CN113897042A - 3D printing wavy structure shape memory composite material and preparation method thereof - Google Patents
3D printing wavy structure shape memory composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a 3D printing wavy structure shape memory composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) pre-baking 50-70 parts of polylactic acid, 30-50 parts of thermoplastic polyurethane, 5-8 parts of multi-walled carbon nano tubes, 3 parts of iron-nickel alloy powder, 3 parts of nano-scale transition element-doped super-magnetic particles and 2 parts of nano-scale conductive copper powder/silver powder; (2) mechanically mixing the pre-dried raw materials to prepare a 3D printing wire; (3) and designing a 3D printing path of the wave structure, and printing to obtain the shape memory composite material. The composite material has excellent mechanical property, shape memory property and low-frequency magnetic field electromagnetic shielding property, and the electromagnetic shielding property of the low-frequency magnetic field is changed along with the change of the shape of the whole structure, so that dynamic magnetic field shielding property is generated.
Description
Technical Field
The invention relates to the technical field of 3D printing preparation of composite materials, in particular to a 3D printing wavy structure shape memory composite material and a preparation method thereof.
Background
In recent years, the problems of electromagnetic pollution, electromagnetic interference and the like caused by low-frequency electromagnetic radiation generated by electronic equipment in the application process are increasingly prominent, the low-frequency magnetic field (< 100kHz) has great influence on the physiology of animals, the harm of the electromagnetic radiation can be effectively reduced through the electromagnetic shielding material, and the interference on the stability of the electronic equipment is reduced. The electromagnetic shielding of the low-frequency electromagnetic shielding material is mainly based on internal absorption loss, and the absorption loss does not interfere with the stability of other equipment, so that the low-frequency electromagnetic shielding material is an ideal shielding mode. The preparation of the low-frequency electromagnetic shielding material needs to add a material with high magnetic conductivity and high electric conductivity, and simultaneously, the magnetic saturation phenomenon is prevented and the electric conductivity of the composite material is improved so as to achieve better low-frequency electromagnetic shielding effect.
The 3D printing nano particle shape memory polymer composite material has wide application prospect in the field of electromagnetic shielding due to the advantages of light weight, easy processing, controllable shielding effectiveness, excellent mechanical property and the like, and compared with the traditional pure metal-based electromagnetic shielding material, the conductive polymer-based composite material prepared by mixing carbon nano particles and metal particles has lower cost and better shielding effect. At present, the preparation of the composite material with a special structure is realized by utilizing melt extrusion type (FDM)3D printing, the shape memory and the electromagnetic shielding performance are combined, the structure of the composite material is changed by the stimulus response behavior of the nano particle shape memory polymer composite material to the temperature, the electromagnetic shielding effectiveness is changed along with the change of the shape, and the requirements under different electromagnetic shielding environments can be met. The existing method for preparing the functional composite material has the disadvantages of complex flow, high cost and slow preparation, and cannot meet the requirement of quickly and efficiently preparing the composite material with special functions and special structures.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a 3D printing wavy structure shape memory composite material and a preparation method thereof. The 3D printing wavy structure shape memory composite material with the controllable low-frequency electromagnetic shielding performance based on the FDM forming technology has innovativeness and research significance.
The technical scheme of the invention is as follows:
A3D printing wavy structure shape memory composite material comprises the following raw materials in parts by weight:
the average particle size of the polylactic acid is 40-50 μm; the average particle size of the thermoplastic polyurethane is 30-35 mu m; the diameter of the multi-walled carbon nano-tube is 3-15 nm, and the length of the multi-walled carbon nano-tube is 15-30 mu m; the average particle size of the iron-nickel alloy powder is 50-80 nm; the average grain diameter of the nano-grade conductive copper powder/silver powder is 50-100 nm; the average particle size of the nano-grade transition element-doped super-magnetic particles is 60-120 nm; the nano-grade transition element-doped super-magnetic particle is Nd-Fe3O4,Gd-Fe3O4、Zr-Fe3O4、Mo-Fe3O4、V-Fe3O4、Cr-Fe3O4、Mn-Fe3O4、Co-Fe3O4One or more of (a).
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) weighing 50-70 parts of polylactic acid (PLA), 30-50 parts of Thermoplastic Polyurethane (TPU), 5-8 parts of multi-walled carbon nanotubes (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50), 3 parts of nano-scale transition element-doped super-magnetic particles and 2 parts of nano-scale conductive copper powder/silver powder according to a ratio, and then respectively placing the weighed materials into an oven for pre-baking;
(2) mechanically mixing the pre-dried raw materials, adding the raw materials into a feed inlet of a single-screw extruder, starting the extruder for preheating, adjusting the preheating temperature, the extrusion head temperature and the extrusion speed of the single-screw extruder, and extruding the raw materials after melt blending to prepare 3D printing wires with uniform diameters;
(3) the 3D who designs wave structure prints the route to carry out the printing of wave structure combined material, the in-process observation sample so that the adjustment parameter improves and prints the quality, and the back is revised and is printed the parameter and carry out combined material's preparation, finally makes 3D who possesses controllable low frequency electromagnetic shield performance and prints wave structure shape memory combined material.
In the step (1), the pre-drying temperature is 65-70 ℃, and the pre-drying time is 8-10 h.
In the step (2), the rotation speed of the mechanical mixing is 700-800 r/min, and the time is 1.5-2 h.
In the step (2), the preheating time of the single-screw extruder is 0.5h, the preheating temperature is 205-215 ℃, the temperature of an extrusion head is 175-185 ℃, and the extrusion speed is 80-100 r/min.
In the step (2), the diameter of the 3D printing wire is 1.75 +/-0.1 mm.
In the step (3), the parameters of 3D printing are: the temperature of the printing nozzle is 215-225 ℃, the height of the printing layer is 0.4-0.6 mm, the diameter of the printing nozzle is 1mm, and the temperature of the printing platform is 60-65 ℃.
In the step (3), an FDM 3D printer is adopted for 3D printing, the preheating temperature is 180-220 ℃, and the preheating time is 2 min.
In the step (3), the wave interval of the wave structure is 10-40 mm; wave spacing is the spacing between two peaks.
The beneficial technical effects of the invention are as follows:
the composite material has excellent mechanical property, shape memory property and low-frequency electromagnetic shielding property, and the low-frequency electromagnetic shielding effectiveness is changed along with the change of the shape, thereby playing the role of dynamic low-frequency magnetic shielding effect.
The invention adopts iron-nickel alloy (Fe/Ni 50/50) and nano-grade copper powder as high-permeability materials, can increase internal absorption loss so as to achieve the aim of low-frequency electromagnetic shielding, and simultaneously adds a certain amount of multi-walled carbon nanotubes (MWCNT) in order to prevent the magnetic saturation phenomenon and improve the conductivity of the composite material so as to achieve better low-frequency electromagnetic shielding effect. The magnetism of the super-magnetic particles doped with the nano-scale transition elements is greatly enhanced, and the super-magnetic particles play a key role in improving the shielding effectiveness of a low-frequency magnetic field.
The preparation method of the composite material utilizes the FDM 3D printing technology, and has the advantages of simple material forming process, environmental protection, material saving, short preparation flow and high finished product quality.
Drawings
FIG. 1 is a schematic diagram of a printing path of a wave structure provided in embodiment 1 of the present invention;
fig. 2 is a schematic diagram of a shape memory recovery process according to embodiment 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 50 parts of polylactic acid (PLA), 50 parts of Thermoplastic Polyurethane (TPU), 5 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-grade V-Fe3O4And 2 parts of nano-scale conductive copper powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 10 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 800r/min for 2h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 210 ℃, the temperature of an extrusion head to 180 ℃ and the extrusion speed to 100r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameters;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file, wherein the printing path is shown in FIG. 1;
the parameters for 3D printing are: the temperature of a printing nozzle is 220 ℃, the height of a printing layer is 0.4mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material. The product of this example was shaped by heating in a water bath, shaping by cooling at room temperature, heating in a water bath, and the shape memory recovery process was recorded, with the results of the performance tests shown in table 1.
TABLE 1
As can be seen from Table 1, the shape memory recovery process of the composite material of the embodiment is shown in FIG. 2, the composite material formed by stretching a 90-degree wave structure to 150 degrees can complete the shape recovery within 10s at 65 ℃, and the shielding effect of the composite material of the invention in the range of 10kHZ to 150kHZ is tested by the method in GJB 8820-.
Example 2
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 50 parts of polylactic acid (PLA), 50 parts of Thermoplastic Polyurethane (TPU), 6 parts of multi-wall carbon nano-tube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-grade Zr-Fe3O4And 2 parts of nano-scale conductive copper powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 9 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 780r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 205 ℃, the temperature of an extrusion head to 175 ℃ and the extrusion speed to 90r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 215 ℃, the height of a printing layer is 0.5mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 3
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 50 parts of polylactic acid (PLA), 50 parts of Thermoplastic Polyurethane (TPU), 8 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-scale Co-Fe3O4And 2 parts of nano-scale silver powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 8 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 700r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 215 ℃, the temperature of an extrusion head to 185 ℃ and the extrusion speed to 80r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 225 ℃, the height of a printing layer is 0.6mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 4
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 60 parts of polylactic acid (PLA), 40 parts of Thermoplastic Polyurethane (TPU), 5 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano Nd-Fe3O4And 2 parts of nano-scale silver powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 10 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 800r/min for 2h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 210 ℃, the temperature of an extrusion head to 180 ℃ and the extrusion speed to 100r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameters;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 220 ℃, the height of a printing layer is 0.4mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 5
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 60 parts of polylactic acid (PLA), 40 parts of Thermoplastic Polyurethane (TPU), 6 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano Nd-Fe3O4And 2 parts of nano-scale conductive copper powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 9 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 780r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 205 ℃, the temperature of an extrusion head to 175 ℃ and the extrusion speed to 90r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 215 ℃, the height of a printing layer is 0.5mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 6
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 60 parts of polylactic acid (PLA), 40 parts of Thermoplastic Polyurethane (TPU), 8 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-scale Cr-Fe3O4And 2 parts of nano-scale conductive copper powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 8 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 700r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 215 ℃, the temperature of an extrusion head to 185 ℃ and the extrusion speed to 80r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 225 ℃, the height of a printing layer is 0.6mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 7
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 70 parts of polylactic acid (PLA), 30 parts of Thermoplastic Polyurethane (TPU), 5 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-grade V-Fe3O42 parts of nano-scale conductive copper powder are weighed according to the proportionAfter being dried, the mixture is respectively put into a drying oven to be pre-dried for 10 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 800r/min for 2h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 210 ℃, the temperature of an extrusion head to 180 ℃ and the extrusion speed to 100r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameters;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 220 ℃, the height of a printing layer is 0.4mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 8
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 70 parts of polylactic acid (PLA), 30 parts of Thermoplastic Polyurethane (TPU), 6 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-grade V-Fe3O4And 2 parts of nano-scale conductive copper powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 9 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 780r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 205 ℃, the temperature of an extrusion head to 175 ℃ and the extrusion speed to 90r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 215 ℃, the height of a printing layer is 0.5mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Example 9
A preparation method of the 3D printing wavy structure shape memory composite material comprises the following steps:
(1) 70 parts of polylactic acid (PLA), 30 parts of Thermoplastic Polyurethane (TPU), 8 parts of multi-walled carbon nanotube (MWCNT), 3 parts of iron-nickel alloy powder (Fe/Ni 50/50) and 3 parts of nano-grade V-Fe3O4And 2 parts of nano-scale conductive copper powder are weighed according to the proportion and then are respectively put into a baking oven to be pre-baked for 8 hours at the temperature of 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 700r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 215 ℃, the temperature of an extrusion head to 185 ℃ and the extrusion speed to 80r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 225 ℃, the height of a printing layer is 0.6mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Comparative example 1
A preparation method of a 3D printing wavy structure shape memory composite material comprises the following steps:
(1) weighing 70 parts of polylactic acid (PLA), 30 parts of Thermoplastic Polyurethane (TPU) and 10 parts of iron-nickel alloy powder (Fe/Ni 50/50) according to the proportion, and respectively placing the weighed materials into a baking oven to be pre-baked for 8 hours at 65 ℃;
(2) mechanically mixing the pre-dried raw materials at the rotating speed of 700r/min for 1.5h, adding the mixture into a feed inlet of a single-screw extruder, starting the extruder for preheating for 0.5h, adjusting the preheating temperature of the single-screw extruder to 215 ℃, the temperature of an extrusion head to 185 ℃ and the extrusion speed to 80r/min, melting and blending the raw materials, and extruding to prepare 3D printing wires (the diameter is 1.75 +/-0.1 mm) with uniform diameter;
(3) designing a 3D printing path of a wave structure (the wave interval is 10mm), and outputting a gcode file;
the parameters for 3D printing are: the temperature of a printing nozzle is 220 ℃, the height of a printing layer is 0.5mm, the diameter of the printing nozzle is 1mm, and the temperature of a printing platform is 60 ℃;
(4) and (3) inputting the gcode file on an FDM (fused deposition modeling) 3D printer, placing the 3D printing wire prepared in the step (2), preheating the machine for 2min (the preheating temperature is 180 ℃), preparing the wave-structure composite material, and finally preparing the shape memory composite material.
Comparative example 1 the electromagnetic shielding effectiveness of the composite material prepared according to the embodiment of the present invention was reduced, and the composite material was tested for a shielding effect in a range of 10kHZ to 150kHZ by a method in the national military standard of the GJB 8820-2015 people's republic of China at 3-10 dB. In addition, the material which exerts the shape memory performance is the matrix material, and the proportion of the functional component in the matrix material is small.
Claims (10)
1. The shape memory composite material for the 3D printing wavy structure is characterized by comprising the following raw materials in parts by weight:
2. the shape memory composite according to claim 1, wherein the polylactic acid has an average particle diameter of 40 to 50 μm; thermoplastic polyurethanesHas an average particle diameter of 30 to 35 μm; the diameter of the multi-walled carbon nano-tube is 3-15 nm, and the length of the multi-walled carbon nano-tube is 15-30 mu m; the average particle size of the iron-nickel alloy powder is 50-80 nm; the average grain diameter of the nano-grade conductive copper powder/silver powder is 50-100 nm; the average particle size of the nano-grade transition element-doped super-magnetic particles is 60-120 nm; the nano-grade transition element-doped super-magnetic particle is Nd-Fe3O4,Gd-Fe3O4、Zr-Fe3O4、Mo-Fe3O4、V-Fe3O4、Cr-Fe3O4、Mn-Fe3O4、Co-Fe3O4One or more of (a).
3. A method for preparing the 3D printed wavy structure shape memory composite material of claim 1, wherein the method comprises the following steps:
(1) weighing 50-70 parts of polylactic acid, 30-50 parts of thermoplastic polyurethane, 5-8 parts of multi-walled carbon nano tubes, 3 parts of iron-nickel alloy powder, 3 parts of nano-scale transition element-doped super-magnetic particles and 2 parts of nano-scale conductive copper powder/silver powder according to a ratio, and then respectively putting into an oven for pre-drying;
(2) mechanically mixing the pre-dried raw materials, adding the raw materials into a feed inlet of a single-screw extruder, starting the extruder for preheating, adjusting the preheating temperature, the extrusion head temperature and the extrusion speed of the single-screw extruder, and extruding the raw materials after melt blending to prepare 3D printing wires with uniform diameters;
(3) the 3D who designs wave structure prints the route to carry out the printing of wave structure combined material, the in-process observation sample so that the adjustment parameter improves and prints the quality, and the back is revised and is printed the parameter and carry out combined material's preparation, finally makes 3D who possesses controllable low frequency electromagnetic shield performance and prints wave structure shape memory combined material.
4. The preparation method according to claim 3, wherein in the step (1), the pre-drying temperature is 65-70 ℃ and the pre-drying time is 8-10 h.
5. The preparation method according to claim 3, wherein in the step (2), the rotation speed of the mechanical mixing is 700-800 r/min, and the time is 1.5-2 h.
6. The preparation method according to claim 3, wherein in the step (2), the preheating time of the single-screw extruder is 0.5h, the preheating temperature is 205-215 ℃, the extrusion head temperature is 175-185 ℃, and the extrusion speed is 80-100 r/min.
7. The manufacturing method according to claim 3, wherein in the step (2), the diameter of the 3D printing wire is 1.75 ± 0.1 mm.
8. The manufacturing method according to claim 3, wherein in the step (3), the parameters of the 3D printing are: the temperature of the printing nozzle is 215-225 ℃, the height of the printing layer is 0.4-0.6 mm, the diameter of the printing nozzle is 1mm, and the temperature of the printing platform is 60-65 ℃.
9. The preparation method according to claim 3, wherein in the step (3), an FDM 3D printer is adopted for 3D printing, the preheating temperature is 180-220 ℃, and the preheating time is 2 min.
10. The method according to claim 3, wherein in the step (3), the wave interval of the wave structure is 10 to 40 mm.
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