CN107936459B - It is a kind of for the composition of fused glass pellet 3D printer, preparation and its application - Google Patents
It is a kind of for the composition of fused glass pellet 3D printer, preparation and its application Download PDFInfo
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- CN107936459B CN107936459B CN201711281110.XA CN201711281110A CN107936459B CN 107936459 B CN107936459 B CN 107936459B CN 201711281110 A CN201711281110 A CN 201711281110A CN 107936459 B CN107936459 B CN 107936459B
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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
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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
- C08J2377/06—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
- 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
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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
- C08L2205/02—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
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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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- 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 for the composition of fused glass pellet 3D printer, preparation and application.The 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 the composition, is put into intermediate frequency electromagnetic induction furnace and heats 6-10 seconds, micron order hole can be formed inside product, obtain porous product.The invention foaming without mold in 200 DEG C or more of Engineering Plastics Parts mainly for fusing point.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, induction heating is used, then lower melting-point metal powder or alloy powder is added.
Description
Technical field
The present invention relates to a kind of for the composition of fused glass pellet 3D printer, preparation and its application, and in particular to
A kind of composition and preparation method thereof preparing porous product based on 3D printing, belongs to the field of functional materials of increasing material manufacturing.
Background technique
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 of removal 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 on one device
Structure part, thus realize " freely manufacturing ", the limitation that solves the processing of traditional handicraft difficulty or can not process, and substantially reduce processing
Period is especially suitable for small lot, personalized, complicated hollow part.3D printing technique mainly includes fusion sediment at present
Form (Fused Deposition Modeling, FDM), selective laser sintering and moulding (Selective Laser
Sintering, SLS), Stereolithography (stereo lithography apparatus, SLA), laminated solid body molding
Technologies such as (Laminated Object Manufacturing, LOM), wherein FDM is with fastest developing speed, using most.
FDM refers to that Filamentous thermoplastic material is sent into spray head by wire feeder, is heated to molten state in the showerhead, squeezes through nozzle
Out.The filamentary material of molten state is extruded out, squeezes and according to the path that the individual-layer data of three-dimensional software controls specified
Position coagulation forming, layer by layer deposition solidification, eventually forms entire three-dimensional objects.The operating environment of FDM is clean, safe, technique letter
It is single, easily operated, and rubbish is not generated, therefore widened operation occasion significantly.Its raw materials is mentioned in the form of spool silk
For being easily portable and quick-replaceable.
However the application range of FDM is limited to by material at present, material category make very little the practical performance of 3D printing by
Limitation, such as thermal conductivity, sound absorption anti-seismic performance are arrived.Therefore, new FDM 3D printing material is developed to answer to widen it
It is very important with range.
Foamed material refers to that foaming agent gasifies in material internal or expands to generate the material of porous structure, can be less
Density of material and dosage are reduced under the premise of loss material mechanical property, while meeting the light-high-strength of material and functionality is wanted
It asks.Foamed material fatigue life is long, have preferable toughness, thermal stability, 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 foamed 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,
Development cycle is long.So this just promotes us to develop a kind of foamable 3D printing material, by preparation method and rapid shaping
Technology combines, to significantly promote the development rate of porous articles, greatly increases the supporting dynamics to individuation product.This
Outside, this foam pattern is that have stronger practicability for engineering plastics.
Summary of the invention
The purpose of the present invention is overcoming above-mentioned the deficiencies in the prior art, provide a kind of for fused glass pellet 3D printer
Composition.
It is a further object to provide a kind of preparation methods 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, can prepare porous system
The preparation method of part and the porous product.
Present invention is generally directed to engineering plastics, and fusing point is at 200 DEG C or more, and the blowing temperature of physical blowing agent exists
150 DEG C or less.Therefore to make engineering plastics not foam during preparation process and 3D printing, and complete 3D printing
Product foaming, it is necessary to use high Temperature Chemical Foaming agent.And printing product to be made to keep its shape, it cannot use traditional
Conduction heating will use induction heating, then lower melting-point metal powder or alloy powder is added.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of composition for fused glass pellet 3D printer, the composition are the masters of fused glass pellet 3D printing
Want raw material.
The 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 ratio, preferably 75-85 weight ratio, 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, preferably 3-4 parts by weight, can be by three diazanyls three
Piperazine, p-toluene sulfonylsemicarbazide or 4, one of 4 '-oxos bis- (benzenesulfonamido- ureas) composition.
The low-melting alloy accounting 15-25 weight ratio, preferably 18-23 weight ratio can be closed by kamash alloy, lead base
One or more of compositions of gold, bismuth-base alloy, preferably kamash alloy powder.
The preparation method of the composition be first by low-melting alloy powder and foaming agent respectively with high molecular polymerization
Object is put into high mixer according to the several times of final accounting and is mixed, and height is made in dual-screw-stem machine extruder progress melt blending and contains
Master batch is measured, two kinds of master batches and high molecular polymer are blended in final ratio then, are processed into pellet through double screw extruder,
Pellet is finally made to the wire rod of 1.75mm diameter through single screw extrusion machine, is used for fused glass pellet 3D printer.
The porous product of meter level can be prepared with the composition, hole is lipostomous, and diameter is about 10-50um.
The porous product, method are to be printed composition recited above using fused glass pellet 3D printer
Product is heated 6-10 seconds by product out in intermediate frequency electromagnetic induction furnace, and preferably 7-9 seconds, induced current 150A, thus making
Micron order hole is formed inside part, 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 accuracy compared with
Height, warpage are small.Furthermore the composition has opened up the new application field of fused glass pellet 3D printing, such as the antidetonation product that absorbs sound
Prototype etc..
Detailed description of the invention
Fig. 1 is the stereoscan photograph of porous product.
Specific 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 range is only limitted to example below.Without departing from the idea of the above method of the present invention, according to the common skill in this field
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 put into high mixer by the weight ratio of 3:1 and mixed 5 minutes, melted in double screw extruder
Melt blending and is made into master batch；
2) p-toluene sulfonylsemicarbazide, ABS are put into high mixer by the weight ratio of 0.2:1 and mixed 5 minutes, squeezed in twin-screw
Machine carries out melt blending and is made into master batch out, 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 put into high mixer by the weight ratio of 2:1:7 to mix 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 diameter；
5) melt index by using the composition of step 3) known to fusion index instrument test under 190 DEG C, 1kg pressure
For 25g/10min；
6) wire rod of step 4) is put into the Creator Pro fused glass pellet 3D printer progress 3D printing for dodging casting.
Embodiment 2
A kind of composition for fused glass pellet 3D printer
1) leypewter, PA6 are put into high mixer by the weight ratio of 3:1 and mixed 5 minutes, melted in double screw extruder
Melt blending and is made into master batch；
2) by trihydrazinotriazine, PA6 by the weight ratio of 0.2:1 be put into high mixer mix 5 minutes, double screw extruder into
Row melt blending is made into 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 put into high mixer by the weight ratio of 3:2:8 to mix 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 diameter；
5) melt index by using the composition of step 3) known to fusion index instrument test under 230 DEG C, 5kg pressure
For 16g/10min；
6) wire rod of step 4) is put into the Creator Pro fused glass pellet 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 put into high mixer by the weight ratio of 4:1 and mixed 5 minutes, carried out in double screw extruder
Melt blending is made into master batch；
2) 4,4 '-oxos bis- (benzenesulfonamido- ureas), PA66 are put into high mixer by the weight ratio of 0.3:1 and mixed 5 minutes,
Melt blending, which is carried out, in double screw extruder is made into master batch, because 4, the decomposition temperature of 4 '-oxos bis- (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) high mixer is put by the weight ratio of 4:2.5:9 to mix 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 diameter；
5) melt index by using the composition of step 3) known to fusion index instrument test under 230 DEG C, 5kg pressure
For 9g/10min；
6) wire rod of step 4) is put into the Creator Pro fused glass pellet 3D printer progress 3D printing for dodging casting.
Embodiment 4
A kind of porous product based on fused glass pellet 3D printing preparation
1) product of embodiment 1 printed is put into intermediate frequency furnace, induced current is that 150A heats 10s, thus making
Micron order hole is formed inside part, obtains porous product.
Embodiment 5
A kind of porous product based on fused glass pellet 3D printing preparation
1) product of embodiment 2 printed is put into intermediate frequency furnace, induced current is that 150A heats 12s, thus making
Micron order hole is formed inside part, obtains porous product.
Embodiment 6
A kind of porous product based on fused glass pellet 3D printing preparation
1) product of embodiment 3 printed is put into intermediate frequency furnace, induced current is that 150A heats 8s, thus in product
Inside forms micron order hole, obtains porous product.
1 data of mechanical of table
Claims (9)
1. a kind of composition for fused glass pellet 3D printer, it is characterised in that: the 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 is 70-90 weight ratio；The high molecular polymer continuous phase is by a kind of or more
Kind macromolecule composition comprising butadiene-acrylonitrile-styrene block copolymer, polyethylene terephthalate or polyamides
Amine 6；
The foaming agent accounts for 2-5 parts by weight；The foaming agent is chemical foaming agent, by trihydrazinotriazine, tolysulfonyl ammonia
One of base urea or 4,4 '-oxos bis- (benzenesulfonamido- ureas) composition；
The low-melting alloy accounting 15-25 weight ratio, by the one or more of kamash alloy, lead-containing alloy, bismuth-base alloy
Composition.
2. composition as described in claim 1, it is characterised in that: the high molecular polymer continuous phase accounting is 75-85 weight
Amount ratio.
3. composition as described in claim 1, it is characterised in that: the foaming agent accounts for 3-4 parts by weight.
4. composition as described in claim 1, it is characterised in that: the low-melting alloy accounting is 18-23 weight ratio.
5. composition as described in claim 1 or 4, which is characterized in that the low-melting alloy is kamash alloy powder.
6. the purposes of any one of the claim 1-4 composition, it is characterised in that: be 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 10-50 μm.
8. purposes as claimed in claims 6 or 7, it is characterised in that: the preparation method of the porous product is heavy using melting
Composition described in claim 1 is printed product by product molding 3D printer, and product is heated in intermediate frequency electromagnetic induction furnace
6-10 seconds, induced current 150A, to form micron order hole inside product, obtain porous product.
9. purposes as claimed in claim 8, which is characterized in that the heating time is 7-9 seconds.
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| CN108856721B (en) * | 2018-07-18 | 2021-07-06 | 申科滑动轴承股份有限公司 | Preparation process of three-dimensional printing composite material based on micron-sized tin-based babbitt metal 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 |
| 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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