Neodymium-iron-boron magnetic powder modified thermoplastic polyurethane wire, preparation method thereof and continuous carbon fiber magnetoelectric functional wire

Abstract

The invention discloses a neodymium iron boron magnetic powder modified thermoplastic polyurethane wire and a preparation method thereof, and a continuous carbon fiber magnetoelectric functional wire, and belongs to the cross technical field of additive manufacturing technology and magnetoelectric functional material preparation. The invention provides a continuous carbon fiber magnetoelectric functional wire material for 3D printing. The continuous carbon fiber magnetoelectric functional wire material comprises the following components in parts by mass: 50-70 parts of a continuous carbon fiber wire material and 30-50 parts of a neodymium iron boron magnetic powder modified thermoplastic polyurethane wire material. The continuous carbon fiber magnetoelectric functional wire material produced by the invention can be directly used for 3D printing, and has conductive and magnetic response functions at the same time. In addition, the continuous carbon fiber magnetoelectric functional wire can be directly printed into a sample piece through fused deposition forming.

Description

Technical Field

[0001] The present invention belongs to the cross-technical field of additive manufacturing technology and preparation of magnetoelectric functional materials, and specifically relates to a thermoplastic polyurethane wire modified with neodymium iron boron magnetic powder and a preparation method and application thereof, especially application in continuous carbon fiber magnetoelectric functional wire. Background Art

[0002] In recent years, due to its light weight and high strength, carbon fiber composites have become increasingly effective in replacing metal alloy material systems, especially in the field of aerospace composites. According to the length of the fiber, carbon fibers are divided into continuous fibers and chopped carbon fibers. Due to the fact that chopped carbon fibers are not connected end to end, it is difficult to significantly improve the strength of composite materials. In contrast, continuous carbon fibers have obvious anisotropy, good impact resistance, can distribute and absorb loads radially, have higher relative strength, and have a high aspect ratio. They are more widely used in the field of composite materials, especially in the field of structural materials.

[0003] In most of the current research on continuous carbon fibers, continuous carbon fibers are used as mechanical bearing components to play the role of high strength and high modulus. For example: The patent with publication number CN110576531A obtains a thermoplastic resin composite material reinforced with continuous carbon fibers by impregnating continuous carbon fibers with PEEK resin, which effectively avoids the risk of interlayer separation and provides a reliable idea for the rapid printing and manufacturing of various complex-shaped components of continuous carbon fibers. The patent with publication number CN114874605B uses a pre-impregnation process to wrap continuous carbon fibers with thermoplastic polyurethane, and then uses epoxy resin to wrap the thermoplastic polyurethane, and finally obtains a thermosetting resin composite material reinforced with continuous carbon fibers. The patent with publication number CN118771888A uses continuous carbon fibers to reinforce WC ceramics. In order to give full play to the high strength advantage of continuous carbon fibers, the patent with publication number CN115744881B loads carbon nanotubes on the surface of continuous carbon fibers to modify them, thereby enhancing the interface strength between the carbon fiber surface and the composite matrix. The patent with publication number CN107815625A uses Al 2 O 3 The surface of SiC continuous fiber was modified to obtain Al-coated 2 O 3 Coated SiC continuous fibers.

[0004] However, in addition to the characteristics of high strength and high modulus, continuous carbon fibers also have many other advantages, such as excellent electrical conductivity, electromagnetic shielding performance, etc. These advantages can give continuous carbon fibers new functions. At the same time, surface modification of continuous carbon fibers can also derive more new functions, thereby providing a basic method for the intelligent and multifunctional development of continuous carbon fiber composite materials. For example, by combining with magnetic materials, the continuous carbon fibers are given magnetic functions, and the continuous carbon fibers themselves have conductive functions, which can help continuous carbon fibers in the fields of load monitoring, energy harvesting, and 4D printing. However, in current reports, there is a lack of research work in this area. Compared with the existing technology, the conductive and magnetic response functions of continuous carbon fibers can be developed simultaneously through the design concept of magneto-electric integration.

[0005] In summary, the functionalization research of continuous carbon fiber is of great significance. The development of the conductivity characteristics can greatly enrich the application scenarios of continuous carbon fiber. Based on the conductivity characteristics, the continuous carbon fiber is given magnetic response ability to further enrich its functions. In short, the functionalization research of continuous carbon fiber will give full play to the advantages of continuous carbon fiber and provide a new technical route for the intelligent development of continuous carbon fiber. Summary of the invention

[0006] In view of the problems or defects in the above-mentioned prior art, the object of the present invention is to provide a NdFeB magnetic powder modified thermoplastic polyurethane wire and a preparation method and application thereof.

[0007] In order to achieve one of the above purposes of the present invention, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing a thermoplastic polyurethane wire modified with neodymium iron boron magnetic powder, the method specifically comprising the following steps:

[0009] (1) Material selection: the magnetic powder is selected from neodymium iron boron magnetic powder, and the thermoplastic polyurethane is selected from thermoplastic polyurethane powder;

[0010] (2) Screening: Screening the NdFeB magnetic powder and thermoplastic polyurethane powder to remove large agglomerated particles;

[0011] (3) Premixing: Preliminary mixing of the sieved NdFeB magnetic powder and thermoplastic polyurethane powder until the mixed powder presents a uniform color;

[0012] (4) Machine mixing: The preliminarily mixed powder is mixed by a powder mixer;

[0013] (5) Drying: Put the pre-mixed powder into an oven to dry;

[0014] (6) Blending: heating, melting, mixing and extruding the mixed powder after drying in step (5) through the heating and rotary shearing action of a twin-screw extruder to obtain a preliminary filament;

[0015] (7) Cooling: Cooling the extruded wire to room temperature through a fan;

[0016] (8) Granulation: The cooled wire is cut into granules by a cutting machine, and the particle size is 0.5-4 mm;

[0017] (9) Wire preparation: The particles obtained in step (8) are extruded into wires through a single screw extruder, and the extruded wires are cooled by water cooling. The diameter of the wires is 1.65-1.85 mm.

[0018] Furthermore, in some embodiments, the mass ratio of the NdFeB magnetic powder to the thermoplastic polyurethane powder in step (1) is 2:8-7:3.

[0019] Furthermore, in some embodiments, the NdFeB magnetic powder in step (1) is selected from NdFeB powder of 800-2000 mesh; the thermoplastic polyurethane is selected from thermoplastic polyurethane powder of 500-1200 mesh, and its number average molecular weight is 50,000-100,000.

[0020] Furthermore, in some embodiments, the size of the sieve used for screening in step (1) does not exceed 200 mesh.

[0021] Furthermore, in some embodiments, the stirring speed of the powder mixer in step (4) is 200 r / min, and the stirring time is 2 hours.

[0022] Furthermore, in some embodiments, the drying temperature in step (5) is 80-105° C., and the drying time is 2-7 hours.

[0023] Furthermore, in some embodiments, in the twin-screw extruder in step (6), the temperature of zone 1 is 138-147°C, the temperature of zone 2 is 142-150°C, the temperature of zone 3 is 142-150°C, the temperature of zone 4 is 142-148°C, the temperature of zone 5 is 142-148°C, and the temperature of the die head is 140-148°C.

[0024] Furthermore, in some embodiments, the diameter of the wire in step (6) is 0.5-2 mm.

[0025] Furthermore, in some embodiments, during the wire preparation process of step (9), the temperature of zone 1 in the single screw extruder is 128-138°C, the temperature of zone 2 is 134-145°C, and the temperature of zone 3 is 123-135°C.

[0026] The second object of the present invention is to provide a thermoplastic polyurethane wire material modified with NdFeB magnetic powder prepared by the above method.

[0027] The third object of the present invention is to provide the use of the NdFeB magnetic powder modified thermoplastic polyurethane wire prepared by the above method in the preparation of continuous carbon fiber magnetoelectric functional wire.

[0028] Furthermore, in some embodiments, the continuous carbon fiber magnetoelectric functional filament described above can be directly used for 3D printing.

[0029] The fourth object of the present invention is to provide a continuous carbon fiber magnetoelectric functional wire for 3D printing, wherein the continuous carbon fiber magnetoelectric functional wire is composed by mass: 50 to 70 parts of continuous carbon fiber wire and 30 to 50 parts of thermoplastic polyurethane wire modified by neodymium iron boron magnetic powder.

[0030] Furthermore, in some embodiments, the continuous carbon fiber filaments are 1 / 4K-48K carbon fibers. For example, the continuous carbon fiber filaments may be one or more of 1 / 4K, 1 / 3K, 1 / 2K, 1K, 3K, 6K, 12K, 24K, 48K, etc.

[0031] The fifth object of the present invention is to provide a method for preparing the above-mentioned continuous carbon fiber magnetoelectric functional wire for 3D printing, which is prepared by a prepreg method.

[0032] Furthermore, in some embodiments, the method steps are as follows:

[0033] a. Fix the continuous carbon fiber wire on the left roller frame of the prepreg equipment, and fix the thermoplastic polyurethane wire modified by NdFeB magnetic powder on the right roller frame of the prepreg equipment;

[0034] b. Set the working temperature of the prepreg equipment to 300-330°C, set the traction speed of the NdFeB magnetic powder-modified thermoplastic polyurethane wire to 0.6-1.5r / min, and set the traction speed of the continuous carbon fiber magnetoelectric functional wire to 0.05-0.25r / min; the NdFeB magnetic powder-modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction; at the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool; in this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder-modified thermoplastic polyurethane, and after the wire passes through the molten pool, the NdFeB magnetic powder-modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, the continuous carbon fiber magnetoelectric functional wire is obtained.

[0035] The continuous carbon fiber magnetoelectric functional wire produced by the present invention can be directly used for 3D printing, and has the functions of conducting electricity and magnetic response. In addition, the continuous carbon fiber magnetoelectric functional wire can be directly used for printing samples through fused deposition modeling.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The conductive ability of continuous carbon fibers will be demonstrated, which will greatly enrich the application scenarios of continuous carbon fibers;

[0038] (2) Endowing continuous carbon fiber with magnetic sensing function further expands the use demand of continuous carbon fiber and lays the foundation for the intelligent and multifunctional development of continuous carbon fiber;

[0039] (3) The design concept of magneto-electric integration will enable continuous carbon fiber to have both electrical conductivity and magnetic response capabilities, providing assistance for continuous carbon fiber in load monitoring, energy harvesting, 4D printing and other fields;

[0040] (4) The prepared continuous carbon fiber magnetoelectric functional filament can be directly used for 3D printing and has good structural designability. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 Resistance test diagram of the continuous carbon fiber magnetoelectric functional wire prepared in Example 1;

[0042] Figure 2 A graph showing the relationship between the voltage of the continuous carbon fiber magnetoelectric functional wire prepared in Example 1 and the time under the condition of continuous deformation;

[0043] Figure 3 A diagram showing the magnetic response capability of the continuous carbon fiber magnetoelectric functional wire prepared in Example 2;

[0044] Figure 4 Optical photograph of the 3D printed part of the continuous carbon fiber magnetoelectric functional filament prepared in Example 3. DETAILED DESCRIPTION

[0045] The present invention is further described in detail below through implementation cases. The technical scheme in the embodiments of the present invention will be clearly and completely described below in combination with the drawings, technical process steps, specific implementation conditions and materials in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] The NdFeB magnetic powders used in the following embodiments of the present invention were purchased from Guangzhou Xinnod Transmission Parts Co., Ltd., and the size was 400 mesh.

[0047] The thermoplastic polyurethane powder used in the following examples of the present invention was purchased from Shanghai Kaiyang Plastic Chemical Co., Ltd., and its number average molecular weight is 100,000.

[0048] Example 1

[0049] The preparation method of a NdFeB magnetic powder-modified thermoplastic polyurethane wire of this embodiment comprises the following steps:

[0050] Weigh 500g of NdFeB magnetic powder and 1000g of thermoplastic polyurethane powder and put them into two different 200-mesh sieves for screening to remove large agglomerated particles, and then use manual labor to preliminarily mix the sieved NdFeB magnetic powder and thermoplastic polyurethane powder until the mixed powder presents a uniform color. Then put the preliminarily mixed powder into a powder mixer and stir it at a speed of 200r / min for 2 hours for pre-mixing; then put the pre-mixed powder into an oven for drying for 2-7 hours at a drying temperature of 80-105°C. Through the heating and rotary shearing action of the twin-screw extruder, the dried mixed powder is heated, melted, mixed and extruded to obtain a preliminary wire with a diameter of 0.5-2mm; wherein: the temperature of the first zone of the twin-screw extruder is 138-147°C, the temperature of the second zone is 142-150°C, the temperature of the third zone is 142-150°C, the temperature of the fourth zone is 142-148°C, the temperature of the fifth zone is 142-148°C, and the temperature of the die head is 140-148°C. The extruded wire is cooled to room temperature by a fan, and then the cooled wire is sheared into particles by a cutter, and the particle size is 0.5-4mm. Finally, the obtained particles are extruded through a single screw extruder to obtain wires, wherein the temperature of zone 1 of the single screw extruder is 128-138°C, the temperature of zone 2 is 134-145°C, and the temperature of zone 3 is 123-135°C; finally, the extruded wire is cooled by water cooling, and the diameter of the wire is 1.65-1.85mm.

[0051] Example 2

[0052] The preparation method of a NdFeB magnetic powder-modified thermoplastic polyurethane wire of this embodiment comprises the following steps:

[0053] Weigh 800g of NdFeB magnetic powder and 2000g of thermoplastic polyurethane powder and put them into two different 200-mesh sieves for screening to remove large agglomerated particles, and then use manual labor to preliminarily mix the sieved NdFeB magnetic powder and thermoplastic polyurethane powder until the mixed powder presents a uniform color. Then put the preliminarily mixed powder into a powder mixer and stir it at a speed of 200r / min for 2 hours for pre-mixing; then put the pre-mixed powder into an oven for drying for 2-7 hours at a drying temperature of 80-105°C. Through the heating and rotary shearing action of the twin-screw extruder, the dried mixed powder is heated, melted, mixed and extruded to obtain a preliminary wire with a diameter of 0.5-2mm; wherein: the temperature of the first zone of the twin-screw extruder is 138-147°C, the temperature of the second zone is 142-150°C, the temperature of the third zone is 142-150°C, the temperature of the fourth zone is 142-148°C, the temperature of the fifth zone is 142-148°C, and the temperature of the die head is 140-148°C. The extruded wire is cooled to room temperature by a fan, and then the cooled wire is sheared into particles by a cutter, and the particle size is 0.5-4mm. Finally, the pellets are extruded through a single screw extruder to obtain wires, wherein the temperature of zone 1 of the single screw extruder is 128-138°C, the temperature of zone 2 is 134-145°C, and the temperature of zone 3 is 123-135°C. The extruded wires are cooled by water cooling, and the diameter of the wires is 1.65-1.85 mm.

[0054] Example 3

[0055] The preparation method of a NdFeB magnetic powder-modified thermoplastic polyurethane wire of this embodiment comprises the following steps:

[0056] Weigh 1000g of NdFeB magnetic powder and 4000g of thermoplastic polyurethane powder and put them into two different 200-mesh sieves for screening to remove large agglomerated particles, and then use manual labor to preliminarily mix the sieved NdFeB magnetic powder and thermoplastic polyurethane powder until the mixed powder presents a uniform color. Then put the preliminarily mixed powder into a powder mixer and stir it at a speed of 200r / min for 2 hours for pre-mixing; then put the pre-mixed powder into an oven for drying for 2-7 hours at a drying temperature of 80-105°C. Through the heating and rotary shearing action of the twin-screw extruder, the dried mixed powder is heated, melted, mixed and extruded to obtain a preliminary wire with a diameter of 0.5-2mm; wherein: the temperature of the first zone of the twin-screw extruder is 138-147°C, the temperature of the second zone is 142-150°C, the temperature of the third zone is 142-150°C, the temperature of the fourth zone is 142-148°C, the temperature of the fifth zone is 142-148°C, and the temperature of the die head is 140-148°C. The extruded wire is cooled to room temperature by a fan, and then the cooled wire is sheared into particles by a cutter, and the particle size is 0.5-4mm. Finally, the pellets are extruded through a single screw extruder to obtain wires, wherein the temperature of zone 1 of the single screw extruder is 128-138°C, the temperature of zone 2 is 134-145°C, and the temperature of zone 3 is 123-135°C. The extruded wires are cooled by water cooling, and the diameter of the wires is 1.65-1.85 mm.

[0057] Application Example 1

[0058] This application example provides a continuous carbon fiber magnetoelectric functional wire material, the raw material ratio of which is: 60 parts by mass of continuous carbon fiber wire material and 40 parts by mass of NdFeB magnetic powder-modified thermoplastic polyurethane wire material. The NdFeB magnetic powder-modified thermoplastic polyurethane wire material in this ratio is the NdFeB magnetic powder-modified thermoplastic polyurethane wire material prepared by the method of Example 1.

[0059] The specific preparation method of the continuous carbon fiber magnetoelectric functional wire is as follows:

[0060] The continuous carbon fiber filaments are fixed on the left roller frame of the prepreg equipment, and the thermoplastic polyurethane filaments modified by NdFeB magnetic powder are fixed on the right roller frame of the prepreg equipment.

[0061] The working temperature of the prepreg equipment is set to 300-330℃, the pulling speed of the NdFeB magnetic powder modified thermoplastic polyurethane wire is set to 0.6-1.5r / min, and the pulling speed of the continuous carbon fiber magnetoelectric functional wire is set to 0.05-0.25r / min. The NdFeB magnetic powder modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction. At the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool. In this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder modified thermoplastic polyurethane. After the wire passes through the molten pool, the NdFeB magnetic powder modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber.

[0062] Application Example 2

[0063] This application example provides a continuous carbon fiber magnetoelectric functional wire material, the raw material ratio of which is: 70 parts by mass of continuous carbon fiber wire material and 30 parts by mass of NdFeB magnetic powder-modified thermoplastic polyurethane wire material. The NdFeB magnetic powder-modified thermoplastic polyurethane wire material in this ratio is the NdFeB magnetic powder-modified thermoplastic polyurethane wire material prepared by the method of Example 1.

[0064] The specific preparation method of the continuous carbon fiber magnetoelectric functional wire is as follows:

[0065] The continuous carbon fiber filaments are fixed on the left roller frame of the prepreg equipment, and the thermoplastic polyurethane filaments modified by NdFeB magnetic powder are fixed on the right roller frame of the prepreg equipment.

[0066] The working temperature of the prepreg equipment is set to 300-330℃, the traction speed of the NdFeB magnetic powder modified thermoplastic polyurethane wire is set to 0.6-1.5r / min, and the traction speed of the continuous carbon fiber magnetoelectric functional wire is set to 0.05-0.25r / min. The NdFeB magnetic powder modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction. At the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool. In this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder modified thermoplastic polyurethane. After the wire passes through the molten pool, the NdFeB magnetic powder modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, a continuous carbon fiber magnetoelectric functional wire that can be used for 3D printing is obtained.

[0067] The continuous carbon fiber magnetoelectric functional wire prepared in this application example is tested for resistance: 5-15 cm of continuous carbon fiber magnetoelectric functional wire is taken, its two ends are connected to the two ends of the multimeter respectively, and the gear is adjusted to the resistance gear to test its resistance. The test results are shown in the figure Figure 1 ,From the test results, it can be seen that the resistance of the selected continuous carbon fiber is 48.3 ohms.

[0068] In order to further demonstrate its conductive ability, a section of continuous carbon fiber magnetoelectric functional wire prepared in this application example is cut and rolled into a coil of 5-10 turns. Then, a pulling force (0.5-3N) of the same magnitude and opposite direction is applied to the left and right sides of the coil at the same time, so that the coil is deformed and an electrical signal is generated by the principle of electromagnetic induction. Repeating the process of applying the pulling force multiple times can repeatedly produce deformation and restore deformation. During the process of applying the pulling force, the two ends of the coil are connected to the two ends of the voltmeter, and the measured voltage changes with time as shown in Figure 2 As shown in the test results, it can be seen that when no tension is applied, the voltage value is 0 and remains unchanged. When the tension is gradually increased, the voltage value also gradually increases. Then, when the tension is reduced, the voltage signal also gradually decreases until it drops to 0.

[0069] Application Example 3

[0070] This application example provides a continuous carbon fiber magnetoelectric functional wire material, the raw material ratio of which is: 65 parts by mass of continuous carbon fiber wire material and 35 parts by mass of NdFeB magnetic powder-modified thermoplastic polyurethane wire material. The NdFeB magnetic powder-modified thermoplastic polyurethane wire material in this ratio is the NdFeB magnetic powder-modified thermoplastic polyurethane wire material prepared by the method of Example 2.

[0071] The preparation method of the continuous carbon fiber magnetoelectric functional wire material is as follows:

[0072] The continuous carbon fiber filaments are fixed on the left roller frame of the prepreg equipment, and the thermoplastic polyurethane filaments modified by NdFeB magnetic powder are fixed on the right roller frame of the prepreg equipment.

[0073] The working temperature of the prepreg equipment is set to 300-330℃, the traction speed of the NdFeB magnetic powder modified thermoplastic polyurethane wire is set to 0.6-1.5r / min, and the traction speed of the continuous carbon fiber magnetoelectric functional wire is set to 0.05-0.25r / min. The NdFeB magnetic powder modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction. At the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool. In this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder modified thermoplastic polyurethane. After the wire passes through the molten pool, the NdFeB magnetic powder modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, a continuous carbon fiber magnetoelectric functional wire that can be used for 3D printing is obtained.

[0074] Application Example 4

[0075] This embodiment provides a continuous carbon fiber magnetoelectric functional wire material, the raw material ratio of which is: 70 parts by mass of continuous carbon fiber wire material and 30 parts by mass of NdFeB magnetic powder modified thermoplastic polyurethane wire material. The NdFeB magnetic powder modified thermoplastic polyurethane wire material in this ratio is the NdFeB magnetic powder modified thermoplastic polyurethane wire material prepared by the method of Example 2.

[0076] The preparation method of the continuous carbon fiber magnetoelectric functional wire is as follows:

[0077] The continuous carbon fiber filaments are fixed on the left roller frame of the prepreg equipment, and the thermoplastic polyurethane filaments modified by NdFeB magnetic powder are fixed on the right roller frame of the prepreg equipment.

[0078] The working temperature of the prepreg equipment is set to 300-330℃, the traction speed of the NdFeB magnetic powder modified thermoplastic polyurethane wire is set to 0.6-1.5r / min, and the traction speed of the continuous carbon fiber magnetoelectric functional wire is set to 0.05-0.25r / min. The NdFeB magnetic powder modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction. At the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool. In this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder modified thermoplastic polyurethane. After the wire passes through the molten pool, the NdFeB magnetic powder modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, a continuous carbon fiber magnetoelectric functional wire that can be used for 3D printing is obtained.

[0079] The schematic diagram of the magnetic response function of the prepared continuous carbon fiber magnetoelectric functional wire is shown in Figure 3The testing process is as follows: when the magnetic block is close to the continuous carbon fiber magnetoelectric functional wire, the continuous carbon fiber magnetoelectric functional wire quickly moves toward the magnetic block and is finally adsorbed on the surface of the magnetic block. As the magnetic block rotates, the continuous carbon fiber magnetoelectric functional wire is firmly attached to the magnetic block and can even be upside down.

[0080] Application Example 5

[0081] This embodiment provides a continuous carbon fiber magnetoelectric functional wire material, the raw material ratio of which is: 70 parts by mass of continuous carbon fiber wire material and 30 parts by mass of NdFeB magnetic powder modified thermoplastic polyurethane wire material. The NdFeB magnetic powder modified thermoplastic polyurethane wire material in this ratio is the NdFeB magnetic powder modified thermoplastic polyurethane wire material prepared by the method of Example 3.

[0082] The preparation method of the continuous carbon fiber magnetoelectric functional wire is as follows: the continuous carbon fiber wire is fixed on the left roller frame of the prepreg equipment, and the NdFeB magnetic powder modified thermoplastic polyurethane wire is fixed on the right roller frame of the prepreg equipment.

[0083] The working temperature of the prepreg equipment is set to 300-330℃, the traction speed of the NdFeB magnetic powder modified thermoplastic polyurethane wire is set to 0.6-1.5r / min, and the traction speed of the continuous carbon fiber magnetoelectric functional wire is set to 0.05-0.25r / min. The NdFeB magnetic powder modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction. At the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool. In this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder modified thermoplastic polyurethane. After the wire passes through the molten pool, the NdFeB magnetic powder modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, a continuous carbon fiber magnetoelectric functional wire that can be used for 3D printing is obtained.

[0084] Application Example 6

[0085] This embodiment provides a continuous carbon fiber magnetoelectric functional wire material, and the raw material ratio thereof is: 50 parts by mass of continuous carbon fiber wire material and 50 parts by mass of NdFeB magnetic powder-modified thermoplastic polyurethane wire material. The NdFeB magnetic powder-modified thermoplastic polyurethane wire material in this ratio is the NdFeB magnetic powder-modified thermoplastic polyurethane wire material prepared by the method of Example 3.

[0086] The preparation method of the continuous carbon fiber magnetoelectric functional wire is as follows:

[0087] The continuous carbon fiber filaments are fixed on the left roller frame of the prepreg equipment, and the thermoplastic polyurethane filaments modified by NdFeB magnetic powder are fixed on the right roller frame of the prepreg equipment.

[0088] The working temperature of the prepreg equipment is set to 300-330℃, the traction speed of the NdFeB magnetic powder modified thermoplastic polyurethane wire is set to 0.6-1.5r / min, and the traction speed of the continuous carbon fiber magnetoelectric functional wire is set to 0.05-0.25r / min. The NdFeB magnetic powder modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction. At the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool. In this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder modified thermoplastic polyurethane. After the wire passes through the molten pool, the NdFeB magnetic powder modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, a continuous carbon fiber magnetoelectric functional wire that can be used for 3D printing is obtained.

[0089] The continuous carbon fiber magnetoelectric functional wire prepared in this application example can be directly used for 3D printing, and the obtained printed part is as follows: Figure 4 As shown. The printing process is: first, the model shape to be printed is constructed by modeling software such as 3DMAX, and then converted into a file in stl format. Next, the gcode file is obtained by slicing software such as Ultimaker Cura. The prepared continuous carbon fiber magnetoelectric functional filament is placed in the fused deposition molding device, and the temperature of the print head is set to 190-230℃. Finally, the fused deposition molding device is started for printing.

[0090] Technical personnel should note that although the present invention has been described according to the above specific implementation methods, the inventive concept of the present invention is not limited to this invention, and any modification using the inventive concept will be included in the scope of protection of this patent.

Claims

1. A method for preparing a thermoplastic polyurethane wire modified with neodymium iron boron magnetic powder, characterized in that: The method specifically comprises the following steps: (1) Material selection: the magnetic powder is selected from neodymium iron boron magnetic powder, and the thermoplastic polyurethane is selected from thermoplastic polyurethane powder; (2) Screening: Screening the NdFeB magnetic powder and thermoplastic polyurethane powder to remove large agglomerated particles; (3) Premixing: Preliminary mixing of the sieved NdFeB magnetic powder and thermoplastic polyurethane powder until the mixed powder presents a uniform color; (4) Machine mixing: The preliminarily mixed powder is mixed by a powder mixer; (5) Drying: Put the pre-mixed powder into an oven to dry; (6) Blending: heating, melting, mixing and extruding the mixed powder after drying in step (5) through the heating and rotary shearing action of a twin-screw extruder to obtain a preliminary filament; (7) Cooling: Cooling the extruded wire to room temperature through a fan; (8) Granulation: The cooled wire is cut into granules by a cutting machine, and the particle size is 0.5-4 mm; (9) Wire preparation: The particles obtained in step (8) are extruded into wires through a single screw extruder, and the extruded wires are cooled by water cooling. The diameter of the wires is 1.65-1.85 mm.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the NdFeB magnetic powder to the thermoplastic polyurethane powder in step (1) is 2:8-7:

3.

3. The preparation method according to claim 1, characterized in that: The NdFeB magnetic powder in step (1) is selected from NdFeB powder of 800-2000 mesh; the thermoplastic polyurethane is selected from thermoplastic polyurethane powder of 500-1200 mesh, and the number average molecular weight is 50,000-100,000.

4. The preparation method according to claim 1, characterized in that: In step (6), the temperature of zone 1 in the twin-screw extruder is 138-147°C, the temperature of zone 2 is 142-150°C, the temperature of zone 3 is 142-150°C, the temperature of zone 4 is 142-148°C, the temperature of zone 5 is 142-148°C, and the temperature of the die head is 140-148°C.

5. The preparation method according to claim 1, characterized in that: In the wire preparation process of step (9), the temperature of zone 1 in the single screw extruder is 128-138°C, the temperature of zone 2 is 134-145°C, and the temperature of zone 3 is 123-135°C.

6. Thermoplastic polyurethane wire modified with NdFeB magnetic powder prepared according to the preparation method according to any one of claims 1 to 5.

7. Use of the NdFeB magnetic powder-modified thermoplastic polyurethane wire prepared by the preparation method according to any one of claims 1 to 5 in the preparation of continuous carbon fiber magnetoelectric functional wire.

8. A continuous carbon fiber magnetoelectric functional wire for 3D printing, characterized in that: The continuous carbon fiber magnetoelectric functional wire is composed of 50 to 70 parts of continuous carbon fiber wire and 30 to 50 parts of NdFeB magnetic powder-modified thermoplastic polyurethane wire by mass; wherein the NdFeB magnetic powder-modified thermoplastic polyurethane wire is the NdFeB magnetic powder-modified thermoplastic polyurethane wire prepared by the preparation method described in any one of claims 1 to 5.

9. The continuous carbon fiber magnetoelectric functional wire for 3D printing according to claim 8, characterized in that: The continuous carbon fiber filament is 1 / 4K-48K carbon fiber.

10. The method for preparing the continuous carbon fiber magnetoelectric functional wire for 3D printing according to claim 8 or 9, characterized in that: Here are the steps: a. Fix the continuous carbon fiber wire on the left roller frame of the prepreg equipment, and fix the thermoplastic polyurethane wire modified by NdFeB magnetic powder on the right roller frame of the prepreg equipment; b. Set the working temperature of the prepreg equipment to 300-330°C, set the traction speed of the NdFeB magnetic powder-modified thermoplastic polyurethane wire to 0.6-1.5r / min, and set the traction speed of the continuous carbon fiber magnetoelectric functional wire to 0.05-0.25r / min; the NdFeB magnetic powder-modified thermoplastic polyurethane wire melts at the working temperature, and the molten wire enters the molten pool of the prepreg equipment under the action of traction; at the same time, the continuous carbon fiber wire also enters the molten pool under the action of traction, and is continuously pulled out of the molten pool; in this process, the surface of the continuous carbon fiber is wrapped by the molten NdFeB magnetic powder-modified thermoplastic polyurethane, and after the wire passes through the molten pool, the NdFeB magnetic powder-modified thermoplastic polyurethane on its surface is quickly cooled at room temperature, and finally completely solidified on the surface of the continuous carbon fiber. Finally, the continuous carbon fiber magnetoelectric functional wire is obtained.

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