Copper-silver-nickel precision area electrochemical deposition 4D printing device and method

Abstract

The present invention relates to a copper-silver-nickel precision area electrochemical deposition 4D printing device and method, belonging to the field of 4D printing technology and electrochemical deposition technology. A frame device is fixed to a base by a locking device, a brush device is welded to a nozzle conversion device, a nozzle conversion device is welded to a frame device, a nozzle device is mounted on the nozzle conversion device by a threaded connection, a z-axis moving device is mounted on the frame device, an x-axis electric linear slide is mounted on a y-axis electric linear slide by a threaded connection, the y-axis electric linear slide is mounted in the z-axis moving device by a threaded connection, and a printing platform is mounted on the x-axis electric linear slide by a threaded connection. The advantage is that the 4D printed component formed by this method has the characteristics of high melting temperature, good mechanical robustness, good electrical conductivity, thermal conductivity, good durability, low price, etc.

Description

Technical Field

[0001] The present invention belongs to the fields of 4D printing technology and electrochemical deposition technology, and specifically relates to a copper-silver-nickel precision area electrochemical deposition 4D printing device and method. Background Art

[0002] 4D printing, also known as variable property rapid prototyping technology, is a technology that combines disciplines such as materials, mathematics, and additive manufacturing. The shape, properties, or functions of structures printed by 4D printing can change over time under environmental stimuli. 4D printing technology can design structures with intelligent dynamic deformation. This intelligent dynamic deformation capability mainly relies on the different distribution and combination of different materials in three-dimensional space. The correct material distribution can make the deformation of the structure occur in the order of design intent. However, in most cases, 4D printed components are made of composite polymer-based materials, which are easy to manufacture, but their poor thermal stability and conductivity limit their maximum operating temperature and transient performance. In some cases, some structures have poor durability due to mechanical degradation during thermo-mechanical cycles.

[0003] Meniscus-constrained electrodeposition is a type of electrochemical three-dimensional micro-deposition technology. It uses a stable micro-nanoscale meniscus-shaped electrolyte bridge formed in the extremely narrow gap between the ultrafine anode tip and the cathode substrate as an electrochemical reaction cell, allowing ultra-high-resolution metal deposition to occur on the cathode surface. It typically uses an ultrafine pipette containing an ultrafine anode to transport the electrolyte to the reaction area required for electrodeposition. Compared with other electrochemical three-dimensional micro-deposition technologies, meniscus-constrained electrodeposition has the advantages of high forming precision and good forming quality. However, due to the inconvenience of electrolyte replacement, meniscus-constrained electrodeposition technology currently only prints single metal materials, limiting the scope of use of the printed components. Summary of the Invention

[0004] The present invention provides a copper-silver-nickel precision area electrochemical deposition 4D printing device and method to solve the problems of low melting temperature, poor mechanical robustness and poor transient performance of common 4D printed components when the operating temperature is higher than 100°C.

[0005] The technical solution adopted by the present invention is to include a base, a locking device, a frame device, a brush device, a nozzle conversion device, a nozzle device, an x-axis electric linear slide, a y-axis electric linear slide, a z-axis moving device and a printing platform, wherein the frame device is fixed to the base through a locking device, the brush device is welded to the nozzle conversion device, the nozzle conversion device is welded to the frame device, the nozzle device is installed on the nozzle conversion device through a threaded connection and can rotate with the nozzle changing device, the z-axis moving device is installed on the frame device and can be moved up and down by the engagement of gears and racks, the x-axis electric linear slide is installed on the y-axis electric linear slide through a threaded connection, the y-axis electric linear slide is installed in the z-axis moving device through a threaded connection, and the printing platform is installed on the x-axis electric linear slide through a threaded connection.

[0006] The base includes a base, a support plate 1, a light hole 1, a support plate 2 and a threaded hole, wherein the support plate 1 is punched with a light hole 1 and is fixedly connected to the base, and the support plate 2 is punched with a threaded hole and is fixedly connected to the base.

[0007] The locking device includes a locking thread, a locking wrench, a boss, a shoulder and an optical axis, wherein the optical axis passes through the optical hole 1 and the optical hole 2 in sequence, the locking thread is connected to the threaded hole by a thread, the diameter of the boss is larger than the diameter of the optical hole 2 and smaller than the diameter of the optical hole 1, when the locking wrench is rotated, the shoulder will press the support frame, thereby pressing the support frame and the support plate 2 at the same time, and the frame device is locked under the action of friction. When the locking device is loosened, the frame device can rotate around the optical axis, which is convenient for installing and disassembling the nozzle device.

[0008] The rack device comprises a supporting frame, a rack and a second light hole. The rack is fixed on the supporting frame and the second light hole is located on the supporting frame.

[0009] The brush device includes a brush slot, a spring and a brush, wherein the brush and the spring are installed in the brush slot, the brush slot is welded to the end cover of the converter, the brush can slide in the brush slot and the brush through hole, and is tightly pressed on the converter under the action of the spring, the brush is connected to the positive pole of the power supply, so that the electrode inside the nozzle is connected to the positive pole of the power supply.

[0010] The nozzle conversion device includes a servo motor, a converter fastening cover, a converter end cover, and a converter, wherein the servo motor output shaft is connected to the converter, the converter is clamped between the converter end cover and the converter fastening cover, and the converter end cover and the converter fastening cover are connected by threads.

[0011] The converter end cover includes a limiting boss, a brush through hole, and a shell, wherein the brush through hole is located on the side of the shell, and the limiting boss limits the position of the converter in the shell, so that the converter can slide stably in the converter end cover.

[0012] The converter includes grooves, circular holes and circular bosses, wherein three grooves are opened in the converter for connecting the electrode inside the nozzle and the circular bosses on the converter. The three circular bosses of the converter are conductive, and the rest are insulated, so that the electrode inside the nozzle is connected to the positive pole of the power supply. Three circular holes are opened on the converter for connecting the nozzle device. The rotation of the servo motor drives the converter to rotate inside the converter end cover.

[0013] The nozzle device includes a pressure sensor, a nozzle cover, an electrode and a nozzle housing, wherein the electrode and the pressure sensor are integrated on the nozzle cover, the nozzle cover is threadedly connected to the nozzle housing, and the pressure sensor is used to control the ejection speed and pressure of the electrolyte.

[0014] The x-axis electric linear slide includes a slider 1, a guide rail 1, a screw 1 and a servo motor, wherein the slider 1 includes a moving platform 1 and a nut block 1, the nut block 1 is fixed to the bottom of the moving platform 1, the nut block 1 is threadedly connected to the screw 1, the screw 1 is installed on the guide rail 1, the servo motor output shaft is fixedly connected to one end of the screw 1, the guide rail 1 is threadedly connected to the slider 2, the servo motor rotates to drive the screw 1 to rotate, and then drives the slider 1 to move along the guide rail 1 to realize the x-axis.

[0015] The y-axis electric linear slide includes a slider 2, a guide rail 2, a screw 2 and a servo motor, wherein the slider 2 includes a moving platform 2 and a nut block 2, the nut block 2 is fixed to the bottom of the moving platform 2, the nut block 2 is used to be threadedly connected to the screw 2, the screw 2 is installed on the guide rail 2, the servo motor output shaft is fixedly connected to one end of the screw 2, the guide rail 2 is threadedly connected to the linear slide placement groove, the rotation of the servo motor drives the screw to rotate, and then drives the slider 2 along the guide rail 2 to realize the y-axis movement.

[0016] The z-axis moving device includes a stepper motor, a linear slide placement slot and a spur gear, wherein the stepper motor is fixedly connected to the side wall of the linear slide placement slot, and the stepper motor drives the spur gear to rotate, thereby causing the spur gear to move up and down relative to the rack to achieve z-axis movement.

[0017] The printing platform includes a deposition tank and a cathode substrate, wherein the deposition tank is fixed on the slider 1, and the cathode substrate is placed in the deposition tank.

[0018] A printing method using a copper-silver-nickel precision area electrochemical deposition 4D printing device includes the following steps:

[0019] (1) Configuration of electrodeposition reaction solution: Electrolyte 1: 16.8 g copper sulfate CuSO4 and 7.68 g sulfuric acid H2SO4 are dissolved in 100 mL deionized water and stirred; Electrolyte 2: 30 g silver nitrate AgNO3 powder, 134.47 g 5-sulfosalicylic acid C7H6O6S·2H2O powder, 9.882 g potassium hydroxide KOH powder, 56 g ammonium acetate CH3COONH4, and 112 g ammonia water NH3·H2O are added into 100 mL deionized water and stirred; Electrolyte 3: 35 g nickel sulfate hexahydrate NiSO4·6H2O, 2 g sodium chloride NaCl powder, 8 g boric acid H3BO3 powder, 12 g sodium sulfate Na2SO4 powder, 0.02 g sodium lauryl sulfate C 12 H 25 SO4Na powder was dissolved in 250 mL of deionized water and stirred;

[0020] (2) Preparation of cathode substrate: The material of the cathode substrate is a silver sheet with stable performance. The purchased silver sheet is cut into a size of 10 mm × 10 mm and a thickness of 100 μm, and is adhered with a conductive tape to facilitate the subsequent connection to the negative pole of the power supply. To ensure the smooth surface of the silver sheet, the silver sheet is polished on a grinding and polishing machine with a polishing cloth and a polishing liquid, and the surface is cleaned with distilled water after polishing. To dissolve the residual grease on the silver sheet, it is cleaned with a prepared NaOH solution and degreased with ultrasonic assistance. After degreasing, it is cleaned with a weak acid and finally cleaned with distilled water and dried.

[0021] (3) Model data conversion: Use Catia software to build a three-dimensional model of the part to be printed, slice the layers and process them into an STL file. By controlling the nozzle device, output voltage, and the movement speed of the x-axis electric linear slide, y-axis electric linear slide, and z-axis moving device, the part is deposited layer by layer according to the scanning path;

[0022] (4) Printing of microscopic metal components: The nozzle device containing electrolyte 1 is rotated to the top of the cathode substrate. At this time, the circular boss on the converter corresponding to the nozzle device is in contact with the brush, thereby connecting to the positive pole of the power supply. Then, the z-axis moving device is adjusted so that the nozzle device maintains an appropriate distance from the cathode substrate. Then, the power is turned on and voltage is applied. The computer program controls the x-axis electric linear slide, the y-axis electric linear slide, and the z-axis moving device to move the printing platform, thereby causing the nozzle device to deposit a copper layer at the corresponding position set by the computer. After the copper layer deposition is completed, the converter is rotated so that the nozzle device containing electrolyte 2 is rotated to the top of the cathode substrate. Silver is deposited on the copper deposition layer in the same manner by using the computer program to control the nozzle device. After the silver deposition is completed, the converter is rotated so that the nozzle device containing electrolyte 3 is rotated to the top of the cathode substrate. Nickel is deposited on the copper deposition layer in the same manner by using the computer program to control the nozzle device.

[0023] (5) Cleaning and drying of parts: After printing is completed, turn off the power supply, move the printing platform to the bottom of the device by the z-axis moving device, remove the cathode substrate from the solution with tweezers, clean the parts and dry them.

[0024] The advantages of the present invention are as follows:

[0025] (1) The present invention creatively utilizes copper-silver-nickel multi-metal materials to manufacture 4D printed components. According to the different thermal expansion coefficients of different metal materials, heating is used to drive the movement of the 4D printed components. The manufactured 4D printed components have a high melting point and mechanical strength, breaking the defect of poor transient performance of 4D printed components manufactured using polymers when the operating temperature is higher than 100°C.

[0026] (2) The 4D printed components manufactured by the present invention have good electrical and thermal conductivity and good durability, which broadens the application range of 4D printed components.

[0027] (3) The 4D printed components manufactured by the present invention are made of cheap pure metal materials at low cost, which opens up the possibility of creating complex high-temperature 4D self-assembled actuated structures using cheap components and materials.

[0028] (4) The present invention creatively adopts meniscus constraint to manufacture 4D printed components, which improves the connection strength between different metals, optimizes printing accuracy and performance, and can realize the manufacture of micro-nano scale 4D printed components.

[0029] (5) The 4D printed components manufactured by the present invention can be used to make micro-robots, such as inchworm-like micro-robots, which use simple body bending to crawl on rough ground through alternating friction, and can adapt to complex terrain and move freely in two-dimensional (2D) or three-dimensional (3D) space, thereby realizing all-terrain off-road movement. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a structural schematic diagram of the present invention;

[0031] Figure 2 It is a structural schematic diagram of the base of the present invention;

[0032] Figure 3 It is a structural schematic diagram of the locking device of the present invention;

[0033] Figure 4 It is a structural schematic diagram of the rack device of the present invention;

[0034] Figure 5 It is a structural schematic diagram of the brush device of the present invention;

[0035] Figure 6 It is a structural schematic diagram of the nozzle conversion device of the present invention;

[0036] Figure 7 It is a schematic structural diagram of the end cover of the converter of the present invention;

[0037] Figure 8 It is a structural schematic diagram of the converter of the present invention;

[0038] Figure 9 It is a structural schematic diagram of the nozzle device of the present invention;

[0039] Figure 10 This is a structural diagram of the x-axis electric linear slide of the present invention.

[0040] Figure 11 It is a structural schematic diagram of a slider 1 of the present invention;

[0041] Figure 12 It is a structural schematic diagram of the Y-axis electric linear slide of the present invention;

[0042] Figure 13 It is a structural schematic diagram of the slider 2 of the present invention;

[0043] Figure 14 It is a structural schematic diagram of the z-axis moving device of the present invention;

[0044] Figure 15 It is a structural schematic diagram of the printing platform of the present invention;

[0045] Figure 16 Schematic diagram of the structure of the copper-silver-nickel inchworm-like microrobot in the experimental example of the present invention;

[0046] Figure 17 Schematic diagram of two thermal driving modes of the copper-silver-nickel inchworm-like microrobot in the experimental example of the present invention;

[0047] Figure 18 Schematic diagram of the structure of the two-dimensional copper-silver-nickel inchworm-like microrobot in the experimental example of the present invention. DETAILED DESCRIPTION

[0048] like Figure 1As shown, it includes a base 1, a locking device 2, a frame device 3, a brush device 4, a nozzle conversion device 5, a nozzle device 6, an x-axis electric linear slide 7, a y-axis electric linear slide 8, a z-axis moving device 9 and a printing platform 10, wherein the frame device 3 is fixed to the base 1 through the locking device 2, the brush device 4 is welded to the nozzle conversion device 5, the nozzle conversion device 5 is welded to the frame device 3, the nozzle device 6 is installed on the nozzle conversion device 5 through a threaded connection, and can rotate with the nozzle conversion device 5, the z-axis moving device 9 is installed on the frame device 3, and can be moved up and down by the engagement of gears and racks, the x-axis electric linear slide 7 is installed on the y-axis electric linear slide 8 through a threaded connection, the y-axis electric linear slide 8 is installed in the z-axis moving device 9 through a threaded connection, and the printing platform 10 is installed on the x-axis electric linear slide 7 through a threaded connection.

[0049] like Figure 2 As shown, the base 1 includes a base 101, a support plate 102, a light hole 103, a support plate 2 104 and a threaded hole 105, wherein the support plate 102 is punched with a light hole 103 and is fixedly connected to the base 101, and the support plate 2 104 is punched with a threaded hole 105 and is fixedly connected to the base 101.

[0050] like Figure 3 As shown, the locking device 2 includes a locking thread 201, a locking wrench 202, a boss 203, a shoulder 204 and an optical axis 205, wherein the optical axis 205 passes through the optical hole 103 and the optical hole 2 303 in sequence, the locking thread 201 is connected to the threaded hole 105 by a thread, the diameter of the boss 203 is larger than the diameter of the optical hole 2 303 and smaller than the diameter of the optical hole 103, when the locking wrench 202 is rotated, the shoulder 204 will press the support frame 301, so that the support frame 301 is pressed against the support plate 2 104 at the same time, and the frame device 3 is locked under the action of friction. When the locking device 2 is loosened, the frame device 3 can rotate around the optical axis 205, which is convenient for installing and disassembling the nozzle device 6.

[0051] like Figure 4 As shown, the rack device 3 includes a support frame 301 , a rack 302 , and a second light hole 303 . The rack 302 is fixed on the support frame 301 , and the second light hole 303 is located on the support frame 301 .

[0052] like Figure 5As shown, the brush device 4 includes a brush slot 401, a spring 402 and a brush 403, wherein the brush 403 and the spring 402 are installed in the brush slot 401, and the brush slot 401 is welded to the converter end cover 503. The brush 403 can slide in the brush slot 401 and the brush through hole 50302, and is tightly pressed against the converter 504 under the action of the spring 402. The brush 403 is connected to the positive pole of the power supply, thereby connecting the electrode 603 in the nozzle to the positive pole of the power supply.

[0053] like Figure 6 As shown, the nozzle conversion device 5 includes a servo motor 501, a converter fastening cover 502, a converter end cover 503, and a converter 504, wherein the output shaft of the servo motor 501 is connected to the converter 504, the converter 504 is clamped between the converter end cover 503 and the converter fastening cover 502, and the converter end cover 503 and the converter fastening cover 502 are connected by threads.

[0054] like Figure 7 As shown, the converter end cover 503 includes a limiting boss 50301, a brush through hole 50302, and a shell 50303, wherein the brush through hole 50302 is located on the side of the shell 50303, and the limiting boss 50301 limits the position of the converter 504 in the shell 50303, so that the converter 504 can slide stably in the converter end cover 503.

[0055] like Figure 8 As shown, the converter 504 includes a groove 50401, a circular hole 50402 and a circular boss 50403, wherein three grooves 50401 are opened in the converter 504 for connecting the electrode 603 in the nozzle and the circular boss 50403 on the converter. The three circular bosses 50403 of the converter are conductive, and the rest are insulated, so that the electrode 603 in the nozzle is connected to the positive pole of the power supply. Three circular holes 50402 are opened on the converter 504 for connecting the nozzle device 6. The rotation of the servo motor 501 drives the converter 504 to rotate in the converter end cover 503.

[0056] like Figure 9 As shown, the nozzle device 6 includes a pressure sensor 601, a nozzle cover 602, an electrode 603 and a nozzle housing 604, wherein the electrode 603 and the pressure sensor 601 are integrated on the nozzle cover 602, the nozzle cover 602 is threadedly connected to the nozzle housing 604, and the pressure sensor 601 is used to control the ejection speed and pressure of the electrolyte.

[0057] like Figure 10 、 11As shown, the x-axis electric linear slide 7 includes a slider 701, a guide rail 702, a screw 703 and a servo motor 704, wherein the slider 701 includes a moving platform 70101 and a nut block 70102, the nut block 70102 is fixed to the bottom of the moving platform 70101, the nut block 70102 is threadedly connected to the screw 703, the screw 703 is installed on the guide rail 702, the output shaft of the servo motor 704 is fixedly connected to one end of the screw 703, the guide rail 702 is threadedly connected to the slider 2 801, the servo motor 704 rotates to drive the screw 703 to rotate, and then drives the slider 701 to move along the guide rail 702 to realize the x-axis.

[0058] like Figure 12 、 13 As shown, the y-axis electric linear slide 8 includes a slider 801, a guide rail 802, a screw 803 and a servo motor 804, wherein the slider 801 includes a moving platform 80101 and a nut block 80102, the nut block 80102 is fixed at the bottom of the moving platform 80101, the nut block 80102 is used to be threadedly connected to the screw 803, the screw 803 is installed on the guide rail 802, the output shaft of the servo motor 804 is fixedly connected to one end of the screw 803, the guide rail 802 is threadedly connected to the linear slide placement slot 902, the servo motor 804 rotates to drive the screw 803 to rotate, and then drives the slider 801 to move along the guide rail 802 to realize the y-axis.

[0059] like Figure 14 As shown, the z-axis moving device 9 includes a stepper motor 901, a linear slide placement slot 902 and a spur gear 903, wherein the stepper motor 901 is fixedly connected to the side wall of the linear slide placement slot 902, and the stepper motor 901 drives the spur gear 903 to rotate, thereby causing the spur gear 903 to move up and down relative to the rack 302 to realize z-axis movement.

[0060] like Figure 15 As shown, the printing platform 10 includes a deposition tank 1001 and a cathode substrate 1002 , wherein the deposition tank 1001 is fixed on the slider 1 701 , and the cathode substrate 1002 is placed in the deposition tank 1001 .

[0061] A printing method using a copper-silver-nickel precision area electrochemical deposition 4D printing device includes the following steps:

[0062] (1) Configuration of electrodeposition reaction solution: Electrolyte 1: 16.8 g copper sulfate CuSO4 and 7.68 g sulfuric acid H2SO4 are dissolved in 100 mL deionized water and stirred; Electrolyte 2: 30 g silver nitrate AgNO3 powder, 134.47 g 5-sulfosalicylic acid C7H6O6S·2H2O powder, 9.882 g potassium hydroxide KOH powder, 56 g ammonium acetate CH3COONH4, and 112 g ammonia water NH3·H2O are added into 100 mL deionized water and stirred; Electrolyte 3: 35 g nickel sulfate hexahydrate NiSO4·6H2O, 2 g sodium chloride NaCl powder, 8 g boric acid H3BO3 powder, 12 g sodium sulfate Na2SO4 powder, 0.02 g sodium lauryl sulfate C 12 H 25 SO4Na powder was dissolved in 250 mL of deionized water and stirred;

[0063] (2) Preparation of cathode substrate 1002: The material of cathode substrate 1002 is selected from silver sheets with stable performance. The purchased silver sheets are cut into 10 mm × 10 mm sizes and 100 μm thick, and are adhered with conductive tape to facilitate subsequent connection to the negative pole of the power supply. To ensure the smooth surface of the silver sheet, the silver sheet is polished on a grinding and polishing machine with a polishing cloth and polishing liquid, and the surface is cleaned with distilled water after polishing. To dissolve the residual grease on the silver sheet, it is cleaned with a prepared NaOH solution and degreased with ultrasonic assistance. After degreasing, it is cleaned with weak acid and finally cleaned with distilled water and dried.

[0064] (3) Model data conversion: Use Catia software to build a three-dimensional model of the part to be printed, slice the layers and process them into an STL file. By controlling the nozzle device 6, the output voltage and the movement speed of the x-axis electric linear slide 7, the y-axis electric linear slide 8, and the z-axis moving device 9, the parts are deposited layer by layer according to the scanning path.

[0065] (4) Printing of microscopic metal components: The nozzle device 6 filled with electrolyte 1 is rotated to the top of the cathode base 1002. At this time, the circular boss 50403 on the corresponding converter of the nozzle device 6 is in contact with the brush 403, thereby connecting to the positive pole of the power supply. Then, the z-axis moving device 9 is adjusted to keep the nozzle device 6 at an appropriate distance from the cathode base 1002. Then, the power is turned on and voltage is applied. The computer program controls the x-axis electric linear slide 7, the y-axis electric linear slide 8, and the z-axis moving device 9 to move the printing platform 10, thereby making the printing platform 10 move. The nozzle device 6 deposits a copper layer at a corresponding position set by the computer. After the copper layer deposition is completed, the converter 504 rotates so that the nozzle device 6 filled with the electrolyte 2 is moved to the top of the cathode substrate 1002. Silver is deposited on the copper deposition layer in the same manner by controlling the nozzle device 6 using the computer program. After the silver deposition is completed, the converter 504 rotates so that the nozzle device 6 filled with the electrolyte 3 is moved to the top of the cathode substrate 1002. Nickel is deposited on the copper deposition layer in the same manner by controlling the nozzle device 6 using the computer program.

[0066] (5) Cleaning and drying of parts: After printing is completed, turn off the power supply, move the printing platform 10 to the bottom of the device by the z-axis moving device 9, remove the cathode substrate 1002 from the solution with tweezers, clean the parts and dry them.

[0067] Experimental Example: Preparation and Testing of Copper-Silver-Nickel Inchworm-like Microrobot

[0068] (1) Preparation of electrodeposition reaction solution: Electrolyte 1: Dissolve 16.8g copper sulfate (CuSO4) and 7.68g sulfuric acid (H2SO4) in 100mL deionized water and stir. Electrolyte 2: Add 30g silver nitrate (AgNO3) powder, 134.47g 5-sulfosalicylic acid (C7H6O6S·2H2O) powder, 9.882g potassium hydroxide (KOH) powder, 56g ammonium acetate (CH3COONH4), and 112g ammonia water (NH3·H2O) to 100mL deionized water and stir. Electrolyte 3: Dissolve 35g nickel sulfate hexahydrate (NiSO4·6H2O), 2g sodium chloride (NaCl) powder, 8g boric acid (H3BO3) powder, 12g sodium sulfate (Na2SO4) powder, 0.02g sodium dodecyl sulfate (C7H6O6S·2H2O) powder, 134.47g 5-sulfosalicylic acid (C7H6O6S·2H2O) powder, 9.882g potassium hydroxide (KOH) powder, 56g ammonium acetate (CH3COONH4), and 112g ammonia water (NH3·H2O) in 100mL deionized water and stir. 12 H 25 SO4Na) powder was dissolved in 250 mL of deionized water and stirred;

[0069] (2) Preparation of cathode substrate 1002: The material of cathode substrate 1002 is selected from silver sheets with stable performance. The purchased silver sheets are cut into 10mm×10mm size and 100μm thickness, and adhered with conductive tape to facilitate the subsequent connection to the negative pole of the power supply. To ensure the smooth surface of the silver sheet, the silver sheet is polished on a grinding and polishing machine with a polishing cloth and polishing liquid. After polishing, the surface is cleaned with distilled water. To dissolve the residual grease on the silver sheet, it is cleaned with a prepared NaOH solution and degreased with ultrasonic assistance. After degreasing, it is cleaned with weak acid and finally cleaned with distilled water and dried.

[0070] (3) Model data conversion: Use Catia software to build Figure 16 The three-dimensional model is sliced ​​and processed into an STL format file, and the nozzle device 6, the output voltage and the movement speed of the x-axis electric linear slide 7, the y-axis electric linear slide 8 and the z-axis moving device 9 are controlled to deposit the shape layer by layer according to the scanning path;

[0071] (4) Printing a copper-silver-nickel inchworm-like microrobot: The nozzle device 6 filled with electrolyte 1 is rotated to the top of the cathode substrate 1002, and the z-axis moving device 9 is adjusted so that the nozzle device 6 maintains an appropriate distance from the cathode substrate 1002. Then, the power is turned on and voltage is applied. The computer program controls the x-axis electric linear slide 7, the y-axis electric linear slide 8, and the z-axis moving device 9 to move the printing platform 10, thereby causing the nozzle device 6 to deposit the copper layer of the copper-silver-nickel inchworm-like microrobot at the corresponding position set by the computer. After the copper layer deposition is completed, the converter 504 is rotated so that the nozzle device 6 filled with electrolyte 2 is transferred to the top of the cathode substrate 1002. Silver is deposited on the copper deposition layer in the same manner by using the computer program to control the nozzle device 6. After the silver deposition is completed, the converter 504 is rotated so that the nozzle device 6 filled with electrolyte 3 is transferred to the top of the cathode substrate 1002. Nickel is deposited on the copper deposition layer in the same manner by using the computer program to control the nozzle device 6.

[0072] (5) Cleaning and drying: After printing is completed, turn off the power supply, move the printing platform 10 to the bottom of the device by the z-axis moving device 9, remove the cathode substrate 1002 from the solution with tweezers, clean the parts and dry them.

[0073] Driving the one-dimensional linear motion of the copper-silver-nickel inchworm-like microrobot: The copper-silver-nickel inchworm-like microrobot can adopt two thermal driving modes, such as Figure 17Mode one is a single heater timed drive, in which a heater is used to heat the copper-silver layer. Since the thermal expansion coefficient of silver is larger than that of copper, the copper-silver layer will bend toward the copper side when heated, and rub against the rough surface during the curling process, driving the copper-silver-nickel inchworm-like microrobot to move forward. Since the copper layer has thermal conductivity, the heat of the copper-silver layer will be transferred to the copper-nickel layer. Since the thermal expansion coefficient of nickel is smaller than that of copper, the copper-nickel layer will bend toward the nickel side, thereby lifting the copper-silver layer and cutting off the heater to stop heating. When the temperature returns to the initial temperature, the copper-silver-nickel inchworm-like microrobot will return to a state close to its initial state. The intermittent heating is repeated in this way. As long as the distance between the silver layer and the nickel layer and the heating temperature of the copper-silver layer are determined, the response time of the copper-silver-nickel inchworm-like microrobot can be controlled, thereby realizing the timed motion of the copper-silver-nickel inchworm-like microrobot on a one-dimensional straight line. Mode 2 is rapid drive with dual heaters. First, the copper-silver layer is quickly heated with a heater to quickly increase the temperature of the copper-silver layer. Before the heat has time to be transferred to the copper-nickel, the copper-silver layer is curled. Then, the heater heating the copper-silver layer is cut off. After that, the copper-nickel layer is heated with a heater to bend the copper-nickel layer, and the copper-silver layer is lifted. The heater heating the copper-nickel layer is cut off. When the temperature returns to the initial temperature, the shape of the component will return to a state close to its initial state. This cycle of intermittent heating can realize the one-dimensional linear rapid movement of the copper-silver-nickel inchworm-like microrobot.

[0074] Driving the copper-silver-nickel inchworm-like microrobot to move in a two-dimensional plane: multiple copper-silver-nickel inchworm-like microrobots are mounted on a poor conductor connector to assemble into a two-dimensional copper-silver-nickel inchworm-like microrobot, such as Figure 18 By driving each copper-silver-nickel inchworm-like microrobot according to the above-mentioned driving mode, the copper-silver-nickel inchworm-like microrobot can move in a two-dimensional plane and also has the ability to move on complex terrain.

Claims

1. A copper-silver-nickel precision area electrochemical deposition 4D printing device, characterized by: It includes a base, a locking device, a frame device, a brush device, a nozzle conversion device, a nozzle device, an x-axis electric linear slide, a y-axis electric linear slide, a z-axis moving device and a printing platform, wherein the frame device is fixed to the base by a locking device, the brush device is welded to the nozzle conversion device, the brush device includes a brush slot, a spring and a brush, wherein the brush and the spring are installed in the brush slot, the brush slot is welded to the end cover of the converter, the brush slides in the brush slot and the brush through hole, and is tightly pressed on the circular boss of the converter under the action of the spring, the brush is connected to the positive pole of the power supply, so that the electrode in the nozzle is connected to the positive pole of the power supply, the converter includes a slot, a circular hole and a circular boss, wherein three slots are opened in the converter, Used to connect the electrode inside the nozzle and the circular boss on the converter. The three circular bosses of the converter are conductive, and the rest are insulated, so that the electrode inside the nozzle is connected to the positive pole of the power supply. The nozzle conversion device is welded to the frame device. The nozzle device is installed on the nozzle conversion device through a threaded connection and rotates with the nozzle replacement device. The nozzle device includes a pressure sensor for controlling the ejection speed and pressure of the electrolyte. The z-axis moving device is installed on the frame device and realizes up and down movement through the engagement of gears and racks. The x-axis electric linear slide is installed on the y-axis electric linear slide through a threaded connection. The y-axis electric linear slide is installed in the z-axis moving device through a threaded connection. The printing platform is installed on the x-axis electric linear slide through a threaded connection.

2. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The base includes a base, a support plate 1, a light hole 1, a support plate 2 and a threaded hole, wherein the support plate 1 is punched with a light hole 1 and is fixedly connected to the base, and the support plate 2 is punched with a threaded hole and is fixedly connected to the base; The locking device includes a locking thread, a locking wrench, a boss, a shoulder, and an optical axis, wherein the optical axis passes through the first optical hole and the second optical hole in sequence, the locking thread is connected to the threaded hole by a thread, the diameter of the boss is larger than the diameter of the second optical hole and smaller than the diameter of the first optical hole, when the locking wrench is rotated, the shoulder presses the support frame, thereby pressing the support frame and the second support plate at the same time, and the frame device is locked under the action of friction. When the locking device is loosened, the frame device can rotate around the optical axis, which is convenient for installing and removing the nozzle device; The rack device comprises a supporting frame, a rack and a second light hole. The rack is fixed on the supporting frame and the second light hole is located on the supporting frame.

3. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The nozzle conversion device includes a servo motor, a converter fastening cover, a converter end cover, and a converter, wherein the servo motor output shaft is connected to the converter, the converter is clamped between the converter end cover and the converter fastening cover, and the converter end cover and the converter fastening cover are connected by threads; The converter end cover includes a limiting convex shoulder, a brush through hole, and a shell, wherein the brush through hole is located on the side of the shell, and the limiting convex shoulder limits the position of the converter in the shell, so that the converter can slide stably in the converter end cover; The converter is provided with three circular holes for connecting the nozzle device, and the servo motor rotates to drive the converter to rotate in the converter end cover.

4. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The nozzle device further comprises a nozzle cover, an electrode and a nozzle housing, wherein the electrode and the pressure sensor are integrated on the nozzle cover, and the nozzle cover is threadedly connected to the nozzle housing.

5. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The x-axis electric linear slide includes a slider 1, a guide rail 1, a screw 1 and a servo motor, wherein the slider 1 includes a moving platform 1 and a nut block 1, the nut block 1 is fixed to the bottom of the moving platform 1, the nut block 1 is threadedly connected to the screw 1, the screw 1 is installed on the guide rail 1, the servo motor output shaft is fixedly connected to one end of the screw 1, the guide rail 1 is threadedly connected to the slider 2, the servo motor rotates to drive the screw 1 to rotate, and then drives the slider 1 to move along the guide rail 1 to realize the x-axis.

6. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The y-axis electric linear slide includes a slider 2, a guide rail 2, a screw 2 and a servo motor, wherein the slider 2 includes a moving platform 2 and a nut block 2, the nut block 2 is fixed to the bottom of the moving platform 2, the nut block 2 is used to be threadedly connected to the screw 2, the screw 2 is installed on the guide rail 2, the servo motor output shaft is fixedly connected to one end of the screw 2, the guide rail 2 is threadedly connected to the linear slide placement groove, the rotation of the servo motor drives the screw to rotate, and then drives the slider 2 along the guide rail 2 to realize the y-axis movement.

7. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The z-axis moving device includes a stepper motor, a linear slide placement slot and a spur gear, wherein the stepper motor is fixedly connected to the side wall of the linear slide placement slot, and the stepper motor drives the spur gear to rotate, thereby causing the spur gear to move up and down relative to the rack to achieve z-axis movement.

8. The copper-silver-nickel precision area electrochemical deposition 4D printing device according to claim 1, characterized in that: The printing platform includes a deposition tank and a cathode substrate, wherein the deposition tank is fixed on the slider 1, and the cathode substrate is placed in the deposition tank.

9. A printing method using the copper-silver-nickel precision area electrochemical deposition 4D printing device according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Preparation of electrodeposition reaction solution: Electrolyte 1: 16.8g copper sulfate CuSO4 and 7.68g sulfuric acid H2SO4 are dissolved in 100mL deionized water and stirred; Electrolyte 2: 30g silver nitrate AgNO3 powder, 134.47g 5-sulfosalicylic acid C7H6O6S•2H2O powder, 9.882g potassium hydroxide KOH powder, 56g ammonium acetate CH3COONH4, and 112g ammonia water NH3•H2O are added to 100mL deionized water and stirred; Electrolyte 3: 35g nickel sulfate hexahydrate NiSO4•6H2O, 2g sodium chloride NaCl powder, 8g boric acid H3BO3 powder, 12g sodium sulfate Na2SO4 powder, 0.02g sodium dodecyl sulfate C 12 H 25 SO4Na powder was dissolved in 250 mL of deionized water and stirred; (2) Preparation of cathode substrate: The material of cathode substrate is selected from silver sheets with stable performance. The purchased silver sheets are cut into 10mm×10mm size and 100μm thickness, and adhered with conductive tape to facilitate the subsequent connection to the negative pole of the power supply. To ensure the smooth surface of the silver sheet, the silver sheet is polished on a grinding and polishing machine with a polishing cloth and polishing liquid, and the surface is cleaned with distilled water after polishing. To dissolve the residual grease on the silver sheet, it is cleaned with a prepared NaOH solution and degreased with ultrasonic assistance. After degreasing, it is cleaned with weak acid and finally cleaned with distilled water and dried. (3) Model data conversion: Use Catia software to build a three-dimensional model of the part to be printed, slice the layers to form an STL format file, and deposit the part layer by layer according to the scanning path by controlling the nozzle device, output voltage, and the movement speed of the x-axis electric linear slide, y-axis electric linear slide, and z-axis moving device; (4) Printing of microscopic metal components: The nozzle device filled with electrolyte 1 is rotated to the top of the cathode substrate. At this time, the circular boss on the converter corresponding to the nozzle device is in contact with the brush, thereby connecting to the positive pole of the power supply. Then, the z-axis moving device is adjusted so that the nozzle device maintains an appropriate distance from the cathode substrate. Then, the power is turned on and voltage is applied. The computer program controls the x-axis electric linear slide, the y-axis electric linear slide, and the z-axis moving device to move the printing platform, thereby causing the nozzle device to deposit a copper layer at the corresponding position set by the computer. After the copper layer deposition is completed, the converter is rotated so that the nozzle device filled with electrolyte 2 is turned to the top of the cathode substrate. Silver is deposited on the copper deposition layer in the same way by using the computer program to control the nozzle device; After the silver deposition is completed, the converter is rotated so that the nozzle device filled with electrolyte 3 is turned to the top of the cathode substrate, and nickel deposition is carried out on the copper deposition layer in the same way by controlling the nozzle device using a computer program; (5) Cleaning and drying of parts: After printing is completed, turn off the power supply, move the printing platform to the bottom of the device using the z-axis moving device, remove the cathode substrate from the solution with tweezers, clean the parts and dry them.

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