CN106751379A - Product prepared by a kind of fused glass pellet technique and preparation method thereof - Google Patents
Product prepared by a kind of fused glass pellet technique and preparation method thereof Download PDFInfo
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- CN106751379A CN106751379A CN201611046952.2A CN201611046952A CN106751379A CN 106751379 A CN106751379 A CN 106751379A CN 201611046952 A CN201611046952 A CN 201611046952A CN 106751379 A CN106751379 A CN 106751379A
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses composite wire used in a kind of product and preparation method thereof, the product and preparation method thereof.The product is prepared by fused glass pellet (FDM) technique, and raw material used is a kind of composite wire in the fused glass pellet technique, and the composite wire includes：The weight portion of polymer 100；The weight portion of chopped fiber 10~60；Coupling agent：0.5~5 weight portion；Antioxidant：0.1~1 weight portion；The draw ratio of the chopped fiber is 10~300.The product has excellent mechanical property, and its tensile strength, bending strength are higher, and any surface finish of the product, cure shrinkage is small, dimensionally stable and good mechanical performance.The preparation process is simple, the application prospect with large-scale production.
Description
Technical field
The invention belongs to 3D printing technique field, and in particular to product prepared by a kind of fused glass pellet (FDM) technique
And preparation method thereof, the composite wire used in said products and preparation method thereof.
Background technology
3D printing technique, is a kind of emerging manufacturing technology in rapid shaping field also known as increases material manufacturing technology.3D printing
Technology is designed a model as source with Computerized three-dimensional, is controlled by computer digit software program, using laser sintered, or heating
The modes such as melting by metal, ceramics or the material successively accumulation molding such as polymer, so as to produce 3D solid product.Unique
Manufacture advantage, quickly grows it, has been widely used at present in fields such as industry, life, medical science and scientific researches.Wherein, it is heavy to melt
Product shaping (FDM) technique is one of the most commonly used 3D printing technique, the material that it the is used generally thermoplastic such as nylon, ABS
Property resin, but due to the particularity of this kind of resin structure, it is easy to cause the mechanical property of final products not good, limiting it should
With the expansion of scope.
Fiber and thermoplastic resin are mixed and made into composite, are the important means for improving resin product mechanical property.
Fiber reinforcement mainly has two kinds of short fiber reinforced and long fiber reinforcement, and long fiber reinforcement is traditional enhancing technique, but process is relative
Complexity, it is relatively costly and not easy to operate, and short fiber reinforced then have it is easy to operate, it is with low cost, enhancing efficiency high the advantages of,
And it is applied to 3D printing technique, the fibre reinforced composites of particularly fused glass pellet (FDM) technique yet there are no report
Road.
The content of the invention
In order to overcome the deficiencies in the prior art, an object of the present invention is to provide a kind of product and preparation method thereof,
The product has preferable mechanical property, that is, have tensile strength and bending strength higher, and the product has surface
Bright and clean, cure shrinkage is small and the advantages of dimensionally stable.
The second object of the present invention is to provide composite wire for being used in a kind of said products and preparation method thereof, described
The chopped fiber of specific draw ratio is added with composite wire, while its mechanical property is strengthened, can well ensure described
The melt-processable of material, when the material is used for the 3D printing based on fused glass pellet (FDM) technique, it is ensured that beat
Print process is smooth, and the product surface of printing is bright and clean, cure shrinkage is small and dimensionally stable.
To achieve the above object, the present invention provides following technical scheme：
A kind of product, it passes through the preparation of fused glass pellet (FDM) technique, in fused glass pellet (FDM) technique
Raw material used is a kind of composite wire, and the composite wire is processed by the composition including following components：
Polymer：100 weight portions；
Chopped fiber：10~60 weight portions；It is preferred that 20~50 weight portions；
Coupling agent：0.5~10 weight portion；It is preferred that 1~5 weight portion；
Antioxidant：0.01~1 weight portion；It is preferred that 0.1~0.8 weight portion；
Wherein, the draw ratio of the chopped fiber is 10~300, preferably 10~70, more preferably 10~30.
In the present invention, described " draw ratio of chopped fiber " refers to the length of chopped fiber and the ratio of its diameter, and length
Unit with diameter is unified, for example, can be rice, centimetre, millimeter, micron etc..
According to the present invention, the chopped fiber is glass fibre, carbon fiber, boron fibre, whisker, asbestos fibre and synthetic fibers
In at least one.Preferably, the chopped fiber is at least one in carbon fiber, glass fibre.
According to the present invention, the polymer is acrylonitrile-butadiene-styrene copolymer (ABS), PLA (PLA), gathers
At least one in carbonic ester (PC), polyether-ether-ketone (PEEK) and nylon series polymer.Preferably, the polymer is propylene
At least one in nitrile-BS (ABS) and nylon series polymer.It is highly preferred that the polymer is
The mixture of acrylonitrile-butadiene-styrene copolymer (ABS) or nylon66 fiber polymer or the arbitrary proportion of the two.
According to the present invention, the coupling agent is 3- aminopropyl triethoxysilanes (KH550), 3- glycidyl ether oxygen propyls
At least one in trimethoxy silane (KH560) or 3- (isobutene acyl-oxygen) propyl trimethoxy silicane (KH570).It is preferred that
Ground, the coupling agent is 3- aminopropyl triethoxysilanes (KH550).
According to the present invention, the antioxidant is 2,6- di-tert-butyl-4-methy phenols, 3,5- di-t-butyl -4- hydroxyls
At least one in benzenpropanoic acid octadecyl ester or triphenyl phosphite.Preferably, the antioxidant is 2,6- di-t-butyl -4- first
Base phenol.
The present invention also provides the preparation method of said products, and the preparation method is comprised the following steps：
1) each component in composition is chosen according to percentage by weight, obtains the composition；
2) by the composition melting extrusion, it is made the composite wire；
3) above-mentioned composite wire is sent into the 3D printer based on fused glass pellet (FDM) technique by wire feeder to spray
Head, is heated fusing and extrudes in shower nozzle, and the above-mentioned composite wire of melting quickly solidifies to form solidification thin layer after being extruded, warp
Layer upon layer is made the product.
According to the present invention, in step 2) in, the melting extrusion technique of described composite wire can use prior art
The melting extrusion technique of known any one wire rod, for example, can be to extrude the composition using double screw extruder to process
Into the filament of a diameter of 1.75mm, within 5%, the draw ratio of the screw rod of the double screw extruder is 40 to diameter error；Also
Can be the filament that the composition is extruded and processed into a diameter of 3.0mm using single screw extrusion machine, diameter error 5% with
Interior, the screw diameter of the single screw extrusion machine is 70mm, and draw ratio is 25.
According to the present invention, in step 3) in, nozzle temperature is 200~300 in fused glass pellet (FDM) technique
DEG C, 60~100 DEG C of hott bed temperature.
In the present invention, the chopped fiber of specific draw ratio, the short fibre are added in the composite wire for processing the product
While being added in mechanical property (the increasing its stretching and bending strength) for improving the product of dimension, has been completely secured described multiple
Melting behaviour of the zygonema material during fusion sediment, it is ensured that the product surface that prints is bright and clean, cure shrinkage is small, chi
Very little stabilization and good mechanical performance.
In the present invention, the draw ratio of the chopped fiber of selection is 10~300, wherein, when draw ratio is less than this scope, its institute
The effect of generation is near with particulates reinforcements, i.e., cannot play the enhanced effect of fiber mechanicses；When draw ratio is more than this scope, fiber
With polymeric matrix in recombination process, fiber skewness and fiber is easily produced to be impregnated by polymeric matrix completely
Phenomenon, and the fluidity of molten that made composite wire is formed in melted by heating is poor, rough surface, influence product layer
Between adhesion and product surface finish etc., so as to be unfavorable for fused glass pellet, therefore cannot meet based on fusion sediment
It is molded the 3D printing demand of (FDM) technique.
The present invention also provides the composite wire used in said products, and the composite wire is by the group including following components
Compound is processed：
Polymer：100 weight portions；
Chopped fiber：10~60 weight portions；It is preferred that 20~50 weight portions；
Coupling agent：0.5~5 weight portion；It is preferred that 1~5 weight portion；
Antioxidant：0.1~1 weight portion；It is preferred that 0.1~0.8 weight portion；
Wherein, the draw ratio of the chopped fiber is 10~300, preferably 10~70, more preferably 10~30.
The present invention furthermore provides the preparation method of above-mentioned composite wire, the described method comprises the following steps：
A) component in the composition is chosen according to percentage by weight；
B) said components are well mixed, are extruded and processed into filament, that is, prepare the composite wire.
According to the present invention, in step b), the melting extrusion technique of any one wire rod known in the art can be used,
For example can be the filament that the composition is extruded and processed into a diameter of 1.75mm using double screw extruder, diameter error exists
Within 5%, the draw ratio of the screw rod of the double screw extruder is 40；Can also be and use single screw extrusion machine by the combination
Thing is extruded and processed into the filament of a diameter of 3.0mm, and within 5%, the screw diameter of the single screw extrusion machine is diameter error
70mm, draw ratio is 25.
Beneficial effects of the present invention：
1. the present invention provides a kind of product and preparation method thereof, and the product is by fused glass pellet (FDM) technique
Prepare, raw material used is a kind of composite wire in fused glass pellet (FDM) technique.The product has excellent
Different mechanical property, its tensile strength, bending strength are higher, and any surface finish of the product, cure shrinkage is small, and size is steady
Fixed and good mechanical performance.
2. the present invention also provides composite wire for being used in said products and preparation method thereof, is added in the composite wire
There is the chopped fiber of specific draw ratio.The chopped fiber can both improve the mechanical property of the product, it can also be ensured that described multiple
The melt-processable of zygonema material；The preparation process is simple, the application prospect with large-scale production.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.Furthermore, it is to be understood that after described content of the invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within limited range of the present invention.
Embodiment 1
By the weight portion of acrylonitrile-butadiene-styrene copolymer (ABS) polymer 100, short glass fiber (draw ratio
About 10~30) 30 weight portion, coupling agent 3- aminopropyl triethoxysilane (KH550) 5 weight portion, antioxidant 2, the tertiary fourths of 6- bis-
The weight portion of base -4- methylphenols 0.4 mixes, and recombination line of the invention is made through double screw extruder or single screw extrusion machine extrusion
Material.
The melting extrusion technique of described composite wire is：The composition is extruded and processed into using double screw extruder
The filament of a diameter of 1.75mm, within 5%, the draw ratio of the screw rod of the double screw extruder is 40 to diameter error；Or,
The composition is extruded and processed into the filament of a diameter of 3.0mm using single screw extrusion machine, diameter error within 5%, institute
The screw diameter of single screw extrusion machine is stated for 70mm, draw ratio is 25.
The composite wire is used for fused glass pellet (FDM) 3D printer, printer extruder head temperature is 200 DEG C,
80 DEG C of hott bed temperature.Specifically：Above-mentioned composite wire is sent into based on fused glass pellet (FDM) technique by wire feeder
3D printer shower nozzle, is heated fusing and extrudes in shower nozzle, and the above-mentioned composite wire of melting is quickly solidified to form after being extruded
Solidification thin layer, the product is made through layer upon layer.
Result shows：Print procedure is smooth, and printing product surface is bright and clean, and cure shrinkage is small, dimensionally stable and mechanical property
Can be excellent, wherein tensile strength relatively strengthens more than 50% with the pure ABS resin product under technique.
Embodiment 2
By the weight portion of nylon66 fiber polymer 100, chopped carbon fiber (draw ratio about 10~30) 30 weight portions, coupling agent 3- ammonia
The weight portion of propyl-triethoxysilicane (KH550) 3, antioxidant 2, the mixing of the weight portion of 6- di-tert-butyl-4-methy phenols 0.3,
Composite wire of the invention is made through double screw extruder or single screw extrusion machine extrusion.
The melting extrusion technique of described composite wire is：The composition is extruded and processed into using double screw extruder
The filament of a diameter of 1.75mm, within 5%, the draw ratio of the screw rod of the double screw extruder is 40 to diameter error；Or,
The composition is extruded and processed into the filament of a diameter of 3.0mm using single screw extrusion machine, diameter error within 5%, institute
The screw diameter of single screw extrusion machine is stated for 70mm, draw ratio is 25.
The composite wire is used for fused glass pellet (FDM) 3D printer, printer extruder head temperature is 240 DEG C,
90 DEG C of hott bed temperature.Specifically：Above-mentioned composite wire is sent into based on fused glass pellet (FDM) technique by wire feeder
3D printer shower nozzle, is heated fusing and extrudes in shower nozzle, and the above-mentioned composite wire of melting is quickly solidified to form after being extruded
Solidification thin layer, the product is made through layer upon layer.
Result shows：Print procedure is smooth, and printing product surface is bright and clean, and cure shrinkage is small, dimensionally stable and mechanical property
Can be excellent, wherein tensile strength relatively strengthens more than 60% with the pure nylon66 fiber product under technique.
Embodiment 3
By the weight portion of nylon66 fiber polymer 100, chopped carbon fiber (draw ratio about 10~30) 45 weight portions, coupling agent 3- ammonia
The weight portion of propyl-triethoxysilicane (KH550) 5, antioxidant 2, the mixing of the weight portion of 6- di-tert-butyl-4-methy phenols 0.5,
Composite wire of the invention is made through double screw extruder or single screw extrusion machine extrusion.
The melting extrusion technique of described composite wire is：The composition is extruded and processed into using double screw extruder
The filament of a diameter of 1.75mm, within 5%, the draw ratio of the screw rod of the double screw extruder is 40 to diameter error；Or,
The composition is extruded and processed into the filament of a diameter of 3.0mm using single screw extrusion machine, diameter error within 5%, institute
The screw diameter of single screw extrusion machine is stated for 70mm, draw ratio is 25.
The composite wire is used for fused glass pellet (FDM) 3D printer, and printer extruder head temperature is 250 DEG C, heat
85 DEG C of bed tempertaure.Specifically：Above-mentioned composite wire is sent into the 3D based on fused glass pellet (FDM) technique by wire feeder
Printer head, is heated fusing and extrudes in shower nozzle, and the above-mentioned composite wire of melting quickly solidifies to form solid after being extruded
Change thin layer, the product is made through layer upon layer.
Result shows：Print procedure is smooth, and printing product surface is bright and clean, and cure shrinkage is small, dimensionally stable and mechanical property
Can be excellent, wherein tensile strength relatively strengthens more than 75% with the pure nylon66 fiber product under technique.
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned implementation method.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of product, it is characterised in that the product is prepared by fused glass pellet (FDM) technique, the fusion sediment
Raw material used is a kind of composite wire in shaping (FDM) technique, and the composite wire is by the composition including following components
Process：
Polymer：100 weight portions；
Chopped fiber：10~60 weight portions；It is preferred that 20~50 weight portions；
Coupling agent：0.5~10 weight portion；It is preferred that 1~5 weight portion；
Antioxidant：0.01~1 weight portion；It is preferred that 0.1~0.8 weight portion；
Wherein, the draw ratio of the chopped fiber is 10~300.
2. product according to claim 1, it is characterised in that the draw ratio of the chopped fiber is 10~70, further excellent
Elect 10~30 as.
3. product according to claim 1 and 2, it is characterised in that the chopped fiber is fine glass fibre, carbon fiber, boron
At least one in dimension, whisker, asbestos fibre and synthetic fibers.Preferably, the chopped fiber is in carbon fiber, glass fibre
It is at least one.
4. the product according to claim any one of 1-3, it is characterised in that the polymer is acrylonitrile-butadiene-benzene
In ethylene copolymer (ABS), PLA (PLA), makrolon (PC), polyether-ether-ketone (PEEK) and nylon series polymer extremely
Few one kind.Preferably, the polymer is in acrylonitrile-butadiene-styrene copolymer (ABS) and nylon series polymer
It is at least one.It is highly preferred that the polymer be acrylonitrile-butadiene-styrene copolymer (ABS) or nylon66 fiber polymer or
The mixture of the arbitrary proportion of the two.
5. the product according to claim any one of 1-4, it is characterised in that the coupling agent is 3- aminopropyl-triethoxies
Silane (KH550), 3- glycidyl ether oxygen propyl trimethoxy silicanes (KH560) or 3- (isobutene acyl-oxygen) propyl trimethoxy
At least one in silane (KH570).Preferably, the coupling agent is 3- aminopropyl triethoxysilanes (KH550).
Preferably, the antioxidant is 2,6- di-tert-butyl-4-methy phenols, 3,5- di-t-butyl -4- hydroxy phenylpropionic acids ten
At least one in octaester or triphenyl phosphite.Preferably, the antioxidant is 2,6- di-tert-butyl-4-methy phenols.
6. the preparation method of product described in any one of claim 1-5, it is characterised in that the preparation method includes following step
Suddenly：
1) each component in composition is chosen according to percentage by weight, obtains the composition；
2) by the composition melting extrusion, it is made the composite wire；
3) above-mentioned composite wire is sent into the 3D printer shower nozzle based on fused glass pellet (FDM) technique by wire feeder,
Fusing is heated in shower nozzle and is extruded, the above-mentioned composite wire of melting quickly solidifies to form solidification thin layer after being extruded, through layer
Layer is piled up and is made the product.
7. preparation method according to claim 6, it is characterised in that in step 3) in, the fused glass pellet (FDM)
Nozzle temperature is 200~300 DEG C, 60~100 DEG C of hott bed temperature in technique.
8. the composite wire for being used in product described in any one of claim 1-5, it is characterised in that the composite wire is by bag
The composition for including following components is processed：
Polymer：100 weight portions；
Chopped fiber：10~60 weight portions；It is preferred that 20~50 weight portions；
Coupling agent：0.5~10 weight portion；It is preferred that 1~5 weight portion；
Antioxidant：0.01~1 weight portion；It is preferred that 0.1~0.8 weight portion；
Wherein, the draw ratio of the chopped fiber is 10~300.
Preferably, the draw ratio of the chopped fiber is 10~70；More preferably 10~30.
9. the preparation method of the composite wire described in claim 8, it is characterised in that the described method comprises the following steps：
A) component in the composition is chosen according to percentage by weight；
B) said components are well mixed, are extruded and processed into filament, that is, prepare the composite wire.
10. preparation method according to claim 9, it is characterised in that in step b), the melting of described composite wire
Expressing technique is：The composition is extruded and processed into the filament of a diameter of 1.75mm, diameter error using double screw extruder
Within 5%, the draw ratio of the screw rod of the double screw extruder is 40；Or, using single screw extrusion machine by the combination
Thing is extruded and processed into the filament of a diameter of 3.0mm, and within 5%, the screw diameter of the single screw extrusion machine is diameter error
70mm, draw ratio is 25.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611046952.2A CN106751379A (en) | 2016-11-23 | 2016-11-23 | Product prepared by a kind of fused glass pellet technique and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611046952.2A CN106751379A (en) | 2016-11-23 | 2016-11-23 | Product prepared by a kind of fused glass pellet technique and preparation method thereof |
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Cited By (10)
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| CN107237002A (en) * | 2017-06-08 | 2017-10-10 | 广东银禧科技股份有限公司 | A kind of polyether-ether-ketone/chopped fiber composite wire material and preparation method thereof |
| CN107673763A (en) * | 2017-10-27 | 2018-02-09 | 西北工业大学 | The method for preparing ceramic structures by fused glass pellet 3D printing using thermoplasticity ceramic forerunner |
| CN108912670A (en) * | 2018-07-23 | 2018-11-30 | 山东大学 | A kind of suction wave functionally gradient material (FGM) and preparation method thereof based on increases material manufacturing technology |
| CN109135224A (en) * | 2018-08-02 | 2019-01-04 | 浙江理工大学 | A kind of 3D printing enhancing consumptive material and preparation method thereof |
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| CN111640963A (en) * | 2020-06-16 | 2020-09-08 | 陕西中丰新能源有限公司 | Manufacturing process of battery pole plate |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107237002A (en) * | 2017-06-08 | 2017-10-10 | 广东银禧科技股份有限公司 | A kind of polyether-ether-ketone/chopped fiber composite wire material and preparation method thereof |
| CN107673763A (en) * | 2017-10-27 | 2018-02-09 | 西北工业大学 | The method for preparing ceramic structures by fused glass pellet 3D printing using thermoplasticity ceramic forerunner |
| CN108912670A (en) * | 2018-07-23 | 2018-11-30 | 山东大学 | A kind of suction wave functionally gradient material (FGM) and preparation method thereof based on increases material manufacturing technology |
| CN109135224A (en) * | 2018-08-02 | 2019-01-04 | 浙江理工大学 | A kind of 3D printing enhancing consumptive material and preparation method thereof |
| CN109438866A (en) * | 2018-10-16 | 2019-03-08 | 吉林化工学院 | 3D printing carbon fiber/ABS composite material and preparation method thereof |
| CN109438866B (en) * | 2018-10-16 | 2021-04-09 | 吉林化工学院 | Carbon fiber/ABS composite material for 3D printing and preparation method thereof |
| CN110408163A (en) * | 2019-08-01 | 2019-11-05 | 南通理工学院 | A kind of FDM printing production technology of ABS carbon fibre composite |
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| CN111640963A (en) * | 2020-06-16 | 2020-09-08 | 陕西中丰新能源有限公司 | Manufacturing process of battery pole plate |
| CN112063158A (en) * | 2020-08-21 | 2020-12-11 | 湖南创瑾科技有限公司 | 3D printing material and preparation method thereof |
| CN114921049A (en) * | 2022-05-26 | 2022-08-19 | 中国重汽集团济南动力有限公司 | ABS (acrylonitrile butadiene styrene) modified material for large-size FDM (frequency-division multiplexing) printing as well as preparation method and application thereof |
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