Device and method for manufacturing wave absorber through photo-thermal auxiliary in-situ curing ink direct writing additive

Abstract

The invention relates to a device and a method for manufacturing a wave absorber through direct writing of photo-thermal auxiliary in-situ cured ink. The device comprises an ink direct writing assembly, a Delta mechanical arm assembly, an ultraviolet light assembly and a heating assembly, and is used for preparing the wave absorber with a complex structure and multiple loss mechanisms. According to the method, composite light-cured resin slurry containing a wave-absorbing agent is extruded through an ink direct-writing spray head, and in-situ light curing and heat curing of the printed composite light-cured resin slurry are achieved through an annular ultraviolet light LED lamp installed below an ink direct-writing printing head and a heating assembly arranged in a printing platform. And the formability and the printing precision of the ink direct-writing additive manufacturing wave absorber are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of material preparation, and in particular to a device and method for photothermal assisted in-situ curing ink direct writing additive manufacturing of an absorber. Background Art

[0002] Structural absorbing materials are usually prepared through special composite structure design and construction, with multi-layer, porous or complex structures, which are used to absorb and scatter electromagnetic waves. Combining processes and materials to study structural absorbing materials can achieve higher absorbing performance and broadband characteristics. The designed structural absorbing materials have both load-bearing and absorbing properties, and have more flexible control methods than absorbing coatings. Traditional mold methods, cutting methods and other methods are often used to prepare traditional structural absorbers, but these methods cannot prepare absorbers with complex structures.

[0003] Additive manufacturing technology has significant advantages when it is necessary to prepare structural absorbers with high precision requirements. Additive manufacturing methods can be divided into fused deposition modeling, selective laser sintering, ink direct writing, photocuring molding, etc. according to the principle. Among them, ink direct writing (DIW) 3D printing is often used in the manufacture of structural absorbers. Ink direct writing 3D printing is an additive manufacturing technology. Compared with other 3D printing methods, ink direct writing has a wide range of printing materials. Different types of inks such as polymer materials, ceramics, metals and biomaterials can be used, which can effectively solve the limitations of traditional manufacturing processes on material types. Ink direct writing technology has high flexibility in the shape and internal structure of printed parts, and can produce parts with complex structures and internal cavities.

[0004] Traditional ink direct writing printing equipment has high requirements for the rheological properties of printing materials. The material needs to have certain rheological properties to maintain appropriate fluidity and plasticity during the printing process. The material needs to show a lower viscosity under the applied shear force so that it can flow and extrude smoothly after the print head applies shear force to ensure that the required shape can be maintained during the printing process. To successfully complete ink direct writing 3D printing, the material is also required to have a certain stability, that is, there is no shear instability, dripping or uneven extrusion during the printing process.

[0005] After ink direct writing printing, the semi-solid material needs to be cured, and the curing conditions usually include photocuring and chemical curing. For photocuring, the ink direct writing printing material is required to be sensitive to ultraviolet light of a specific wavelength. Photosensitive substances, such as photoinitiators or photosensitive monomers, need to be added to the printing material to undergo a cross-linking reaction under ultraviolet light to achieve material curing. For chemical curing, if a chemical curing method is used, the printing material needs to have a certain chemical reactivity, and curing can be achieved by adding a cross-linking agent, a catalyst or a curing agent. This type of curing method usually requires the control of appropriate environmental conditions such as temperature, humidity and oxygen, and in the additive manufacturing process of large-size parts, collapse is prone to occur during the printing process.

[0006] Chinese patent CN113666764B discloses a method for ink direct writing of chopped carbon fiber reinforced silicon carbide ceramic composite materials. First, silicon carbide (SiC) ceramic powder, chopped carbon fiber (Csf), carbon source, deionized water, dispersant, and binder are mixed and ball-milled to obtain a uniformly dispersed Csf / SiC composite slurry, and then an ink direct writing molding device is used to print it into a Csf / SiC composite green body, and then a Csf / SiC secondary green body is obtained through carbonization treatment, and then it is densified through liquid phase siliconization to finally obtain a Csf / SiC composite material.

[0007] Chinese patent CN121690877A discloses a method and technology of ink direct writing 3D printing based on near-infrared light polymerization. The direct writing nozzle moves or remains stationary in three-dimensional space. The ink is squeezed out from the direct writing nozzle and is irradiated with near-infrared light. After curing, the three-dimensional object is formed, and the curing time t does not exceed the diameter d of the near-infrared light. l and ink extrusion speed v i Ratio, that is, t≤d l / vi. As near-infrared light has good medium penetration, it can penetrate the structure during molding to promote a high degree of solidification both inside and outside, thus enabling 3D printing of cross-scale structures.

[0008] The above patents either fail to achieve in-situ real-time curing, or use lasers with small illumination areas, which do not allow sufficient time to completely cure the slurry with high absorbance that requires a long curing time. Therefore, it is necessary to develop an in-situ curing ink direct writing 3D printing method suitable for slurries with high absorbance. Summary of the invention

[0009] Based on the problem that the prior art lacks a device and a corresponding method for manufacturing structural absorbing materials by direct writing of ink with high absorbency slurry in situ curing, the purpose of the present invention is to provide a device and a method for manufacturing absorbers by direct writing of ink with photothermal assisted in situ curing, and to apply the photothermal assisted in situ curing ink direct writing additive manufacturing technology to the preparation of absorber materials. By designing and printing complex absorber structures, improving the impedance matching of absorbers, and introducing more diverse loss mechanisms, the absorbing performance of absorbers can be improved.

[0010] The present invention can be implemented by the following technical solutions:

[0011] One of the technical solutions of the present invention provides a device for additively manufacturing an absorber by direct writing of photothermally assisted in-situ curing ink, the device comprising an ink direct writing component, a Delta robot arm component, an ultraviolet light component and a heating component;

[0012] The ink direct writing component is located above the printing platform and is directly controlled by the Delta mechanical arm component, and the Delta mechanical arm component is controlled by the integrated control component; the ink direct writing component is used for filling and extruding ink slurry, and additively manufacturing the absorber through photothermal assisted in-situ curing technology;

[0013] The heating component is installed inside the printing platform, and its temperature is controlled by the integrated control component; the heating component is used to heat the printing platform, so that the ink slurry is cured in situ after being heated; the material in the ink slurry that can be cured by heat is a thermal initiator;

[0014] The ultraviolet light component is connected to the ink direct writing component, and its light intensity is controlled by the integrated control component; the ultraviolet light provided by the ultraviolet light component is used to cure the ink slurry in situ after being exposed to light; the material in the ink slurry that can be cured by light is a photoinitiator;

[0015] The integrated control component is used to receive signals, send instructions, control the movement, heating, lighting, and pressure in the entire device, and assist in printing the absorber.

[0016] In one embodiment of the present invention, the ink direct writing assembly includes a pressure sensor, a piston, a filling cylinder, a first hose, a second hose, a screw extrusion device and an ink direct writing nozzle; the ink direct writing nozzle, the screw extrusion device, the first hose and the filling cylinder are connected in sequence;

[0017] The filler cylinder has a built-in piston; the filler cylinder is connected to the air pump through a second hose; a pressure sensor is installed on the second hose, and the pressure sensor is connected to the integrated control component; the filler cylinder is used to hold / fill ink slurry; the extrusion flow of the slurry is adjusted by changing the pressure above the piston in the filler cylinder, and its pressure value is displayed by the pressure sensor and regulated by the air pump; the air pump and the pressure sensor are connected to the integrated control component, and the integrated control component can obtain pressure through the pressure sensor and control the air pump to pressurize / depressurize the piston, so that the piston moves, thereby realizing the control of the pressure in the filler cylinder. When pressurized, the ink slurry in the filler cylinder flows into the screw extrusion device through the first hose.

[0018] The screw extruder is connected to a stepper motor drive, and the stepper motor is connected to an integrated control component and controlled by the integrated control component; the stepper motor runs to rotate the screw extruder, and the slurry is delivered downward through the rotating screw extruder; the screw extruder is connected to a Delta mechanical arm component and is lifted / supported by the Delta mechanical arm component;

[0019] The ink direct writing nozzle is a dispensing nozzle, which is connected to the screw extrusion device; the ink direct writing nozzle is used for extruding slurry.

[0020] In one embodiment of the present invention, the Delta robot arm assembly is arranged in three groups, each group includes a guide rail, a slider, and a connecting rod; one end of the connecting rod is connected to the slider and is moved by the slider, and the other end of the connecting rod is connected to a screw extrusion device; the slider moves longitudinally on the vertically placed guide rail, and the movements of the sliders in each group are independent of each other and do not interfere with each other; the slider is connected to a drive motor, and the drive motor is connected to an integrated control component, and the integrated control component controls the drive motor, thereby controlling the three independently movable sliders to move up and down on the guide rail, driving the movement of the connecting rod, and thereby controlling the screw extrusion device in the ink direct writing component to move along the three axes of the XYZ space according to the set route.

[0021] In one embodiment of the present invention, the ultraviolet light assembly includes a quartz light guide ring and a plurality of ultraviolet light LED lamps; the ultraviolet light LED lamps are embedded in the quartz light guide ring and are installed around the lower end of the ink direct writing nozzle; the emitted ultraviolet light is emitted in a ring shape around the ink direct writing nozzle through the quartz light guide ring, and the generated energy induces the occurrence of a photocuring reaction in the slurry. The ultraviolet light assembly is connected to an integrated control assembly, and the switch and power of the ultraviolet light LED lamp are controlled by the integrated control assembly.

[0022] In one embodiment of the present invention, the power of the ultraviolet light is 0-45W, and the wavelength range is 365-405nm.

[0023] In one embodiment of the present invention, the quartz light guide ring is in the shape of a hollow truncated cone, and the inner wall of the quartz light guide ring is plated with an aluminum film.

[0024] In one embodiment of the present invention, the heating component includes a heating resistor and a temperature sensor; the heating resistor is connected to an integrated control component, and when in use, the heating component is controlled by the integrated control component to start heating, and the temperature is detected by the temperature sensor, the temperature sensor is connected to the integrated control component, and the integrated control component controls the heating resistor by receiving a signal from the temperature sensor, and adjusts the heating power to maintain the temperature within a set temperature range / value.

[0025] In one embodiment of the present invention, the heating component can directly heat the printing platform.

[0026] In one embodiment of the present invention, the temperature range of the heating component is from room temperature to 150 degrees.

[0027] A second technical solution of the present invention provides an application of a device for additively manufacturing an absorber by photothermal-assisted in-situ curing ink direct writing. In this application, the device is used to prepare an absorber with a complex structure.

[0028] A third technical solution of the present invention provides a method for additively manufacturing an absorber by direct writing of photothermal-assisted in-situ curing ink, which is performed in the device described in the first technical solution and is based on the photothermal-assisted in-situ curing ink direct writing technology, comprising the following steps:

[0029] S1. Setting the parameters of the ink direct writing nozzle in the additive manufacturing slicing software, including the printing layer thickness, moving speed and wall thickness, and performing slicing processing to generate slicing data; turning on the power / switch of the stepping motor, drive motor, ultraviolet light component and heating component in the additive manufacturing device, importing the slicing data into the integrated control component, and setting the power and heating temperature of the ultraviolet light;

[0030] S2. Prepare a composite photosensitive resin slurry doped with an absorbent; then load the composite photosensitive resin slurry into the filler tube; adjust the air pump to a set air pressure and start printing; during printing, the ink direct writing component is controlled by the Delta robotic arm component, moves in the three-dimensional direction of space according to the trajectory of the slice data set in step S1, and squeezes out the ink slurry from the ink direct writing nozzle, and the ink slurry is cured in situ under the dual effects of the ultraviolet light component and the heating component, and finally a finished absorber is obtained.

[0031] Furthermore, the composition of the composite photosensitive resin (ink, slurry) in step S2 includes, by weight, 30 to 80 parts of oligomer, 11 to 30 parts of monomer, 1 to 7 parts of photoinitiator, 1 to 5 parts of thermal initiator, 0.01 to 0.3 parts of dispersant, 0 to 25 parts of thixotropic agent and not 0, 0 to 11 parts of electric loss absorber and not 0, and 0 to 50 parts of magnetic loss absorber and not 0.

[0032] Further, the oligomer includes one or more of polyurethane acrylate, epoxy acrylate, aliphatic epoxy resin, polyester acrylate, fluorine-modified acrylate, and polyester acrylate;

[0033] Further, the monomer includes one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, and a multifunctional acrylate monomer;

[0034] Further, the photoinitiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, diphenyl glycol ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, and 2-isopropylthioxanthone;

[0035] Further, the thermal initiator includes one or more of tert-butyl perbenzoate, diisopropylbenzene peroxide, and tert-butyl peroxy-2-ethylhexanoate;

[0036] Further, the dispersant is one or more of BYKP-115, N,N-dimethylformamide, and Disper711;

[0037] Further, the thixotropic agent includes one or more of organic bentonite, fumed silica, talc, and titanium dioxide;

[0038] Furthermore, the absorber includes an electric loss absorber and a magnetic loss absorber; the electric loss absorber includes carbon nanotubes, conductive carbon black, graphene, and MXene; the magnetic loss absorber includes one or more of ferrite and carbonyl iron powder.

[0039] In one embodiment of the present invention, the carbon nanotube content in the absorbent has a great influence on the fluidity of the composite photosensitive resin, and the fluidity and the absorbing performance of the composite photosensitive resin are adjusted by changing the ratio of the carbon nanotubes to the thixotropic agent.

[0040] In one embodiment of the present invention, in step S2, the air pressure is adjusted to 0.05-0.15 MPa; during printing, the moving speed of the ink direct writing component is 0-5.0 mm / s.

[0041] Compared with the prior art, the beneficial effects of the present invention are embodied in the following aspects:

[0042] 1. This application uses ultraviolet light to cure the photoinitiator in situ. The overflowing ultraviolet light may cause the photosensitive resin slurry at the ink direct writing nozzle to solidify and cause blockage. The introduction of a quartz light guide ring can control the irradiation path of the ultraviolet light and only solidify the slurry that has been printed near the nozzle, avoiding the solidification of the slurry at the nozzle.

[0043] 2. The introduction of quartz light guide ring can optimize the focusing effect of ultraviolet light, increase the light intensity irradiated to the slurry, and increase the penetration depth of the slurry.

[0044] 3. The penetration depth of ultraviolet light into photosensitive resin slurry doped with absorbers is limited. This application introduces multiple curing mechanisms such as photocuring and heat curing to achieve in-situ curing of the material during the printing process, thereby improving the printing success rate, formability and printing accuracy.

[0045] 4. Mixing the absorber with the photosensitive resin for in-situ curing ink direct writing additive manufacturing can prepare complex structure absorbers, optimize the impedance matching of the absorbing material, and introduce multiple loss mechanisms.

[0046] 5. The mechanical properties and absorbing properties of the absorber can be flexibly adjusted by changing the types and ratios of oligomers, monomers, photoinitiators, thermal initiators, absorbers, and thixotropic agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for describing the embodiments are briefly introduced below.

[0048] Figure 1 Schematic diagram of a device for additively manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink in an embodiment of the present invention;

[0049] Figure 2 Schematic diagram of an ink direct writing component in an embodiment of the present invention;

[0050] Figure 3 It is a cross-sectional schematic diagram of a part of the ink direct writing component in an embodiment of the present invention;

[0051] Figure 4 Schematic diagram of a Delta robot arm assembly in an embodiment of the present invention;

[0052] Figure 5 is a schematic diagram of an ultraviolet light assembly in an embodiment of the present invention;

[0053] Figure 6 This is a flow chart for preparing a photosensitive resin slurry doped with a wave absorbing agent according to an embodiment of the present invention;

[0054] Figure 7Schematic diagram of the photothermal assisted in-situ curing ink direct writing additive manufacturing of the absorber in an embodiment of the present invention;

[0055] Figure 8 The absorber prepared in the specific implementation mode of the present invention;

[0056] Fig. 9 It is a frequency-thickness-reflection loss diagram of the absorber prepared in a specific embodiment of the present invention;

[0057] The numbers in the figure show:

[0058] 1. Pressure sensor; 2. Piston; 3. Filling cylinder; 4. Hose, 4-1. First hose, 4-2. Second hose; 5. Air pump; 6. Connecting rod; 7. Slider; 8. Guide rail; 9. UV lamp; 10. Quartz light guide ring; 11. Screw extruder; 12. Ink direct writing nozzle; 13. Printing platform; 14. Heating resistor wire; 15. Temperature sensor; 16. Integrated control component. DETAILED DESCRIPTION

[0059] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, several variations and improvements can also be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0060] All raw materials of the present invention are not particularly limited in their sources and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0061] Example 1: A device for photothermal assisted in-situ curing ink direct writing additive manufacturing of absorbers

[0062] This embodiment combines Figures 1 to 7 A device for photothermal-assisted in-situ curing ink direct writing additive manufacturing of an absorber provided by the present invention is described in detail. The device is used to prepare a complex structure absorber through an ink direct writing additive manufacturing process.

[0063] The device comprises an ink direct writing component, a Delta mechanical arm component, an ultraviolet light component and a heating component; the ink direct writing component is as follows Figures 2-3 As shown, it is located above the printing platform 13 and is directly controlled by the Delta robot arm assembly; the ink direct writing assembly is used for filling and extruding the ink slurry, and realizes additive manufacturing through photothermal assisted in-situ curing technology; the Delta robot arm assembly is as shown Figure 4 As shown, it is controlled by an integrated control component; the ultraviolet light component is as shown Figure 5As shown, it is connected to the ink direct writing component, and its intensity is controlled by the integrated control component; the ultraviolet light provided by the ultraviolet light component is used to make the photoinitiator in the ink slurry cure in situ after being exposed to light; the heating component is installed inside the printing platform 13, and its temperature is controlled by the integrated control component; the heating component is used to heat the printing platform 13, thereby making the thermal initiator in the ink slurry cure in situ after being heated.

[0064] The integrated control component 16 is the control component of the entire device, which receives signals from the pressure sensor 1 and the temperature sensor 15, and sends instructions to the stepper motor, the drive motor, the ultraviolet light component, and the heating component according to the set slice data / printing program, controls the operation of the Delta mechanical arm component, the screw extruder 11, the heating component, and the ultraviolet light component, and then controls the movement, heating, illumination, and pressure in the entire device to assist in printing the absorber. In this device, the ultraviolet light component and the heating component are used in coordination to respectively cure the photoinitiator and the thermal initiator in the ink slurry in situ, so that the printing effect is better, and the printed absorber can be quickly formed and is not easy to collapse.

[0065] The Delta robot arm assembly in this embodiment includes three sets of guide rails 9, sliders 8, and connecting rods 7; the sliders 7 move longitudinally on the vertically placed guide rails 8; the connecting rod 6 is connected to the slider 7 and is moved by the slider 7, and the other end of the connecting rod 6 is connected to the ink direct writing assembly; the slider 7 is connected to the integrated control assembly 16, and the integrated control assembly 16 controls the movement of the screw extruder on the XYZ three axes by controlling the positions of the three independently movable sliders 7.

[0066] The ink direct writing assembly described in this embodiment includes a pressure sensor 1, a piston 2, a filling tube 3, a hose 4, a screw extrusion device 11, and an ink direct writing nozzle 12; the ink direct writing nozzle 12, the screw extrusion device 11, the first hose 4-1 and the filling tube 3 are connected in sequence; the filling tube 3 has a piston 2 built in. The filling tube 3 is connected to the air pump 5 through the second hose 4-2; the second hose 4-2 is equipped with a pressure sensor 1, and the pressure sensor 1 is connected to the integrated control component 16 to transmit a pressure signal to the integrated control component 16; the screw extrusion device 11 is connected to the integrated control component 16 and driven by a stepper motor controlled by the integrated control component 16. Among them, the extrusion speed of the slurry is adjusted by changing the pressure above the piston 2 in the filling tube 3, and its pressure value is obtained by the pressure sensor 1.

[0067] The ultraviolet light assembly in this embodiment includes a quartz light guide ring 10 and a plurality of ultraviolet LED lamps 9. The ultraviolet LED lamps 9 are embedded in the quartz light guide ring 10 and are installed around the lower end of the ink direct writing nozzle 12. The ultraviolet light emitted by the ultraviolet LED lamp 9 is emitted in a ring shape around the ink direct writing nozzle 12 through the quartz light guide ring 10, and the energy generated induces the occurrence of a photocuring reaction. Among them, the quartz light guide ring 10 is a hollow truncated cone, and the inner wall of the quartz light guide ring 10 is coated with an aluminum film. Among them, the power of the ultraviolet LED lamp 9 is 0 to 45W, and the wavelength range is 365 to 405nm.

[0068] In this embodiment, the heating component includes a heating resistor 14 and a temperature sensor 15; the heating resistor 14 is connected to an integrated control component 16. When in use, the heating component starts heating through the integrated control component 16, and the temperature is detected by the temperature sensor 15. The temperature sensor 15 is connected to the integrated control component 16, and the integrated control component 16 controls the heating component by receiving a signal from the temperature sensor 15, and adjusts the heating power to maintain the temperature within a set temperature range / value. The temperature range of the heating component is from room temperature to 150 degrees.

[0069] In this embodiment, the integrated control component includes a computer, and the Klipper software / application is pre-installed on the computer. The computer uses the Klipper software to achieve high-precision stepping motion of the printer, and uses a microcontroller to control the movement of the printer (i.e., the device for additive manufacturing absorbers); the microcontroller determines when to send signals to the stepper motor / drive motor / heating component / ultraviolet light component, compresses these signals and sends them to the corresponding components; the microcontroller will execute each signal at the requested time; the microcontroller is respectively set on the stepper motor, drive motor, heating component and ultraviolet light component to achieve different functions; the microprocessor is a single-chip microcomputer or one of the x86 architecture, ARM architecture, and RISC-V architecture processors.

[0070] Example 2 A wave absorber manufactured by direct writing additively with photothermal assisted in-situ curing ink

[0071] This embodiment is based on the device for manufacturing an absorber by direct writing of photothermal assisted in-situ curing ink provided in Example 1, and prepares an absorber. Specifically, the preparation of the composite photosensitive resin is carried out by Figure 6 The specific steps of the process are as follows:

[0072] A. In a 250 mL three-necked flask, add 80 g of bifunctional aliphatic polyurethane acrylate (oligomer), 20 g of isobornyl acrylate (monomer), 5 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (photoinitiator), and 0.03 g of dispersant BYKP-115, mix at 70°C, and stir for 30 min to obtain a transparent uniform liquid;

[0073] B. After the solution is cooled, take 74.5 mL of the above solution, add 15 g of fumed silica (thixotropic agent), 0.5 g of carbon nanotubes (electric loss absorber), 3 g of tert-butyl peroxybenzoate (thermal initiator), and 25 g of carbonyl iron powder (magnetic loss absorber), and mechanically stir for 30 min to obtain a composite photosensitive resin slurry;

[0074] Specifically, the process of photothermal assisted in-situ curing ink direct writing additive manufacturing absorber is as follows: Figure 7 As shown, the composite photosensitive resin is placed in the filling tube 3, and the printed model is sliced ​​in the computer. The slicing software used in this embodiment is Cura. After the slicing is completed, the moving speed of the ink direct writing component is set to 2.0mm / s, and the diameter of the ink direct writing nozzle is 1mm; start printing, and the air pressure is 0.09MPa.

[0075] The print result is as follows Figure 8 As shown, the absorber material has a good three-dimensional structure, and its shapes are arranged neatly and evenly. Fig. 9 The present application also uses a vector network analyzer to test the frequency-thickness-reflection loss curve of the absorber product obtained by the present embodiment. Fig. 9 The X coordinate is the frequency, in GHz, the Y coordinate is the material thickness, in mm, and the Z coordinate is the reflection loss, in dB. Fig. 9 It can be clearly seen that at the target frequency, the reflection loss presents an obvious trough value, which has excellent electromagnetic wave absorption function.

[0076] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A device for photothermal assisted in-situ curing ink direct writing additive manufacturing absorber, characterized in that: The device includes an ink direct writing component, a Delta mechanical arm component, an ultraviolet light component and a heating component; The ink direct writing component is located above the printing platform (13) and is directly controlled by the Delta mechanical arm component, and the Delta mechanical arm component is controlled by the integrated control component (16); the ink direct writing component is used for filling and extruding ink slurry, and realizes additive manufacturing through photothermal assisted in-situ curing technology; The heating component is installed inside the printing platform (13), and its temperature is controlled by the integrated control component (16); the heating component is used to heat the printing platform (13), thereby causing the ink slurry to solidify in situ after being heated; The ultraviolet light component is connected to the ink direct writing component, and its light intensity is controlled by the integrated control component (16); the ultraviolet light provided by the ultraviolet light component is used to cure the ink slurry in situ after exposure to light; The integrated control component (16) is used to receive signals, send instructions, control the movement, heating, lighting and pressure in the entire device, and assist in printing the absorber.

2. The device for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 1 is characterized in that: The ink direct writing component comprises a pressure sensor (1), a piston (2), a filling cylinder (3), a first hose (4-1), a second hose (4-2), a screw extrusion device (11) and an ink direct writing nozzle (12); the ink direct writing nozzle (12), the screw extrusion device (11), the first hose (4-1) and the filling cylinder (3) are connected in sequence; The filling cylinder (3) has a built-in piston (2); the filling cylinder (3) is connected to the air pump (5) through a second hose (4-2); a pressure sensor (1) is installed on the second hose (4-2), and the pressure sensor (1) is connected to the integrated control component (16); the filling cylinder (3) is used to contain / fill ink slurry; the extrusion flow rate of the ink slurry is adjusted by changing the pressure above the piston (2) in the filling cylinder (3), and the pressure value is displayed by the pressure sensor (1) and regulated by the air pump (5); the air pump (5) and the pressure sensor (1) are connected to the integrated control component (16), and the integrated control component (16) can obtain pressure through the pressure sensor (1) and control the air pump (5) to pressurize / depressurize the piston (2), so that the piston moves, thereby realizing the control of the pressure in the filling cylinder (3); The screw extruder (11) is connected to a stepper motor, and the stepper motor is connected to an integrated control component (16) and is controlled by the integrated control component (16); when the stepper motor is running, the screw extruder (11) is rotated, and the slurry is delivered downward through the rotating screw extruder (11); the screw extruder (11) is connected to a Delta mechanical arm component and is lifted / supported by the Delta mechanical arm component; The ink direct writing nozzle (12) is a glue dispensing nozzle, which is connected to the screw extrusion device (11); the ink direct writing nozzle (12) is used for extruding slurry.

3. The device for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 2, characterized in that: The Delta mechanical arm assembly is provided in three groups, each group comprising a guide rail (8), a slider (7), and a connecting rod (6); One end of the connecting rod (6) is connected to the slider (7), and the other end of the connecting rod (6) is connected to the screw extruder (11); The sliders (7) move longitudinally on the vertically placed guide rails (8), and the movements of the sliders (7) in each group are independent of each other and do not interfere with each other; The slider (7) is connected to a driving motor, and the driving motor is connected to an integrated control component (16). The integrated control component (16) controls the driving motor, thereby controlling the three independently movable sliders (7) to move up and down on the guide rail (8), driving the movement of the connecting rod (6), and thereby controlling the movement of the screw extruder (11) in the ink direct writing component on the three axes of the XYZ space according to a set route.

4. The device for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 3 is characterized in that: The ultraviolet light component comprises a quartz light guide ring (10) and a plurality of ultraviolet LED lamps (9); the ultraviolet LED lamps (9) are embedded in the quartz light guide ring (10) and are installed around the lower end of the ink direct writing nozzle (12); the ultraviolet light emitted by the ultraviolet LED lamps (9) is emitted in a ring shape around the ink direct writing nozzle through the quartz light guide ring, and the energy generated induces a photocuring reaction in the slurry; The ultraviolet light component is connected to an integrated control component (16), and the switch and power level of the ultraviolet light LED lamp are controlled by the integrated control component (16).

5. The device for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 1, characterized in that: The heating component comprises a heating resistor (14) and a temperature sensor (15); the heating resistor (14) is connected to an integrated control component (16); when in use, the heating component is controlled by the integrated control component (16) to start heating, and the temperature is detected by the temperature sensor (15); the temperature sensor (15) is connected to the integrated control component (16); the integrated control component (16) controls the heating resistor (14) by receiving a signal from the temperature sensor (15), and adjusts the heating power so that the temperature is maintained within a set temperature range / value.

6. Application of a device for manufacturing absorbers by direct writing with photothermal assisted in-situ curing ink according to any one of claims 1 to 5, characterized in that: The photothermal-assisted in-situ curing ink direct writing additive manufacturing device is used to manufacture a wave absorbing body.

7. A method for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink, characterized in that: The device for manufacturing an absorber by direct writing of photothermally assisted in-situ curing ink according to any one of claims 1 to 6 comprises the following steps: S1. Setting the parameters of the ink direct writing nozzle (12) in the additive manufacturing slicing software, the parameters including the printing layer thickness, moving speed and wall thickness, and performing slicing processing to generate slicing data; turning on the power / switch of the stepping motor, driving motor, ultraviolet light component and heating component in the additive manufacturing device, importing the slicing data into the integrated control component (16), and setting the power of the ultraviolet light and the heating temperature; S2. Prepare a composite photosensitive resin slurry doped with an absorbent, and use the composite photosensitive resin slurry as ink slurry; then fill the composite photosensitive resin slurry into the filler tube (3); adjust the air pump (5) to a set air pressure and start printing; during printing, the ink direct writing component is controlled by the Delta robot arm component, moves in the three-dimensional direction of space according to the trajectory of the slice data set in step S1, and squeezes out the ink slurry from the ink direct writing nozzle; the ink slurry is cured in situ under the dual action of the ultraviolet light component and the heating component, and finally a finished absorber is obtained.

8. The method for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 7, characterized in that: The composition of the composite photosensitive resin in step S2, in parts by weight, includes: 30 to 80 parts of oligomers, 11 to 30 parts of monomers, 1 to 7 parts of photoinitiators, 1 to 5 parts of thermal initiators, 0.01 to 0.3 parts of dispersants, 0 to 25 parts of thixotropic agents and not 0, 0 to 11 parts of electrical loss absorbers and not 0, and 0 to 50 parts of magnetic loss absorbers and not 0.

9. The method for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 8, characterized in that: The oligomer includes one or more of polyurethane acrylate, epoxy acrylate, aliphatic epoxy resin, polyester acrylate, fluorine-modified acrylate, and polyester acrylate; the monomer includes one or more of monofunctional acrylate monomer, difunctional acrylate monomer, and multifunctional acrylate monomer; the photoinitiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, diphenyl glycol ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, 2-isopropylthioxanthone, or The invention relates to a novel nanostructured carbonyl polymer comprising: a nanostructured carbonyl polymer; a nanostructured carbonyl polymer; a nanostructured carbonyl polymer; and a nanostructured carbonyl polymer. The invention relates to a nanostructured carbonyl polymer comprising: a nanostructured carbonyl polymer; a nanostructured carbonyl polymer; and a nanostructured carbonyl polymer. The invention relates to a nanostructured carbonyl polymer comprising: a nanostructured carbonyl polymer; and a nanostructured carbonyl polymer.

10. The method for manufacturing an absorber by direct writing with photothermal assisted in-situ curing ink according to claim 7, characterized in that: In step S2, during printing, the air pressure is adjusted to 0.05-0.15 MPa; the moving speed of the ink direct writing component is 0-5.0 mm / s, and is not 0.

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