CN113215625B - Electrochemical metal 3D printing method for processing serial-type variable-diameter metal column structure - Google Patents
Electrochemical metal 3D printing method for processing serial-type variable-diameter metal column structure Download PDFInfo
- Publication number
- CN113215625B CN113215625B CN202110498128.5A CN202110498128A CN113215625B CN 113215625 B CN113215625 B CN 113215625B CN 202110498128 A CN202110498128 A CN 202110498128A CN 113215625 B CN113215625 B CN 113215625B
- Authority
- CN
- China
- Prior art keywords
- meniscus
- nozzle
- metal column
- metal
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/003—3D structures, e.g. superposed patterned layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
Abstract
An electrochemical metal 3D printing method for processing a tandem type variable-diameter metal column structure belongs to the technical field of metal 3D printing technology and electrochemical manufacturing. The electrolyte is extruded from the nozzle and is in contact with the cathode substrate to form a meniscus, and the meniscus is divided into three parts, namely an inverted cone, a cylinder and a cone; the distance between the printing nozzle and the cathode substrate is adjusted to enable the deposition layers to be respectively positioned on different parts of the meniscus; when the deposition layers are respectively positioned in the conical shape, the cylindrical shape and the inverted conical shape of the meniscus, the deposition layers can be deposited along the shape of the liquid-gas interface of the meniscus to form a corresponding inverted conical metal column, a cylindrical metal column and a conical metal column. When the series-connection type variable-diameter metal column structure is processed, electrochemical reaction is firstly carried out on the cathode substrate to deposit the conical column, then inverted conical column deposition with large diameter change gradient is carried out, and then the conical column deposition and the inverted conical column deposition are alternately carried out until the processing is finished. The invention has the advantages of easy operation, low cost, good controllability and the like.
Description
Technical Field
The invention belongs to the technical field of metal 3D printing technology and electrochemical manufacturing, and relates to an electrochemical metal 3D printing method for processing a variable-diameter metal column structure and a method for processing a serial tapered hydrophilic self-conveying lead based on the method.
Background
Due to the special geometric characteristics of the conical column structure, spontaneous and directional movement of liquid drops on the surface of the conical column structure can be realized, and the conical column structure has wide application prospects in the fields of pumpless transportation, heat dissipation and cooling, mist collection and the like. In 2004, concentrated matter physics of france, etc. found that droplets on tapered fibers spontaneously moved to the downward curvature region under the action of laplace pressure gradient, indicating that tapered hydrophilic thin wires could serve as the matrix for spontaneous droplet transport (j. fluid mech.2004,510: 29-45). In 2014, Wang et al used an electrochemical etching method to etch uniform copper wires into tapered hydrophilic thin wires that enable directional transport of droplets (ACS Nano 2014,8,8757 and 8764). Researchers find that the tandem type tapered metal column structure can realize long-distance, spontaneous and directional transportation. In 2018, Shi et al processed and obtained serial tapered hydrophilic copper wires by a method combining chemical etching and electrochemical etching, and the wires have serial tapered column structures, so that liquid drops can be directionally transported for a long distance under the action of Laplace pressure difference (ACS appl.Mater.Inter.2018,10, 34735-. However, the processing method of the series connection type tapered metal column structure is mostly material-reducing manufacturing, a target tapered structure is obtained by removing a large amount of metal materials, a large amount of metal materials are wasted, and a complex geometric structure is difficult to obtain; and additive manufacturing (3D printing) can efficiently improve metal utilization, reduce machining processes, and can manufacture complex structural members.
At present, the metal 3D printing method mainly comprises the following steps: laser sintering metal 3D printing, electron beam melting metal 3D printing, electrochemical metal 3D printing and the like. Electrochemical metal 3D printing as a novel metal 3D printing technology, metal ions are reduced to metal simple substances to be deposited on a cathode substrate by using an electrochemical deposition manner; compared with the traditional metal 3D printing technology such as laser sintering, electron beam melting and the like, the method has low processing cost because expensive heat sources and inert gas protection are not needed, and great interest is brought to researchers in various countries. In 2010, Hu et al proposed an electrochemical metal 3D printing technique based on meniscus confinement, which utilizes half-moon shaped electrolyte between the printing nozzle and the cathode to limit the current spreading, so that the current can be concentrated at one point, and the metal pillar structure can be efficiently manufactured (Science 2010,329: 313-316). In 2015, Seol et al processed solid equal-diameter columns and equal-diameter hollow tubes (Small.2015,11: 3896-. In 2020, Liao et al proposed a closed-loop constant current control method for meniscus-electrochemical metal 3D printing technology, further improving the stability of processing of equal-diameter columns (AIP Advances.2020,10: 045118).
In summary, the current tandem type tapered metal column structure has complex processing procedures and large processing difficulty, and is difficult to meet the current processing requirements; the electrochemical metal 3D printing method has excellent application prospect in manufacturing metal column structures. However, at present, electrochemical metal 3D printing can only process a columnar structure with the same diameter along the growth direction, and the research on processing a variable-diameter metal column is fresh. Therefore, it is necessary to develop an electrochemical metal 3D printing method for processing a tandem variable diameter metal pillar structure.
Disclosure of Invention
The invention aims to provide an electrochemical metal 3D printing method for processing a tandem type variable-diameter metal column structure, aiming at the problem that the electrochemical metal 3D printing technology can only process a metal column structure with the same diameter along the growth direction but cannot process a variable-diameter metal column structure.
In order to achieve the purpose, the invention adopts the technical scheme that:
in the method, electrolyte is extruded from a nozzle and is contacted with a cathode substrate to form a meniscus, and the meniscus is divided into three parts, namely an inverted cone, a cylinder and a cone; the distance between the printing nozzle and the cathode substrate is adjusted to enable the deposition layers to be respectively positioned on different parts of the meniscus; when the deposition layers are respectively positioned in the conical shape, the cylindrical shape and the inverted conical shape of the meniscus, the deposition layers can be deposited along the shape of the liquid-gas interface of the meniscus to form a corresponding inverted conical metal column, a cylindrical metal column and a conical metal column. When the series-connection type variable-diameter metal column structure is processed, electrochemical reaction is firstly carried out on the cathode substrate to deposit the conical column, then inverted conical column deposition with large diameter change gradient is carried out, and then the conical column deposition and the inverted conical column deposition are alternately carried out until the processing is finished. The method specifically comprises the following steps:
firstly, configuring corresponding metal ion solution/electrolyte 9 according to metal to be printed, adding the electrolyte 9 into a printing nozzle 1 through an electrolyte replacing port 8, and fixedly mounting the printing nozzle 1 on a printing nozzle clamp bracket 3 through a printing nozzle clamp 2; respectively connecting an anode bar 5 and a cathode substrate 11 with the anode and the cathode of a power supply, and inserting the anode bar 5 into the printing nozzle 1; the computer controls the micro-feeding pump 7 to adjust the air pressure in the printing nozzle 1, and supplies a small amount of electrolyte 9, so that the electrolyte 9 is extruded out from a nozzle 10 at the bottom of the printing nozzle 1, meanwhile, a porous hydrogel 12 is arranged below the inner part of the nozzle 10, and the electrolyte 9 is pushed by the air pressure to penetrate through the nozzle 10 and the porous hydrogel 12, and a meniscus 13 (liquid arc) is formed at the bottom of the nozzle 10. The micro-feed pump 7 is connected with the printing nozzle 1 through the gas connecting pipe 6, the air pressure in the printing nozzle 1 can be controlled by adjusting the micro-feed pump 7, and the pressure of the meniscus 13 is controlled: when the air pressure in the printing nozzle 1 is reduced, the air pressure outside the nozzle is atmospheric pressure, and the air pressure in the printing nozzle is smaller than the atmospheric pressure, the meniscus 13 is contracted, and the electrolyte 9 is sucked; when the air pressure in the printing nozzle 1 is increased, the air pressure outside the nozzle is atmospheric pressure, and at the moment, the air pressure in the printing nozzle 1 is greater than the atmospheric pressure, the meniscus 13 is expanded, and the electrolyte 9 is extruded out.
Before the printing is started, the nozzles 10 are separated from the cathode substrate 11; when printing is started, the bottom of the nozzle 10 is gradually lifted to 80-120 μm away after contacting the cathode substrate 11; subsequently, the pressure in the nozzle 10 is contracted by adjusting the micro-feed pump 7, so that the meniscus 13 is kept continuous and not disconnected; due to the capillary effect, the nozzle 10 forms a meniscus 13 with the cathode substrate 11.
In a second step, the meniscus 13 is divided into three parts according to the shape approximation: from the bottom of the nozzle 10 to the surface of the cathode substrate 11 are an inverted cone portion 14, a cylindrical portion 15, and a cone portion 16, respectively. If the distance in the vertical direction between the bottom of the nozzle 10 and the surface of the cathode substrate 11 is L, the heights in the vertical direction of the reverse tapered portion 14, the cylindrical portion 15, and the tapered portion 16 are 2/5L, 1/5L, and 2/5L, respectively.
When the electrochemical deposition is started, the meniscus 13 is in contact with the cathode substrate 11, and under the action of current, metal ions in the meniscus 13, which are in contact with the cathode substrate 11, obtain electrons and are reduced into a simple metal substance; as the reaction continues, the metal simple substance is gradually accumulated to form a metal column, such as the tapered metal column 17, and the region of the metal column in contact with the meniscus is the region where the electrochemical reaction is located, which is called the electrochemical reaction interface.
When a metal column is processed, the distance between the bottom of the nozzle 10 and the electrochemical reaction interface is observed by a high-magnification industrial camera, the distance is adjusted by moving the printing nozzle 1, the electrochemical reaction interface is deposited along the shape of the liquid-gas interface of the meniscus 13 (namely, the electrochemical reaction interface can be respectively positioned at different parts of the meniscus by adjusting the distance between the nozzle 10 and the cathode substrate 11), as the reaction proceeds, the electrochemical reaction interface gradually passes through the conical part 16, the cylindrical part 15 and the inverted conical part 14 of the meniscus in sequence, a column structure with the shape corresponding to the meniscus 13 is formed in the reacted area, namely, when the electrochemical reaction interface is respectively positioned at the conical part 16, the cylindrical part 15 and the inverted conical part 14 of the meniscus, the electrochemical reaction interface is deposited along the shape of the meniscus-gas interface, and a corresponding conical metal column 17, a conical metal column and a conical column are formed, A cylindrical metal pillar and an inverted conical metal pillar 19.
The invention can be used for processing the conical metal column 17 and also can be used for processing the inverted conical metal column 19.
Thirdly, the concrete process of processing the tapered metal column 17 is as follows:
if the tapered metal post 17 is machined: when the electrochemical deposition is started, the printing nozzle 1 is kept still, after the high-magnification industrial camera observes that metal simple substances are generated on the surface of the cathode substrate 11, the printing nozzle 1 is moved, and the top of the metal column is always kept in the conical part 16 of the meniscus; in the process of moving the printing nozzle 1, the micro-feeding pump 7 is controlled in real time to reduce the amount of the electrolyte 9 extruded, and at the moment, the meniscus 13 is contracted to form a meniscus as shown in fig. 3; because the porous hydrogel 12 is arranged in the nozzle 10, the electrolyte 9 outside the nozzle 10 can be slowly reduced, and the shape of the original meniscus 13 is not influenced; as the reaction proceeds, the electrochemical reaction interface will move along the meniscus 13 from the cathode substrate 11 towards the nozzle 10; controlling the distance between the nozzle 10 and the cathode substrate 11, and adjusting the micro-feeding pump 7 to control the air pressure of the printing nozzle 1; the shape of the meniscus 13 is maintained with a meniscus-tapered portion 16, a cylindrical portion 15 and an inverted conical portion 14; and the electrochemical reaction interface is gradually deposited along the electrolyte conical part 16, the diameter of the top of the conical metal column 17 generated by electrochemical deposition is continuously reduced along the outer edge of the electrolyte conical part 16 along with the deposition; the electrochemical reaction interface is maintained at the tapered portion 16 until the tapered metal pillar 17 to be printed is completed.
Fourthly, the specific process of processing the inverted cone-shaped metal column is as follows:
processing the inverted conical metal column 19: on the basis of the third step, continuously moving the printing nozzle 1, reducing the distance between the nozzle 10 and the cathode substrate 11, and enabling the electrochemical reaction interface to be positioned within L/2 of the reverse conical part 14 of the electrolyte, namely directly skipping over the cylindrical part 15 of the electrolyte; the micro-feed pump 7 is used for adjusting the air pressure in the printing nozzle 1, the extrusion amount of the electrolyte 9 is increased in a proper amount, the curvature of the meniscus is increased, and the electrochemical reaction interface is kept in the inverted conical part 14 of the electrolyte meniscus 13; as the reaction proceeds, the electrochemical reaction interface will move along the meniscus 13 from the shaped region towards the nozzle 10; controlling the distance between the nozzle and the cathode substrate, and adjusting the micro-feed pump 7 to control the air pressure of the printing nozzle 1; keeping the shape of the meniscus 13 with only the inverted conical portion 14; the electrochemical reaction interface will continue to grow from the cathode substrate 11 to the nozzle 10 in the inverted cone-shaped part 14 as the reaction proceeds gradually; the diameter of the top of the inverted conical metal column 19 is kept to be increased continuously until the inverted conical metal column 19 to be printed is completed.
The tapered metal posts 17 and the reverse tapered metal posts 19 printed at this time form a first layer structure of the tandem type variable diameter metal posts.
A fifth step of forming a second layer structure
5.1) forming a second layer of meniscus 13, and after finishing the processing of the structures of the conical metal column and the inverted conical metal column of the first layer, moving the printing nozzle 1 to enable the distance between the printing nozzle 1 and the cathode substrate to be separated by the length of L again; controlling the micro feed pump 7 in real time to adjust the air pressure inside the print head 1, contracting the meniscus 13 to regain the conical 16, cylindrical 15 and inverted conical 14 portions of the meniscus;
5.2) depositing a second layer of tapered metal pillar structures: 5.2) depositing a second layer of tapered metal pillar structures: and repeating the processes of the third step and the fourth step, and sequentially printing the conical metal column 17 and the inverted conical metal column 19 with the designed height to form a second layer structure of the serial-type variable-diameter metal column.
For example, the process of depositing the second layer of tapered metal posts 17 is: starting electrodeposition, controlling the distance between the nozzle 10 and the cathode substrate 11 in real time, and adjusting the micro-feed pump 7 to control the air pressure of the printing nozzle 1; the shape of the meniscus 13 is maintained with a meniscus-tapered portion 16, a cylindrical portion 15 and an inverted conical portion 14; and the electrochemical reaction interface is gradually deposited along the electrolyte conical part 16, the diameter of the top of the conical metal column 17 generated by electrochemical deposition is continuously reduced along the outer edge of the electrolyte conical part 16 along with the deposition; the electrochemical reaction interface is kept continuously in the tapered portion 16, so that the diameter of the top of the tapered metal pillar 17 is uniformly reduced until the tapered metal pillar 17 with the designed height is completed.
Sixthly, the specific process of processing the tandem type variable-diameter metal column structure is as follows:
repeating the fifth step of the method, namely continuously and sequentially processing the conical metal column 17 and the inverted conical metal column 19 by adjusting the position of the electrochemical reaction interface at each deposition stage until the design height of the serial-type variable-diameter metal column structure is reached, and finally finishing the manufacture of the serial-type variable-diameter metal column structure;
and seventhly, after the processing is finished, controlling the printing nozzle 1 to separate the meniscus 13 from the serial-type variable-diameter metal column, cleaning the obtained serial-type variable-diameter metal column, and drying after removing the electrolyte 9 and impurities remained on the surface.
Further, the electrolyte 9 is a soluble salt solution of a printing metal simple substance, and the soluble salt solution with a specific concentration can be obtained by dissolving the metal soluble salt in deionized water with a specific volume.
Further, the porous hydrogel 12 serves to provide back pressure to prevent excessive extrusion/inhalation of the electrolyte 9 due to pressure shock.
The invention has the beneficial effects that:
(1) the invention provides a method for processing a variable-diameter metal column structure.
(2) The invention provides an electrochemical metal 3D printing method for processing a tandem type variable-diameter metal column structure, which can realize continuous growth of a tandem type variable-diameter metal column by continuously adjusting a deposition area.
(3) The invention combines 3D printing and electrochemical deposition, and solves the defects of complicated process route and high processing cost of the traditional metal 3D printing metal column manufacturing process.
(4) The invention utilizes the micro-feed pump to control the extrusion amount of the electrolyte at the nozzle, and the porous hydrogel arranged in the nozzle provides back pressure to prevent the electrolyte from being extruded/sucked excessively due to sudden change of pressure, thereby maintaining the shape of the original meniscus and realizing the uniform and continuous growth of the variable-diameter metal column.
(5) The cathode substrate material and the processed metal column material can be various metal materials, and the processing application range is wide.
Drawings
FIG. 1 is a three-dimensional schematic diagram of an electrochemical 3D printed structure using a variable diameter metal pillar structure;
FIG. 2 is a two-dimensional cross-sectional view of a print head of the printing apparatus;
FIG. 3 is a schematic illustration of meniscus formation;
FIG. 4 is a schematic diagram of the operation of machining a tapered metal post;
FIG. 5 is a schematic diagram of the operation of machining a metal stud with an inverted cone shape;
FIG. 6 is a pictorial view of a machined tapered metal post and an inverted tapered metal post; FIG. 6(a) is a tapered metal pillar, and FIG. 6(b) is an inverted tapered metal pillar;
FIG. 7 is a schematic diagram of the operation of processing the tandem type variable diameter metal column;
FIG. 8 is a schematic view of a prepared tandem variable diameter metal pillar.
In the figure: 1, printing a spray head; 2 printing the nozzle clamp; 3 printing nozzle clamp bracket; 4, rubber stopper; 5 an anode rod; 6, connecting an air pipe; 7 a micro-feed pump; 8, an electrolyte replacing port; 9 an electrolyte; 10 a nozzle; 11 a cathode substrate; 12 a porous hydrogel; 13 a meniscus; 14 a meniscus inverted cone portion; 15 a meniscus cylindrical portion; 16 a meniscus tapered section; 17 a tapered metal post; 19 a metal column of reverse taper shape.
Detailed Description
The present invention will be further described with reference to the accompanying drawings. The inventive embodiments of the present invention will be described in detail by taking an example of processing a tandem variable diameter metal pillar.
A serial-type variable-diameter metal column processing method realized based on an electrochemical 3D printing method for processing variable-diameter metal columns comprises the following steps:
firstly, configuring corresponding metal ion solution/electrolyte 9 according to metal to be printed, adding the electrolyte 9 into a printing nozzle 1 through an electrolyte replacing port 8, and fixedly mounting the printing nozzle 1 on a printing nozzle clamp bracket 3 through a printing nozzle clamp 2; the anode bar 5 and the cathode substrate 11 are respectively connected with the anode and the cathode of a power supply; the micro-feeding pump 7 is connected with the printing nozzle 1 through the air connecting pipe 6, and the air pressure in the printing nozzle 1 can be controlled by adjusting the micro-feeding pump 7 to control the pressure on the meniscus; when the air pressure in the printing nozzle is reduced, the air pressure outside the nozzle is the atmospheric pressure, and the air pressure in the printing nozzle is smaller than the atmospheric pressure, the meniscus 13 is contracted, and the electrolyte 9 is sucked; when the air pressure in the printing nozzle is increased, the air pressure outside the nozzle is atmospheric pressure, the air pressure in the printing nozzle is greater than the atmospheric pressure, the meniscus 13 is expanded, and the electrolyte 9 is extruded out; the computer controls the micro-feeding pump 7 to adjust the air pressure in the printing spray head 1, and supplies a small amount of electrolyte 9, so that the electrolyte 9 is extruded out from a nozzle 10 at the bottom of the printing spray head 1, meanwhile, the porous hydrogel 12 is arranged below the inner part of the nozzle 10, and the electrolyte 9 is pushed by the air pressure to penetrate through the nozzle 10 and the porous hydrogel 12, so that a liquid arc is formed at the bottom of the nozzle. The porous hydrogel 12 is used to provide a back pressure that prevents excessive extrusion/aspiration of the electrolyte 9 due to pressure surges. Before the printing is started, the nozzles 10 are separated from the cathode substrate 11; when printing starts, the bottom of the nozzle 10 is contacted with the cathode substrate 11 and then gradually lifted to be 100 μm away; subsequently, the micro-feed pump is adjusted to shrink the pressure in the nozzle 10, so that the meniscus 13 is kept continuous and not disconnected; due to the capillary effect, the nozzle 10 forms a meniscus 13 with the cathode substrate 11. The electrolyte 9 of this example is 1mol/L CuSO4 solution (250 g of the metal soluble salt is dissolved in 1L of deionized water to obtain 1mol/L CuSO4A salt solution).
In a second step, the meniscus 13 is divided into three parts according to the shape approximation: from the bottom of the nozzle 10 to the surface of the cathode substrate 11 are an inverted conical portion 14, a cylindrical portion 15, and a conical portion 16, respectively; if the distance between the bottom of the nozzle 10 and the surface of the cathode substrate 11 in the vertical direction is 100 μm, the heights of the reverse tapered portion 14, the cylindrical portion 15, and the tapered portion 16 in the vertical direction are 60 to 100 μm, 40 to 60 μm, and 0 to 40 μm, respectively.
When the electrochemical deposition is started, the meniscus 13 is in contact with the cathode substrate 11, and under the action of current, metal ions in the meniscus 13, which are in contact with the cathode substrate 11, obtain electrons and are reduced into a simple metal substance; as the reaction continues, the metal simple substance is gradually accumulated to form a metal column, such as the tapered metal column 17, and the region of the metal column in contact with the meniscus is the region where the electrochemical reaction is located, which is called the electrochemical reaction interface.
When the device is used for processing a metal column, the distance between the bottom of the nozzle 10 and the electrochemical reaction interface is observed by a high-magnification industrial camera, the printing nozzle 1 can be moved to adjust the distance, the electrochemical reaction interface can be deposited along the shape of the liquid-gas interface of the meniscus 13 (namely, the electrochemical reaction interface can be respectively positioned at different parts of the meniscus by adjusting the distance between the printing nozzle 1 and the cathode substrate 11), as the reaction progresses, the electrochemical reaction interface gradually passes through the conical part 16, the cylindrical part 15 and the inverted conical part 14 of the meniscus, a column structure with the shape corresponding to the meniscus 13 is formed in the reacted area, namely, when the electrochemical reaction interface is respectively positioned at the conical part 16, the cylindrical part 15 and the inverted conical part 14 of the meniscus, the electrochemical reaction interface can be deposited along the shape of the liquid-gas interface of the meniscus, corresponding tapered metal posts 17, cylindrical metal posts and inverted tapered metal posts 19 are formed. The invention can be used for processing the conical metal column 17 and also can be used for processing the inverted conical metal column 19.
Thirdly, the concrete process of processing the tapered metal column 17 is as follows:
if the tapered metal post 17 is machined: when the electrochemical deposition is started, the printing nozzle 1 is kept still, after the high-magnification industrial camera observes that metal simple substances are generated on the surface of the cathode substrate 11, the printing nozzle 1 is moved, and the top of the metal column is always kept in the conical part 16 of the meniscus; in the process of moving the printing nozzle 1, the micro-feeding pump 7 is controlled in real time to reduce the amount of the electrolyte 9 extruded, and at the moment, the meniscus 13 is contracted to form a meniscus as shown in fig. 3; because the porous hydrogel 12 is arranged in the nozzle 10, the electrolyte 9 outside the nozzle 10 can be slowly reduced, and the shape of the original meniscus 13 is not influenced; as the reaction proceeds, the electrochemical reaction interface will move along the meniscus 13 from the cathode substrate 11 towards the nozzle 10; controlling the distance between the nozzle and the cathode substrate, and adjusting the micro-feed pump 7 to control the air pressure of the printing nozzle 1; the shape of the meniscus 13 is maintained with a meniscus-tapered portion 16, a cylindrical portion 15 and an inverted conical portion 14; and the electrochemical reaction interface is gradually deposited along the electrolyte conical part 16, the diameter of the top of the conical metal column 17 generated by electrochemical deposition is continuously reduced along the outer edge of the electrolyte conical part 16 along with the deposition; the electrochemical reaction interface is maintained at the tapered portion 16 until the tapered metal pillar 17 to be printed is completed.
Fourthly, the specific process of processing the inverted cone-shaped metal column is as follows:
processing the inverted conical metal column 19: moving the printing nozzle 1, reducing the distance between the nozzle 10 and the cathode substrate 11, enabling an electrochemical reaction interface to be positioned within 30 micrometers of the reverse conical part 14 of the electrolyte, and directly skipping over the cylindrical part 15 of the electrolyte; the micro-feed pump 7 is used for adjusting the air pressure in the printing nozzle 1, the extrusion amount of the electrolyte 9 is increased in a proper amount, the curvature of the meniscus is increased, and the electrochemical reaction interface is kept in the inverted conical part 14 of the electrolyte meniscus 13; as the reaction proceeds, the electrochemical reaction interface will move along the meniscus 13 from the shaped region towards the nozzle 10; controlling the distance between the nozzle and the cathode substrate, and adjusting the micro-feed pump 7 to control the air pressure of the printing nozzle 1; keeping the shape of the meniscus 13 with only the inverted conical portion 14; the electrochemical reaction interface will continue to grow from the cathode substrate 11 to the nozzle 10 in the inverted cone-shaped part 14 as the reaction proceeds gradually; keeping the diameter of the top of the inverted conical metal column 19 to be increased continuously until the inverted conical metal column 19 to be printed is completed;
the tapered metal posts 17 and the reverse tapered metal posts 19 printed at this time form a first layer structure of the tandem type variable diameter metal posts.
A fifth step of forming a second layer structure
5.1) forming a second layer of meniscus 13: after the first layer of the conical metal column and the inverted conical metal column structure is processed, moving the printing nozzle 1 to enable the distance between the printing nozzle 1 and the cathode substrate to be the length of L again; controlling the micro feed pump 7 in real time to adjust the air pressure inside the print head 1, contracting the meniscus 13 to regain the conical 16, cylindrical 15 and inverted conical 14 portions of the meniscus;
5.2) depositing a second layer of tapered metal pillar structures: repeating the processes of the third step and the fourth step, and printing the conical metal column 17 and the inverted conical metal column 19 with the designed height in sequence to form a second layer structure of the series-connected variable-diameter metal column;
the process of depositing the second layer of tapered metal studs 17 is: starting electrodeposition, controlling the distance between the nozzle 10 and the cathode substrate 11 in real time, and adjusting the micro-feed pump 7 to control the air pressure of the printing nozzle 1; the shape of the meniscus 13 is maintained with a meniscus-tapered portion 16, a cylindrical portion 15 and an inverted conical portion 14; and the electrochemical reaction interface is gradually deposited along the electrolyte conical part 16, the diameter of the top of the conical metal column 17 generated by electrochemical deposition is continuously reduced along the outer edge of the electrolyte conical part 16 along with the deposition; the electrochemical reaction interface is kept continuously in the tapered portion 16, so that the diameter of the top of the tapered metal pillar 17 is uniformly reduced until the tapered metal pillar 17 with the designed height is completed. The process of depositing the second layer of the inverted tapered metal pillar 19 is the same as the fourth step.
Sixthly, the specific process of processing the tandem type variable-diameter metal column structure is as follows:
repeating the fifth step, namely continuously and sequentially processing the conical metal column 17 and the inverted conical metal column 19 by adjusting the position of the electrochemical reaction interface at each deposition stage until the design height of the serial-type variable-diameter metal column structure is reached, and finally finishing the manufacture of the serial-type variable-diameter metal column structure;
and seventhly, after the processing is finished, controlling the printing nozzle 1 to separate the meniscus 13 from the serial-type variable-diameter metal column, cleaning the obtained serial-type variable-diameter metal column, and drying after removing the electrolyte 9 and impurities remained on the surface.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (3)
1. An electrochemical metal 3D printing method for processing a tandem type variable-diameter metal column structure is characterized by comprising the following steps of:
firstly, configuring corresponding electrolyte (9) according to metal to be printed, and adding the electrolyte (9) into a printing nozzle (1); the anode bar (5) and the cathode substrate (11) are respectively connected with the anode and the cathode of a power supply; the micro-feeding pump (7) is connected with the printing nozzle (1), the porous hydrogel (12) is arranged in the nozzle (10), the computer adjusts the air pressure in the printing nozzle (1) by controlling the micro-feeding pump (7), and then supplies the electrolyte (9) in a micro-scale manner, so that the electrolyte (9) penetrates through the nozzle (10) and the porous hydrogel (12), and a meniscus (13) is formed at the bottom of the nozzle (10);
before printing is started, the nozzle (10) is separated from the cathode substrate (11), and the distance between the bottom of the nozzle (10) and the surface of the cathode substrate (11) in the vertical direction is L; when printing is started, the bottom of the nozzle (10) is contacted with the cathode substrate (11) and then gradually lifted to be 80-120 mu m away from the cathode substrate; subsequently, the pressure in the micro-feeding pump (7) is adjusted to shrink the nozzle (10) so as to keep the meniscus (13) continuous and not disconnected; the nozzle (10) and the cathode substrate (11) form a meniscus (13) due to capillary effect; the meniscus (13) comprises three portions: an inverted conical part (14), a cylindrical part (15) and a conical part (16) are respectively arranged between the bottom of the nozzle (10) and the surface of the cathode substrate (11);
secondly, when the electrochemical deposition is started, the meniscus (13) is in contact with the cathode substrate (11), metal ions in the meniscus (13) in contact with the cathode substrate (11) are reduced into metal simple substances, and the metal simple substances are gradually accumulated to form a metal column along with the reaction; the contact area of the metal column and the meniscus (13) is an area where electrochemical reaction is located, and the area is an electrochemical reaction interface;
when the metal column is processed, the distance between the bottom of the nozzle (10) and the electrochemical reaction interface is observed by a high-magnification industrial camera, and the electrochemical reaction interface can be respectively positioned at different parts of the meniscus (13) by adjusting the distance; as the reaction proceeds, the electrochemical reaction interface gradually passes through the conical part (16), the cylindrical part (15) and the inverted conical part (14) of the meniscus (13), and the electrochemical reaction interface is deposited along the shape of the liquid-gas interface of the meniscus to form a corresponding conical metal column (17), a corresponding cylindrical metal column (18) and an inverted conical metal column (19);
thirdly, the process of processing the conical metal column (17) is as follows:
when the electrochemical deposition is started, the printing nozzle (1) is kept still, when the situation that metal simple substances are generated on the surface of the cathode substrate (11) is observed, the printing nozzle (1) is moved, and the top of the metal column is kept in the conical part (16) all the time; meanwhile, in the process of moving the printing nozzle (1), the micro-feed pump (7) is controlled in real time to reduce the extrusion amount of the electrolyte (9), and the meniscus (13) is contracted at the moment; as the reaction proceeds, the electrochemical reaction interface will move along the meniscus (13) from the cathode substrate (11) towards the nozzle (10);
controlling the distance between the nozzle (10) and the cathode substrate (11), adjusting the micro-feeding pump (7) to control the air pressure of the printing nozzle (1), and keeping the shape of the meniscus (13); and the electrochemical reaction interface is gradually deposited along the tapered part (16), the diameter of the top of the tapered metal column (17) generated by electrochemical deposition is continuously reduced along the outer edge of the tapered part (16) of the electrolyte along with the progress of deposition until the tapered metal column (17) with the designed height is printed;
fourthly, the process of processing the inverted cone-shaped metal column is as follows:
reducing the distance between the nozzle (10) and the cathode substrate (11) by moving the printing nozzle (1) so that the electrochemical reaction interface is positioned in the region of the inverted conical part (14); the extrusion amount of the electrolyte (9) is increased by controlling the micro-feeding pump (7), the curvature of the meniscus (13) is increased, and the electrochemical reaction interface is kept in the inverted conical part (14); as the reaction proceeds, the electrochemical reaction interface will move from the formed area to the nozzle (10) along the meniscus (13), the distance between the nozzle (10) and the cathode substrate (11) is controlled, the micro-feed pump (7) is adjusted, and the shape of the meniscus (13) is maintained to have only the inverted conical portion (14); the electrochemical reaction interface continuously grows from the cathode substrate (11) to the direction of the nozzle (10) in the inverted cone-shaped part (14) along with the reaction until the inverted cone-shaped metal column (19) with the designed height is printed;
the printed conical metal column (17) and the inverted conical metal column (19) form a first layer structure of the series-type variable-diameter metal column;
a fifth step of forming a second layer structure
5.1) forming a second layer of meniscus (13): after the first layer structure is processed, the distance between the bottom of the nozzle (10) and the cathode substrate (11) is kept L again; controlling a micro-feeding pump (7) in real time to adjust air pressure in the printing nozzle (1), and shrinking a meniscus (13) to obtain a conical part (16), a cylindrical part (15) and an inverted conical part (14) again;
5.2) depositing a second layer of tapered metal pillar structures: repeating the processes of the third step and the fourth step, and printing the conical metal column (17) and the inverted conical metal column (19) with the designed height in sequence to form a second layer structure of the series-type variable-diameter metal column;
sixthly, repeating the fifth step, namely continuously and sequentially processing the tapered metal column (17) and the inverted conical metal column (19) by adjusting the position of the electrochemical reaction interface at each deposition stage until the design height of the series-type variable-diameter metal column structure is reached, and finally finishing manufacturing the series-type variable-diameter metal column structure;
and seventhly, after the processing is finished, controlling the printing nozzle (1) to separate the meniscus (13) from the serial-type variable-diameter metal column.
2. The electrochemical metal 3D printing method for processing the tandem type variable-diameter metal column structure as claimed in claim 1, wherein the pressure in the printing nozzle (1) can be controlled by adjusting the micro-feeding pump (7), so as to control the pressure on the meniscus (13): when the air pressure in the printing nozzle (1) is reduced, the air pressure in the printing nozzle (1) is smaller than the atmospheric pressure, the meniscus (13) is contracted, and the electrolyte (9) is sucked; when the air pressure in the printing nozzle (1) is increased, the air pressure in the printing nozzle (1) is larger than the atmospheric pressure, the meniscus (13) is expanded, and the electrolyte (9) is extruded.
3. The electrochemical metal 3D printing method for processing the tandem type variable diameter metal pillar structure according to claim 1 or 2, wherein in the first step, the heights of the reverse tapered portion (14), the cylindrical portion (15) and the tapered portion (16) in the meniscus (13) in the vertical direction are 2/5L, 1/5L and 2/5L respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110498128.5A CN113215625B (en) | 2021-05-08 | 2021-05-08 | Electrochemical metal 3D printing method for processing serial-type variable-diameter metal column structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110498128.5A CN113215625B (en) | 2021-05-08 | 2021-05-08 | Electrochemical metal 3D printing method for processing serial-type variable-diameter metal column structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113215625A CN113215625A (en) | 2021-08-06 |
| CN113215625B true CN113215625B (en) | 2022-03-29 |
Family
ID=77091640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110498128.5A Active CN113215625B (en) | 2021-05-08 | 2021-05-08 | Electrochemical metal 3D printing method for processing serial-type variable-diameter metal column structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113215625B (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU633940A1 (en) * | 1977-04-04 | 1978-11-25 | Предприятие П/Я Р-6762 | Contacting device for electrolytic coating of tubular articles |
| US20150321419A1 (en) * | 2014-05-06 | 2015-11-12 | Todd Linthicum | Extrusion system for additive manufacturing and 3-d printing |
| KR102044963B1 (en) * | 2015-07-15 | 2019-11-18 | 한국전기연구원 | 3d printing apparatus and method using electroplating |
| WO2017140239A1 (en) * | 2016-02-15 | 2017-08-24 | Shanghai Jiao Tong University | Method to print microneedle patches rapidly |
| CN106191946B (en) * | 2016-08-08 | 2018-10-09 | 江苏大学 | A kind of device and method of more current potential imbibition electro-deposition 3D printings |
| CN107320780B (en) * | 2017-06-27 | 2020-04-28 | 上普博源（北京）生物科技有限公司 | Multilayer hydrogel with hollow tube structure and preparation method and application thereof |
| CN107874853A (en) * | 2017-10-23 | 2018-04-06 | 广东省新材料研究所 | A kind of 3D printing root of the tooth implant with multi-segment structure |
| CN110306210B (en) * | 2019-07-16 | 2021-07-02 | 吉林大学 | Electrochemical 3D printing device and method for metal-based composite material part |
| CN110369860B (en) * | 2019-07-19 | 2020-12-11 | 大连理工大学 | Method for manufacturing variable-diameter complex inner runner structure |
| CN110306219B (en) * | 2019-08-15 | 2021-03-16 | 四川长虹电器股份有限公司 | Metal 3D printer based on electrochemical reaction and printing method thereof |
-
2021
- 2021-05-08 CN CN202110498128.5A patent/CN113215625B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113215625A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Nature‐inspired boiling enhancement by novel nanostructured macroporous surfaces | |
| CN106191946B (en) | A kind of device and method of more current potential imbibition electro-deposition 3D printings | |
| CN113215625B (en) | Electrochemical metal 3D printing method for processing serial-type variable-diameter metal column structure | |
| CN110359065B (en) | Jet electrodeposition nozzle and method for manufacturing seamless metal pipe by using same | |
| CN110769645A (en) | Ultrathin flat plate heat pipe liquid absorption core and manufacturing method thereof | |
| CN106835303B (en) | Metal 3D printing device and method combining laser sintering and electrospinning of carbon fibers | |
| CN110042449B (en) | Hydrophobic liquid-injection aluminum alloy surface with liquid storage tank and preparation method thereof | |
| CN113215604B (en) | Bionic wettability gradient cone cluster electrode | |
| CN104668675A (en) | Electrode with micro-conical tower array end surface and processing method and application thereof | |
| CN112779567B (en) | Micro machining tool preparation device and method and in-situ material increase and reduction manufacturing method | |
| JP2012052209A (en) | Device and method for continuously manufacturing nanoscale conductive particles | |
| CN100580149C (en) | Method and equipment for manufacturing metal parts directly by using electrodeposition technique of laminated template | |
| CN110644015B (en) | Wedge-shaped spiral curved surface electrode and preparation method thereof | |
| CN112458507A (en) | Electrodeposition writing system and method for preparing metal micro-nano structure in direct writing mode | |
| CN108080782A (en) | The lateral wall insulation method of micro hole Electrolyzed Processing electrode and application | |
| CN108468078A (en) | A kind of preparation method and application on gradient wellability surface | |
| CN112981479A (en) | Spray head for micro electro-deposition processing and micro electro-deposition processing device | |
| CN112481660A (en) | Preparation method of ordered metal nanowire array | |
| Bilal et al. | High throughput electrochemically driven metal microprinting with multicapillary droplet cell | |
| CN112091337A (en) | Method for electrolytic machining of silicon carbide reinforced aluminum matrix composite material by using jet flow | |
| CN105598537A (en) | Method for processing super-hydrophobic surface with high-adhesion micro-patterns through electro-stream process | |
| CN108115233A (en) | A kind of device and method of template electro-stream machining metal surface micro-structure | |
| CN202007125U (en) | System for batch preparation of three-dimensional microstructures with large aspect ratio | |
| KR101857460B1 (en) | Manufacturing device of nanoparticles with collecting unit of cartridge type | |
| CN115007957B (en) | Liquid bridge constrained electrochemical machining method for complex three-dimensional microstructure array |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |