CN111004499A - Nylon 12 wire for 3D printing and preparation method and application thereof - Google Patents
Nylon 12 wire for 3D printing and preparation method and application thereof Download PDFInfo
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- CN111004499A CN111004499A CN201911338086.8A CN201911338086A CN111004499A CN 111004499 A CN111004499 A CN 111004499A CN 201911338086 A CN201911338086 A CN 201911338086A CN 111004499 A CN111004499 A CN 111004499A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
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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
- B33Y10/00—Processes of additive manufacturing
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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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92619—Diameter or circumference
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention provides a nylon 12 wire for 3D printing and a preparation method and application thereof, wherein the nylon 12 wire for 3D printing comprises the following components in parts by weight: nylon 12 resin: 100 parts of hyperbranched resin: 0.3-1.5 parts of antioxidant: 0.01-0.5 parts of lubricant: 0.1 to 0.3 portion. According to the invention, the 3D printing nylon wire material is prepared by using the waste nylon 12 powder of SLS, so that the problem of recycling the waste nylon 12 powder in the SLS process is effectively solved, the manufacturing cost is reduced, the pollution of the powder material to the environment can be reduced, and the requirement of green development is met. The wire has good printing process performance, high strength, low shrinkage rate, low buckling deformation and easy removal of support.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a nylon 12 wire for 3D printing and a preparation method and application thereof.
Background
The 3D printing technology (also called additive manufacturing technology) is a technology for manufacturing solid parts by adopting a layer-by-layer material accumulation mode on the basis of three-dimensional model data, is completely different from the traditional removal processing (cutting processing) method, can quickly manufacture complex parts with any shape structures in a short period, and realizes personalized manufacturing. Selective Laser Sintering (SLS) and Fused Deposition (FDM) are two of the most widely used techniques.
The SLS technology uses a laser as an energy source, uses a computer to control laser beams to scan and sinter powder materials, and finally forms solid parts after layer stacking. The nylon 12 has the advantages of high strength, good toughness, wide processing temperature range, low water absorption, low molding shrinkage and the like, is the most common material in the SLS process, and occupies more than 95 percent of the market share of the SLS high polymer powder material.
After a single SLS process, only less than 20% of the powder raw material is generally converted into a solid part, more than 80% of the powder raw material is still in powder form, the nylon 12 molecules of the powder can undergo condensation reaction due to long-time exposure to a high-temperature environment, so that the molecular weight of the nylon 12 molecules is increased, the melt viscosity of the high-molecular powder is an important parameter for determining the sintering characteristic of the nylon 12 powder, and therefore, the recycling of the unsintered powder is limited, a large amount of new powder materials are required to be used for updating, otherwise, the surface roughness of the manufactured part is large, the orange peel texture is generated, the mechanical property and the thermal property are deteriorated, and even a complete part cannot be formed. Old powder material after several sinterings must be discarded altogether to avoid significant deterioration of part quality and waste of new material, and therefore the SLS process produces a large quantity of waste nylon 12 powder. However, the nylon 12 powder is expensive, and abandoning it not only wastes resources but also pollutes the environment, so the problem of recycling the abandoned nylon 12 powder needs to be solved.
Disclosure of Invention
In view of this, the invention aims to provide a nylon 12 wire for 3D printing to solve the problem of low recycling rate of a large amount of waste nylon 12 powder generated by the existing SLS process.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a nylon 12 wire for 3D printing comprises the following components in parts by weight: nylon 12 resin: 100 parts of hyperbranched resin: 0.3-1.5 parts of antioxidant: 0.01-0.5 parts of lubricant: 0.1 to 0.3 portion.
Optionally, the nylon 12 resin is nylon 12 powder recovered after selective laser sintering.
Optionally, the hyperbranched resin has a density of 1.3g/cm3The melting range is 140-160 ℃.
Optionally, the antioxidant comprises, in mass percent: main antioxidant: 60% -85%, auxiliary antioxidant: 15 to 40 percent.
Optionally, the primary antioxidant is a hindered phenolic antioxidant; the auxiliary antioxidant is one or more of phosphite antioxidant and thioester antioxidant.
Optionally, the hindered phenol antioxidant is one or more of antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant 264, antioxidant CA, antioxidant 330 and antioxidant 245; the phosphite antioxidant is one or more of antioxidant 168 and antioxidant TNP; the thioester antioxidant is one or more of antioxidant DLTP and antioxidant DSTP.
Optionally, the lubricant is one of calcium stearate, polyethylene wax, ethylene bis stearamide, glycerol monostearate.
The second purpose of the invention is to provide a method for preparing the nylon 12 wire for 3D printing, which comprises the following steps:
1) adding the hyperbranched resin, the antioxidant and the lubricant into the nylon 12 resin, and uniformly mixing to obtain mixed powder A;
2) melting and blending the mixed powder A in a double-screw extruder, extruding and granulating to obtain granules B;
3) and after vacuum drying, adding the granules B into a single-screw extruder for melt extrusion, drawing wires through a traction device, and winding and collecting the wires through a wire coil device to obtain the nylon 12 wires for 3D printing.
Optionally, the melt extrusion temperature parameters of the single-screw extruder in the step 3) are as follows: temperature control of a first-stage host: 210-250 ℃; temperature control of other sections: 200-240 ℃; the diameter of the wire drawn by the traction device in the step 2) is controlled to be 1.75 +/-0.05 mm, or 3.00 +/-0.05 mm, or 2.85 +/-0.05 mm.
The third purpose of the invention is to provide an application of the nylon 12 wire for 3D printing in 3D printing, which comprises the following steps:
carrying out layer-by-layer fused deposition printing on nylon 12 wires for 3D printing by fused deposition forming equipment to form a product, wherein the forming process parameters are as follows: single-layer thickness: 0.1 ~ 0.3mm, frame width: 0.8-1.2 mm, bottom thickness: 0.8-1.2 mm, bottom printing speed: 20-30 mm/s, printing speed: 30-60 mm/s, printing temperature: 240-260 ℃, hot bed temperature: 110-120 ℃, filling rate: 50 to 100 percent.
Compared with the prior art, the nylon 12 wire for 3D printing has the following advantages:
1. according to the invention, the 3D printing nylon wire material is prepared by using the waste nylon 12 powder of SLS, so that the problem of recycling the waste nylon 12 powder in the SLS process is effectively solved, the manufacturing cost is reduced, the pollution of the powder material to the environment can be reduced, and the requirement of green development is met.
2. The nylon 12 wire prepared by the invention not only keeps the original excellent mechanical property and forming processability of nylon 12, but also overcomes the defect that the wire is easy to warp and deform during printing.
3. The invention greatly improves the processing fluidity of the recycled nylon 12 powder by using the hyperbranched resin, improves the molding processability reduction caused by melt viscosity increase of the recycled powder due to long-time heating, reduces the phenomena of gaps and mechanical property reduction in the product caused by unsmooth filament discharge in the fused deposition molding process, and provides possibility for adding other additives such as reinforcing agents and the like to form a composite material in the later period.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an external view of a standard sample strip printed with nylon 12 wire for 3D printing according to example 2 of the present invention;
FIG. 2 is an appearance view of a standard sample bar printed with the nylon 12 wire for 3D printing of comparative example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
A nylon 12 wire for 3D printing is prepared by the following steps:
1) 500g of nylon 12 powder recovered after selective laser sintering, 1.5g of hyperbranched resin, 1.5g of antioxidant 1098, 0.5g of antioxidant 168, and 1.0g of lubricant EBS (ethylene bis stearamide)Wherein the density of the hyperbranched resin is 1.3g/cm3The melting range is 140-160 ℃;
2) sequentially adding the weighed raw materials into a high-speed stirrer, and uniformly mixing to obtain mixed powder A;
3) carrying out melt blending extrusion on the mixed powder A by using a double-screw extruder, and granulating to obtain granules B;
4) and (2) drying the granules B in a vacuum drying oven at 80 ℃ for 4h, adding the granules B into a single-screw extruder for melt extrusion, drawing a wire material by a traction device, adjusting the diameter of the wire material to be 1.75 +/-0.05 mm in the drawing process, winding and collecting the wire material by a wire disk device to obtain a nylon 12 wire material for 3D printing, wherein the melt extrusion temperature parameters of the double-screw extruder and the single-screw extruder are 220-240 ℃, and the diameter of the wire material is measured by an infrared caliper.
And (3) performing injection molding on the dried granules B by using a three-dimensional injection molding machine according to national standards to obtain straight sample strips and dumbbell-shaped sample strips, wherein the temperature parameter of a charging barrel of the injection molding machine is 230-240 ℃. And respectively sealing and storing the injection-molded sample strips by using sealing bags, balancing for 24 hours, and testing the melt flow rate, the tensile strength, the bending modulus, the notch impact strength and the Vicat softening point of the material according to the standard, wherein the test results are shown in Table 1.
Example 2
A nylon 12 wire for 3D printing is prepared by the following steps:
1) weighing 500g of nylon 12 powder recovered after selective laser sintering, 3.0g of hyperbranched resin, 1.5g of antioxidant 1098, 0.5g of antioxidant 168 and 1.0g of lubricant EBS (ethylene bis stearamide), wherein the density of the hyperbranched resin is 1.3g/cm3The melting range is 140-160 ℃;
2) sequentially adding the weighed raw materials into a high-speed stirrer, and uniformly mixing to obtain mixed powder A;
3) carrying out melt blending extrusion on the mixed powder A by using a double-screw extruder, and granulating to obtain granules B;
4) and (2) drying the granules B in a vacuum drying oven at 80 ℃ for 4h, adding the granules B into a single-screw extruder for melt extrusion, drawing a wire material by a traction device, adjusting the diameter of the wire material to be 1.75 +/-0.05 mm in the drawing process, winding and collecting the wire material by a wire disk device to obtain a nylon 12 wire material for 3D printing, wherein the melt extrusion temperature parameters of the double-screw extruder and the single-screw extruder are 220-240 ℃, and the diameter of the wire material is measured by an infrared caliper.
And (3) performing injection molding on the dried granules B by using a three-dimensional injection molding machine according to national standards to obtain straight sample strips and dumbbell-shaped sample strips, wherein the temperature parameter of a charging barrel of the injection molding machine is 230-240 ℃. And respectively sealing and storing the injection-molded sample strips by using sealing bags, balancing for 24 hours, and testing the melt flow rate, the tensile strength, the bending modulus, the notch impact strength and the Vicat softening point of the material according to the standard, wherein the test results are shown in Table 1.
The nylon 12 wire for 3D printing of the embodiment is subjected to 3D printing and forming, and the method specifically comprises the following steps:
carrying out layer-by-layer fused deposition printing on nylon 12 wires for 3D printing by fused deposition modeling equipment (FDM modeling equipment) to obtain a product, wherein the modeling technological parameters are as follows: single-layer thickness: 0.1mm, frame width: 1.2mm, bottom thickness: 1.2mm, bottom printing speed: 20mm/s, printing speed: 40mm/s, printing temperature: 250 ℃, hot bed temperature: 115 ℃, filling ratio: 100 percent.
The printed standard sample strips were subjected to mechanical property tests such as tensile strength, flexural modulus, notched impact strength, and the like, and the test results are shown in table 2.
The printed standard bars were tested for appearance and the results are shown in figure 1.
As can be seen from FIG. 1, the printed standard sample strip is light yellow, does not warp, has good formability, and can be directly used as a functional part.
Example 3
A nylon 12 wire for 3D printing is prepared by the following steps:
1) weighing 500g of nylon 12 powder recovered after selective laser sintering, 4.5g of hyperbranched resin, 1.5g of antioxidant 1098, 0.5g of antioxidant 168 and 1.0g of lubricant EBS (ethylene bis stearamide), wherein the density of the hyperbranched resin is 1.3g/cm3The melting range is 140-160 ℃;
2) sequentially adding the weighed raw materials into a high-speed stirrer, and uniformly mixing to obtain mixed powder A;
3) carrying out melt blending extrusion on the mixed powder A by using a double-screw extruder, and granulating to obtain granules B;
4) and (2) drying the granules B in a vacuum drying oven at 80 ℃ for 4h, adding the granules B into a single-screw extruder for melt extrusion, drawing a wire material by a traction device, adjusting the diameter of the wire material to be 1.75 +/-0.05 mm in the drawing process, winding and collecting the wire material by a wire disk device to obtain a nylon 12 wire material for 3D printing, wherein the melt extrusion temperature parameters of the double-screw extruder and the single-screw extruder are 220-240 ℃, and the diameter of the wire material is measured by an infrared caliper.
And (3) performing injection molding on the dried granules B by using a three-dimensional injection molding machine according to national standards to obtain straight sample strips and dumbbell-shaped sample strips, wherein the temperature parameter of a charging barrel of the injection molding machine is 230-240 ℃. And respectively sealing and storing the injection-molded sample strips by using sealing bags, balancing for 24 hours, and testing the melt flow rate, the tensile strength, the bending modulus, the notch impact strength and the Vicat softening point of the material according to the standard, wherein the test results are shown in Table 1.
Example 4
A nylon 12 wire for 3D printing is prepared by the following steps:
1) weighing 500g of nylon 12 powder recovered after selective laser sintering, 6.0g of hyperbranched resin, 1.5g of antioxidant 1098, 0.5g of antioxidant 168 and 1.0g of lubricant EBS (ethylene bis stearamide), wherein the density of the hyperbranched resin is 1.3g/cm3The melting range is 140-160 ℃;
2) sequentially adding the weighed raw materials into a high-speed stirrer, and uniformly mixing to obtain mixed powder A;
3) carrying out melt blending extrusion on the mixed powder A by using a double-screw extruder, and granulating to obtain granules B;
4) and (2) drying the granules B in a vacuum drying oven at 80 ℃ for 4h, adding the granules B into a single-screw extruder for melt extrusion, drawing a wire material by a traction device, adjusting the diameter of the wire material to be 1.75 +/-0.05 mm in the drawing process, winding and collecting the wire material by a wire disk device to obtain a nylon 12 wire material for 3D printing, wherein the melt extrusion temperature parameters of the double-screw extruder and the single-screw extruder are 220-240 ℃, and the diameter of the wire material is measured by an infrared caliper.
And (3) performing injection molding on the dried granules B by using a three-dimensional injection molding machine according to national standards to obtain straight sample strips and dumbbell-shaped sample strips, wherein the temperature parameter of a charging barrel of the injection molding machine is 230-240 ℃. And respectively sealing and storing the injection-molded sample strips by using sealing bags, balancing for 24 hours, and testing the melt flow rate, the tensile strength, the bending modulus, the notch impact strength and the Vicat softening point of the material according to the standard, wherein the test results are shown in Table 1.
Comparative example 1
A nylon 12 wire for 3D printing is prepared by the following steps:
1) weighing 500g of new nylon 12 resin, 1.5g of antioxidant 1098, 0.5g of antioxidant 168 and 1.0g of lubricant EBS (ethylene bis stearamide);
2) sequentially adding the weighed raw materials into a high-speed stirrer, and uniformly mixing to obtain mixed powder A;
3) carrying out melt blending extrusion on the mixed powder A by using a double-screw extruder, and granulating to obtain granules B;
4) and (2) drying the granules B in a vacuum drying oven at 80 ℃ for 4h, adding the granules B into a single-screw extruder for melt extrusion, drawing a wire material by a traction device, adjusting the diameter of the wire material to be 1.75 +/-0.05 mm in the drawing process, winding and collecting the wire material by a wire disk device to obtain a nylon 12 wire material for 3D printing, wherein the melt extrusion temperature parameters of the double-screw extruder and the single-screw extruder are 220-240 ℃, and the diameter of the wire material is measured by an infrared caliper.
And (3) performing injection molding on the dried granules B by using a three-dimensional injection molding machine according to national standards to obtain straight sample strips and dumbbell-shaped sample strips, wherein the temperature parameter of a charging barrel of the injection molding machine is 230-240 ℃. And respectively sealing and storing the injection-molded sample strips by using sealing bags, balancing for 24 hours, and testing the melt flow rate, the tensile strength, the bending modulus, the notch impact strength and the Vicat softening point of the material according to the standard, wherein the test results are shown in Table 1.
The nylon 12 wire for 3D printing of the comparative example is subjected to 3D printing forming, and the method specifically comprises the following steps:
carrying out layer-by-layer fused deposition printing on nylon 12 wires for 3D printing by fused deposition modeling equipment (FDM modeling equipment) to obtain a product, wherein the modeling technological parameters are as follows: single-layer thickness: 0.1mm, frame width: 1.2mm, bottom thickness: 1.2mm, bottom printing speed: 20mm/s, printing speed: 40mm/s, printing temperature: 250 ℃, hot bed temperature: 115 ℃, filling ratio: 100 percent.
The printed standard sample strips were subjected to mechanical property tests such as tensile strength, flexural modulus, notched impact strength, and the like, and the test results are shown in table 2.
The printed standard bars were tested for appearance and the results are shown in figure 2.
As can be seen from FIG. 2, the printed standard sample strip is semitransparent white, the warping deformation is serious, the printed sample strip is not firmly adhered to the bottom plate, and even the sample strip can be separated from the hot bed in the printing process.
As can be seen from Table 1, the melt flow rate of the pellets B in examples 1 to 4 of the present invention increased with the increase of the content of the hyperbranched resin (the melt flow rate of the recycled nylon 12 powder was 6.99g/10min), the tensile strength, flexural modulus and notched impact strength of the pellet B injection molded samples of examples 1 to 4 slightly decreased with the increase of the content of the hyperbranched resin, and the Vicat softening temperature of the pellet B injection molded samples of examples 1 to 4 was slightly higher than that of the new nylon 12 pellet injection molded sample.
TABLE 1
As can be seen from Table 2, the tensile strength and notched impact strength of the samples printed by using the nylon 12 wire for 3D printing of example 2 of the present invention were higher than those of the samples printed in comparative example 1, and the flexural modulus was substantially the same.
TABLE 2
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nylon 12 wire for 3D printing is characterized by comprising the following components in parts by weight: nylon 12 resin: 100 parts of hyperbranched resin: 0.3-1.5 parts of antioxidant: 0.01-0.5 parts of lubricant: 0.1 to 0.3 portion.
2. The nylon 12 filament for 3D printing according to claim 1, wherein the nylon 12 resin is nylon 12 powder recovered after selective laser sintering.
3. The nylon 12 wire for 3D printing according to claim 1, wherein the hyperbranched resin has a density of 1.3g/cm3The melting range is 140-160 ℃.
4. The nylon 12 wire for 3D printing according to claim 1, wherein the antioxidant comprises, in mass percent: main antioxidant: 60% -85%, auxiliary antioxidant: 15 to 40 percent.
5. The nylon 12 wire for 3D printing according to claim 4, wherein the primary antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is one or more of phosphite antioxidant and thioester antioxidant.
6. The nylon 12 wire for 3D printing according to claim 5, wherein the hindered phenol antioxidant is one or more of antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant 264, antioxidant CA, antioxidant 330 and antioxidant 245; the phosphite antioxidant is one or more of antioxidant 168 and antioxidant TNP; the thioester antioxidant is one or more of antioxidant DLTP and antioxidant DSTP.
7. The nylon 12 wire for 3D printing according to claim 1, wherein the lubricant is one of calcium stearate, polyethylene wax, ethylene bis stearamide, glycerol monostearate.
8. A method of preparing a nylon 12 filament for 3D printing according to any of claims 1 to 7, comprising the steps of:
1) adding the hyperbranched resin, the antioxidant and the lubricant into the nylon 12 resin, and uniformly mixing to obtain mixed powder A;
2) melting and blending the mixed powder A in a double-screw extruder, extruding and granulating to obtain granules B;
3) and after vacuum drying, adding the granules B into a single-screw extruder for melt extrusion, drawing wires through a traction device, and winding and collecting the wires through a wire coil device to obtain the nylon 12 wires for 3D printing.
9. The method for preparing nylon 12 wire for 3D printing according to claim 8, wherein the melt extrusion temperature parameters of the single screw extruder in the step 3) are as follows: temperature control of a first-stage host: 210-250 ℃; temperature control of other sections: 200-240 ℃; the diameter of the wire drawn by the traction device in the step 3) is controlled to be 1.75 +/-0.05 mm, or 3.00 +/-0.05 mm, or 2.85 +/-0.05 mm.
10. Use of a nylon 12 filament for 3D printing according to any of claims 1 to 7 in 3D printing, comprising the steps of:
carrying out layer-by-layer fused deposition printing on nylon 12 wires for 3D printing by fused deposition forming equipment to form a product, wherein the forming process parameters are as follows: single-layer thickness: 0.1 ~ 0.3mm, frame width: 0.8-1.2 mm, bottom thickness: 0.8-1.2 mm, bottom printing speed: 20-30 mm/s, printing speed: 30-60 mm/s, printing temperature: 240-260 ℃, hot bed temperature: 110-120 ℃, filling rate: 50 to 100 percent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911338086.8A CN111004499A (en) | 2019-12-23 | 2019-12-23 | Nylon 12 wire for 3D printing and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911338086.8A CN111004499A (en) | 2019-12-23 | 2019-12-23 | Nylon 12 wire for 3D printing and preparation method and application thereof |
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| CN111004499A true CN111004499A (en) | 2020-04-14 |
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| CN201911338086.8A Pending CN111004499A (en) | 2019-12-23 | 2019-12-23 | Nylon 12 wire for 3D printing and preparation method and application thereof |
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| CN113416411A (en) * | 2021-07-21 | 2021-09-21 | 贵州森远增材制造科技有限公司 | Selective laser printing method for recycling and reusing four-stage nylon 12 residual powder |
| CN113478831A (en) * | 2021-07-21 | 2021-10-08 | 贵州省冶金化工研究所 | Selective laser printing method for recycling nylon 12 full residual powder |
| CN113637176A (en) * | 2021-08-19 | 2021-11-12 | 郑州大学 | Thermoplastic polyamide elastomer wire for fused deposition 3D printing and preparation method thereof |
| CN113956610A (en) * | 2021-11-29 | 2022-01-21 | 上海理工大学 | Preparation method of PEEK composite material wire for 3D printer |
| CN114231022A (en) * | 2021-12-10 | 2022-03-25 | 杭州晟天新材料科技有限公司 | Nylon composite material suitable for FDM type 3D printing and preparation method thereof |
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| CN113956610B (en) * | 2021-11-29 | 2023-11-24 | 上海理工大学 | Preparation method of PEEK composite material wire for 3D printer |
| CN114231022A (en) * | 2021-12-10 | 2022-03-25 | 杭州晟天新材料科技有限公司 | Nylon composite material suitable for FDM type 3D printing and preparation method thereof |
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Application publication date: 20200414 |