CN114232058A - Electrochemical 3D printing device and method based on hollow AFM cantilever beam probe - Google Patents
Electrochemical 3D printing device and method based on hollow AFM cantilever beam probe Download PDFInfo
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- CN114232058A CN114232058A CN202111578227.0A CN202111578227A CN114232058A CN 114232058 A CN114232058 A CN 114232058A CN 202111578227 A CN202111578227 A CN 202111578227A CN 114232058 A CN114232058 A CN 114232058A
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- 239000000523 sample Substances 0.000 title claims abstract description 50
- 238000010146 3D printing Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 59
- 238000007639 printing Methods 0.000 claims abstract description 38
- 230000003287 optical effect Effects 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000000919 ceramic Substances 0.000 claims description 34
- 239000012266 salt solution Substances 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000004590 computer program Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 238000005137 deposition process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
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- 238000010276 construction Methods 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
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- 239000012141 concentrate Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
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- 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
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- 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
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Light Control Or Optical Switches (AREA)
Abstract
The invention relates to an electrochemical 3D printing device and method based on a hollow AFM cantilever beam probe, and belongs to the technical field of 3D printing and local electrodeposition. The micro-adjustment mechanism is fixed on the base, the USB optical microscope is installed on the micro-adjustment mechanism, the fixing device is fixedly connected with the micro-adjustment mechanism, the semi-transparent semi-return mirror is sleeved on the spray head device, the semiconductor laser and the position sensitive detector are installed on the fixing device, the combined high-speed scanner is fixedly connected with the micro-adjustment mechanism, and the printing chamber is fixed on the combined high-speed scanner. The method has the advantages that the hollow AFM cantilever beam probe is combined with an electrochemical deposition technology, a novel method for 3D printing of the micro-nano metal structure is developed, microscopic operation is achieved by the hollow AFM cantilever beam probe, printing precision, printing speed and part performance are greatly improved, manufacturing of a complex three-dimensional structure can be achieved, high-speed movement in the xyz direction can be achieved by the combined high-speed scanner, and printing precision is improved.
Description
Technical Field
The invention belongs to the technical field of 3D printing and local electrodeposition, and particularly relates to an electrochemical 3D printing device and method based on a hollow AFM cantilever probe.
Background
The 3D printing technique, also known as additive manufacturing, is a technique for constructing objects by layer-by-layer printing using bondable materials such as powdered metals or polymers based on digital model files. Local electrochemical deposition (LECD) is an emerging, unconventional fabrication technique, originating from precision electroforming and electroplating, which is a novel additive manufacturing technique that forms three-dimensional structures layer by layer on an atomic scale. As a method, the LECD can print micro-components or design a structure without any mold or support directly from an atomic scale at a certain position, and does not need any additional heat source, so that no thermal stress is generated during the deposition process, and the LECD does not need a strict vacuum environment nor an inert gas environment, so that the process is simple and convenient to operate and low in cost.
The existing LECD technology comprises crescent electrolyte restraining electrodeposition, micro anode local electrodeposition and the like, wherein crescent electrolyte restraining electrodeposition utilizes the surface tension of liquid to form a micro-nano crescent electrolyte cluster between an anode and a cathode to serve as an electrochemical deposition reaction tank, but is limited by insufficient hydraulic pressure of a hydraulic head, so that the crescent electrolyte cluster cannot exist stably under the outlet diameter of hundreds of micrometers, and the printing scale and the printing speed are reduced. Micro-anodic local electrodeposition uses a micro-anode as a print head and a cathode as a print substrate, both anode and cathode being immersed in an electrolyte. When a voltage is applied between the anode electrode and the cathode substrate, the intensity of the electric field generated will concentrate in the vicinity of the micro-anode, and the metal ions in the electrolyte solution will be reduced around the periphery below the micro-anode to form metal atoms, thereby generating deposits on the cathode. However, the printing accuracy of this method is limited by the size of the micro-anode, and the positioning accuracy is insufficient.
Disclosure of Invention
The invention provides an electrochemical 3D printing device and method based on a hollow AFM cantilever beam probe, and aims to solve the problems that the existing printing device is low in printing precision and low in printing speed, and a complex structure body cannot be manufactured.
The technical scheme adopted by the invention is that the device comprises a base, a fine adjustment mechanism, a USB optical microscope, a spray head device, a fixing device, a semiconductor laser, a position sensitive detector, a semi-permeable semi-return mirror, a printing chamber and a combined high-speed scanner 10, wherein the fine adjustment mechanism is fixed on the base, the USB optical microscope is installed on the fine adjustment mechanism, the fixing device is fixedly connected with the fine adjustment mechanism, the semi-permeable semi-return mirror is sleeved on the spray head device, the semiconductor laser and the position sensitive detector are installed on the fixing device, the combined high-speed scanner is fixedly connected with a fine adjustment mechanism 2, and the printing chamber is fixed on the combined high-speed scanner.
The micro-adjustment mechanism comprises a support, a fine adjuster, a lens groove and a sleeve, wherein the fine adjuster is installed in the support, the sleeve is fixedly connected with the front of the support, an adjusting column of the fine adjuster is connected with the sleeve in a sliding mode, the lens groove is located in the support, and the USB optical microscope is installed on the micro-adjustment mechanism through the lens groove.
The fine adjuster comprises a fine adjusting knob, a fine adjusting shaft, a gear, an adjusting column and a rack, wherein the fine adjusting knob is fixedly connected with two ends of the fine adjusting shaft, the gear is fixedly connected to the middle of the fine adjusting shaft, the adjusting column is fixedly connected with the rack, and the gear is meshed with the rack.
The USB optical microscope comprises a USB port and an optical microscope, wherein the USB port is connected with the upper part of the optical microscope.
The spray head device comprises a pressure controller, a pipette, a hollow cantilever beam and a hollow probe, wherein the pressure controller is connected with the top end of the pipette, the upper end of the hollow cantilever beam is connected with an outlet at the bottom end of the pipette, and the hollow probe is connected with the lower end of the hollow cantilever beam.
The fixing device comprises a fixing plate, a sleeve and a fixing support, wherein the fixing plate is used for being fixedly connected with a support of the fine adjustment mechanism and fixing the optical microscope, the fixing plate is used for fixing the spray head device, and the fixing support is used for fixing the semiconductor laser and the position sensitive detector.
And laser beams emitted by the semiconductor laser are reflected by the semi-transparent semi-return mirror and then irradiate the back of the hollow cantilever beam.
The position sensitive detector is characterized in that a laser beam emitted by the semiconductor laser is projected by the semi-transparent semi-return mirror and then is incident on the back surface of the hollow cantilever beam, and the laser beam is reflected by the back surface of the hollow cantilever beam, then passes through the semi-transparent semi-return mirror again and is incident on the photosensitive surface of the position sensitive detector.
And the semi-transparent semi-return mirror is used for projecting a laser beam emitted by the semiconductor laser through the semi-transparent semi-return mirror and then irradiating the laser beam on the back surface of the hollow cantilever beam, and the laser beam is reflected by the back surface of the hollow cantilever beam and then passes through the semi-transparent semi-return mirror again and then is irradiated on a photosensitive surface of the position sensitive detector.
The printing chamber comprises a glass cover, a silver reference electrode, a cathode substrate, an insulating layer and a platinum counter electrode, wherein the insulating layer is fixedly connected with the upper part of the platinum counter electrode, the cathode substrate is placed on the insulating layer, the glass cover is fixedly connected with the upper part of the platinum counter electrode, the silver reference electrode is connected with the inner surface of the glass cover, the silver reference electrode, the cathode substrate and the platinum counter electrode form a three-electrode electrochemical cell, the platinum counter electrode is used for being connected with a power supply anode, and the cathode substrate is used for being connected with a power supply cathode.
The combined high-speed scanner comprises a four-quadrant sheet piezoelectric ceramic scanner, a tripod scanner and a scanner base, wherein the four-quadrant sheet piezoelectric ceramic scanner is glued on a metal table of the tripod scanner through four cushion blocks, and the tripod scanner is fixedly connected in the scanner base.
The four-quadrant sheet-shaped piezoelectric ceramic scanner comprises a metal sheet, an aluminum cylinder, sheet-shaped piezoelectric ceramics and a cushion block, wherein the lower part of the metal sheet is fixedly connected with the aluminum cylinder, the lower part of the aluminum cylinder is fixedly connected with the upper part of the four-sheet-shaped piezoelectric ceramics, the lower part of the sheet-shaped piezoelectric ceramics is fixedly connected with the cushion block,
the tripod scanner comprises a metal table, a metal block and tubular piezoelectric ceramics, wherein the lower part of the metal table is fixedly connected with the metal block, the tubular piezoelectric ceramics which are mutually vertical in the xy direction are respectively fixedly connected with the side surface of the metal block and fixedly connected with the inner side of a scanner base, the upper part of the tubular piezoelectric ceramics in the z direction is fixedly connected with the bottom surface of the metal block, and the lower part of the tubular piezoelectric ceramics in the z direction is fixedly connected with the inner side bottom surface of the scanner base.
An electrochemical 3D printing method based on a hollow AFM cantilever probe comprises the following steps:
(1) preparation of an electrodeposited metal salt solution: the prepared material is a single metal ion salt solution, powdery sulfate is dissolved in deionized water, and a proper amount of concentrated sulfuric acid is added for stabilizing the pH value of the solution to obtain the required electro-deposition metal salt solution;
(2) and (3) converting part model data: constructing a part model by using Catia software, slicing and layering the model from the Z direction to enable the thickness of each layer to be nano-scale, and importing the graphic information of each layer of the model into a calculated control program;
(3) injecting a metal salt solution: the pressure controller of the spray head device is dismounted, the metal salt solution is injected into the pipette, and the pressure controller is mounted;
(4) printing the microscopic metal parts: immersing the hollow cantilever beam into a three-electrode electrochemical cell comprising a silver reference electrode and a platinum counter electrode, observing by using a USB optical microscope, reducing the distance between a cathode substrate and the hollow probe by using a fine adjustment mechanism to generate atomic force, accurately controlling a metal salt solution by using a pressure controller, and enabling metal ions to flow out of the hollow probe through the hollow cantilever beam to locally reduce the cathode substrate below the hollow probe; in the deposition process, a laser beam emitted by the semiconductor laser is projected by the semi-transparent semi-return mirror and then is incident on the back surface of the hollow cantilever beam, the laser beam is reflected by the back surface of the hollow cantilever beam and then passes through the semi-transparent semi-return mirror again and is incident on the photosensitive surface of the position sensitive detector, when a deposit grows to contact with the hollow probe, the hollow cantilever beam deflects to cause the deflection of the position of a light spot on the photosensitive surface of the position sensitive detector, so that a photocurrent signal output by the position sensitive detector to a computer program is changed, the computer program further controls the speed of the pressure controller for conveying a metal salt solution, the metal salt solution at an outlet is gradually reduced, and the metal deposition under the hollow probe is gradually stopped; then, the printing chamber is moved through the combined high-speed scanner, and the hollow probe is deposited at the next deposition position, and the deposition is carried out in a circulating reciprocating mode to finish the deposition of one layer;
(5) cleaning and drying parts: after printing, the electrochemical direct current power supply is turned off, the three-electrode electrochemical cell is disconnected from the anode and cathode leads of the electrochemical direct current power supply, the printing chamber is moved to the bottom end of the device by the fine adjustment mechanism, the cathode substrate is taken out of the solution by tweezers, and parts are cleaned and dried.
The invention has the following advantages:
(1) the hollow AFM cantilever beam probe is combined with an electrochemical deposition technology, a novel method for 3D printing of the micro-nano metal structure is developed, microscopic operation is achieved by the hollow AFM cantilever beam probe, printing precision, printing speed and part performance are greatly improved, and manufacturing of a complex three-dimensional structure can be achieved.
(2) The combined high-speed scanner replaces the transmission of a stepping motor and a servo motor of the traditional electrochemical 3D printing, has light structure and quick response, can realize high-speed movement in the xyz direction, and improves the printing precision.
(3) The invention is used for manufacturing micron-sized metal parts and has potential in the field of precision machinery manufacturing such as aerospace, medical treatment, electronics and the like.
(4) The invention avoids generating residual internal stress in the metal parts, and the performance of the parts is more excellent.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention;
FIG. 2 is a schematic diagram of the fine adjustment mechanism of the present invention;
FIG. 3 is a schematic diagram of the construction of the fine actuator of the present invention;
FIG. 4 is a schematic structural diagram of a USB optical microscope according to the present invention;
FIG. 5 is a schematic structural view of a head unit according to the present invention;
FIG. 6 is a schematic view of the construction of the fastening device of the present invention;
FIG. 7 is a schematic structural view of a printing chamber configuration of the present invention;
FIG. 8 is a schematic view of the configuration of the ejection head apparatus and print chamber of the present invention;
FIG. 9 is a schematic diagram of the combined high speed scanner of the present invention;
FIG. 10 is a sectional view A-A of FIG. 9;
FIG. 11 is a schematic view of a tripod scanner of the present invention;
FIG. 12 is a schematic view of a four-quadrant chip piezo-ceramic scanner according to the present invention;
FIG. 13 is an optical path diagram of a semiconductor laser, position sensitive detector, half mirror and showerhead arrangement of the present invention.
Detailed Description
Referring to fig. 1, the apparatus comprises a base 1, a fine adjustment mechanism 2, a USB optical microscope 3, a nozzle device 4, a fixing device 5, a semiconductor laser 6, a position sensitive detector 7, a semi-transparent semi-return mirror 8, a printing chamber 9, and a combined high-speed scanner 10, wherein the fine adjustment mechanism 2 is fixed on the base 1, the USB optical microscope 3 is installed on the fine adjustment mechanism 2, the fixing device 5 is fixedly connected with the fine adjustment mechanism 2, the semi-transparent semi-return mirror 8 is sleeved on the nozzle device 4, the semiconductor laser 6 and the position sensitive detector 7 are installed on the fixing device 5, the combined high-speed scanner 10 is fixedly connected with the fine adjustment mechanism 2 and moves along a z axis, the printing chamber 9 is fixed on the combined high-speed scanner 10, and the combined high-speed scanner 10 can control the printing chamber 9 to move on an xyz axis.
Referring to fig. 2, the fine adjustment mechanism 2 includes a bracket 201, a fine adjuster 202, a mirror groove 203 and a sleeve 204, wherein the fine adjuster 202 is installed in the bracket 201, the sleeve 204 is fixedly connected with the front of the bracket 201, an adjusting post 20204 of the fine adjuster 202 is slidably connected with the sleeve 204, the mirror groove 203 is located in the bracket 201, and the USB optical microscope 3 is installed on the fine adjustment mechanism 2 through the mirror groove 203.
Before printing, the fine actuator 202 is adjusted to cause the probes 404 to generate atomic force with the cathode substrate 904.
Referring to fig. 3, the fine adjuster includes a fine adjustment knob 20201, a fine adjustment shaft 20202, a gear 20203, an adjustment post 20204, and a rack 20205, wherein the fine adjustment knob 20201 is fixedly connected to both ends of the fine adjustment shaft 20202, the gear 20203 is fixedly connected to the middle of the fine adjustment shaft 20202, the adjustment post 20204 is fixedly connected to the rack 20205, and the gear 20203 is engaged with the rack 20205.
The fine adjustment knob 20201 is rotated to drive the gear 20203 to rotate, so as to drive the rack 20205 and the adjustment column 20204 to perform lifting movement, and the sleeve 204 ensures that the adjustment column 20204 can only slide up and down in the sleeve 204 in parallel with the sleeve 204.
Referring to fig. 4, the USB optical microscope 3 includes a USB port 301 and an optical microscope 302, wherein the USB port 301 is connected to an upper portion of the optical microscope 302.
The USB port 301 is connected to a computer to observe whether the hollow probe 404 and the cathode substrate 904 generate atomic force during adjustment of the fine actuator 202.
Referring to fig. 5, the nozzle device 4 includes a pressure controller 401, a pipette 402, a hollow cantilever 403 and a hollow probe 404, wherein the pressure controller 401 is connected to the top end of the pipette 402, the upper end of the hollow cantilever 403 is connected to the bottom outlet of the pipette 402, and the hollow probe 404 is connected to the lower end of the hollow cantilever 403.
The pressure controller 401 controls the flow of the metal salt solution out of the hollow probe 404. One end of the pressure controller 401 is connected with a computer, and the computer controls the pressure controller 401 through a program.
Referring to fig. 6, the fixing device 5 includes a fixing plate 501, a sleeve 502 and a fixing bracket 503, wherein the fixing plate 501 is used for fixedly connecting with the bracket 201 of the fine adjustment mechanism 2 and fixing the optical microscope 302, the fixing plate 502 is used for fixing the nozzle device 4, and the fixing bracket 503 is used for fixing the semiconductor laser 6 and the position-sensitive detector 7.
The semiconductor laser 6, the laser beam emitted by the semiconductor laser 6, after being reflected by the semi-transparent semi-return mirror 8, irradiates the back of the hollow cantilever 403.
Referring to fig. 13, in the position sensitive detector 7, a laser beam emitted by the semiconductor laser 6 is projected by the semi-transparent half-returning mirror 8 and then is incident on the back surface of the hollow cantilever 403, the laser beam is reflected by the back surface of the hollow cantilever 403 and then passes through the semi-transparent half-returning mirror 8 again and is incident on the photosensitive surface of the position sensitive detector 7, when a deposit grows to contact the hollow probe 404, the hollow cantilever 403 deflects to deflect a spot position on the photosensitive surface of the position sensitive detector 7, so that a photocurrent signal output from the position sensitive detector 7 to a computer program changes, the computer program further controls the rate at which the pressure controller 401 delivers the metal salt solution, the metal salt solution at an outlet is gradually reduced, and the metal deposition under the hollow probe 404 is gradually stagnated.
And in the semi-transparent semi-return mirror 8, a laser beam emitted by the semiconductor laser 6 is projected by the semi-transparent semi-return mirror 8 and then is incident on the back surface of the hollow cantilever beam 403, and the laser beam is reflected by the back surface of the hollow cantilever beam 403, then passes through the semi-transparent semi-return mirror 8 again and is incident on the photosensitive surface of the position sensitive detector 7.
Referring to fig. 7, the printing chamber 9 includes a glass cover 901, a silver reference electrode 902, a cathode substrate 903, an insulating layer 904 and a platinum counter electrode 905, wherein the insulating layer 904 is fixedly connected to the upper side of the platinum counter electrode 905, the cathode substrate 903 is disposed on the insulating layer 904, the glass cover 901 is fixedly connected to the upper side of the platinum counter electrode 905, the silver reference electrode 902 is connected to the inner surface of the glass cover 901, the silver reference electrode 902, the cathode substrate 903 and the platinum counter electrode 905 form a three-electrode electrochemical cell, the platinum counter electrode 905 is used for connecting to the positive pole of a power supply, and the cathode substrate 903 is used for connecting to the negative pole of the power supply.
Referring to fig. 9, 10, 11 and 12, the combined high-speed scanner 10 includes a four-quadrant sheet-shaped piezo-ceramic scanner 1001, a tripod scanner 1002 and a scanner base 1003, the four-quadrant sheet-shaped piezo-ceramic scanner 1001 is glued on a metal table 100201 of the tripod scanner 1002 through four spacers 100104, the tripod scanner 1002 is fixedly connected in the scanner base 1003,
the four-quadrant sheet-shaped piezoelectric ceramic scanner 1001 comprises a metal sheet 100101, an aluminum cylinder 100102, a sheet-shaped piezoelectric ceramic 100103 and a cushion block 100104, wherein the lower part of the metal sheet 100101 is fixedly connected with the aluminum cylinder 100102, the lower part of the aluminum cylinder 100102 is fixedly connected with the upper part of the four-sheet-shaped piezoelectric ceramic 100103, the lower part of the sheet-shaped piezoelectric ceramic 100103 is fixedly connected with the cushion block 100104,
the tripod scanner 1002 comprises a metal table 100201, a metal block 100202 and a tubular piezoelectric ceramic 100203, wherein the lower part of the metal table 100201 is fixedly connected with a metal block 100202, the tubular piezoelectric ceramic 100203 which is mutually vertical in the xy direction is respectively fixedly connected with the side surface of the metal block 100202 and fixedly connected with the inner side of the scanner base 1003, and the upper part of the tubular piezoelectric ceramic 100203 in the z direction is fixedly connected with the bottom surface of the metal block 100202, and the lower part of the tubular piezoelectric ceramic 100203 is fixedly connected with the inner side bottom surface of the scanner base 1003;
An electrochemical 3D printing method based on a hollow AFM cantilever probe comprises the following steps:
(1) preparation of an electrodeposited metal salt solution: the prepared material is a single metal ion salt solution, powdery sulfate is dissolved in deionized water, and a proper amount of concentrated sulfuric acid is added for stabilizing the pH value of the solution to obtain the required electro-deposition metal salt solution;
(2) and (3) converting part model data: constructing a part model by using Catia software, slicing and layering the model from the Z direction to enable the thickness of each layer to be nano-scale, and importing the graphic information of each layer of the model into a calculated control program;
(3) injecting a metal salt solution: the pressure controller 401 of the shower head device 4 is detached, the metal salt solution is injected into the pipette 402, and the pressure controller 401 is attached;
(4) printing the microscopic metal parts: immersing the hollow cantilever 403 in a three-electrode electrochemical cell comprising a silver reference electrode 902 and a platinum counter electrode 905, observing by using a USB optical microscope 3, reducing the distance between the cathode substrate 903 and the hollow probe 404 by using a fine adjustment mechanism 2 until atomic force can be generated, precisely controlling a metal salt solution by using a pressure controller 401, and enabling metal ions to flow out of the hollow probe 404 through the hollow cantilever 403 so as to partially reduce the cathode substrate 903 below the hollow probe 404; in the deposition process, a laser beam emitted by the semiconductor laser 6 is projected by the semi-transparent semi-return mirror 8 and then is incident on the back surface of the hollow cantilever 403, the laser beam is reflected by the back surface of the hollow cantilever 403 and then passes through the semi-transparent semi-return mirror 8 again and is incident on the photosensitive surface of the position sensitive detector 7, when a deposit grows to contact with the hollow probe 404, the hollow cantilever 403 deflects to cause the position of a light spot on the photosensitive surface of the position sensitive detector 7 to deflect, so that a photocurrent signal output to a computer program by the position sensitive detector 7 is changed, the computer program further controls the speed of the pressure controller for conveying a metal salt solution, the metal salt solution at an outlet is gradually reduced, and the metal deposition under the hollow probe 404 is gradually stopped; then, the printing chamber 9 is moved by the combined high-speed scanner 10, and the hollow probe 404 is deposited at the next deposition position, and the deposition is performed in a circulating reciprocating manner to complete the deposition of one layer;
(5) cleaning and drying parts: after printing is completed, the electrochemical dc power supply is turned off, the three-electrode electrochemical cell is disconnected from the anode and cathode leads of the electrochemical dc power supply, the print chamber 9 is moved to the bottom end of the device by the fine adjustment mechanism 2, the cathode substrate 903 is removed from the solution with tweezers, the parts are washed and dried.
Claims (10)
1. The utility model provides an electrochemistry 3D printing device based on hollow AFM cantilever beam probe which characterized in that: the device comprises a base, a fine adjustment mechanism, a USB optical microscope, a spray head device, a fixing device, a semiconductor laser, a position sensitive detector, a semi-transparent half-returning mirror, a printing chamber and a combined high-speed scanner 10, wherein the fine adjustment mechanism is fixed on the base, the USB optical microscope is installed on the fine adjustment mechanism, the fixing device is fixedly connected with the fine adjustment mechanism, the semi-transparent half-returning mirror is sleeved on the spray head device, the semiconductor laser and the position sensitive detector are installed on the fixing device, the combined high-speed scanner is fixedly connected with the fine adjustment mechanism 2, and the printing chamber is fixed on the combined high-speed scanner.
2. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, wherein: the micro-adjustment mechanism comprises a support, a fine adjuster, a lens groove and a sleeve, wherein the fine adjuster is installed in the support, the sleeve is fixedly connected with the front of the support, an adjusting column of the fine adjuster is connected with the sleeve in a sliding mode, the lens groove is located in the support, and the USB optical microscope is installed on the micro-adjustment mechanism through the lens groove.
3. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 2, characterized in that: the fine adjuster comprises a fine adjusting knob, a fine adjusting shaft, a gear, an adjusting column and a rack, wherein the fine adjusting knob is fixedly connected with two ends of the fine adjusting shaft, the gear is fixedly connected to the middle of the fine adjusting shaft, the adjusting column is fixedly connected with the rack, and the gear is meshed with the rack.
4. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, characterized in that: the USB optical microscope comprises a USB port and an optical microscope, wherein the USB port is connected with the upper part of the optical microscope.
5. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, characterized in that: the spray head device comprises a pressure controller, a pipette, a hollow cantilever beam and a hollow probe, wherein the pressure controller is connected with the top end of the pipette, the upper end of the hollow cantilever beam is connected with an outlet at the bottom end of the pipette, and the hollow probe is connected with the lower end of the hollow cantilever beam.
6. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, characterized in that: the fixing device comprises a fixing plate, a sleeve and a fixing support, wherein the fixing plate is used for being fixedly connected with a support of the fine adjustment mechanism and fixing the optical microscope, the fixing plate is used for fixing the spray head device, and the fixing support is used for fixing the semiconductor laser and the position sensitive detector.
7. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, characterized in that: the laser beam emitted by the semiconductor laser is reflected by the semi-transparent semi-return mirror and then irradiates the back of the hollow cantilever beam;
the position sensitive detector is characterized in that a laser beam emitted by the semiconductor laser is projected by the semi-transparent semi-return mirror and then is incident on the back surface of the hollow cantilever beam, and the laser beam is reflected by the back surface of the hollow cantilever beam, then passes through the semi-transparent semi-return mirror again and is incident on a photosensitive surface of the position sensitive detector;
and the semi-transparent semi-return mirror is used for projecting a laser beam emitted by the semiconductor laser through the semi-transparent semi-return mirror and then irradiating the laser beam on the back surface of the hollow cantilever beam, and the laser beam is reflected by the back surface of the hollow cantilever beam and then passes through the semi-transparent semi-return mirror again and then is irradiated on a photosensitive surface of the position sensitive detector.
8. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, characterized in that: the printing chamber comprises a glass cover, a silver reference electrode, a cathode substrate, an insulating layer and a platinum counter electrode, wherein the insulating layer is fixedly connected with the upper part of the platinum counter electrode, the cathode substrate is placed on the insulating layer, the glass cover is fixedly connected with the upper part of the platinum counter electrode, the silver reference electrode is connected with the inner surface of the glass cover, the silver reference electrode, the cathode substrate and the platinum counter electrode form a three-electrode electrochemical cell, the platinum counter electrode is used for being connected with a power supply anode, and the cathode substrate is used for being connected with a power supply cathode.
9. The electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, characterized in that: the combined high-speed scanner comprises a four-quadrant sheet-shaped piezoelectric ceramic scanner, a tripod scanner and a scanner base, wherein the four-quadrant sheet-shaped piezoelectric ceramic scanner is glued on a metal table of the tripod scanner through four cushion blocks, and the tripod scanner is fixedly connected in the scanner base;
the four-quadrant flaky piezoelectric ceramic scanner comprises a metal sheet, an aluminum cylinder, flaky piezoelectric ceramics and a cushion block, wherein the lower part of the metal sheet is fixedly connected with the aluminum cylinder, the lower part of the aluminum cylinder is fixedly connected with the upper part of the four flaky piezoelectric ceramics, and the lower part of the flaky piezoelectric ceramics is fixedly connected with the cushion block;
the tripod scanner comprises a metal table, a metal block and tubular piezoelectric ceramics, wherein the lower part of the metal table is fixedly connected with the metal block, the tubular piezoelectric ceramics which are mutually vertical in the xy direction are respectively fixedly connected with the side surface of the metal block and fixedly connected with the inner side of a scanner base, the upper part of the tubular piezoelectric ceramics in the z direction is fixedly connected with the bottom surface of the metal block, and the lower part of the tubular piezoelectric ceramics in the z direction is fixedly connected with the inner side bottom surface of the scanner base.
10. The printing method of the electrochemical 3D printing device based on the hollow AFM cantilever probe according to claim 1, comprising the following steps:
(1) preparation of an electrodeposited metal salt solution: the prepared material is a single metal ion salt solution, powdery sulfate is dissolved in deionized water, and a proper amount of concentrated sulfuric acid is added for stabilizing the pH value of the solution to obtain the required electro-deposition metal salt solution;
(2) and (3) converting part model data: constructing a part model by using Catia software, slicing and layering the model from the Z direction to enable the thickness of each layer to be nano-scale, and importing the graphic information of each layer of the model into a calculated control program;
(3) injecting a metal salt solution: the pressure controller of the spray head device is dismounted, the metal salt solution is injected into the pipette, and the pressure controller is mounted;
(4) printing the microscopic metal parts: immersing the hollow cantilever beam into a three-electrode electrochemical cell comprising a silver reference electrode and a platinum counter electrode, observing by using a USB optical microscope, reducing the distance between a cathode substrate and the hollow probe by using a fine adjustment mechanism to generate atomic force, accurately controlling a metal salt solution by using a pressure controller, and enabling metal ions to flow out of the hollow probe through the hollow cantilever beam to locally reduce the cathode substrate below the hollow probe; in the deposition process, a laser beam emitted by the semiconductor laser is projected by the semi-transparent semi-return mirror and then is incident on the back surface of the hollow cantilever beam, the laser beam is reflected by the back surface of the hollow cantilever beam and then passes through the semi-transparent semi-return mirror again and is incident on the photosensitive surface of the position sensitive detector, when a deposit grows to contact with the hollow probe, the hollow cantilever beam deflects to cause the deflection of the position of a light spot on the photosensitive surface of the position sensitive detector, so that a photocurrent signal output by the position sensitive detector to a computer program is changed, the computer program further controls the speed of the pressure controller for conveying a metal salt solution, the metal salt solution at an outlet is gradually reduced, and the metal deposition under the hollow probe is gradually stopped; then, the printing chamber is moved through the combined high-speed scanner, and the hollow probe is deposited at the next deposition position, and the deposition is carried out in a circulating reciprocating mode to finish the deposition of one layer;
(5) cleaning and drying parts: after printing, the electrochemical direct current power supply is turned off, the three-electrode electrochemical cell is disconnected from the anode and cathode leads of the electrochemical direct current power supply, the printing chamber is moved to the bottom end of the device by the fine adjustment mechanism, the cathode substrate is taken out of the solution by tweezers, and parts are cleaned and dried.
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