CN111086204A - 3D printing method - Google Patents
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- CN111086204A CN111086204A CN201911268126.6A CN201911268126A CN111086204A CN 111086204 A CN111086204 A CN 111086204A CN 201911268126 A CN201911268126 A CN 201911268126A CN 111086204 A CN111086204 A CN 111086204A
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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
- 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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Abstract
The invention belongs to the technical field of 3D printing, and particularly relates to a 3D printing method. The method provided by the invention comprises the following steps: mixing the modified carbon nanotube filaments with molten resin to enable the molten resin to coat the surfaces of the modified carbon nanotube filaments to form a 3D printing material with the modified carbon nanotube filaments as a core layer; wherein, the modified carbon nanotube filament is a carbon nanotube fiber with a surface modified with a rubber layer; according to the preset printing model, 3D printing materials are deposited on the substrate, and the 3D printing object is printed. The method is simple and convenient, the operability is strong, and the 3D printed object prepared by the method has high stability and uniformity and excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a 3D printing method.
Background
3D printing, also known as three-dimensional printing or additive manufacturing, refers to an additive printing process for manufacturing a three-dimensional object or part according to a preset printing model of a computer, and can realize accurate manufacturing of complex three-dimensional structures from a submicron level to a meter level, and has been widely applied to a plurality of technical fields in recent years, such as aerospace, automotive fields, energy storage, electronics, engineering composite materials, biotechnology, tissue engineering, medicine and other fields.
3D printing three-dimensional objects can be printed using a variety of techniques, including: inkjet printing (Inkjetprinting), Fused Deposition Modeling (FDM), Powder bed technology (Powder-bed technology), Micro-stereolithography (MSL), Direct-write assembly (DW), and Selective Laser Sintering (SLS), among others. Among the most common 3D printing techniques is Fused Deposition Modeling (FDM), typically a filament (1.75mm) is fed from a spool into a compression assembly, fed into a temperature-controlled melting chamber using motorized gears, extruded through the tip of a nozzle after the filament has melted and deposited onto a previously printed coating, hardened and bonded onto the previously printed layer, and after one layer is completed, the build platform is lowered slightly to make room for the next layer to be printed, and so on, iteratively, until the printing of the target object is completed.
In order to improve the mechanical properties of three-dimensional objects or parts, fillers such as carbon nanotube powder, carbon black, graphene or chopped fibers are often added to the printing material. The carbon nano tube has excellent mechanical, electrical and thermal properties, so that the carbon nano tube is a suitable choice for the 3D printing material reinforcement. However, since the carbon nanotube powder has a high surface energy, it is likely to cause agglomeration, and the carbon nanotube powder has a weak adhesive force with a resin matrix during dispersion, and is likely to generate voids, so that the excellent properties of the carbon nanotube cannot be sufficiently exhibited, and thus the mechanical properties of the three-dimensional object or member obtained therefrom are limited to be enhanced.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a 3D printing method, and aims to solve the problem that a three-dimensional object or part printed by the existing method is poor in mechanical property.
Means for solving the problems
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of 3D printing, comprising the steps of:
mixing the modified carbon nanotube filament with molten resin, so that the molten resin coats the surface of the modified carbon nanotube filament to form a 3D printing material with the modified carbon nanotube filament as a core layer; the modified carbon nanotube filament is a carbon nanotube fiber with a surface modified with a rubber layer;
and according to a preset printing model, depositing the 3D printing material on a substrate, and printing a 3D printing object.
Preferably, the 3D printing method further includes: and carrying out microwave heating treatment on the 3D printed object.
Preferably, the 3D printed object is irradiated with electromagnetic waves having a frequency of 2.48 to 2.64GHz at 1.0 to 1.5kW for 3 to 6 seconds.
Preferably, the volume percentage of the modified carbon nanotube filaments in the 3D printing material is 50% to 70%.
Preferably, the preparation method of the modified carbon nanotube filament comprises the following steps: and depositing a rubber layer on the surface of the carbon nanotube fiber to obtain the modified carbon nanotube filament.
Further preferably, the step of depositing the rubber layer on the surface of the carbon nanotube fiber comprises: and (3) enabling the carbon nanotube fiber to pass through the rubber solution at a constant speed at a preset speed, and then carrying out curing treatment.
Further preferably, before the step of passing the carbon nanotube fiber through the rubber solution at a constant speed, the method further comprises: and enabling the carbon nanotube fiber to pass through an organic solvent at a constant speed at a preset speed, wherein the organic solvent is at least one selected from dichloromethane, acetone, ethanol, ethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide.
Further preferably, the preparation method of the carbon nanotube fiber comprises the following steps:
obtaining a carbon nanotube array, pulling out a carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to obtain a carbon nanotube fiber;
and twisting and doubling the carbon nanotube fiber yarn to prepare the carbon nanotube fiber.
More preferably, the carbon nanotube array is prepared by reacting for 5-10 minutes by a chemical vapor deposition method in a carbon source atmosphere at 500-900 ℃; and/or
Drawing a carbon nanotube film with the width of 0.1-20 cm from the carbon nanotube array, and twisting the carbon nanotube film according to the twist of 100-15000 tpm; and/or
Twisting and doubling 120-350 carbon nanotube fiber yarns according to the twist of 50-150 tpm to obtain the carbon nanotube fiber.
Preferably, the step of mixing the modified carbon nanotube filaments with the molten resin comprises:
feeding a resin filament and a modified carbon nanotube filament into a 3D printer, wherein the resin filament and the modified carbon nanotube filament enter a melting cavity of the 3D printer;
and the resin filament is heated and melted in the melting cavity to form molten resin, and the molten resin is mixed with the modified carbon nanotube filament to form the 3D printing material.
Preferably, in the step of depositing the 3D printing material on the substrate, the 3D printing material is extruded through a nozzle of the 3D printer and deposited on the substrate.
Preferably, the material of the molten resin includes at least one of polylactic acid, acrylonitrile-butadiene-styrene copolymer, polyvinyl alcohol, polycarbonate, polypropylene, polyamide, thermoplastic elastomer, high impact polystyrene, and polyethylene terephthalate-1, 4-cyclohexanedimethanol ester.
Effects of the invention
According to the 3D printing method, the carbon nanotube fiber with the surface modified with the rubber layer is mixed with the molten resin to prepare the 3D printing material, the 3D printing material is deposited on the substrate according to the preset printing model, the method is simple and convenient, the operability is strong, and the prepared 3D printing object has high stability and uniformity and excellent mechanical property. The 3D printing material is prepared by adopting the carbon nanotube fiber with the surface modified by the rubber layer, so that the problem of agglomeration of carbon nanotube powder in molten resin is solved, the surface modified rubber layer has good compatibility with the resin, the interface bonding force of the carbon nanotube fiber and the resin is improved, the carbon nanotube fiber and the resin can be fully mixed, and the reinforcing performance of the carbon nanotube fiber is fully exerted. Therefore, the 3D printed object or part prepared by the 3D printing method has high stability and uniformity and excellent mechanical properties.
The 3D printing method obtained by the invention further comprises the following steps: the 3D prints the object and carries out microwave heating processing, through utilizing this characteristic that carbon nanotube fibre self is very sensitive to the thermal response of microwave for modified carbon nanotube filament not only plays the reinforcing effect with the resin is compound, still plays the effect of local heat source under the microwave effect and promotes the resin of adjacent 3D printing picture layer to combine together, has further improved the mechanical properties that 3D printed object or part.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method of 3D printing, comprising the steps of:
s01, mixing the modified carbon nanotube filament with molten resin, so that the molten resin coats the surface of the modified carbon nanotube filament to form a 3D printing material with the modified carbon nanotube filament as a core layer; the modified carbon nanotube filament is a carbon nanotube fiber with a surface modified with a rubber layer;
s02, depositing the 3D printing material on the substrate according to a preset printing model, and printing the 3D printing object.
According to the 3D printing method, the carbon nanotube fiber with the surface modified with the rubber layer is mixed with the molten resin to prepare the 3D printing material, the 3D printing material is deposited on the substrate according to the preset printing model, the method is simple and convenient, the operability is strong, and the prepared 3D printing object has high stability and uniformity and excellent mechanical property. The 3D printing material is prepared by adopting the carbon nanotube fiber with the surface modified by the rubber layer, so that the problem of agglomeration of carbon nanotube powder in molten resin is solved, the surface modified rubber layer has good compatibility with the resin, the interface bonding force of the carbon nanotube fiber and the resin is improved, the carbon nanotube fiber and the resin can be fully mixed, and the reinforcing performance of the carbon nanotube fiber is fully exerted. Therefore, the 3D printed object or part prepared by the 3D printing method has high stability and uniformity and excellent mechanical properties.
Specifically, in step S01, the modified carbon nanotube filament is a carbon nanotube fiber with a surface modified with a rubber layer, and the rubber layer is physically coated on the surface of the carbon nanotube fiber, so that the interfacial bonding force between the carbon nanotube fiber and the resin is effectively improved, the problem of agglomeration of carbon nanotube powder in the molten resin is solved, and the problem that the excellent performance of the carbon nanotube cannot be fully exerted due to the fact that the existing carbon nanotube material is likely to generate a cavity due to weak bonding force with the resin matrix is solved. Meanwhile, as the rubber has good toughness, when the composite material is subjected to external load, the energy can be absorbed, and the crack is prevented from expanding, so that good buffering and toughening effects are achieved, and the interface toughness of the material can be improved to a certain extent.
In one embodiment, the diameter of the carbon nanotube fiber in the modified carbon nanotube filament is 0.875 mm to 1.225mm, and the thickness of the rubber layer is 0.02mm to 0.05 mm. When the thickness of the rubber layer is less than 0.02mm, the effect of toughening the interface can not be achieved; when the thickness of the rubber layer is greater than 0.05mm, the mechanical properties of the carbon nanotube fiber are rather deteriorated.
As an embodiment, the method for preparing the modified carbon nanotube filament includes: and depositing a rubber layer on the surface of the carbon nanotube fiber to prepare the modified carbon nanotube fiber.
The deposition method includes, but is not limited to, spin coating, dip coating, magnetron sputtering, chemical vapor deposition, evaporation, inkjet printing, etc., so that the rubber layer can be uniformly and firmly fixed on the surface of the carbon nanotube fiber.
In some embodiments, the step of depositing a rubber layer on the surface of the carbon nanotube fibers comprises: and (3) enabling the carbon nanotube fiber to pass through the rubber solution at a constant speed at a preset speed, and then carrying out curing treatment.
By the method, the rubber solution can be uniformly coated on the surface of the carbon nanotube fiber, the thickness of the rubber layer prepared after curing is uniform, the rubber can completely cover the carbon nanotube fiber, meanwhile, the rubber is prevented from being agglomerated on the surface of the carbon nanotube fiber, and the mechanical property of the material is favorably improved.
In a further embodiment, the carbon nanotube fiber core layer passes through the rubber solution at a constant speed of 0.004-0.2m/s, ensuring that the thickness of the prepared rubber layer is moderate.
In a further embodiment, before the step of passing the carbon nanotube fiber through the rubber solution at a constant speed, the method further comprises: and enabling the carbon nanotube fiber to pass through an organic solvent at a constant speed at a preset speed, wherein the organic solvent is at least one selected from dichloromethane, acetone, ethanol, ethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide. The carbon nano tube passes through the organic solvents at a constant speed, so that the carbon nano tube fiber is more compact, the toughness of the carbon nano tube fiber can be improved to a certain degree, and the subsequent rubber deposition on the surface of the carbon nano tube fiber is promoted.
The rubber solution is a solution in which rubber is dissolved, and in some embodiments, the rubber solution contains 5.0-8.0g of rubber per 100mL of the rubber solution, so that the rubber can be uniformly coated on the surface of the carbon nanotube fiber. When the concentration of the rubber is lower than 5.0g/100mL, the rubber layer on the surface of the carbon nanotube fiber is too thin, so that the rubber layer can not completely cover the carbon nanotube fiber; when the concentration of the rubber is more than 8.0g/100mL, part of the rubber can agglomerate on the surface of the carbon nanotube fiber, so that the thickness of the rubber layer is uneven. In some embodiments, the solvent of the rubber solution is at least one selected from the group consisting of dichloromethane, acetone, ethanol, ethylene glycol, N-methylpyrrolidone, dimethylsulfoxide, and N, N-dimethylformamide, which can sufficiently completely dissolve the rubber, and these solvents can perform a densification process on the carbon nanotubes, which can improve the toughness of the carbon nanotube fibers to some extent and facilitate the subsequent deposition of the rubber on the surface of the carbon nanotube fibers.
The rubber can be made of conventional rubber materials in the field, so that the formed rubber layer can be firmly attached to the surface of the carbon nanotube fiber and can be compatible with the resin matrix of most existing 3D printing materials. In some embodiments, the material of the rubber layer is selected to be a functional end group liquid rubber. In a further embodiment, the material of the rubber layer is selected from at least one of nitrile rubber, polysulfide rubber, polyurethane rubber and silicone rubber. In a further embodiment, the number average molecular weight of the material of the rubber layer is 2000-.
The carbon nanotube fiber is a macroscopic fiber wire formed by combining at least one carbon nanotube fiber bundle, and in some embodiments, the carbon nanotube fiber is a single carbon nanotube fiber bundle and is prepared by twisting a carbon nanotube film; in some embodiments, the carbon nanotube fibers are formed by combining a plurality of carbon nanotube fibers, for example, 3 carbon nanotube fibers, and are formed by doubling a plurality of carbon nanotube fibers obtained by twisting a carbon nanotube film. The carbon nano tube fiber has better mechanical property and can meet the requirement of subsequent application.
As an embodiment, the method for preparing the carbon nanotube fiber includes the steps of:
a. obtaining a carbon nanotube array, pulling out a carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to obtain a carbon nanotube fiber;
b. and twisting and doubling the carbon nanotube fiber yarn to prepare the carbon nanotube fiber.
In some embodiments, in step a, the carbon nanotube array is prepared by reacting in a carbon source atmosphere at 500-900 ℃ for 5-10 minutes by using a chemical vapor deposition method.
In some embodiments, in step a, a carbon nanotube film with a width of 0.1-20 cm is drawn from the carbon nanotube array, and the carbon nanotube film is twisted with a twist of 100-15000 tpm to obtain carbon nanotube fiber.
In some embodiments, in step a, 120-350 carbon nanotube fibers are twisted and doubled according to a twist degree of 50-150 tpm to obtain the carbon nanotube fibers. The carbon nanotube fiber in the twist range has higher fiber strength, and when the twist is too low, the formed carbon nanotube fiber is not compact and firm, and the fiber performance is not good; when the twist is too high, the carbon nanotubes are subjected to too much tension, which may adversely affect the properties of the fiber.
Specifically, the molten resin is a resin in a molten state, and as a base material of the 3D printing material, as one embodiment, the resin includes at least one of polylactic acid (PLA), acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl alcohol (PVA), Polycarbonate (PC), polypropylene (PP), polyamide (also called nylon), thermoplastic elastomer (including TPU, TPE, TPR, and the like), High Impact Polystyrene (HIPS), and polyethylene terephthalate-1, 4-cyclohexanedimethanol (PTEG). The resin materials can meet the requirements of 3D printing materials on high mechanical strength, low shrinkage rate, proper melting temperature, no toxicity, environmental friendliness and the like, and are often used as main consumables of FDM type 3D printers. In some embodiments, the resin is selected from PLA, which is a degradable environmentally friendly plastic, is inexpensive, has a relatively low melting temperature, has good tensile strength and ductility, is easily attached and extended after melting, has good printing properties, and is suitable for various printing conditions compared to ABS, and has good printing properties.
Specifically, in step S01, the modified carbon nanotube filament is mixed with a molten resin, so that the molten resin coats the surface of the modified carbon nanotube filament, thereby forming a 3D printed material with the modified carbon nanotube filament as a core layer.
As one embodiment, the step of mixing the modified carbon nanotube filaments with the molten resin includes:
s011, feeding the resin filament and the modified carbon nanotube filament into a 3D printer, and feeding the resin filament and the modified carbon nanotube into a melting cavity of the 3D printer;
and S012, heating and melting the resin filament in the melting cavity to form molten resin, and mixing the molten resin and the modified carbon nanotube filament to form the 3D printing material.
By the method, the resin heated and melted in the melting cavity can be mixed with the modified carbon nanotube filament in the melting cavity at the same time, and the molten resin coats the surface of the modified carbon nanotube filament to form the 3D printing material taking the modified carbon nanotube filament as the core layer. The method is simple and convenient and has high operability.
As an embodiment, the modified carbon nanotube filament in the 3D printing material has a volume percentage of 50% to 70%. Specifically, the volume percentage of the modified carbon nanotube filament is 50-70% and the volume percentage of the molten resin is 30-50% based on 100% of the total volume of the 3D printing material. When the volume percentage of the carbon nanotube fiber is more than 70%, the resin content on the stressed section of the modified carbon nanotube filament is correspondingly reduced, so that the stress bearing point of the modified carbon nanotube filament is too high, and the material strength and the modulus are deteriorated; when the volume percentage of the carbon nanotube fiber is less than 50%, the carbon nanotube fiber has poor reinforcing effect, and the mechanical strength of the modified carbon nanotube filament is not correspondingly enhanced.
Specifically, in step S02, the 3D printing material is deposited on the substrate according to a preset printing model, and the 3D printed object is printed.
The printing model is a three-dimensional model established by utilizing three-dimensional computer aided design or modeling software or through three-dimensional scanning equipment, and provides path information to be printed for subsequent 3D printing.
Depositing a 3D printing material onto the substrate to form a printed image layer. As an embodiment, in the step of depositing the 3D printing material on the substrate, the 3D printing material is extruded through a nozzle of the 3D printer and deposited on the substrate. The substrate may be a clean glass substrate for bearing a 3D printed object, or may be a glass substrate on which a part of a printed image layer is formed.
As an implementation manner, the method for 3D printing provided by the embodiment of the present invention further includes:
and S03, performing microwave heating treatment on the 3D printed object.
By utilizing the characteristic that the carbon nanotube fiber is sensitive to the thermal response of microwave, the carbon nanotube fiber is used as a local heat source while being used as a reinforcement of a 3D printing material, and the resin of adjacent 3D printing layers is promoted to be combined together, so that the interlayer bonding strength of a 3D printing object is improved, and the mechanical property and the structural stability of the 3D printing object are improved. The microwave heating temperature rise is rapid, the processing time is short, and the problem that the product is deformed due to the method of integrally heating the 3D printing object is solved.
In some embodiments, the 3D printed object is irradiated with electromagnetic waves having a frequency of 2.48-2.64GHz at 1.0-1.5kW for 3-6 seconds. Under corresponding frequency, the carbon nanotube fiber has quick thermal response to microwaves, and only a few seconds are needed, so that the carbon nanotube fiber can be quickly heated to reach the melting temperature of resin around the carbon nanotube fiber, and mutual melting and remodeling of the resin in adjacent 3D printing layers are promoted. The 3D printed product is a three-dimensional product formed by linear 3D printed materials through arrangement on a plane and lamination in a three-dimensional space, the bonding force between the linear 3D printed materials influences the mechanical property of the product, the carbon nanotube fiber in the center of the linear 3D printed materials is rapidly heated through short-time microwave treatment, the bonding force between the linear 3D printed materials is enhanced, the enhancement of the mechanical property of the whole 3D product is facilitated, the operation is carried out in short time, and the shape of the whole 3D product is not influenced.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and the advanced performance of the method of 3D printing according to the embodiment of the present invention is remarkably embodied, the implementation of the present invention is exemplified by the following embodiments.
Example 1
The embodiment prepares a 3D printed object, and the specific process flow thereof is as follows:
s11, pulling out a carbon nanotube film with the width of 7.5cm from the carbon nanotube array, and twisting the film by using a twist meter, wherein the twist is 1200tpm to obtain carbon nanotube fiber yarns with the diameter of about 0.09 mm; then, 5 carbon nanotube fibers prepared by the method are subjected to doubling treatment to obtain carbon nanotube fibers; and then, allowing the carbon nanotube fiber to pass through 5.5g/100mL hydroxyl-terminated butadiene-acrylonitrile rubber acetone solution at a constant speed of 0.004m/s, and curing to obtain the modified carbon nanotube filament.
S12, feeding the modified carbon nanotube filament and the polylactic acid filament at a speed of 100mm/min, and melting and mixing in an extrusion nozzle at a temperature of 210 ℃ and a hot stage temperature of 80 ℃ to obtain a 3D printing material; wherein the volume percentage of the modified carbon nanotube filaments in the 3D printing material is 60%.
And S13, 3D printing is carried out according to a route indicated by a preset 3D printing model in the 3D printer, the number of layers is 3, and a 3D printed object is obtained and is a bending test sample strip.
S14, placing the 3D printed object into a microwave oven, and irradiating for 5S under 1.3kW by adopting electromagnetic waves with the frequency of 2.54GHz to obtain the microwave-enhanced 3D printed object.
Example 2
This example prepared a 3D printed object, the process of which differed from example 1 in that: in step S11, the step of passing the carbon nanotube fiber through 5.5g/100mL of hydroxyl-terminated butadiene-acrylonitrile rubber acetone solution at a uniform speed of 0.004m/S further comprises: the carbon nano tube fiber passes through acetone at a constant speed of 0.004 m/s; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Comparative example 1
This comparative example prepared a 3D printed object, the process of which differed from example 1 in that: in step S12, feeding the polylactic acid filament at a speed of 100 mm/min; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Comparative example 2
This comparative example prepared a 3D printed object, the process of which differed from example 1 in that: omitting the step S11, feeding the modified carbon nanotube filament and the polylactic acid filament at a speed of 100mm/min in the step S12; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Comparative example 3
This comparative example prepared a 3D printed object, the process of which differed from example 1 in that: step S14 is omitted; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Test example
Bending test bars (60 mm. times.11 mm) prepared in example 1 and comparative examples 1 to 3 were used, and the bending strength of each sample was measured at room temperature by a three-point load simple beam method using an electronic universal tester, and the tensile strength was measured at a speed of 2mm/min, and the test results are shown in Table 1.
As shown in table 1, the samples prepared in example 1 have good mechanical properties. Compared with the embodiment 1, the polylactic acid filament is directly adopted for 3D printing in the comparative example 1, the carbon nano tube fiber which is not subjected to surface modification is compounded with the polylactic acid and then subjected to 3D printing in the comparative example 2, and the 3D printed product is not subjected to microwave enhancement treatment in the comparative example 3, so that the mechanical property of the 3D printed product can be effectively improved by adopting the modified carbon nano tube filament as a reinforcement to be compounded with resin in the embodiment of the invention; meanwhile, the resin can be heated by utilizing the rapid thermal response performance of the carbon nano tube through further microwave irradiation on the 3D printed product, so that the interlayer adhesion is improved, the mechanical strength of the 3D printed product is further improved, and the product structure is ensured to be more stable.
TABLE 1
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Flexural Strength (MPa) | 198 | 53.5 | 72.5 | 156 |
| Tensile Strength (MPa) | 124 | 28 | 80 | 91 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. A method of 3D printing, comprising the steps of:
mixing the modified carbon nanotube filament with molten resin, so that the molten resin coats the surface of the modified carbon nanotube filament to form a 3D printing material with the modified carbon nanotube filament as a core layer; the modified carbon nanotube filament is a carbon nanotube fiber with a surface modified with a rubber layer;
and according to a preset printing model, depositing the 3D printing material on a substrate, and printing a 3D printing object.
2. The method of 3D printing according to claim 1, wherein the method of 3D printing further comprises: and carrying out microwave heating treatment on the 3D printed object.
3. The method of 3D printing according to claim 2, characterized in that the 3D printed object is irradiated with electromagnetic waves having a frequency of 2.48-2.64GHz for 3-6 seconds at 1.0-1.5 kW.
4. The method of 3D printing according to claim 2, wherein the modified carbon nanotube filaments in the 3D printing material are present in an amount of 50% to 70% by volume.
5. The method of 3D printing according to claim 1, wherein the method of preparing the modified carbon nanotube filament comprises: and depositing a rubber layer on the surface of the carbon nanotube fiber to obtain the modified carbon nanotube filament.
6. The method of 3D printing according to claim 5, wherein the step of depositing a rubber layer on the surface of the carbon nanotube fiber comprises: and enabling the carbon nanotube fibers to pass through the rubber solution at a preset speed at a constant speed, and then carrying out curing treatment.
7. The 3D printing method according to claim 6, wherein the step of uniformly passing the carbon nanotube fiber through the rubber solution at a predetermined speed is preceded by: and enabling the carbon nanotube fiber to pass through an organic solvent at a constant speed at a preset speed, wherein the organic solvent is at least one selected from dichloromethane, acetone, ethanol, ethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide.
8. The method of 3D printing according to claim 5, wherein the method of preparing the carbon nanotube fiber comprises the steps of:
obtaining a carbon nanotube array, pulling out a carbon nanotube film from the carbon nanotube array, and twisting the carbon nanotube film to obtain a carbon nanotube fiber;
and twisting and doubling the carbon nanotube fiber yarn to prepare the carbon nanotube fiber.
9. The method of 3D printing according to claim 8, wherein the carbon nanotube array is prepared by a chemical vapor deposition reaction in a carbon source atmosphere at 500-900 ℃ for 5-10 minutes; and/or
Drawing a carbon nanotube film with the width of 0.1-20 cm from the carbon nanotube array, and twisting the carbon nanotube film according to the twist of 100-15000 tpm; and/or
Twisting and doubling 120-350 carbon nanotube fiber yarns according to the twist of 50-150 tpm to obtain the carbon nanotube fiber.
10. The method of 3D printing according to any one of claims 1 to 9, wherein the step of mixing the modified carbon nanotube filaments with a molten resin comprises:
feeding a resin filament and a modified carbon nanotube filament into a 3D printer, wherein the resin filament and the modified carbon nanotube filament enter a melting cavity of the 3D printer;
and the resin filament is heated and melted in the melting cavity to form molten resin, and the molten resin is mixed with the modified carbon nanotube filament to form the 3D printing material.
11. The method of 3D printing according to any of claims 1 to 9, wherein the material of the molten resin comprises at least one of polylactic acid, acrylonitrile butadiene styrene, polyvinyl alcohol, polycarbonate, polypropylene, polyamide, thermoplastic elastomer, high impact polystyrene, and polyethylene terephthalate-1, 4-cyclohexanedimethanol ester.
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Cited By (2)
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