CN107936459A - A kind of composition, preparation and its application for fused glass pellet 3D printer - Google Patents
A kind of composition, preparation and its application for fused glass pellet 3D printer Download PDFInfo
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- CN107936459A CN107936459A CN201711281110.XA CN201711281110A CN107936459A CN 107936459 A CN107936459 A CN 107936459A CN 201711281110 A CN201711281110 A CN 201711281110A CN 107936459 A CN107936459 A CN 107936459A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- 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
- 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
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K2003/0837—Bismuth
-
- 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
- C08L2205/02—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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of composition, preparation and application for fused glass pellet 3D printer.Said composition is by high molecular polymer continuous phase, foaming agent phase, three phase composition of low-melting alloy phase.Fusion sediment 3D printing is carried out into product using said composition, is put into intermediate frequency electromagnetic induction furnace and heats 6 10 seconds, micron order hole can be internally formed in product, obtain porous product.Engineering Plastics Parts of the invention mainly for fusing point more than 200 DEG C foam without mould.To make engineering plastics not foam during preparation process and 3D printing, and the product foaming for completing 3D printing, it is necessary to use the higher chemical foaming agent of decomposition temperature.And to keep its shape after printing product foaming, traditional conduction heating cannot be used, to use sensing heating, then to add fusing point relatively low metal dust or alloy powder.
Description
Technical field
The present invention relates to a kind of composition, preparation and its application for fused glass pellet 3D printer, and in particular to
A kind of composition that porous product is prepared based on 3D printing and preparation method thereof, belongs to the field of functional materials of increasing material manufacturing.
Background technology
Over nearly twenties years, as a kind of emerging technology of rapid shaping field, 3D printing technique develops very fast, mesh
It is preceding to be applied in fields such as aerospace, biomedicine, defence and military, engineering education, new product developments.3D printing skill
Art is also known as increases material manufacturing technology, and different from traditional method for removing material processing, it is by way of successively accumulating material
Directly manufacture product.3D printing technique can rapidly and precisely produce complicated knot using three-dimensional CAD model in an equipment
Structure part, so as to fulfill " freely manufacturing ", solves the difficult processing of traditional handicraft or the limitation that can not be processed, and substantially reduce processing
In the cycle, be especially suitable for small lot, personalized, baroque hollow part.3D printing technique mainly includes fusion sediment at present
It is molded (Fused Deposition Modeling, FDM), selective laser sintering and moulding (Selective Laser
Sintering, SLS), Stereolithography (stereo lithography apparatus, SLA), laminated solid body shaping
Technologies such as (Laminated Object Manufacturing, LOM), wherein FDM is with fastest developing speed, using most.
FDM refers to that Filamentous thermoplastic is sent into nozzle by wire feeder, is heated to molten state in the showerhead, is squeezed through nozzle
Go out.The filamentary material of molten state is extruded out, and the path controlled according to the individual-layer data of three-dimensional software extrudes and specified
Position coagulation forming, layer by layer deposition solidification, eventually forms whole three-dimensional objects.The operating environment of FDM is clean, safety, technique letter
It is single, easily operated, and rubbish is not produced, therefore operation occasion has been widened significantly.Its raw materials is carried in the form of spool silk
For being easily portable and quick-replaceable.
But the application range of FDM is limited to by material at present, material category cause very little the practical performance of 3D printing by
Limitation, such as thermal conductivity, sound absorption anti-seismic performance are arrived.Therefore, develop new FDM 3D printings material and answered to widen it
It is very important with scope.
Expanded material refers to that foaming agent gasifies or expands so as to produce the material of loose structure in material internal, can be less
Density of material and dosage are reduced on the premise of loss material mechanical property, while meets that the light-high-strength of material and feature will
Ask.Expanded material fatigue life grow, there is preferable toughness, heat endurance, energy absorption and insulation performance, automobile, household electrical appliances,
Electronics, building, consumer goods industries and military field have broad application prospects.The preparation method baseset of expanded material at present
In in conventionally manufactured field, such as supercritical fluid prepares polymer foaming technology, two times opening mold, and required die sinking is costly,
Construction cycle is grown.So this just promotes us to develop a kind of foamable 3D printing material, by its preparation method and rapid shaping
Technology is combined, so as to significantly lift the development rate of porous articles, greatly increases the supporting dynamics to individuation product.This
Outside, this foam pattern is to be directed to engineering plastics, there is stronger practicality.
The content of the invention
The purpose of the present invention is overcome above-mentioned the deficiencies in the prior art, there is provided one kind is used for fused glass pellet 3D printer
Composition.
It is a further object to provide a kind of preparation method for fused glass pellet 3D printer composition.
Another object of the present invention is to be to provide a kind of application field of above-mentioned composition, you can prepares porous system
Part, and the preparation method of the porous product.
Present invention is generally directed to engineering plastics, its fusing point is more than 200 DEG C, and the blowing temperature of physical blowing agent exists
Less than 150 DEG C.Therefore to make engineering plastics not foam during preparation process and 3D printing, and make what 3D printing was completed
Product foams, it is necessary to uses high Temperature Chemical Foaming agent.And make it that printing product keeps its shape, cannot use traditional
Conduction heating, will use sensing heating, then to add fusing point relatively low metal dust or alloy powder.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of composition for fused glass pellet 3D printer, said composition are the masters of fused glass pellet 3D printing
Want raw material.
Said composition is by high molecular polymer continuous phase, foaming agent phase, three phase composition of low-melting alloy phase.
The high molecular polymer continuous phase accounting 70-90 weight ratios, are preferably 75-85 weight ratios, can by a kind of or
A variety of macromolecule compositions, including butadiene-acrylonitrile-styrene block copolymer, polyethylene terephthalate or polyamides
Amine 6.
The foaming agent is preferably chemical foaming agent, accounts for 2-5 parts by weight, is preferably 3-4 parts by weight, can be by three diazanyls three
Piperazine, p-toluene sulfonylsemicarbazide or 4, a kind of composition in 4 '-oxo double (benzenesulfonamido- urea).
The low-melting alloy accounting 15-25 weight ratios, are preferably 18-23 weight ratios, can be closed by kamash alloy, lead base
One or more of compositions of gold, bismuth-base alloy, are preferably kamash alloy powder.
The preparation method of the composition for first by low-melting alloy powder and foaming agent respectively with high molecular polymerization
Thing is put into high mixer according to the several times of final accounting and is mixed, and height, which is made, in dual-screw-stem machine extruder progress melt blending contains
Master batch is measured, then two kinds of master batches and high molecular polymer are blended in final ratio, pellet is processed into through double screw extruder,
Pellet is finally made to the wire rod of 1.75mm diameters through single screw extrusion machine, is used for fused glass pellet 3D printer.
The porous product of meter level can be prepared with said composition, hole is lipostomous, and diameter is about 10-50um.
The porous product, its method are to be printed composition recited above using fused glass pellet 3D printer
Go out product, product is heated 6-10 seconds in intermediate frequency electromagnetic induction furnace, be preferably 7-9 seconds, sensing electric current is 150A, so as to make
Part is internally formed micron order hole, obtains porous product.
Composition of the present invention paves that performance is good, and wire drawing is few during 3D printing, make 3D printing product precision compared with
Height, warpage are small.In addition said composition has opened up the new application field of fused glass pellet 3D printing, such as the antidetonation product that absorbs sound
Prototype etc..
Brief description of the drawings
Fig. 1 is the stereoscan photograph of porous product.
Embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as this hair
Bright scope is only limitted to following example.Without departing from the idea of the above method of the present invention, according to the common skill in this area
The various replacements or change that art knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of composition for fused glass pellet 3D printer
1) babbit, ABS are pressed 3:1 weight ratio is put into high mixer and mixes 5 minutes, is melted in double screw extruder
Melt blending and make master batch；
2) p-toluene sulfonylsemicarbazide, ABS are pressed 0.2:1 weight ratio is put into high mixer and mixes 5 minutes, is squeezed in twin-screw
Go out machine and carry out melt blending to make master batch, because the decomposition temperature of p-toluene sulfonylsemicarbazide is close to 235 DEG C, and processing temperature is
220 DEG C, so ABS does not foam in process；
3) master batch and ABS of step 1) and step 2) are pressed 2:1:7 weight ratio is put into high mixer and mixes 5 minutes, double
Screw extruder carries out melt blending granulation；
4) composition of step 3) is put into single screw extrusion machine, prepares the wire rod of 1.75mm diameters；
5) melt index of the composition of step 3) under 190 DEG C, 1kg pressure is understood by using fusion index instrument test
For 25g/10min；
6) wire rod of step 4) is put into the Creator Pro fused glass pellets 3D printer progress 3D printing for dodging casting.
Embodiment 2
A kind of composition for fused glass pellet 3D printer
1) leypewter, PA6 are pressed 3:1 weight ratio is put into high mixer and mixes 5 minutes, is melted in double screw extruder
Melt blending and make master batch；
2) trihydrazinotriazine, PA6 are pressed 0.2:1 weight ratio be put into high mixer mix 5 minutes, double screw extruder into
Row melt blending makes master batch, because the decomposition temperature of trihydrazinotriazine is close to 250 DEG C, and processing temperature is 230 DEG C, so
PA6 does not foam in process；
3) master batch and PA6 of step 1) and step 2) are pressed 3:2:8 weight ratio is put into high mixer and mixes 5 minutes, double
Screw extruder carries out melt blending granulation；
4) composition of step 3) is put into single screw extrusion machine, prepares the wire rod of 1.75mm diameters；
5) melt index of the composition of step 3) under 230 DEG C, 5kg pressure is understood by using fusion index instrument test
For 16g/10min；
6) wire rod of step 4) is put into the Creator Pro fused glass pellets 3D printer progress 3D printing for dodging casting.
Embodiment 3
A kind of composition for fused glass pellet 3D printer
1) lead bismuth alloy, PA66 are pressed 4:1 weight ratio is put into high mixer and mixes 5 minutes, is carried out in double screw extruder
Melt blending makes master batch；
2) 4,4 '-oxo double (benzenesulfonamido- ureas), PA66 are pressed 0.3:1 weight ratio is put into high mixer and mixes 5 minutes,
Melt blending, which is carried out, in double screw extruder makes master batch, because 4, the decomposition temperature of 4 '-oxo double (benzenesulfonamido- ureas) connects
Nearly 260 DEG C, and processing temperature is 240 DEG C, so PA66 does not foam in process；
3) master batch and PA66 of step 1) and step 2) are pressed 4:2.5:9 weight ratio is put into high mixer and mixes 5 minutes,
Double screw extruder carries out melt blending granulation；
4) composition of step 3) is put into single screw extrusion machine, prepares the wire rod of 1.75mm diameters；
5) melt index of the composition of step 3) under 230 DEG C, 5kg pressure is understood by using fusion index instrument test
For 9g/10min；
6) wire rod of step 4) is put into the Creator Pro fused glass pellets 3D printer progress 3D printing for dodging casting.
Embodiment 4
A kind of porous product prepared based on fused glass pellet 3D printing
1) product printed of embodiment 1 is put into intermediate frequency furnace, sensing electric current heats 10s for 150A, so as to make
Part is internally formed micron order hole, obtains porous product.
Embodiment 5
A kind of porous product prepared based on fused glass pellet 3D printing
1) product printed of embodiment 2 is put into intermediate frequency furnace, sensing electric current heats 12s for 150A, so as to make
Part is internally formed micron order hole, obtains porous product.
Embodiment 6
A kind of porous product prepared based on fused glass pellet 3D printing
1) product printed of embodiment 3 is put into intermediate frequency furnace, sensing electric current heats 8s for 150A, so that in product
Micron order hole is internally formed, obtains porous product.
1 data of mechanical of table
Claims (8)
- A kind of 1. composition for fused glass pellet 3D printer, it is characterised in that：Said composition is by high molecular polymer Continuous phase, foaming agent phase, three phase composition of low-melting alloy phase.
- 2. composition as claimed in claim 1, it is characterised in that：High molecular polymer continuous phase accounting 70-90 weight ratios, it is excellent Elect 75-85 weight ratios as, can be made of one or more macromolecules, including butadiene-acrylonitrile-styrene block copolymer, Polyethylene terephthalate or polyamide 6.
- 3. composition as claimed in claim 1, it is characterised in that：Foaming agent is preferably chemical foaming agent, accounts for 2-5 parts by weight, Preferably 3-4 parts by weight, can be by trihydrazinotriazine, p-toluene sulfonylsemicarbazide or 4, in 4 '-oxo double (benzenesulfonamido- ureas) A kind of composition.
- 4. composition as claimed in claim 1, it is characterised in that：Low-melting alloy accounting 15-25 weight ratios, are preferably 18- 23 weight ratios, can be made of the one or more of kamash alloy, lead-containing alloy, bismuth-base alloy, be preferably kamash alloy powder.
- 5. the preparation method of composition described in claim 1, it is characterised in that：First by low-melting alloy powder and foaming agent point High mixer is not put into according to the several times of final accounting to be mixed, melted in dual-screw-stem machine extruder with high molecular polymer Melt blending and high-content master batch is made, then two kinds of master batches and high molecular polymer are blended in final ratio, through twin-screw extrusion Pellet is made in machining, pellet is finally made to the wire rod of 1.75mm diameters through single screw extrusion machine, for fused glass pellet 3D Printer uses.
- 6. the purposes of composition described in claim 1, it is characterised in that：It is used to prepare micron-sized porous product.
- 7. purposes as claimed in claim 6, it is characterised in that：Hole is lipostomous, and diameter is about 10-50um.
- 8. purposes as claimed in claim 6, it is characterised in that：The preparation method of the porous product be using fusion sediment into Composition described in claim 1 is printed product by type 3D printer, and product is heated 6-10 in intermediate frequency electromagnetic induction furnace Second, it is preferably 7-9 seconds, sensing electric current is 150A, so as to be internally formed micron order hole in product, obtains porous product.
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| CN201711281110.XA CN107936459B (en) | 2017-12-07 | 2017-12-07 | It is a kind of for the composition of fused glass pellet 3D printer, preparation and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108856721A (en) * | 2018-07-18 | 2018-11-23 | 申科滑动轴承股份有限公司 | A kind of preparation process of the 3 D-printing composite material based on micron order tin-base babbit powder |
| CN109456565A (en) * | 2018-09-13 | 2019-03-12 | 苏州巴夏科技发展有限公司 | A kind of intelligent macromolecule material, preparation method and its utilize method |
| CN113943408A (en) * | 2020-07-16 | 2022-01-18 | 中国科学院福建物质结构研究所 | Polymer-based composite material foaming part and preparation method thereof |
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| CN106041086A (en) * | 2015-04-09 | 2016-10-26 | 韩国电子通信研究院 | Metal material for 3-dimensional printing, method for manufacturing the same, and method for 3-dimensional printing using the same |
| CN107189423A (en) * | 2017-05-12 | 2017-09-22 | 平潭综合实验区启智三维科技有限公司 | Method based on FDM3D antifriction materials printed and preparation method thereof and enhancing material product Wear vesistance |
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| CN1625785A (en) * | 2002-03-19 | 2005-06-08 | 热力蒂思科有限公司 | PTC conductive composition containing a low molecular weight polyethylene processing aid |
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| CN105218939A (en) * | 2015-11-05 | 2016-01-06 | 中国科学院福建物质结构研究所 | A kind of foamable 3D printed material and preparation method thereof |
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| CN107189423A (en) * | 2017-05-12 | 2017-09-22 | 平潭综合实验区启智三维科技有限公司 | Method based on FDM3D antifriction materials printed and preparation method thereof and enhancing material product Wear vesistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108856721A (en) * | 2018-07-18 | 2018-11-23 | 申科滑动轴承股份有限公司 | A kind of preparation process of the 3 D-printing composite material based on micron order tin-base babbit powder |
| CN109456565A (en) * | 2018-09-13 | 2019-03-12 | 苏州巴夏科技发展有限公司 | A kind of intelligent macromolecule material, preparation method and its utilize method |
| CN113943408A (en) * | 2020-07-16 | 2022-01-18 | 中国科学院福建物质结构研究所 | Polymer-based composite material foaming part and preparation method thereof |
| CN113943408B (en) * | 2020-07-16 | 2022-09-06 | 福建泉州海滨防护装备有限公司 | Polymer-based composite material foaming part and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN107936459B (en) | 2019-08-20 |
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