FDM 3D printer consumables capable of achieving fast printing and shortening cycle and preparation method thereof

Abstract

The present invention discloses FDM 3D printer consumables and a preparation method thereof that can achieve fast printing and shorten the cycle. The FDM 3D printer consumables that can achieve fast printing and shorten the cycle include: 60 to 90 parts of PLA; 5 to 20 parts of PBAT; 5 to 20 parts of powder; 0.01 to 0.1 parts of coupling agent; 1 to 5 parts of compatibilizer; 5 to 20 parts of nucleating agent; 0.1 to 1 part of dispersant; 0.5 to 1.5 parts of antioxidant. The preparation method includes the following steps: S1, drying; S2, mixing and stirring; S3, twin-screw extrusion granulation; S4, single-screw extrusion wire drawing; S5, obtaining the 3D printing consumables that can achieve fast printing and shorten the product processing cycle. The present invention can achieve fast printing of customer products, qualified quality, and delicate texture, meeting the requirements of 3D printing; the composite material prepared by the method has excellent fluidity and low molding shrinkage, and is suitable for hot-melt 3D fast printing molding.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing materials, and in particular to a 3D printing consumable material capable of achieving rapid printing and shortening a product processing cycle, and a preparation method thereof. Background Art

[0002] 3D printing, scientifically known as "additive manufacturing", is a rapid prototyping technology, known as the core technology of the "third industrial revolution". This technology is based on digital model files, uses specific materials, and constructs objects by printing layer by layer. In recent years, rapid prototyping has made great progress, among which three-dimensional (3D) printing technology has become increasingly mature and industrialized, and has been gradually promoted and applied in the fields of bioengineering, aerospace, architecture, design, etc. There are 9 types of 3D printing processes, such as FDM, DLP, MJF, DLMS, SLA, SLS, SLM, EBM and Polyjet. The most prominent advantage of 3D printing technology is that it can directly generate parts of any shape from computer graphics data without mechanical processing or the use of any molds, which greatly shortens the product development cycle, improves production efficiency and reduces production costs. Fused deposition modeling (FDM) is the most mature and widely used processing method in the field of rapid prototyping. It uses high-temperature heat energy to melt the wire into a liquid state, extrude it through a nozzle and solidify it, and finally stack and arrange it layer by layer in a three-dimensional space to form a three-dimensional object.

[0003] At present, most of the FDM 3D printing consumables on the market are mainly PLA (polylactic acid), ABS (acrylonitrile-butadiene-styrene terpolymer) and other plastics. PLA plastic is derived from corn starch. After use, it can be completely degraded by microorganisms in nature, and finally produces carbon dioxide and water, which does not pollute the environment. This is very beneficial to protecting the environment and is a recognized environmentally friendly material. PLA has a wide range of applications in the 3D printing industry and is the most popular 3D printing material in the market. The printing temperature of PLA is about 190-230℃, with small printing shrinkage and high precision. The printed model is not easy to crack and deform, and the printing success rate is relatively high.

[0004] PBAT (co-butylene adipate-terephthalate) is a synthetic polymer biodegradable material. It is a biodegradable aromatic polyester, which is polymerized by direct esterification or transesterification of butylene adipate (PBA) and butylene terephthalate (PBT). Due to its flexible aliphatic chain segment, PBAT can be fully biodegraded under certain conditions, and will not cause harm to the environment in composting experiments. At the same time, it has excellent mechanical properties, heat resistance and impact resistance, especially the elongation at break is as high as 600 parts, and its melting temperature is low (130°C), so it is a low-melting elastomer biodegradable material with excellent flexibility. PBAT is a semi-crystalline polymer, usually with a crystallization temperature of around 110°C, a melting point of around 130°C, and a density of between 1.18g / ml and 1.3g / ml. The crystallinity of PBAT is about 30 parts, and the Shore hardness is above 85. PBAT is a copolymer of aliphatic and aromatic polyesters, which combines the excellent degradation properties of aliphatic polyesters and the good mechanical properties of aromatic polyesters. Polybutylene adipate / terephthalate (PBAT) is a new type of biodegradable polymer with good ductility and elongation at break, which can improve the toughness of PLA materials.

[0005] At present, FDM 3D printing has the problem of long product processing time. If the printer printing speed is increased rashly, the surface curing will not be timely, which will lead to the disadvantage of rough and not delicate surface of the printed product. In order to solve the above problems, the present invention proposes a 3D printing consumables formula and preparation method that can achieve fast printing and shorten the product processing cycle. At the same time, the printing speed of the printer is appropriately increased, which can successfully solve the problem of long product processing cycle of customers. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide FDM 3D printer consumables and a preparation method thereof that can achieve fast printing and shorten the cycle, which can achieve fast printing of customer products with qualified quality, excellent appearance and delicate texture, and meet the requirements of 3D printing; the composite material prepared by this method has excellent fluidity and low molding shrinkage, and is suitable for hot-melt 3D rapid printing molding.

[0007] The technical solution adopted by the present invention is:

[0008] FDM 3D printer consumables capable of achieving fast printing and shortening the cycle, characterized in that, in terms of weight ratio, they include:

[0009]

[0010] The powder includes the following according to its weight ratio:

[0011]

[0012] The coupling agent is at least one of titanate, aluminate, chromate, silane, aluminum-titanium composite and rare earth coupling agent.

[0013] PLA is polylactic acid with a number average molecular weight of 35,000 to 120,000 and a melt index of 2 to 10 g / 10 min.

[0014] PBAT: It is a copolymer of butylene adipate and butylene terephthalate, with a melt index of (2-10g) / 10min / 190℃ / 2.16KG.

[0015] The compatibilizer is one or more of styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer, and ethylene-acrylate-glycidyl ester copolymer.

[0016] The nucleating agent is at least one of an inorganic nucleating agent, an organic nucleating agent, a polymer nucleating agent, and a β-crystal nucleating agent; the inorganic nucleating agent is any one of silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, and carbon black; the organic nucleating agent is a low molecular weight organic compound, and the organic nucleating agent is any one of a fatty carboxylic acid metal compound, a sorbitol benzyl derivative, an aromatic carboxylic acid metal compound, an organic phosphate, lignin acid and its derivatives, sodium benzoate, and bis(p-tert-butylbenzoic acid) carboxyaluminum; the polymer nucleating agent is poly-3-methylbutene-1-polyvinylcyclosilane.

[0017] A method for preparing 3D printing consumables that can achieve fast printing and shorten product processing cycle, comprising the following steps:

[0018] S1. Drying: Dry PLA and PBAT at 60-85°C for more than 4 hours. Other components do not need to be dried.

[0019] S2, mixing and stirring: putting the dried PLA and PBAT as well as the powder, coupling agent, compatibilizer, nucleating agent, dispersant and antioxidant into a high-speed mixer at a speed of 300 to 1500 rpm and stirring for 3 to 10 minutes;

[0020] S3, twin-screw extrusion granulation: add the mixed materials into the hopper of the twin-screw extruder, and obtain the PLA / PBAT blended modified granulation material through melt blending, extrusion, water cooling and air drying; wherein, the temperature of the twin-screw extruder is set as follows: zone 1: 160-175°C; zone 2: 170-180°C; zone 3: 175-185°C; zone 4: 180-190°C; zone 5: 180-190°C; zone 6: 185-195°C; zone 7: 185-195°C; zone 8: 185-195°C; zone 9: 190-200°C; die head temperature: 190-210°C; screw speed is controlled at 80-350r / min, and the cooling water temperature is required to be 20 to 25°C;

[0021] S4, single screw extrusion wire drawing: the PLA / PBAT blended modified granules are dried at 60-85°C for 4 hours, introduced into a single screw extruder, and after extrusion, they are pulled by a traction machine and water-cooled to be processed into wires that meet the requirements of 3D printers. The screw speed of the single screw extruder is 50 rpm, the barrel temperature is 190-240°C, and the pulling and winding speed is 70 m / min;

[0022] S5, obtaining the 3D printing consumables that can achieve fast printing and shorten the product processing cycle

[0023] In step S4, after extrusion, the wire is pulled by a traction machine and water-cooled to be processed into a φ1.75±0.03 mm wire that meets the requirements of a 3D printer.

[0024] The beneficial effects of the present invention are: achieving rapid printing of customer products with qualified quality, excellent appearance and delicate texture, meeting the requirements of 3D printing; the composite material prepared by the method has excellent fluidity and low molding shrinkage, and is suitable for hot-melt 3D rapid printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the steps of the present invention. DETAILED DESCRIPTION

[0026] like Figure 1 As shown, the present invention can realize fast printing and shorten the cycle of FDM 3D printer consumables, characterized in that it includes, by weight ratio:

[0027]

[0028]

[0029] The powder includes the following according to its weight ratio:

[0030]

[0031] The coupling agent is at least one of titanate, aluminate, chromate, silane, aluminum-titanium composite and rare earth coupling agent.

[0032] PLA is polylactic acid with a number average molecular weight of 35,000 to 120,000 and a melt index of 2 to 10 g / 10 min.

[0033] PBAT: It is a copolymer of butylene adipate and butylene terephthalate, with a melt index of (2-10g) / 10min / 190℃ / 2.16KG.

[0034] The compatibilizer is one or more of styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer, and ethylene-acrylate-glycidyl ester copolymer.

[0035] The nucleating agent is at least one of an inorganic nucleating agent, an organic nucleating agent, a polymer nucleating agent, and a β-crystal nucleating agent; the inorganic nucleating agent is any one of silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, and carbon black; the organic nucleating agent is a low molecular weight organic compound, and the organic nucleating agent is any one of a fatty carboxylic acid metal compound, a sorbitol benzyl derivative, an aromatic carboxylic acid metal compound, an organic phosphate, lignin acid and its derivatives, sodium benzoate, and bis(p-tert-butylbenzoic acid) carboxyaluminum; the polymer nucleating agent is poly-3-methylbutene-1-polyvinylcyclosilane.

[0036] A method for preparing 3D printing consumables that can achieve fast printing and shorten product processing cycle, comprising the following steps:

[0037] S1. Drying: Dry PLA and PBAT at 60-85°C for more than 4 hours. Other components do not need to be dried.

[0038] S2, mixing and stirring: putting the dried PLA and PBAT as well as the powder, coupling agent, compatibilizer, nucleating agent, dispersant and antioxidant into a high-speed mixer at a speed of 300 to 1500 rpm and stirring for 3 to 10 minutes;

[0039] S3, twin-screw extrusion granulation: add the mixed materials into the hopper of the twin-screw extruder, and obtain the PLA / PBAT blended modified granulation material through melt blending, extrusion, water cooling and air drying; wherein, the temperature of the twin-screw extruder is set as follows: zone 1: 160-175°C; zone 2: 170-180°C; zone 3: 175-185°C; zone 4: 180-190°C; zone 5: 180-190°C; zone 6: 185-195°C; zone 7: 185-195°C; zone 8: 185-195°C; zone 9: 190-200°C; die head temperature: 190-210°C; screw speed is controlled at 80-350r / min, and the cooling water temperature is required to be 20 to 25°C;

[0040] S4, single screw extrusion wire drawing: the PLA / PBAT blended modified granules are dried at 60-85°C for 4 hours, introduced into a single screw extruder, and after extrusion, they are pulled by a traction machine and water-cooled to be processed into wires that meet the requirements of 3D printers. The screw speed of the single screw extruder is 50 rpm, the barrel temperature is 190-240°C, and the pulling and winding speed is 70 m / min;

[0041] S5, obtaining the 3D printing consumables that can achieve fast printing and shorten the product processing cycle

[0042] In step S4, after extrusion, the wire is pulled by a traction machine and water-cooled to be processed into a φ1.75±0.03 mm wire that meets the requirements of a 3D printer.

[0043] Polylactic acid absorbs moisture from the air, which is why PLA 3D printing filaments need to be dried after being stored for a long time. Because when the moisture in the air is absorbed into the filament, the following changes occur when the filament is heated and extruded by the 3D printer: When the nozzle heats the 3D printing filament, the absorbed moisture turns into steam, and there will be a sound when printing. At the same time, the steam will affect the precision quality of the model surface, that is, it is relatively rough. Therefore, before using 3D printing filaments, 3D printing filaments are generally placed in a 3D printing filament drying box for 4-5 hours to reduce the water content in the filament.

[0044] In this application, the moisture absorbed into the 3D printing consumables is fully utilized, and the moisture is absorbed by the powder. The powder is extruded in the nozzle to form a mixing and stirring effect. After the powder is mixed with water, the hardening speed can be increased. The extruded consumable hardens quickly, so it is suitable for fast printing, because the current fast printing is mainly because the temperature of the newly extruded consumables is too high, and the speed from the softened state to the hardened state is too slow, resulting in the fast printing. There is no time to harden, and the nozzle moves to the unhardened position to print. Therefore, when printing the second layer of slices, it will be flattened and deformed due to gravity, especially for models with smaller cross-sectional diameters. The impact is even greater.

[0045] Each portion in the following experiments is calculated as 500 grams.

[0046] Embodiment 1:

[0047] PLA 60 parts, PBAT 10 parts, maleic anhydride grafted PBAT 15 parts, powder 8.5 parts, aluminate coupling agent 0.01 parts, sodium benzoate 1.5 parts, diffusion oil 4.39 parts, antioxidant 10100.3 parts, antioxidant 1680.3 parts.

[0048] Embodiment 2:

[0049] PLA 70 parts, PBAT 15 parts, maleic anhydride grafted PLA 5 parts, powder 5 parts, titanate coupling agent 0.05 parts, alum 1.2 parts, white mineral oil 3.15 parts, antioxidant 1076 0.3 parts, antioxidant 168 0.3 parts.

[0050] Embodiment 3:

[0051] PLA 55 parts, PBAT 20 parts, styrene-acrylonitrile-maleic anhydride copolymer 10 parts, powder 10 parts, silane coupling agent 0.07 parts, poly 3-methylbutene-1-polyvinylcyclosilane 1 part, silicone powder 2.43 parts, antioxidant 1076 1 part, antioxidant 164 0.5 parts.

[0052] Embodiment 4:

[0053] PLA 65 parts, PBAT 15 parts, styrene-acrylonitrile-maleic anhydride copolymer 5 parts, powder 10 parts, rare earth coupling agent 0.07 parts, β-crystal nucleating agent 0.8 parts, erucic acid amide 3.13 parts, antioxidant 1010 0.5 parts, antioxidant DLTP 0.5 parts.

[0054] Comparative Example 1: Pure PLA 4032D.

[0055] Comparative Example 2: Pure PBAT C1200.

[0056] The granulated materials of Examples 1 to 4 and the raw materials of Comparative Examples 1 and 2 were prepared into 3D printing consumables, and then the 3D printing consumables were subjected to printing tests on a 3D printer. The test results are shown in Table 1.

[0057] Table 1 Test results comparison

[0058]

[0059]

[0060] The beneficial effects of the present invention are: achieving rapid printing of customer products with qualified quality, excellent appearance and delicate texture, meeting the requirements of 3D printing; the composite material prepared by the method has excellent fluidity and low molding shrinkage, and is suitable for hot-melt 3D rapid printing.

Claims

1. FDM 3D printer consumables that can achieve fast printing and shorten the cycle. Features In parts by weight: PLA 60~90 parts; PBAT 5~20 copies; 5~20 parts of powder; Coupling agent 0.01~0.1 parts; 1 to 5 parts of compatibilizer; 5 to 20 parts of nucleating agent; Dispersant 0.1~1 part; 0.5~1.5 parts of antioxidant; The powder includes the following according to its weight ratio: 760 parts of sulphoaluminate cement; 180 parts of quartz powder; Calcium chloride 13.7 parts; 7.5 parts of lithium chloride; 6 parts of talcum powder; Zinc stearate 5.7 parts; Hydroxypropyl methylcellulose 6 parts; 5 parts of water reducing agent; Wollastonite powder 4.5 parts; 1.5 parts of titanium dioxide; 10.1 parts of sodium hexametaphosphate.

2. The FDM 3D printer consumables capable of achieving fast printing and shortening the cycle according to claim 1, Features: PBAT: It is a copolymer of butylene adipate and butylene terephthalate, with a melt index of (2-10g) / 10min / 190℃ / 2.16KG.

3. The FDM 3D printer consumables capable of achieving fast printing and shortening the cycle according to claim 1, Features: The coupling agent is at least one of titanate, aluminate, chromate, silane, aluminum-titanium composite and rare earth coupling agent.

4. The FDM 3D printer consumables capable of achieving fast printing and shortening the cycle according to claim 1, Features: The compatibilizer is one or more of styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer, and ethylene-acrylate-glycidyl ester copolymer.

5. A method for preparing FDM 3D printer consumables capable of achieving fast printing and shortening the cycle as claimed in any one of claims 1 to 4, It is characterized in that The following steps are involved: S1. Drying: Dry PLA and PBAT at 60-85°C for more than 4 hours. Other components do not need to be dried. S2, mixing and stirring: the dried PLA and PBAT as well as the powder, coupling agent, compatibilizer, nucleating agent, dispersant and antioxidant are placed in a high-speed mixer at a speed of 300 to 1500 rpm and stirred for 3 to 10 min; S3, twin-screw extrusion granulation: add the mixed materials into the hopper of the twin-screw extruder, and obtain PLA / PBAT blended modified granulation materials through melt blending, extrusion, water cooling and air drying; wherein, the temperature of the twin-screw extruder is set as follows: zone 1: 160-175°C; zone 2: 170-180°C; zone 3: 175-185°C; zone 4: 180-190°C; zone 5: 180~190°C; zone 6: 185-195°C; zone 7: 185-195°C; zone 8: 185-195°C; zone 9: 190-200°C; head temperature: 190-210°C; screw speed is controlled at 80-350r / min, and the cooling water temperature is required to be 20 to 25°C; S4, single screw extrusion wire drawing: the PLA / PBAT blended modified granules are dried at 60-85°C for 4 hours, introduced into a single screw extruder, and after extrusion, they are pulled by a traction machine and water-cooled to be processed into wires that meet the requirements of 3D printers. The screw speed of the single screw extruder is 50rpm, the barrel temperature is 190-240°C, and the pulling and winding speed is 70m / min; S5, obtaining the FDM 3D printer consumables capable of achieving fast printing and shortening the cycle.

6. A method for preparing FDM 3D printer consumables capable of achieving fast printing and shortening the cycle according to claim 5, Features: In step S4, after extrusion, the wire is pulled by a tractor and water-cooled to be processed into a φ1.75±0.03 mm wire that meets the requirements of a 3D printer.

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