 3D printing of the rare earth doped element of claim 27-31 any one of them,
Include the following steps：
1) each component in the composition is mixed；
2) by step 1）The mixture obtained after mixing is granulated by double screw extruder fusion plastification, and by pelleter；
Wherein, further include first by thermoplastic resin particle in liquid nitrogen before the thermoplastic resin in the composition being mixed
The step of ball milling forms powder is carried out under environment；The grain size of the powder formed after the ball milling is 100 ~ 1000 μm.
33. preparation method according to claim 32, which is characterized in that the preparation method further includes：
3) by step 2）Obtained pellet wire drawing, obtains filament；A diameter of 0.5 ~ 5mm of the filament.
34. preparation method according to claim 32, which is characterized in that step 1）In, it is fully mixed by high-speed mixer
It closes 5 ~ 30 minutes；
Step 2）In, the temperature of the double screw extruder fusion plastification is 60 ~ 150 DEG C.
35. preparation method according to claim 32, which is characterized in that the grain size of the powder formed after the ball milling is
200~500μm。
36. preparation method according to claim 32, which is characterized in that carry out the alloy powder containing rare earth element
Further include the step being dispersed in silane coupling agent in the alloy powder containing rare earth element before mixing.
37. a kind of product passes through the material for 3D printing of the rare earth doped element of claim 27-31 any one of them
It is made through 3D printing.
38. according to the product described in claim 37, which is characterized in that the product is by above-mentioned material through made from 3D printing
Permanent magnet.
39. according to the product described in claim 37, which is characterized in that the product is to embed by above-mentioned material through 3D printing system
The plastic products of the permanent magnet obtained.
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| CN107974027B (en) * | 2016-10-25 | 2021-09-10 | 合肥杰事杰新材料股份有限公司 | Low-shrinkage amorphous composite material for rapid molding and preparation method thereof |
| EP3321002A1 (en) * | 2016-11-15 | 2018-05-16 | Höganäs AB | Feedstock for an additive manufacturing method, additive manufacturing method using the same, and article obtained therefrom |
| US10316184B2 (en) * | 2016-12-30 | 2019-06-11 | Nano And Advanced Materials Institute Limited | Low printing temperature filaments for 3D printing |
| CN107189423B (en) * | 2017-05-12 | 2020-03-27 | 平潭综合实验区启智三维科技有限公司 | Antifriction material based on FDM 3D printing, preparation method thereof and method for enhancing antifriction performance of material product |
| CN109082091A (en) * | 2018-07-09 | 2018-12-25 | 福建师范大学 | A kind of 3D printing wire rod of Desulphurization filling degradable low temperature and preparation method thereof |
| CN109719297B (en) * | 2019-01-31 | 2020-12-15 | 广东科技学院 | Porous metal composite material and preparation method thereof |
| CN114174573B (en) * | 2019-12-02 | 2023-11-14 | 花王株式会社 | Resin composition for melt spinning, method for producing same, and method for producing fiber |
| CN111070673A (en) * | 2019-12-24 | 2020-04-28 | 广东工业大学 | Method for 3D printing of polymer in condensed state |
| CN112694706B (en) * | 2020-12-11 | 2022-01-11 | 中国科学技术大学 | 3D printing method of high-flexibility high-elasticity low-modulus magnetorheological elastomer |
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