CN112144146B - Composite material for 3D printing and preparation method thereof - Google Patents
Composite material for 3D printing and preparation method thereof Download PDFInfo
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- CN112144146B CN112144146B CN202011032415.9A CN202011032415A CN112144146B CN 112144146 B CN112144146 B CN 112144146B CN 202011032415 A CN202011032415 A CN 202011032415A CN 112144146 B CN112144146 B CN 112144146B
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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
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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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- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the field of composite materials, and relates to a composite material for 3D printing and a preparation method thereof. The invention provides a composite material for 3D printing, which has a skin-core structure, wherein an inner core layer is a polymer 1/fiber composite material, and an outer skin layer is a polymer 2/fiber composite material; wherein the content of the fibers in the core layer material accounts for 30-50% of the mass of the polymer 1/fiber composite material; the content of the fibers in the skin layer material accounts for 10-20% of the mass of the polymer 2/fiber composite material; and, polymer 1 and polymer 2 satisfy: melting point of polymer 1 the melting point of polymer 2 is 10 to 40 ℃. The composite material obtained by the invention can be used for 3D printing base materials, and has the advantages of low water absorption, high dimensional stability, high mechanical property and high temperature resistance.
Description
Technical Field
The invention belongs to the field of composite materials, and relates to a composite material for 3D printing and a preparation method thereof.
Background
3D printing, also known as additive manufacturing, is a rapid manufacturing technique that forms three-dimensional entities by adding material. Compared with the traditional material reduction technology, the 3D printing can manufacture geometric solid bodies with any shapes.
Compared with the traditional resin composite material printing and forming technology, the fiber reinforced thermoplastic composite material 3D printing technology has obvious advantages, especially mechanical property advantages, existing mature products are mostly concentrated on a nylon-based composite material system, but the fiber content is generally lower than 30%, and the dimensional accuracy of a high-fiber-content composite material wire is difficult to guarantee, so that the final printed product is poor in mechanical property, high in water absorption rate and poor in dimensional stability.
Disclosure of Invention
Aiming at the defects, the invention provides the composite material for 3D printing, and the obtained composite material can be used for a 3D printing base material and has the advantages of low water absorption rate, high dimensional stability, high mechanical property and high temperature resistance.
The technical scheme of the invention is as follows:
the invention provides a composite material for 3D printing, which has a skin-core structure, wherein an inner core layer is a polymer 1/fiber composite material, and an outer skin layer is a polymer 2/fiber composite material; wherein the content of the fibers in the core layer material accounts for 30-50% of the mass of the polymer 1/fiber composite material; the content of the fibers in the skin layer material accounts for 10-20% of the mass of the polymer 2/fiber composite material; and, polymer 1 and polymer 2 satisfy: the melting point of polymer 1-the melting point of polymer 2 is 10 to 40 ℃.
Further, the polymer 1 or the polymer 2 is selected from one of the following polymers: poly (hexamethylene terephthalamide)/isophthalamide (PA6T-6I), poly (hexamethylene terephthalamide)/adipamide (PA6T-66) or poly (hexamethylene terephthalamide)/caprolactam (PA 6T-6).
Preferably, in the composite material:
polymer 1 is poly (phenylene terephthalamide)/hexamethylene isophthalamide, polymer 2 is poly (phenylene terephthalamide)/hexamethylene adipamide; or:
polymer 1 is poly (phenylene terephthaloyl)/m-phenylene terephthaloyl hexamethylene diamine, polymer 2 is poly (phenylene terephthaloyl hexamethylene diamine)/caprolactam; or:
polymer 1 was poly (hexamethylene terephthalamide)/hexamethylene adipamide and polymer 2 was poly (hexamethylene terephthalamide)/caprolactam.
Further, the fibers are selected from: at least one of carbon fiber, glass fiber, or quartz fiber.
The second technical problem to be solved by the present invention is to provide a preparation method of the above composite material for 3D printing, wherein the preparation method comprises: the composite material for 3D printing is prepared by taking a polymer 1/fiber composite material as a core layer material and a polymer 2/fiber composite material as a skin layer material by adopting the existing method for preparing a material with a skin-core structure; wherein the content of the fibers in the core layer material accounts for 30-50% of the mass of the polymer 1/fiber composite material; the content of the fibers in the skin layer material accounts for 10-20% of the mass of the polymer 2/fiber composite material; and, polymer 1 and polymer 2 satisfy: the melting point of polymer 1-the melting point of polymer 2 is 10 to 40 ℃.
Further, the preparation method comprises the following steps:
step 1): melting and blending the polymer 1 and the fibers by a double-screw extruder, and then drawing to obtain a wire as a core layer;
step 2): melting and blending the polymer 2 and the fibers by a double-screw extruder, granulating and drying to obtain a skin layer;
step 3): introducing the wire rod prepared in the step 1) into a mould as a continuous reinforcement, feeding the blended particles prepared in the step 2) from a main feeding port of an extruder, and performing melt extrusion into the mould; and then wrapping the wires prepared in the step 1) with the molten material prepared in the step 2), and then drawing out and shaping through an oral mold to obtain the composite material for 3D printing with the skin-core structure.
The invention has the beneficial effects that:
the composite material substrate for 3D printing is of a skin-core structure, the core layer is made of carbon fiber reinforced PA6T-6I or PA6T-66 (high melting point) composite material, the fiber content is 30-50%, and the overall mechanical property and the dimensional stability of the composite material substrate for 3D printing are guaranteed; the core layer is made of a carbon fiber reinforced PA6T-66 or PA6T-6 (slightly low melting point) composite material, the fiber content is 10% -20%, and the dimensional accuracy of the composite material 3D printing base material is guaranteed.
Detailed Description
The invention provides a composite material for 3D printing, which has a skin-core structure, wherein an inner core layer is a polymer 1/fiber composite material, and an outer skin layer is a polymer 2/fiber composite material; wherein the content of the fibers in the core layer material accounts for 30-50% of the mass of the composite material; the content of the fibers in the skin layer material accounts for 10-20% of the mass of the composite material; and, polymer 1 and polymer 2 satisfy: a melting point of polymer 1-a melting point of polymer 2 of 10 to 40 ℃; namely, the difference between the melting points is 10-40 ℃.
In the present invention, the preferred composite material combination is: PA6T-6I (Polymer 1) and PA6T-66 (Polymer 2); PA6T-6I (Polymer 1) and PA6T-6 (Polymer 2); PA6T-66 (Polymer 1) and PA6T-6 (Polymer 2); wherein PA6T-6I is poly (phenylene terephthamide)/hexamethylene isophthalamide, and the melting point is 325 ℃; PA6T-66 is poly (p-phenylene terephthalamide)/hexamethylene adipamide, melting point 312 ℃; PA6T/6 is polyhexamethylene terephthalamide/caprolactam having a melting point of 295 ℃.
The invention also provides a preparation method of the composite material for 3D printing, which can be prepared by adopting the following implementation modes:
step 1: fusing and blending the dried PA6T-6I and a certain content of carbon fibers by a double-screw extruder, and then drawing to obtain a wire, wherein the wire is used for a core layer of a composite material printing wire, and the core layer has a sufficiently high fiber content;
step 2: melting and blending the dried PA6T-6 and carbon fiber with a certain content by a double-screw extruder, granulating and drying, wherein the material is used for a surface layer (coating layer) of a composite material printing wire material, and the integral size precision and the forming manufacturability of the composite material printing wire material are ensured;
and step 3: and (3) enabling the 3D wire core layer to pass through the blend melt pool prepared in the step (2) to realize surface coating of the composite printing wire, and obtaining the high-precision PA 6T-based composite printing wire, wherein the core layer and the surface layer are both semi-aromatic polyamide systems, the interface between the core layer and the surface layer is completely fused with each other, and the water absorption rate is lower than 0.5%.
The composite material is of a skin-core layer structure, the core layer is high in fiber content by adopting a carbon fiber reinforced PA6T-6I (high melting point) composite material structure, and the overall mechanical property and the dimensional stability of the composite material are ensured; the skin layer (surface layer) adopts a carbon fiber reinforced PA6T-6 (slightly low melting point) composite material structure, the fiber content is low, and the size precision and post-forming manufacturability of the composite material are ensured; in the structural system, PA6T-6I and PA6T-6 are in the same resin system, the interfaces between the two are completely fused with each other, the interface performance is good, the water absorption is lower than 0.5%, and the product dimensional stability is excellent.
In addition, in the system, the melting point difference between PA6T-6I and PA6T-6 is 30-50 ℃, the processing window is wider, and the manufacturability is better; in addition, the 3D printing substrate product is reshaped after secondary printing, two resin systems can be remixed, and the overall stability and uniformity of a target product can be ensured;
in order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
The carbon fiber is used as a reinforcing material, PA6T-6I and PA6T-6 are used as base materials, and the high-performance 3D printing wire with the diameter of 1.75mm is prepared by the following specific preparation steps:
step 1: feeding the dried PA6T-6 from a main feeding port of an extruder, feeding carbon fibers from a side feeding port of the extruder, and carrying out melt blending granulation to obtain a PA 6T-6/fiber composite material with the fiber mass content of 20% of the total amount of a PA6T-6 composite material system as a skin layer;
and 2, step: feeding the dried PA6T-6I from a main feeding port of an extruder, feeding carbon fibers from a side feeding port of the extruder, and preparing into a 3D printing wire with the diameter of 1.5mm as a core layer by a melt extrusion molding process, wherein the mass content of the fibers is 40%;
and step 3: and (3) introducing the 3D printing wire rod prepared in the step (2) into a die as a continuous reinforcement, feeding the blending particles prepared in the step (1) from a main feeding port of an extruder, carrying out melt extrusion into the die, and drawing out and shaping the 3D printing wire rod prepared in the step (2) through a die port to obtain the 3D printing wire rod with the diameter of 1.75 mm.
The 3D printing wire prepared by the method disclosed by the invention is high in carbon fiber content, low in water absorption rate of a product, good in dimensional stability, high in mechanical property and high in temperature resistance, and specific test data are shown in table 1.
Table 1 properties of the 3D printing wire obtained in the example
Example 2
The carbon fiber is used as a reinforcing material, PA6T-66 and PA6T-6 are used as base materials, and the high-performance 3D printing wire with the diameter of 1.75mm is prepared by the following specific preparation steps:
step 1: feeding the dried PA6T-6 from a main feeding port of an extruder, feeding glass fiber from a side feeding port of the extruder, and carrying out melt blending granulation to obtain the PA 6T-6/fiber composite material with the fiber mass content of 10 percent of the total amount of a PA6T-6 composite material system
Step 2: feeding the dried PA6T-66 from a main feeding port of an extruder, feeding glass fiber from a side feeding port of the extruder, and preparing into a 3D printing wire with the diameter of 1.5mm by a melt extrusion molding process, wherein the mass content of the fiber is 30%;
and step 3: and (3) introducing the 3D printing wire rod prepared in the step (2) into a die as a continuous reinforcement, feeding the blended particles prepared in the step (1) from a main feeding port of an extruder, carrying out melt extrusion into the die, and drawing out and shaping the 3D printing wire rod prepared in the step (2) through a die port to obtain the 3D printing wire rod with the diameter of 1.75 mm.
The 3D printing wire prepared by the method disclosed by the invention is high in carbon fiber content, low in water absorption rate of a product, good in dimensional stability, high in mechanical property and high in temperature resistance, and specific test data are shown in table 1.
Claims (4)
1. The composite material for 3D printing is characterized by having a skin-core structure, wherein an inner core layer is a polymer 1/fiber composite material, and an outer skin layer is a polymer 2/fiber composite material; wherein the content of the fibers in the core layer material accounts for 30-50% of the mass of the polymer 1/fiber composite material; the content of the fibers in the skin layer material accounts for 10-20% of the mass of the polymer 2/fiber composite material; and, polymer 1 and polymer 2 satisfy: melting point of polymer 1-melting point of polymer 2 = 10-40 ℃;
the polymer 1 and the polymer 2 are respectively selected from the following materials:
polymer 1 is poly (phenylene terephthalamide)/hexamethylene isophthalamide, polymer 2 is poly (phenylene terephthalamide)/hexamethylene adipamide; or:
polymer 1 is poly (phenylene terephthaloyl)/m-phenylene terephthaloyl hexamethylene diamine, polymer 2 is poly (phenylene terephthaloyl hexamethylene diamine)/caprolactam; or:
polymer 1 was poly (hexamethylene terephthalamide)/hexamethylene adipamide and polymer 2 was poly (hexamethylene terephthalamide)/caprolactam.
2. The composite for 3D printing according to claim 1, wherein the fibers are selected from the group consisting of: at least one of carbon fiber, glass fiber, or quartz fiber.
3. The method for preparing the composite material for 3D printing according to claim 1 or 2, wherein the method for preparing comprises: the polymer 1/fiber composite material is used as a core layer material, the polymer 2/fiber composite material is used as a skin layer material, and the composite material for 3D printing is prepared by adopting the existing method for preparing a material with a skin-core structure; wherein the content of the fibers in the core layer material accounts for 30-50% of the mass of the polymer 1/fiber composite material; the content of the fibers in the skin layer material accounts for 10-20% of the mass of the polymer 2/fiber composite material; and, polymer 1 and polymer 2 satisfy: melting point of polymer 1-melting point of polymer 2 =10 to 40 ℃.
4. The method for preparing a composite material for 3D printing according to claim 3, comprising the steps of:
step 1): melting and blending the polymer 1 and the fibers by a double-screw extruder, and then drawing to obtain a wire as a core layer;
step 2): melting and blending the polymer 2 and the fibers by a double-screw extruder, granulating and drying to obtain a skin layer;
and step 3): introducing the wire rod prepared in the step 1) into a mould as a continuous reinforcement, feeding the blended particles prepared in the step 2) from a main feeding port of an extruder, and performing melt extrusion into the mould; and then wrapping the wires prepared in the step 1) with the molten material prepared in the step 2), and then drawing out and shaping through an oral mold to obtain the composite material for 3D printing with the skin-core structure.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011032415.9A CN112144146B (en) | 2020-09-27 | 2020-09-27 | Composite material for 3D printing and preparation method thereof |
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| CN202011032415.9A CN112144146B (en) | 2020-09-27 | 2020-09-27 | Composite material for 3D printing and preparation method thereof |
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| CN112144146B true CN112144146B (en) | 2022-06-14 |
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| CN116171223A (en) * | 2021-12-29 | 2023-05-26 | 苏州聚复科技股份有限公司 | 3D printing wire rod, preparation method thereof, 3D printing method and printing equipment |
| WO2023125367A1 (en) * | 2021-12-29 | 2023-07-06 | 苏州聚复科技股份有限公司 | 3d printing wire and preparation method therefor, 3d printing method, and printing apparatus |
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| CN107686636A (en) * | 2016-08-04 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of core-sheath composition, core-sheath material and its application |
| CN109203449A (en) * | 2018-07-12 | 2019-01-15 | 东华大学 | A kind of preparation method of low porosity 3D printing product |
| WO2019170463A1 (en) * | 2018-03-06 | 2019-09-12 | Basf Se | Filaments based on a core material comprising a fibrous filler |
| CN111423720A (en) * | 2020-04-09 | 2020-07-17 | 大连理工大学 | 3D printing-oriented modified carbon fiber reinforced polyamide 6 composite material and preparation method and application thereof |
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- 2020-09-27 CN CN202011032415.9A patent/CN112144146B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686636A (en) * | 2016-08-04 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of core-sheath composition, core-sheath material and its application |
| WO2019170463A1 (en) * | 2018-03-06 | 2019-09-12 | Basf Se | Filaments based on a core material comprising a fibrous filler |
| CN109203449A (en) * | 2018-07-12 | 2019-01-15 | 东华大学 | A kind of preparation method of low porosity 3D printing product |
| CN111423720A (en) * | 2020-04-09 | 2020-07-17 | 大连理工大学 | 3D printing-oriented modified carbon fiber reinforced polyamide 6 composite material and preparation method and application thereof |
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