CN113583435B - Continuous carbon nano tube composite fiber 3D printing wire rod and preparation method and application thereof - Google Patents
Continuous carbon nano tube composite fiber 3D printing wire rod and preparation method and application thereof Download PDFInfo
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- CN113583435B CN113583435B CN202111059900.XA CN202111059900A CN113583435B CN 113583435 B CN113583435 B CN 113583435B CN 202111059900 A CN202111059900 A CN 202111059900A CN 113583435 B CN113583435 B CN 113583435B
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 176
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 176
- 238000010146 3D printing Methods 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 51
- 229920001778 nylon Polymers 0.000 claims description 36
- 239000004677 Nylon Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 9
- 239000004626 polylactic acid Substances 0.000 claims description 9
- 238000005491 wire drawing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 238000004050 hot filament vapor deposition Methods 0.000 claims description 3
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- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 238000007639 printing Methods 0.000 description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010128 melt processing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000007499 fusion processing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- -1 carbon nanotube compound Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
-
- 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
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/14—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length of filaments or wires
-
- 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
-
- 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
-
- 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
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a continuous carbon nano tube composite fiber 3D printing wire rod, a preparation method and application thereof. The continuous carbon nanotube composite fiber 3D printing wire comprises stranded carbon nanotube fibers serving as a framework structure and thermoplastic polymers, wherein the stranded carbon nanotube fibers are formed by aggregation of a plurality of carbon nanotube fibers, the thermoplastic polymers are uniformly dispersed among the plurality of carbon nanotube fibers and wrapped on the surfaces of the plurality of carbon nanotube fibers, and the thermoplastic polymers at least enable the plurality of carbon nanotube fibers to be bonded. The 3D printing wire material phase prepared by adopting the ply-bonding carbon nano tube fibers has excellent mechanical properties, and the preparation method is simple, is suitable for large-scale production, and provides good technical support for the application of the carbon nano tube fibers in the field of 3D printing.
Description
Technical Field
The invention belongs to the technical field of composite fibers, and relates to a continuous carbon nano tube composite fiber 3D printing wire rod, a preparation method and application thereof.
Background
The 3D printing continuous fiber reinforced thermoplastic polymer has the potential of high efficiency and low cost and has great development prospect. 3D printing fiber reinforced polymers, particularly continuous fiber reinforced thermoplastic polymers, have great potential in the low cost, high efficiency manufacture of lightweight, high performance, complex structural components. 3D printing of continuous carbon fiber reinforced polymers has now achieved commercial development. Carbon nanotubes have greater advantages in mechanical and electrical properties over conventional materials due to their excellent electrochemical, mechanical and thermal properties. At present, a common way is to apply carbon nanotubes as a filler in the field of 3D printing. However, in the 3D printing of the carbon nanotube ink, the dispersibility of the carbon tubes is not good, a large amount of dispersing agent is added, the carbon tubes are difficult to orient, the carbon tube content is low, the dispersing agent is difficult to remove, and the mechanical strength of the powder carbon nanotubes is difficult to reach the level of carbon nanotube fibers. Therefore, the composite fiber obtained by using the carbon nano tube fiber reinforced thermoplastic polymer has wider research value in the field of 3D printing. The polyamide has excellent comprehensive properties such as excellent mechanical properties, wear resistance, self lubrication, oil resistance, weak acid and weak base resistance and the like, but also has the defects of large water absorption, poor dimensional stability, poor creep resistance, inapplicability to long-term use at the temperature higher than 80 ℃ under the conditions of humidity and high load and the like, and is a hot spot for research on reinforcing, toughening and modifying.
Disclosure of Invention
The invention mainly aims to provide a continuous carbon nano tube composite fiber 3D printing wire rod, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a continuous carbon nano tube composite fiber 3D printing wire rod, which comprises the following components: the carbon nanotube fiber comprises stranded carbon nanotube fibers serving as a skeleton structure and thermoplastic polymers, wherein the stranded carbon nanotube fibers are formed by aggregation of a plurality of carbon nanotube fibers, the thermoplastic polymers are uniformly dispersed among the plurality of carbon nanotube fibers and wrapped on the surfaces of the plurality of carbon nanotube fibers, and the thermoplastic polymers at least bond the plurality of carbon nanotube fibers.
The embodiment of the invention also provides a preparation method of the continuous carbon nano tube composite fiber 3D printing wire rod, which comprises the following steps:
performing stranding treatment on the plurality of carbon nano tube fibers to obtain stranding carbon nano tube fibers;
and contacting the stranded carbon nanotube fibers with a thermoplastic polymer solution or a molten thermoplastic polymer to uniformly disperse the thermoplastic polymer among the plurality of carbon nanotube fibers and wrap the surfaces of the plurality of carbon nanotube fibers, thereby preparing the continuous carbon nanotube composite fiber 3D printing wire.
In some embodiments, the carbon nanotube fibers are continuous fibers prepared using a floating catalytic chemical vapor deposition process.
The embodiment of the invention also provides application of the continuous carbon nano tube composite fiber 3D printing wire in the 3D printing field.
The embodiment of the invention also provides a preparation method of the 3D printing workpiece, which comprises the following steps: and providing the continuous carbon nanotube composite fiber 3D printing wire, and printing by using 3D printing equipment to obtain the 3D printing workpiece.
Compared with the prior art, the invention has the beneficial effects that: the continuous carbon nano tube composite fiber 3D printing wire provided by the invention has higher mechanical strength; meanwhile, thermoplastic polymers (nylon polymers) can be uniformly dispersed among fiber bundles of the carbon nanotube fibers, the thermoplastic polymers serve as adhesives to bond the carbon nanotube fibers, and the adhesive plays a role in a 3D printing process, meanwhile, the preparation method of the continuous carbon nanotube composite fiber 3D printing wire is simple, is suitable for large-scale production, and provides good technical support for the application of the carbon nanotube fibers to the field of 3D printing.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIGS. 1a to 1b are surface and cross-sectional scanning electron microscope views of a continuous carbon nanotube composite fiber 3D printing wire prepared in example 1 of the present invention;
FIG. 2 is a graph showing the mechanical properties of the continuous carbon nanotube composite fiber 3D printing wire prepared in example 1 of the present invention;
FIG. 3 is a graph showing the TG pattern of 3D printing wires of continuous carbon nanotube composite fibers prepared in example 1 of the present invention;
FIG. 4 is a picture of a 3D print prepared in example 1 of the present invention;
FIG. 5 is a drawing of a tensile comparison of a 3D printed matter swatch sample and pure nylon prepared in example 2 of the present invention;
FIG. 6 is a photograph of a stretched 3D printed matter strip sample prepared in example 2 of the present invention;
FIG. 7 is a schematic flow chart of a solution process for preparing a 3D printing wire of continuous carbon nanotube composite fiber in an exemplary embodiment of the invention;
FIG. 8 is a schematic flow chart of a 3D printing wire for preparing continuous carbon nanotube composite fiber by a fusion process in an exemplary embodiment of the invention;
fig. 9 is a photograph of a continuous carbon nanotube composite fiber 3D printing wire prepared in example 1 of the present invention;
fig. 10 is a photograph of a 3D printing wire of the continuous carbon nanotube composite fiber prepared by the fusion process of example 7 of the present invention.
Detailed Description
The inventor of the present application proposes that carbon nanotube fiber is compounded with nylon before being made into fiber, and the prepared fiber belongs to composite fiber, and single carbon nanotube fiber and nylon form a uniform double-network structure, and obviously the strength of the composite fiber is obviously reduced obviously due to the influence of densification degree and nylon molecules, and the preparation method is inconvenient, and the composite fiber cannot be prepared in a large scale.
Therefore, in view of the shortages of the existing material systems and the strong demands of people for applying continuous carbon nanotube fibers to the 3D printing field, the inventor of the present invention has long studied and put forward a great deal of practice, and has aimed at providing a method for preparing a 3D printing wire (also referred to as a "continuous carbon nanotube composite fiber 3D printing wire") of a ply-twisted carbon nanotube fiber composite thermoplastic polymer (for example, nylon), which is prepared by using pure carbon nanotube fibers and thermoplastic polymers such as nylon through a solution method or a melting method, wherein the carbon nanotube fibers are coated with the thermoplastic polymers, the carbon nanotube fibers are filled with the thermoplastic polymers, and the thermoplastic polymers belong to a printing carrier. The pure carbon nanotube fibers are stranded, so that the excellent mechanical strength of the carbon nanotube fibers is reserved, and the thermoelectric performance of the carbon nanotube fibers is reserved.
The technical scheme, the implementation process, the principle and the like are further explained as follows.
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
One aspect of an embodiment of the present invention provides a continuous carbon nanotube composite fiber 3D printing wire, comprising: the carbon nanotube fiber comprises stranded carbon nanotube fibers serving as a skeleton structure and thermoplastic polymers, wherein the stranded carbon nanotube fibers are formed by aggregation of a plurality of carbon nanotube fibers, the thermoplastic polymers are uniformly dispersed among the plurality of carbon nanotube fibers and wrapped on the surfaces of the plurality of carbon nanotube fibers, and the thermoplastic polymers at least bond the plurality of carbon nanotube fibers.
In some more specific embodiments, the content of the ply-stranded carbon nanotube fiber in the continuous carbon nanotube composite fiber 3D printing wire is 40-80 wt% and the content of the thermoplastic polymer is 20-60 wt%.
In some more specific embodiments, the thermoplastic polymer includes any one or a combination of two or more of nylon, polyphenylene sulfide, polyvinyl alcohol, polylactic acid, and polyetherketoneketone, and is not limited thereto.
Further, the thermoplastic polymer includes nylon, and is not limited thereto.
In some more specific embodiments, the continuous carbon nanotube composite fiber 3D printed wire has a diameter of 400 μm.
Further, the tensile strength of the continuous carbon nano tube composite fiber 3D printing wire rod is 20-1000 MPa, preferably 100-500 MPa.
In the invention, the continuous carbon nanotube composite fiber 3D printing wire has excellent mechanical strength, and the 3D printing wire comprises ply-bonding carbon nanotube fibers and thermoplastic polymers, wherein the ply-bonding carbon nanotube fibers are uniformly distributed in the 3D printing wire to play the mechanical property advantage as a continuous fiber reinforcement; the 3D printing wire has bending resistance, maintains structural integrity after being folded thousands of times, and has tensile strength of 20-1000 MPa, preferably 100-500 MPa.
Another aspect of the embodiment of the present invention further provides a method for preparing a 3D printing wire of a continuous carbon nanotube composite fiber as described above, which includes:
performing stranding treatment on the plurality of carbon nano tube fibers to obtain stranding carbon nano tube fibers;
and contacting the stranded carbon nanotube fibers with a thermoplastic polymer solution or a molten thermoplastic polymer to uniformly disperse the thermoplastic polymer among the plurality of carbon nanotube fibers and wrap the surfaces of the plurality of carbon nanotube fibers, thereby preparing the continuous carbon nanotube composite fiber 3D printing wire.
In some more specific embodiments, the carbon nanotube fibers are continuous fibers prepared using a floating catalytic chemical vapor deposition process.
Further, the diameter of the carbon nanotube fiber is 10um to 100 um.
Further, the number of the carbon nanotube fibers in the ply-bonding carbon nanotube fibers is 2 to 200.
In some more specific embodiments, the method of making comprises: and (3) contacting the stranded carbon nano tube fibers with a thermoplastic polymer solution or a thermoplastic polymer in a molten state for compounding, and then carrying out melting treatment to obtain the continuous carbon nano tube composite fiber 3D printing wire.
Further, the thermoplastic polymer is dissolved in a solvent to form a thermoplastic polymer solution.
Further, nylon is dissolved in formic acid to form a nylon solution.
Further, the polyetherketoneketone is dissolved in dichloroacetic acid to form a polyetherketoneketone solution.
Further, polyvinyl alcohol is dissolved in water to form a polyvinyl alcohol solution.
Further, nylon is dissolved in formic acid to form a nylon solution, the nylon solution has a nylon content of 10 to 30wt%
Further, polyvinyl alcohol is dissolved in water to form a polyvinyl alcohol solution, and the content of the polyvinyl alcohol in the polyvinyl alcohol solution is 1-15 wt%.
Further, when the thermoplastic polymer is polyvinyl alcohol, the temperature of the melt-processing is 230 to 250 ℃.
Further, when the thermoplastic polymer is polyphenylene sulfide, the temperature of the melt processing is 285 to 330 ℃.
Further, when the thermoplastic polymer is polylactic acid, the temperature of the melt processing is 170 to 230 ℃.
Further, when the thermoplastic polymer is polyetherketoneketone, the temperature of the melting treatment is 305-380 ℃.
Further, the melting treatment is performed under a set temperature condition, the set temperature being greater than or equal to the melting point of the thermoplastic polymer and lower than the decomposition temperature of the thermoplastic polymer.
In the invention, the stranded carbon nano tube fibers can be dried after passing through a certain polymer solution and then enter another polymer solution, so that different layers can be formed to wrap a plurality of carbon nano tube fibers. The melting method can be used by mixing with each other, but the premise is that the polymers with similar melting points are not easy to mix, are not uniform and even are decomposed.
In some more specific embodiments, the method of preparing a continuous carbon nanotube composite fiber 3D printing wire includes: performing stranding treatment on a plurality of carbon nanotube fibers to obtain stranding carbon nanotube fibers with a certain diameter, then passing the stranding carbon nanotube fibers through nylon/formic acid solution with a certain concentration or nylon in a molten state to uniformly compound the nylon among the carbon nanotube fibers as an adhesive, and further performing melt treatment on the compound fibers through a tubular CVD (chemical vapor deposition) furnace to form a 3D printing wire rod in order to ensure uniform compound of the nylon, wherein a solution method preparation flow diagram of the prepared continuous carbon nanotube compound fiber 3D printing wire rod is shown in fig. 7; a schematic flow chart of a melting method preparation of the continuous carbon nano tube composite fiber 3D printing wire is shown in FIG. 8.
The number of the carbon nano tube fibers which are doubled is between 2 and 200, and the process has special operation equipment, so that continuous industrialized preparation can be realized.
As a preferable scheme, the concentration of the nylon solution is between 10wt% and 30wt%, so that the nylon solution and the carbon nano tube fiber are uniformly compounded.
As a preferable scheme, the nylon solution can be replaced by nylon in a molten state (the temperature of the nylon in the molten state is controlled between 230 ℃ and 280 ℃), so that the nylon solution and the carbon nano tube fibers are uniformly compounded.
Preferably, the melting treatment is performed under a set temperature condition, wherein the set temperature is greater than or equal to the melting point (220 ℃ to 260 ℃) of the nylon and is lower than the decomposition temperature 310 ℃ of the nylon.
Another aspect of the embodiment of the present invention further provides an application of the foregoing continuous carbon nanotube composite fiber 3D printing wire in the 3D printing field.
Another aspect of the embodiment of the present invention also provides a method for preparing a 3D printed workpiece, including: and providing the continuous carbon nanotube composite fiber 3D printing wire, and printing by using 3D printing equipment to obtain the 3D printing workpiece.
Furthermore, the 3D printing workpiece can meet the application requirements of various fields such as daily life, aerospace and the like.
According to the invention, the pure carbon nanotube fibers are stranded, so that not only the excellent mechanical strength of the carbon nanotube fibers is reserved, but also the thermoelectric performance of the carbon nanotube fibers is reserved, the preparation method of the 3D printing material is simple and can be used for large-scale preparation, and finally the 3D printing material shows excellent mechanical strength, and the requirement on light weight is met.
In summary, by the technical scheme, the preparation method provided by the invention has mature operation technology, the preparation method of the 3D printing wire rod is simple, and the carbon nano tube fiber composite structure can be well constructed by the composite treatment of the carbon nano tube fiber and the thermoplastic polymer solution. The thermoplastic polymer is used as the binder, so that the carbon nanotube fibers are uniformly distributed in the 3D printing wire, and the continuous fiber 3D printing wire with bending resistance and excellent mechanical property is obtained. Compared with the traditional printing wire, the printing wire has wider application value.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
(1) Performing stranding treatment on 20 carbon nanotube fibers, wherein the diameter of the carbon nanotube fibers is 20 mu m, so as to obtain stranding carbon nanotube fibers with a certain diameter;
(2) The doubled carbon nanotube fibers are passed through a 20wt% nylon/formic acid solution, so that nylon is uniformly compounded among a plurality of carbon nanotube fibers as an adhesive to obtain a preliminary 3D printing wire, the preliminary 3D printing wire is further dried by a tubular CVD furnace at a treatment temperature of 260 ℃ for 25min, and then passed through a wire drawing die with a certain aperture at a treatment temperature of 260 ℃ to obtain a 3D printing wire (namely, a continuous carbon nanotube composite fiber 3D printing wire), wherein the wire is shown in fig. 9.
(3) Printing of the 3D printed article is performed by a continuous fiber composite 3D printer to produce printed articles of different shapes (as shown in fig. 4).
The surface and cross-section scanning electron microscope diagrams of the continuous carbon nanotube composite fiber 3D printing wire rod prepared in the embodiment are shown in fig. 1 a-1 b, and the mechanical properties of the continuous carbon nanotube composite fiber 3D printing wire rod prepared in the embodiment are shown in fig. 2; TG data of the continuous carbon nanotube composite fiber 3D printing wire prepared in this example is shown in fig. 3.
Example 2
(1) Performing stranding treatment on 50 carbon nanotube fibers, wherein the diameter of the carbon nanotube fibers is 20 mu m, so as to obtain stranding carbon nanotube fibers with a certain diameter;
(2) The method comprises the steps of enabling the ply-bonding carbon nano tube fibers to pass through a nylon/formic acid solution with the weight percentage of 20% so that nylon is uniformly compounded among a plurality of carbon nano tube fibers as an adhesive to obtain a preliminary 3D printing wire, further drying the preliminary 3D printing wire through a tubular CVD furnace at the treatment temperature of 260 ℃ for 25min, and then passing through a wire drawing die with a certain aperture at the treatment temperature of 260 ℃ to obtain the 3D printing wire (namely, the 3D printing wire of the continuous carbon nano tube composite fibers);
(3) Printing a 3D printing piece by a continuous fiber composite material 3D printer, wherein the mechanical properties of the printing piece are represented by a printing strip sample, a comparison chart of the mechanical properties and the tensile properties of nylon is shown in fig. 5, and fig. 6 is a picture of the 3D printing piece after the drawing of the printing strip sample prepared in the embodiment of the invention.
Example 3
(1) Performing stranding treatment on 50 carbon nanotube fibers, wherein the diameter of the carbon nanotube fibers is 20 mu m, so as to obtain stranding carbon nanotube fibers with a certain diameter;
(2) The method comprises the steps of enabling the ply-bonding carbon nano tube fibers to pass through a nylon/formic acid solution with the weight percentage of 30% so that nylon is uniformly compounded among a plurality of carbon nano tube fibers as an adhesive to obtain a preliminary 3D printing wire, further drying the preliminary 3D printing wire through a tubular CVD furnace at the treatment temperature of 260 ℃ for 25min, and then passing through a wire drawing die with a certain aperture at the treatment temperature of 260 ℃ to obtain the 3D printing wire (namely, the 3D printing wire of the continuous carbon nano tube composite fibers);
(3) Printing the 3D printing piece by a continuous fiber composite material 3D printer to obtain the printing pieces with different shapes.
Example 4
(1) 2 carbon nano tube fibers are subjected to stranding treatment, wherein the diameter of the carbon nano tube fibers is 100 mu m, and the stranding carbon nano tube fibers with a certain diameter are obtained;
(2) The method comprises the steps of enabling the stranded carbon nano tube fibers to pass through 10wt% of polyvinyl alcohol aqueous solution, enabling polyvinyl alcohol to be used as an adhesive to be uniformly compounded among the plurality of carbon nano tube fibers, obtaining a preliminary 3D printing wire, further drying the preliminary 3D printing wire through a tubular CVD furnace at the treatment temperature of 240 ℃ for 45min, and then passing through a wire drawing die with a certain aperture at the treatment temperature of 240 ℃ to obtain the 3D printing wire (namely the stranded carbon nano tube fiber composite polyvinyl alcohol 3D printing wire);
(3) Printing the 3D printing piece by a continuous fiber composite material 3D printer to obtain the printing pieces with different shapes.
Example 5
(1) Performing stranding treatment on 100 carbon nanotube fibers, wherein the diameter of the carbon nanotube fibers is 50 mu m, so as to obtain stranding carbon nanotube fibers with a certain diameter;
(2) The method comprises the steps of enabling the stranded carbon nano tube fibers to pass through molten polylactic acid, enabling the polylactic acid to be uniformly compounded among the plurality of carbon nano tube fibers as an adhesive, obtaining a preliminary 3D printing wire rod, further rolling the preliminary 3D printing wire rod to ensure uniform compounding of the polylactic acid among the carbon nano tube fibers, and then enabling the preliminary 3D printing wire rod to pass through a wire drawing die with a certain aperture, wherein the processing temperature is 200 ℃, so that the 3D printing wire rod (namely the stranded carbon nano tube fiber composite polylactic acid 3D printing wire rod) is obtained;
(3) Printing the 3D printing piece by a continuous fiber composite material 3D printer to obtain the printing pieces with different shapes.
Example 6
(1) Performing stranding treatment on 200 carbon nanotube fibers, wherein the diameter of the carbon nanotube fibers is 10 mu m, so as to obtain stranding carbon nanotube fibers with a certain diameter;
(2) The method comprises the steps of enabling the stranded carbon nanotube fibers to pass through a 30wt% polyether ketone/dichloroacetic acid solution, enabling the polyether ketone to be uniformly compounded among a plurality of carbon nanotube fibers as an adhesive to obtain a preliminary 3D printing wire, enabling the preliminary 3D printing wire to be further subjected to drying treatment through a tubular CVD (chemical vapor deposition) furnace, wherein the treatment temperature is 330 ℃, the heating and heating process is completed for 35min, and then enabling the treatment temperature to be 330 ℃ through a wire drawing die with a certain aperture to obtain the 3D printing wire (namely the stranded carbon nanotube fiber composite polyether ketone 3D printing wire);
(3) Printing the 3D printing piece by a continuous fiber composite material 3D printer to obtain the printing pieces with different shapes.
Example 7
(1) Performing stranding treatment on 100 carbon nanotube fibers, wherein the diameter of the carbon nanotube fibers is 50 mu m, so as to obtain stranding carbon nanotube fibers with a certain diameter;
(2) The method comprises the steps of enabling the stranded carbon nano tube fibers to pass through polyphenylene sulfide in a molten state, enabling polylactic acid to be used as an adhesive to be uniformly compounded among the plurality of carbon nano tube fibers, obtaining a preliminary 3D printing wire rod, further rolling the preliminary 3D printing wire rod to ensure uniform compounding of the polylactic acid among the carbon nano tube fibers, and enabling the preliminary 3D printing wire rod to pass through a wire drawing die with a certain aperture, wherein the processing temperature is 320 ℃, so that the 3D printing wire rod (namely the stranded carbon nano tube fiber composite polyphenylene sulfide 3D printing wire rod is shown in fig. 10) is obtained;
(3) Printing the 3D printing piece by a continuous fiber composite material 3D printer to obtain the printing pieces with different shapes.
Comparative example 1
The method is the same as in example 1, except that the carbon nanotube fibers are not subjected to the stranding treatment, and the prepared composite wire has far poorer performance than the continuous carbon nanotube composite fiber 3D printing wire prepared in example 1.
In addition, the inventor also uses other raw materials listed above and other process conditions to replace various raw materials and corresponding process conditions in the above embodiments to perform corresponding tests, and also prepares the carbon nanotube fiber ply-bonding composite thermoplastic polymer 3D printing wire with excellent mechanical properties.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (6)
1. The preparation method of the continuous carbon nano tube composite fiber 3D printing wire is characterized by comprising the following steps:
performing stranding treatment on the plurality of carbon nano tube fibers to obtain stranding carbon nano tube fibers;
and contacting and compositing the stranded carbon nanotube fibers with a molten thermoplastic polymer, then carrying out rolling treatment, and uniformly dispersing the thermoplastic polymer among the plurality of carbon nanotube fibers and wrapping the thermoplastic polymer on the surfaces of the plurality of carbon nanotube fibers through a wire drawing die to prepare a continuous carbon nanotube composite fiber 3D printing wire; the wire drawing die is processed under the condition of a set temperature, wherein the set temperature is higher than or equal to the melting point of the thermoplastic polymer and lower than the decomposition temperature of the thermoplastic polymer;
wherein, continuous carbon nanotube composite fiber 3D prints the wire rod and includes: the thermoplastic polymer at least ensures that the plurality of carbon nano tube fibers are bonded; the content of the ply-bonding carbon nano tube fibers in the continuous carbon nano tube composite fiber 3D printing wire is 40-80wt% and the content of the thermoplastic polymer is 20-60wt%; the thermoplastic polymer is selected from any one of nylon, polyphenylene sulfide, polylactic acid and polyether ketone;
the diameter of the carbon nano tube fiber is 10-100 mu m; the number of the carbon nano tube fibers in the ply-bonding carbon nano tube fibers is 2-200.
2. The method of manufacturing according to claim 1, characterized in that: the carbon nanotube fiber is a continuous fiber prepared by adopting a floating catalytic chemical vapor deposition method.
3. The method of manufacturing according to claim 1, characterized in that: the thermoplastic polymer is nylon.
4. The method of manufacturing according to claim 1, characterized in that: the tensile strength of the stranded carbon nano tube fiber composite 3D printing wire is 20-1000 MPa.
5. Use of the continuous carbon nanotube composite fiber 3D printing wire prepared by the method of any one of claims 1-4 in the field of 3D printing.
6. A method of preparing a 3D printed workpiece, comprising: the continuous carbon nanotube composite fiber 3D printing wire prepared by the method of any one of claims 1-4 is printed by a 3D printing device to prepare a 3D printing workpiece.
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