OPTIMIZED METHOD AND DEVICE FOR INSOLUBLE ANODE ACID SULFATE COPPER ELECTROPLATING PROCESS
20240060202 ยท 2024-02-22
Inventors
Cpc classification
C25D17/00
CHEMISTRY; METALLURGY
C25D5/00
CHEMISTRY; METALLURGY
C25D17/002
CHEMISTRY; METALLURGY
C25D5/08
CHEMISTRY; METALLURGY
International classification
C25D21/04
CHEMISTRY; METALLURGY
Abstract
The present invention provided an optimized method for an insoluble anode acid sulfate copper electroplating process, comprising following steps: providing an insoluble anode made of coated titanium in the form of a mesh or a perforated plate; providing at least one liquid outlet pipe/port on the side of the insoluble anode away from the cathode, to generate a liquid flow of an electroplating solution by overflow and/or power driven suction at the liquid outlet pipe/port; initiating an electroplating process by switching on an electroplating power supply, while the electroplating solution flows away due to the overflow and/or power driven suction at the liquid outlet pipe/port, the electroplating solution in the electroplating cell forms a liquid flow towards the liquid outlet pipe/port, and accordingly, adding electroplating solution to the electroplating cell to maintain the liquid volume in the cell until the electroplating process is completed and the electroplated cathode is removed.
Claims
1. An optimized method for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell (5), an electroplating power supply (6), an insoluble anode (1), a cathode (4), and an acid sulfate copper electroplating solution as an electroplating solution, wherein the method comprises following steps: step 1: providing an insoluble anode (1) made of coated titanium in the form of a mesh or a perforated plate, and then the insoluble anode (1) and the cathode (4) are placed in the electroplating cell; providing at least one liquid outlet pipe/port (2) on a side of the insoluble anode (1) away from the cathode (4), to generate a liquid flow of the electroplating solution by overflow and/or power driven suction at the liquid outlet pipe/port (2); and step 2: initiating an electroplating process by switching on the electroplating power supply (6), while the electroplating solution flows away due to the overflow and/or the power driven suction at the liquid outlet pipe/port, the electroplating solution in the electroplating cell (5) forms the liquid flow towards the liquid outlet pipe/port (2), and accordingly, adding another electroplating solution to the electroplating cell (5) to maintain a liquid volume in the cell until the electroplating process is completed and the electroplated cathode is removed.
2. The method according to claim 1, wherein at least one liquid ejecting pipe/port (10) is provided on a side of the insoluble anode (1) facing the cathode (4); the liquid ejecting pipe/port (10) connects to an external liquid ejecting pipeline to spray liquid towards the anode; and in conjunction with the liquid outlet pipe/port (2), produces the more stable and more controllable liquid flow in a vicinity of the insoluble anode (1) that flows away from the cathode (4).
3. The method according to claim 2, wherein a gas-liquid separator (8) is further provided, so that a gas-liquid mixture from the electroplating cell (5) is discharged via the liquid outlet pipe/port (2) and a connecting pipe into the gas-liquid separator (8); a gas in the gas-liquid mixture is released inside the gas-liquid separator (8) and a liquid is then diverted back to the electroplating cell (5) for circulation.
4. The method according to claim 3, wherein an electroplating cell divider (11) is provided in the electroplating cell (5), dividing the electroplating cell into an electroplating anode zone and an electroplating cathode zone; the electroplating solution in the electroplating anode zone is an anolyte, which is specifically composed of an aqueous solution comprises at least one inorganic acid and/or at least one inorganic salt, or the acid sulfate copper electroplating solution; the electroplating solution in the electroplating cathode zone is the acid sulfate copper electroplating solution; during the electroplating process, the insoluble anode (1) and the cathode (4) are placed separately in the electroplating anode zone and the electroplating cathode zone; the liquid outlet pipe/port (2) and the liquid ejecting pipe/port (10) are located within the electroplating anode zone.
5. The method according to claim 4, wherein the electroplating anode zone is in the form of an anode box (13) inside the electroplating cell (5), dividing the electroplating cell into the electroplating anode zone and the electroplating cathode zone; particularly, the anode box (13) is shaped as a cubic box, in which the insoluble anode (1) is provided; a side of the anode box (13) facing the cathode (4) is the electroplating cell divider (11), making an inner space of the anode box (13) to be the electroplating anode zone, and a space in the electroplating cell (5) outside the anode box (13) to be the electroplating cathode zone; the liquid outlet pipe/port (2) is provided at the anode box (13), specifically in an area inside the anode box (13) or on a wall of the anode box (13) on the side of the insoluble anode (1) away from the cathode (4); furthermore, the liquid ejecting pipe/port (10) is provided in the area inside the anode box (13) between the anode and the nearby wall of the anode box on the side of the insoluble anode (1) facing the cathode (4).
6. The method according to claim 1, wherein a fixed frame (16) is provided at edges of the insoluble anode; the fixed frame (16) is made of material that is insoluble as an anode, heat-resisting, acid-resisting and relatively rigid.
7. The method according to claim 6, wherein a conductor (17) connected to a positive electrode of the electroplating power supply (6) is attached to the insoluble anode (1) on the side away from the cathode (4).
8. The method according to claim 7, wherein the insoluble anode (1) and/or the fixed frame (16) and/or the conductor (17) is provided on its side facing the cathode (4) with a reverse-pulse protective screen (15), and the reverse-pulse protective screen (15) is made of uncoated titanium in the form of a protrusion, or a protruding mesh or bar.
9. The method according to claim 8, wherein when the reverse-pulse protective screen (15) is provided attaching to the insoluble anode (1), the reverse-pulse protective screen (15) is made of uncoated titanium in the form of the protrusion, or the protruding mesh or bar, protruding from the side of the insoluble anode (1) facing the cathode (4) and directly connecting to a titanium substrate of the insoluble anode (1); when the reverse-pulse protective screen (15) is provided with the fixed frame (16) made of uncoated or coated titanium, the reverse-pulse protective screen (15) is connected to either the titanium substrate of the insoluble anode (1) or the titanium of the fixed frame (16), or to both; when the reverse-pulse protective screen (15) is provided on the conductor (17), the reverse-pulse protective screen (15) extends out of a surface of the insoluble anode (1) through the holes of the anode and towards the cathode (4).
10. The method according to claim 9, wherein the protrusion is in any one of the form of a bump, a spike, or a vertical bar; the protruding mesh or bar is a mesh or bar extending towards the cathode with its supporting foot fixed on the side of the insoluble anode (1) and/or the fixed frame (16) and/or the conductor (17) facing the cathode, or a mesh or bar formed by interconnecting an upper part of the protrusions, a plane surface formed by the protruding mesh or bar is parallel or substantially parallel to the surface of the anode (1).
11. An optimized device for an insoluble anode acid sulfate copper electroplating process, comprising an electroplating cell (5), an insoluble anode (1), a cathode (4), and an electroplating power supply (6), wherein: the electroplating cell is provided with at least one liquid outlet pipe/port (2) on a side of the insoluble anode (1) away from the cathode, to generate a liquid flow in the electroplating cell (5) by overflow and/or power driven suction of an electroplating solution at the liquid outlet pipe/port (2); the insoluble anode (1) is made of coated titanium in the form of a mesh or a perforated plate; a positive electrode and a negative electrode of the electroplating power supply (6) are respectively connected to the insoluble anode (1) and the cathode (4) in the electroplating process.
12. The device according to claim 11, wherein the electroplating cell (5) is provided with at least one liquid jet pipe/port (10), the liquid jet pipe/port (10) is located in an area on a side of the insoluble anode (1) facing the cathode (4) and between the anode and the cathode; the liquid ejecting pipe/port (10) connects to an external liquid ejecting pipeline to spray liquid towards the anode (1); the device is provided with a fluid circulating system, which mainly consists of a power driven device and a connecting pipe, with one end connecting to the liquid outlet pipe/port (2) and the other end connecting to the liquid ejecting pipe/port (10); the fluid circulating system is utilized to make the electroplating solution flow away from the liquid outlet pipe/port (2) and return to the electroplating cell (5), forming the liquid flow in the electroplating cell (5) towards the liquid outlet pipe/port (2) located at the anode.
13. The device according to claim 12, wherein the liquid outlet pipe/port (2) is connected to a gas-liquid separator (8) via a connection pipe; the gas-liquid separator (8) is also connected to the electroplating cell (5) via a pump and the connection pipe to form a fluid circulating system, which returns the gas-released liquid back into the electroplating cell (5) for circulation.
14. The device according to claim 13, wherein an electroplating cell divider (11) is provided in the electroplating cell (5), dividing the electroplating cell (5) into an electroplating anode zone and an electroplating cathode zone.
15. The device according to claim 14, wherein an anode box (13) is provided inside the electroplating cell (5), dividing the electroplating cell into the electroplating anode zone and the electroplating cathode zone: the anode box (13) is shaped as a cubic box, in which the insoluble anode (1) is provided; a side of the anode box (13) facing the cathode (4) is the electroplating cell divider (11), making an inner space of the anode box (13) to be the electroplating anode zone, and a space in the electroplating cell outside the anode box to be the electroplating cathode zone; the liquid outlet pipe/port (2) is provided at the anode box (13), specifically in an area inside the anode box (13) or on a wall of the anode box on the side of the insoluble anode (1) away from the cathode (4); furthermore, the liquid ejecting pipe/port (10) is provided inside the anode box (13), specifically in the area inside the anode box (13) between the anode and the nearby wall of the anode box on the side of the insoluble anode (1) facing the cathode (4).
16. The device according to claim 15, wherein an electroplating solution ejecting pipe (14) is provided at a side edge of the anode box on the side facing the cathode, and each electroplating solution ejecting pipe (14) is equipped with a flow regulator to adjust an ejection effect of the electroplating solution towards the cathode.
17. The device according to claim 16, wherein the insoluble anode (1) is provided with a reverse-pulse protective screen (15), the reverse-pulse protective screen (15) is made of uncoated titanium protruding from the side of the insoluble anode (1) facing the cathode (4) and directly connecting to a titanium substrate of the insoluble anode (1); the reverse-pulse protective screen is in any one of the form of a bump, a spike, a vertical bar, or a mesh or bar connected to the protrusions.
18. The device according to claim 17, wherein the insoluble anode (1) is further provided with a fixed frame (16) at its edges.
19. The device according to claim 18, wherein a conductor (17) connected to the positive electrode of the electroplating power supply (6) is attached to the insoluble anode (1) on the side away from the cathode (4).
20. The device according to claim 19, wherein an insoluble anode (1) with the reverse-pulse protective screen (15), the fixed frame (16) and the conductor (17), together with the insoluble anode accessories including the liquid outlet pipe/port (2) and the liquid ejecting pipe/port (10) are provided in the anode box (13) as an anode box assembly.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0133] The present disclosure will be further described with reference to the accompanying drawings.
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[0151] FIG. A is a schematic diagram of the insoluble anode of embodiment 1 of the present disclosure.
[0152] FIG. B is a schematic diagram of the insoluble anode in embodiment 2 of the present disclosure.
[0153] FIG. C is a schematic diagram of the insoluble anode in embodiment 3 of the present disclosure.
[0154] FIG. D is a schematic diagram of the insoluble anode in embodiment 4 of the present disclosure.
[0155] FIG. E is a schematic diagram of the insoluble anode in embodiment 5 of the present disclosure.
[0156] FIG. F is a schematic diagram of the insoluble anode in embodiment 6 of the present disclosure.
[0157] FIG. G is a schematic diagram of the structure of the insoluble anode cartridge in embodiments 7 and 11 of the present disclosure.
[0158] FIG. H is a schematic diagram of the insoluble anode cartridge structure in embodiment 8 of the present disclosure.
[0159] FIG. J is a schematic diagram of the insoluble anode cartridge structure in embodiments 9 and 12 of the present disclosure.
[0160] FIG. K is a schematic diagram of the insoluble anode cartridge structure in embodiments 10 and 13 of the present disclosure.
[0161] Reference signs: 1insoluble anode; 1-1hole of insoluble anode; 2liquid liquid outlet pipe/port; 3feed line installation hole; 4cathode; 5electroplating cell; 6electroplating power supply; 7acid sulfate copper electroplating solution; 8gas-liquid separator; 9liquid returning circulation pipe; 10liquid ejecting pipe/port; 11electroplating cell divider; 12anolyte; 13anode box; 14electroplating solution ejecting pipe; 15reverse-pulse protective screen; 16fixed frame; 17conductor (in the form of rod/mesh/plate); 18fixing device; 19reverse-pulse electroplating power supply; 20electroplating solution regenerating device; 21detection device; 22liquid circulation pipe; 23corrosion resistant pump; 24stirring device; 25gas extraction hood; 26-28electroplating additives; 29inverter pump; 30liquid flow regulator with pump; 31copper metal block; 32temporary storage tank; 33solid-liquid separation filter; 34automatic detection and replenishment controller; 35flow meter; 36cool-heat exchanger; 37anode coating; 38overflow tank; 39titanium basket.
DESCRIPTION OF THE EMBODIMENTS
[0162] The disclosure is further described by the following embodiments.
[0163] In the following embodiments, the copper sulfate used is a commercially available copper sulfate product. The sulfuric acid used is preferably produced by Guangzhou Chemical Reagent Factory. The titanium-based coated electroplating anode and the electroplating cell used are produced by Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd. The ion exchange membrane used is produced by Membranes International Inc. The bipolar membrane used is produced by Guochu Technology. The ultrafiltration membrane, the filter cloth, the ceramic filter plate, the PE filter plate and the reverse osmosis membrane are commercially available products. The microscope used is preferably a computer microscope produced by Guangzhou Optical Instrument Co., Ltd. The electroplating power supply and reverse-pulse electroplating power supply used are produced by Guangzhou Guangxing Electroplating Equipment Factory. The acid copper electroplating additive is the produced by Foshan Gaoli Group Company. In addition to the above-listed products, those of skill in the art can also select products and equipment with similar properties to those listed herein to achieve the objective of the current disclosure.
Embodiment 1
[0164] As shown in
[0165] The electroplating cell 5 is provided with a liquid outlet pipe 2, which is located on the side of the insoluble anode 1 away from the cathode 4; the liquid outlet pipe 2 is connected to the gas-liquid separator 8 through a connecting pipe, and the other end of the gas-liquid separator 8 is connected to the electroplating cell 5 through a pipe and a pump 23, so that the gas-liquid mixture is discharged from the electroplating cell through the liquid outlet pipe 2 and the connecting pipe and release gas in the gas-liquid separator, and the gas-released liquid returns back into the electroplating cell for circulation.
[0166] The insoluble anode 1 is provided with the structure shown in FIG. A, which is a perforated plate made of coated titanium, and a feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
[0167] The positive and negative electrodes of the electroplating power supply 6 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
[0168] The cathode 4 is a flat copper plate.
[0169] An optimized method for an insoluble anode acid sulfate copper electroplating process, wherein the method comprises the following steps: [0170] (1) The electroplating solution was prepared as specified in Table 1 and poured into the electroplating cell; [0171] (2) The insoluble anode was installed in the electroplating cell a liquid outlet pipe provided on the side of the insoluble anode away from the cathode; the positive electrode of the electroplating power supply was connected to the insoluble anode, and the negative electrode of the electroplating power supply was connected to the cathode; [0172] (3) An appropriate amount of electroplating additives was added to the electroplating solution; the electroplating power supply was turned on to initiate electroplating production using the acid sulfate copper electroplating solution; [0173] (4) After electroplating was completed, the electroplating cathode (i.e., the cathode electroplating product) was removed; the electroplating cathode 14 was washed with water and dried with hot air; the surface of the coating was observed using a computer microscope and the observation results were recorded in Table 1.
[0174] During the electroplating process, the structure of the insoluble anode cooperate with the liquid outlet pipe located on the side of the anode away from the cathode, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode by overflow. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried away from the cathode for external discharge.
[0175] The COD value of the electroplating solution was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
Embodiment 2
[0176] As shown in
[0177] The insoluble anode 1 is provided with the structure shown in FIG. B, which is a mesh made of coated titanium, and welded to a fixed frame 16 made of coated titanium around the four sides of the insoluble anode; feed lines are provided through the feed line installation holes on both sides of the anode for structural modification.
[0178] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1.
Embodiment 3
[0179] As shown in
[0180] The electroplating cell 5 is provided with a liquid outlet port 2, a liquid ejecting pipe 10, a stirring blade 24.2 and a pneumatic stirring device 24.1; the liquid outlet port 2 is located on the wall of the electroplating cell 5 and on the side of the insoluble anode 1 away from the cathode 4; the liquid ejecting pipe 10 is provided in the space between the insoluble anode 1 and the cathode 4; the liquid outlet port 2 is connected to the gas-liquid separator 8 via a pipe and a pump; the gas-liquid separator 8 is further connected to a solid-liquid separation filter 33 and the liquid ejecting pipe 10 through a liquid returning circulation pipe 9, so that the gas-released liquid is able to return to the electroplating cell 5 after filtration via the liquid ejecting pipe 10.
[0181] The insoluble anode 1 is provided with the structure shown in FIG. C, which is a perforated plate made of coated titanium, and welded to a fixed frame 16 made of uncoated titanium around the four sides of the insoluble anode; a reverse-pulse protective screen 15 consisting of uncoated titanium spikes is provided and connected to the insoluble anode 1 and the fixed frame 16; a feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
[0182] The positive and negative electrodes of the electroplating power supply 6 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process. The cathode 4 is a flat copper plate.
[0183] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1 and Table 2.
[0184] During the electroplating process, the perforated structure of the insoluble anode cooperates with the liquid outlet port located on the side of the anode away from the cathode, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried away from the cathode and discharged to the gas-liquid separator for gas release. And the remaining liquid returns back into the electroplating cell for circulation.
Embodiment 4
[0185] As shown in
[0186] The electroplating cell 5 is provided with a liquid outlet pipe 2 and a liquid ejecting pipe 10; the liquid outlet pipe 2 is located on the side of the insoluble anode 1 away from the cathode 4; the liquid ejecting pipe 10 is installed in the space between the insoluble anode 1 and the cathode 4; the liquid outlet pipe 2 is connected to the gas-liquid separator 8 via a pipe and pump 23, so that the liquid treated in the gas-liquid separator 8 can be returned to the electroplating cell via a liquid return circulation pipe 9.
[0187] The insoluble anode 1 is provided with the structure shown in FIG. D, which is a perforated plate made of coated titanium. A reverse-pulse protective screen 15 is provided on the side of the insoluble anode 1 facing the cathode, connecting directly to the titanium substrate of the insoluble anode 1. The reverse-pulse protective screen consists of uncoated titanium protrusions in the form of spikes and vertical bars, and a mesh formed by interconnecting the upper part of the protrusions. A conductor 17, which is a conducting rod, is attached to the insoluble anode 1 on the side away from the cathode. A feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
[0188] The cathode 4 is a flat copper plate with small through-holes.
[0189] The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
[0190] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1. The COD value of the electroplating solution was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
[0191] In the electroplating process, the perforated structure of the insoluble anode cooperates with and the liquid outlet port located on the side of the anode away from the cathode and the liquid ejecting pipe on the side of the anode facing the cathode, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried away from the cathode and discharged to the gas-liquid separator for gas release. And the remaining liquid returns back into the electroplating cell for circulation. During reverse pulse electroplating, the reverse-pulse protective screen can effectively reduce the electrochemical reaction of hydrogen generation on the surface of the insoluble anode coating.
Embodiment 5
[0192] As shown in
[0193] The electroplating cell 5 is provided with an electroplating cell divider 11 separating it into an electroplating anode zone and an electroplating cathode zone; the electroplating cell divider 11 is specifically a combination of an ultrafiltration membrane and a filter cloth. The electroplating anode zone is provided with a liquid outlet pipe 2 and a liquid ejecting port 10; the liquid ejecting port 10 is installed at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4, and is connected to the electroplating anode zone on the side away from the electroplating cathode zone via a pipe and a pump 23.1. The liquid outlet pipe 2 is provided with two liquid outlet ports and is located on the side of the insoluble anode 1 away from the cathode 4. The liquid outlet pipe 2 is connected to a pipe with a pump 23.2 to divert the liquid with oxygen bubbles to area in the electroplating anode zone away from the cathode 4 for gas release.
[0194] As shown in FIG. E, the insoluble anode 1 in the electroplating anode zone is a coated titanium mesh; the insoluble anode 1 is also welded to a fixed frame 16 made of uncoated titanium around its four sides; the conductor 17, provided on the side of the insoluble anode 1 away from the cathode 4, is a bypass structure conductor in the shape of a mesh, and is welded to the fixed frame 16 around the four sides of the frame via titanium meshes. The fixed frame 16 and the conductor 17 are welded together as plates and frames, and welded surrounding the edges of the insoluble anode 1 on the side of the anode away from the cathode 4, forming a cubic box with two sides of mesh in parallel and connecting electrically. The conductor 17 is provided with a reverse-pulse protective screen 15, which is welded to the conductor 17; the reverse-pulse protective screen 15 consists of uncoated titanium spikes that extend through the mesh holes of the insoluble anode 1 without contacting with it. The upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for feeding from the top of the anode.
[0195] The cathode 4 is a flat copper plate with small holes, and is provided in the electroplating cathode zone.
[0196] The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
[0197] An optimized method for an insoluble anode acid sulfate copper electroplating process, wherein the method comprises the following steps: [0198] (1) The electroplating solutions including the anolyte and the catholyte were prepared as specified in Table 1 and poured into the electroplating anode zone and the electroplating cathode zone respectively; [0199] (2) The insoluble anode was installed in the electroplating cell a liquid outlet pipe provided on the side of the insoluble anode away from the cathode; the positive electrode of the electroplating power supply was connected to the insoluble anode, and the negative electrode of the electroplating power supply was connected to the cathode; [0200] (3) An appropriate amount of electroplating additives was added to the electroplating solution; the electroplating power supply was turned on to initiate electroplating production; [0201] (4) After electroplating was completed, the electroplating cathode (i.e., the cathode electroplating product) was removed; the electroplating cathode 14 was washed with water and dried with hot air; the surface of the coating was observed using a computer microscope and the observation results were recorded in Table 1.
[0202] During the electroplating process, the mesh structure of the insoluble anode cooperates with the liquid outlet port located on the side of the anode away from the cathode and the liquid ejecting pipe located at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the anode and the conductive mesh by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode and the conductive mesh more concentratedly with the liquid flow, and be carried away from the cathode and released. In the case of reverse pulse electrolysis, the spikes of the reverse-pulse protective screen have no contact with the insoluble anode, so that the reverse pulse current is diverted from the upper part of the spikes into the conductor as a bypass current, effectively reducing electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, and hence preventing the coating of the insoluble anode from falling off. The design of the electroplating cell divider also effectively reduces the consumption of electroplating additives.
Embodiment 6
[0203] As shown in
[0204] The electroplating cell divider 11 is specifically a combination of a PE filter plate and a ceramic filter plate.
[0205] The liquid ejecting pipe 10 is designed to have an oblate flared mouth, and is installed at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4. The liquid ejecting pipe 10 is connected to the electroplating anode zone on the side away from the electroplating cathode zone via a pipe and a pump 23.1. The liquid outlet pipe 2 with a flared mouth is located on the side of the insoluble anode 1 away from the cathode 4; the liquid outlet pipe 2 drains the liquid with oxygen bubbles through a pipe connected to the pump 23.2 to the area away from the cathode 4 in the electroplating anode zone for gas release.
[0206] As shown in FIG. F, the insoluble anode 1 in the electroplating anode zone is a coated titanium plate with through holes, and is welded to a fixed frame 16 around its edges. The fixed frame is made of uncoated titanium. The conductor 17, provided on the side of the insoluble anode 1 away from the cathode 4, is a titanium plate with through holes and is welded to the fixed frame 16 around its edges as a bypass conductor. The insoluble anode 1 is electrically connected to the fixed frame 16 and the conductor 17, forming a cubic box with two sides of perforated titanium plate in parallel and the other four sides of enclosed structure. The conductor 17 is also provided with a reverse-pulse protective screen 15, which is welded to the conductor 17; the reverse-pulse protective screen 15 consists of uncoated titanium spikes that extend through the holes of the insoluble anode 1 without contacting with it. The upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for feeding from the top of the anode.
[0207] The cathode 4 is a flat copper plate with small holes, and is provided in the electroplating cathode zone.
[0208] The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
[0209] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
[0210] During the electroplating process, the perforated structure of the insoluble anode cooperates with the liquid outlet pipe with a flared mouth located on the side of the anode away from the cathode and the liquid ejecting pipe with an oblate flared mouth located at the bottom of the electroplating anode zone on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode and the conductor by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode more concentratedly with the liquid flow, and be carried away from the cathode and released. In the case of reverse pulse electrolysis, the spikes of the reverse-pulse protective screen have no contact with the insoluble anode, so that the reverse pulse current is diverted from the upper part of the spikes into the conductor as a bypass current, effectively reducing electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, and hence preventing the coating of the insoluble anode from falling off. The design of the electroplating cell divider also effectively reduces the consumption of electroplating additives.
Embodiment 7
[0211] As shown in
[0212] The electroplating cell 5 is provided with an anode box 13, the side of the anode box 13 facing the cathode 4 is an electroplating cell divider 11, which is specifically a cation exchange membrane; the inner space of the anode box 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode box 13 is the electroplating cathode zone.
[0213] As shown in FIG. G, the anode box 13 is connected to a liquid outlet pipe 2 and is provided with a liquid ejecting port 10 inside it; the liquid outlet pipe 2 is provided with four liquid outlets located inside the anode box 13 and on the side of the insoluble anode 1 away from the cathode 4, and the liquid ejecting port 10 is located on the side of the insoluble anode 1 facing the cathode 4; the liquid outlet pipe 2 is connected to the gas-liquid separator 8 through a pipe and a pump 23, and the gas-liquid separator 8 is then connected to the liquid ejecting port 10 through a liquid returning circulation pipe 9 to return the gas-released liquid to the anode box 13.
[0214] The insoluble anode 1 of the present embodiment is provided with the structure shown in FIG. D, which is a coated titanium plate with a perforated structure. The insoluble anode 1 is provided with a reverse-pulse protective screen 15 on the side facing the cathode; the reverse-pulse protective screen consists of uncoated titanium protrusions connecting directly to the titanium substrate of the insoluble anode 1, and a conductive mesh formed by interconnecting the upper part of the protrusions using titanium wire. The insoluble anode 1 is connected to the reverse pulse electroplating power supply 19 during the electroplating process. The insoluble anode 1 is also provided with a conductor 17, which is a conductive rod, on the side of the anode away from the cathode. The upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The above-mentioned anode assembly is provided in the anode box 13 as shown in FIG. G.
[0215] The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19.
[0216] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
[0217] During the electroplating process, the liquid outlet pipe located in the anode box on the side of the anode away from the cathode cooperates with and the liquid ejecting port located at the bottom of the anode box on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes created by the structure of the insoluble anode with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives.
Embodiment 8
[0218] As shown in
[0219] The electroplating cell divider 11 is specifically a combination of a reverse osmosis membrane and a filter cloth.
[0220] As shown in FIG. H, the anode box 13 is connected to a liquid outlet pipe 2 and a liquid ejecting pipe 10. The liquid outlet pipe 2 is provided with a large flared mouth, and the liquid ejecting pipe 10 is provided with several liquid outlets set in a line.
[0221] The anode assembly provided in the present embodiment is the same as that in embodiment 5, comprising an insoluble anode 1, a conductor 17, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. E, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. H. The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0222] The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0223] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
[0224] During the electroplating process, the anode box of the present embodiment is provided with the structure as shown in FIG. H, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode and the conductive mesh by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode and the conductive mesh with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives by avoiding contact with the anode.
Embodiment 9
[0225] As shown in
[0226] The present embodiment further comprises an electroplating solution ejecting pipe 14.
[0227] The electroplating cell divider 11 is specifically a combination of an anion exchange membrane and a filter cloth.
[0228] As shown in FIG. J, the anode box 13 is connected to a liquid outlet pipe 2 and a liquid ejecting pipe 10; inside the anode box, the liquid outlet pipe 2 is provided with a large flared mouth, and the liquid ejecting pipe 10 is provided with several liquid outlets set in lines. The liquid outlet pipe 2 is connected to a gas-liquid separator 8 via a pipe and a pump 23.1, and the gas-liquid separator 8 is then connected to the liquid ejecting pipe 10 through a liquid returning circulation pipe 9 to return the treated liquid to the anode box 13; An electroplating solution ejecting pipe 14 is provided at the side edges of the anode box 13 on the side facing the cathode, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone via a pipe and a pump 23.2, to eject an electroplating solution at the cathode 4.
[0229] The anode assembly provided in the present embodiment is the same as that in embodiment 6, comprising an insoluble anode 1, a conductor 17, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. F, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. J. The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0230] The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0231] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1. The COD value of the catholyte was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
[0232] During the electroplating process, the anode box of the present embodiment is provided with the structure as shown in FIG. J, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode and the perforated conductor by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode and the perforated conductor with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, and the electroplating solution inside the holes can be replenished and renewed. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives by avoiding contact with the anode.
Embodiment 10
[0233] As shown in
[0234] The present embodiment further comprises an electroplating solution ejecting pipe 14.
[0235] The electroplating cell divider 11 is specifically a combination of a bipolar membrane and a filter cloth;
[0236] As shown in FIG. K, the anode box 13 is connected to a liquid outlet pipe 2, and a liquid ejecting port 10 provided inside the box; the liquid outlet pipe 2 has 4 liquid outlets located inside the anode box 13 and on the side of the insoluble anode 1 away from the cathode 4, and the liquid ejecting port 10 is located on the side of the insoluble anode 1 facing the cathode 4. The liquid outlet pipe 2 is connected to a gas-liquid separator 8 through a pipe and a pump 23.1, and the gas-liquid separator 8 is then connected to the liquid ejecting port 10 through a liquid returning circulation pipe 9 to return the treated liquid to the anode box 13. An electroplating solution ejecting pipe 14 is provided at the side edges of the anode box 13 on the side facing the cathode, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone via a pipe and a pump 23.2, to eject an electroplating solution at the cathode 4.
[0237] The anode assembly provided in the present embodiment is the same as that in embodiment 3, comprising an insoluble anode 1, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. C, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. K. The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0238] The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0239] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1. The COD value of the catholyte was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
[0240] During the electroplating process, the anode box of the present embodiment is provided with the structure as shown in FIG. K, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can pass through the holes of the insoluble anode with the liquid flow, and be carried to the gas-liquid separator and released. The gas-released liquid is then return to the anode box 13. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, and the electroplating solution inside the holes can be replenished and renewed. The design of the anode box with the electroplating cell divider also effectively reduces the consumption of electroplating additives by avoiding contact with the anode.
Embodiment 11
[0241] As shown in
[0242] The electroplating cell 5 is provided with three anode boxes 13, each side of the anode boxes 13 facing the cathode 4 is an electroplating cell divider 11, which is specifically a cation exchange membrane; the inner space of the anode boxes 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode boxes 13 is the electroplating cathode zone.
[0243] As shown in FIG. G, the structure of the anode box 13 is the same as in embodiment 7 that each anode box 13 is connected to a liquid outlet pipe 2 and is provided with a liquid ejecting port inside it. The liquid outlet pipe 2 of each anode box 13 is connected to a pump, and then a gas-liquid separator 8; the gas-liquid separator 8 is provided above the surface of the electroplating solution, and is connected to the liquid ejecting port 10 of each anode box 13 through liquid returning circulation pipes 9 to return the gas-released liquid to each anode box 13.
[0244] The electroplating cathode zone is provided with a detection device 21 and a stirring device 24. The detection device 21 comprises a hydrometer, a photoelectric colourimeter and an acidity meter, and the stirring device 24 is a liquid circulating device. The electroplating cathode zone is connected to an overflow tank 38, a pump 23.4, a filter 33.1, an electroplating solution regenerating device 20, a liquid flow regulator with pump 30 and a filter 33.2 in order, forming a liquid circulation system; the catholyte in the electroplating cathode zone overflows into the overflow tank 38 and is pumped to the electroplating solution regenerating device 20 by the pump 23.4 after treated by filter 33.1. The feeding action of the liquid flow regulator with pump 30 is controlled by an automatic detection and replenishment controller 34, according to the results detected by the detection device 21, so that the catholyte is replenished with a copper source. A gas extraction hood 25 is provided above the electroplating cell 5.
[0245] The anode assembly provided in the present embodiment is the same as that in embodiment 4, comprising an insoluble anode 1, a conductor 17, and a reverse-pulse protective screen 15; as shown in FIG. D, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification of feeding. The anode assembly is provided in an anode box 13, as shown in FIG. G. The insoluble anode 1 is connected to the positive electrode of the electroplating power supply 6 during the electroplating process.
[0246] The cathode 4 is a flat copper plate provided in the electroplating cathode zone, and is connected to the negative electrode of the electroplating power supply 6 during the electroplating process.
[0247] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
[0248] During the electroplating process, the liquid outlet pipe located in the anode box on the side of the anode away from the cathode cooperates with and the liquid ejecting port located at the bottom of the anode box on the side of the insoluble anode 1 facing the cathode 4, to generate a liquid flow in the vicinity of the insoluble anode, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can be carried to the gas-liquid separator with the liquid flow for gas release. The gas-released liquid is then return to the anode box 13. The design of the anode box with the electroplating cell divider separates the anolyte and the catholyte, effectively reducing the consumption of electroplating additives. In addition, the gas released from the gas-liquid separator can be collected for further processing.
Embodiment 12
[0249] As shown in
[0250] The electroplating cell 5 is provided with six anode boxes 13, each side of the anode boxes 13 facing the cathode 4 is an electroplating cell divider 11, which is specifically a combination of an anion exchange membrane and a filter cloth; the inner space of the anode boxes 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode boxes 13 is the electroplating cathode zone. The electroplating cathode zone is provided with a detection device 21, which comprises a level gauge, an oxidation-reduction potentiometer, a photoelectric colorimeter, a pH meter and a thermometer. The detection device 21 is connected to an automatic detection and replenishment controller 34, to control the liquid level of the electroplating cell, temperature adjustment, power output current, concentration detection of the electroplating solution, electroplating time and other process parameters so that the electroplating process is carried out according to the process requirements.
[0251] The structure of the anode box 13 is as shown in FIG. J. Same as the structure of the anode box 13 of embodiment 9, each anode box 13 is connected with a liquid outlet pipe 2 and a liquid ejecting pipe 10. The liquid outlet pipe 2 in each anode box 13 is respectively connected to a pump 23 through a pipe, and is then connected to a temporary storage tank 32; wherein the pumps 23.1, 23.2, and 23.3 are utilized to pump the liquid into the temporary storage tank 32.1, and the pumps 23.4, 23.5, 23.6 are utilized to pump the liquid into the temporary storage tank 32.2. The liquid from the two temporary storage tanks is transferred with oxygen bubbles through a pump 23.7 and pipes to the gas-liquid separator 8 which contains copper metal 31, to make full use of the sulfuric acid and oxygen in the anolyte and allow them participating in the chemical reaction of converting copper metal to copper sulfate. The anolyte is chemically reacted in the gas-liquid separator 8, and has gas released in the gas-liquid separator 8 before being diverted to the liquid ejecting pipe 10 of each anode box 13 via a pump 23.8 and a liquid return circulation pipe 9, and is pumped into the anode box 13. Each anode box 13 is provided with an electroplating solution ejecting pipe 14 at the side edges on the side facing the cathode 4, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone. The liquid ejection motions of the electroplating solution ejecting pipes 14 towards the cathodes 4 are controlled as programmed.
[0252] The anode assembly provided in the present embodiment is the same as that in embodiment 6, comprising an insoluble anode 1, a conductor 17, a fixed frame 16, and a reverse-pulse protective screen net 15; as shown in FIG. F, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification. The anode assembly is provided in an anode box 13, as shown in FIG. J. The insoluble anode 1 is connected to the positive electrode of the electroplating power supply 19 during the electroplating process.
[0253] The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone, and is connected to the negative electrode of the reverse pulse electroplating power supply 19 during the electroplating process.
[0254] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
[0255] During the electroplating process, a liquid flow is generated in the vicinity of the insoluble anode in each anode box, which flows away from the cathode and through the holes of the insoluble anode by power driven suction. Therefore the oxygen bubbles generated on the surface of the anode can be carried to the two temporary storage tanks with the liquid flow, and pumped to the gas-liquid separator 8 for the chemical reaction of copper metal. The liquid in the gas-liquid separator 8 is pumped back to each anode box after gas release. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, the electroplating solution inside the holes can be replenished and renewed, and the electroplating solution is also stirred. During the electroplating process, the cathode can be moved parallelly in one direction or back and forth in both directions to achieve a more uniform layer. In addition, the design of the anode box with the electroplating cell divider prevents the catholyte from entering the electroplating anode zone, which effectively reduces the consumption of electroplating additives and facilitates the collection of anolyte with bubbles from the anode box for use in the chemical reaction of copper metal in the temporary storage tank to produce more copper sulfate.
Embodiment 13
[0256] As shown in
[0257] The electroplating cell 5 is provided with six anode boxes 13, each side of the anode boxes 13 facing the cathode 4 is an electroplating cell divider 11, which is a combination of a bipolar film and a filter cloth; the inner space of the anode boxes 13 is the electroplating anode zone, and the space in the electroplating cell 5 outside the anode boxes 13 is the electroplating cathode zone. The electroplating cathode zone is provided with a detection device 21, which comprises a level gauge, a hydrometer and an acidity meter. The detection device 21 is connected to an automatic detection and replenishment controller 34, which controls the electroplating current as well as the electroplating solution parameters of the process and alarms according to the detected results of the detection device 21.
[0258] As shown in FIG. K, the structure of the anode box 13 is the same as in embodiment 10 that each anode box 13 is connected to a liquid outlet pipe 2 and is provided with a liquid ejecting port inside it. Each liquid outlet pipe 2 is provided with four liquid outlets located inside the anode box 13 and on the side of the insoluble anode 1 away from the cathode 4, and the liquid ejecting port 10 is located on the side of the insoluble anode 1 facing the cathode 4. Each liquid outlet pipe 2 is connected via a pipe to the gas-liquid separator 8, into which the overflow liquid is diverted for gas release. The gas-released liquid in the gas-liquid separator 8 is pumped through the solid-liquid separator 33 by a pump 23.1 and into a liquid returning circulation pipe 9, which is connected to the liquid ejecting port 10 of each anode box 13 to return the treated liquid to the anode boxes 13. Each anode box 13 is provided with an electroplating solution ejecting pipe 14 at the side edges on the side facing the cathode 4, and the electroplating solution ejecting pipe 14 is connected to the electroplating cathode zone via a pipe and a pump 23.2. The liquid ejection motions of the electroplating solution ejecting pipes 14 towards the cathodes 4 are controlled by the set program of the automatic detection and replenishment controller 34.
[0259] The anode assembly provided in the present embodiment is the same as that in embodiment 3, comprising an insoluble anode 1, a fixed frame 16, and a reverse-pulse protective screen 15; as shown in FIG. C, the upper part of the insoluble anode 1 is provided with feed line installation holes from which a feed line is provided for structural modification. The anode assembly is provided in an anode box 13, as shown in FIG. K.
[0260] The cathode 4 is a flat copper plate with small holes provided in the electroplating cathode zone.
[0261] During the electroplating process, the titanium substrates of the insoluble anodes 1 are connected to the positive electrode of the corresponding one of the two reverse pulse electroplating power supplies 19, whereas the four cathodes 4 are co-connected to the negative electrodes of the two reverse pulse electroplating power supplies.
[0262] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 5 were repeated for electroplating operation, and the results were recorded in Table 1.
[0263] During the electroplating process, a liquid flow is generated in the vicinity of the insoluble anode in each anode box, which flows away from the cathode and through the holes of the insoluble anode due to power driven ejection of liquid from the liquid ejecting port. Therefore the oxygen bubbles generated on the surface of the anode can be carried to the gas-liquid separator with the liquid flow for gas release. The gas-released liquid is then return to each anode box of the electroplating cell. In the case of reverse pulse electrolysis, the reverse-pulse protective screen can effectively reduce electrochemical formation of hydrogen on the surface of the insoluble anode during the reverse pulse operation, preventing the coating of the insoluble anode from falling off. The electroplating solution ejecting pipe outside the anode box ejects the electroplating solution towards the cathode via a pump, so that the electroplating solution can be poured deeply into the small holes of the cathode, the electroplating solution inside the holes can be replenished and renewed. During the electroplating process, the cathodes move parallelly in one direction or back and forth in both directions, and the output current of each electroplating power supply is adjusted according to the quality requirements of the cathode electroplating process, to achieve a better cathode electroplating layer. In addition, the design of the anode boxes with the electroplating cell divider can effectively reduce the consumption of electroplating additives.
Embodiment 14
[0264] As shown in
[0265] The electroplating cell 5 is provided with a liquid outlet pipe 2, which is located on the side of the insoluble anode 1 away from the cathode 4, and the insoluble anode 1 is a coated titanium mesh.
[0266] The insoluble anode 1 is provided with the structure shown in FIG. A, which is a perforated plate made of coated titanium, and a feed line is provided from the top of the insoluble anode through the feed line installation holes at the upper part of the anode.
[0267] The positive and negative electrodes of the electroplating power supply 6 are respectively connected to the insoluble anode 1 and the cathode 4 during the electroplating process.
[0268] The cathode 4 is a flat copper plate.
[0269] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1.
Embodiment 15
[0270] As shown in
[0271] A reverse pulse electroplating power supply 19 is used instead of the electroplating power supply 6.
[0272] As shown in FIG. C, the insoluble anode 1 is a perforated plate made of coated titanium, and is welded to a fixed frame 16 made of non-conductive material; a reverse-pulse protective screen 15 consisting of electric discharge spikes is provided and connected to the insoluble anode 1 and the fixed frame 16; a feed line is provided through the feed line installation holes at the upper part of the anode for structural modification.
[0273] The positive and negative electrodes of the reverse pulse electroplating power supply 19 are respectively connected to the insoluble anode 1 and cathode 4 during the electroplating process.
[0274] The cathode 4 is a flat copper plate.
[0275] According to each parameter specified in Table 1, the steps of the optimized method for an insoluble anode acid sulfate copper electroplating process described in embodiment 1 were repeated for electroplating operation, and the results were recorded in Table 1.
Comparative Example 1
[0276] As shown in
[0277] The electroplating cell 5 is provided with an insoluble anode 14 and a cathode 4.
[0278] The insoluble anode 1 is made of coated titanium, and the cathode 4 is a flat copper plate with small holes.
[0279] The insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19, and the cathode 4 is connected to the negative electrode of the power supply 19.
[0280] According to each parameter specified in Table 1, the reverse pulse electroplating power supply 19 was turned on to initiate electroplating production, and the results were recorded in Table 1. The COD value of the electroplating solution was analyzed before and after the electroplating process, so that the consumption of the electroplating additives can be tracked through the change in obtained values, and the results were recorded in Table 2.
[0281] In the present comparative example, the presence of a large number of oxygen bubbles in the electroplating solution between the cathode and the insoluble anode affected the current distribution in the electric field, and hydrogen generates massively on the surface of the insoluble anode coating during reverse pulse electrolysis. Both of these factors lead to uneven plating and damage to the anode coating.
Comparative Example 2
[0282] As shown in
[0283] The electroplating cell 5 is provided with a titanium basket 39, inside which an insoluble anode 1 is placed; the titanium basket is wrapped around by a neutral filter membrane 11, making the inner space enclosed by the titanium basket 39 and the neutral filter membrane 11 is the electroplating anode zone and the remaining space in the electroplating cell is the electroplating cathode zone; the electroplating cell 5 is also provided with a stirring device 24 and a cathode 4.
[0284] The insoluble anode 1 is made of coated titanium, and the cathode 4 is a flat copper plate with small holes.
[0285] The insoluble anode 1 and the titanium basket 39 are connected to the positive electrode of the reverse pulse electroplating power supply 19, and the cathode 4 is connected to the negative electrode of the reverse pulse electroplating power supply 19.
[0286] According to each parameter specified in Table 1, the stirring device 24 and the reverse pulse electroplating power supply 19 were turned on to initiate electroplating production, and the results were recorded in Table 1.
[0287] In the present comparative example, the presence of a large number of oxygen bubbles in the electroplating solution between the cathode and the anode affected the current distribution in the electric field, and hydrogen generates massively on the surface of the anode coating during reverse pulse electrolysis. Both of these factors lead to uneven plating and damage to the anode coating.
[0288] The process conditions for the embodiments and the comparative examples of the present disclosure are as follows: [0289] (1) the electroplating current was 2 A/dm.sup.2; [0290] (2) the reverse pulsed power supply operated with a forward current of 2 A/dm.sup.2 and a reverse pulsed current of 6 A/dm.sup.2, with a time ratio of 20:1 between the forward current and the reverse pulsed current; [0291] (3) the electroplating time was 40 minutes, and the working temperature was 30 C.; [0292] (4) the acid sulfate copper electroplating solution comprised: [0293] CuSO.sub.4 200 g/L; [0294] H.sub.2SO.sub.4 60 g/L; [0295] Cl.sup. 70 g/L;
[0296] Commercially available Gaoli brand copper electroplating additive 9 mg/L.
[0297] Method of identifying the condition and uniformity of the electroplating layer.
[0298] After electroplating operation, three points on the electroplated cathode chosen uniformly from top to bottom were cut out and polished, and the electroplating layer of the cut-out samples were observed and measured in thickness using a microscope; for cathodes with small holes, the condition and the copper electroplating layer inside the holes were also observed; the measured results and the conclusions were recorded in Table 1.
[0299] Method of identifying the condition of the anode coating.
[0300] After electroplating operation, the anode coating was visually observed, and lightly brushed to test whether the coating would be peeled off; the conclusions were recorded in Table 1.
[0301] Method of identifying of the consumption of electroplating additives.
[0302] The COD value of the electroplating solution or catholyte was analyzed before and after the electroplating operation using the COD analytical method mentioned in the national standard, and the consumption of the electroplating additives was evaluated through the difference in the COD values of the electroplating solution or catholyte before and after the electroplating operation; the conclusions were recorded in Table 2.
TABLE-US-00001 TABLE 1 Thickness of plated Condition Electroplating layer (m) Surface quality of of anode System solution top middle bottom plated layer coating Embodiment Acid copper 15.5 14.9 14.3 Uniform and flat In perfect 1 electroplating condition solution Embodiment Acid copper 15.1 15.0 15.1 Uniform and flat In perfect 2 electroplating condition solution Embodiment Acid copper 15 15 15 Uniform and flat In perfect 3 electroplating condition solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 4 Acidic copper holes with 0.2 mm condition sulfate diameter and 2 mm solution; depth fully plated Catholyte: Acid copper electroplating solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 5 Acidic copper holes with 0.2 mm condition sulfate diameter and 2 mm solution; depth fully plated Catholyte: Acid copper electroplating solution Embodiment Anolyte: Acid 15 15 15 Uniform and flat, small In perfect 6 copper holes with 0.2 mm condition electroplating diameter and 2 mm solution; depth fully plated Catholyte: Acid copper electroplating solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 7 Sulfuric acid holes with 0.2 mm condition solution; diameter and 2 mm Catholyte: depth fully plated Acid copper electroplating solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 8 Acidic copper holes with 0.2 mm condition sulfate diameter and 2 mm solution; depth fully plated Catholyte: Acid copper electroplating solution Embodiment Anolyte: Acid 15 15 15 Uniform and flat, small In perfect 9 copper holes with 0.2 mm condition electroplating diameter and 2 mm solution; depth fully plated Catholyte: Acid copper electroplating solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 10 Sulfuric acid holes with 0.2 mm condition solution; diameter and 2 mm Catholyte: depth fully plated Acid copper electroplating solution Embodiment Anolyte: Acid 15 15 15 Uniform and flat In perfect 11 copper condition electroplating solution; Catholyte: Acid copper electroplating solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 12 Acidic copper holes with 0.2 mm condition sulfate diameter and 2 mm solution; depth fully plated with Catholyte: high quality Acid copper electroplating solution Embodiment Anolyte: 15 15 15 Uniform and flat, small In perfect 13 Sulfuric acid holes with 0.2 mm condition solution; diameter and 2 mm Catholyte: depth fully plated with Acid copper high quality electroplating solution Embodiment Acid copper 15.6 14.8 14.3 Uniform and flat In perfect 14 electroplating condition solution Embodiment Acid copper 15.2 15.0 14.8 Uniform and flat Anode 15 electroplating coating at solution upper part slightly fell off when lightly brushed Comparative Acid copper 14.1 15.3 16.4 Rough plated surface, Anode Example 1 electroplating small holes with 0.2 mm coating solution diameter and 2 mm obviously depth not fully plated fell off when lightly brushed Comparative Anolyte: Acid 13.6 15.2 16.9 Rough plated surface, Anode Example 2 copper small holes with 0.2 mm coating electroplating diameter and 2 mm obviously solution; depth not fully plated fell off Catholyte: when Acid copper lightly electroplating brushed solution
TABLE-US-00002 TABLE 2 COD value of electroplating solution (mg/L) Before elec- After elec- Differ- System troplating troplating ence Conclusion Comparative 5122 4889 233 Relatively large Example 1 consumption of electroplating additives Embodiment 4933 4721 212 Relatively large 1 consumption of electroplating additives Embodiment 5320 5111 209 Relatively large 4 consumption of electroplating additives Embodiment 4902 4837 65 Small consumption of 9 electroplating additives Embodiment 5076 5002 74 Small consumption of 10 electroplating additives
[0303] It can be concluded from Table 1 that, when comparing the electroplating quality obtained in embodiments 1-15 with that obtained in comparative examples 1-2 of the prior art, the plated layer obtained in embodiments 1-15 showed a more even thickness at three points (top, middle and bottom) than in comparative example 1. Since a fixed frame or a conductor with connection points was provided in embodiments 2-13 acting as a feed line, the plated layer obtained were uniform in overall thickness and flat, with small holes fully plated. Whereas in comparative examples 1-2, the current distribution in the electroplating solution was affected by the bubbles during electroplating, resulting in a plated layer with rough surface, uneven thickness, and unsatisfactory electroplating quality inside the small holes. It can be summarized that the plated layer obtained in the process of the present disclosure is more uniform and flat, with a higher electroplating quality of through-holes, showing that the present disclosure can effectively improve the electroplating quality and meet the requirements of the electroplating industry for high quality products after optimizing the insoluble anode copper electroplating process with gas generation.
[0304] It can also be concluded from Table 1 that, when comparing the anode coating condition in embodiments 4-10, embodiments 12-13 and embodiment 15 with comparative examples 1-2 of the prior art: the insoluble anode was provided with a reverse-pulse protective screen in embodiments 4-10, embodiments 12-13 and embodiment 15, wherein the anode coating in embodiments 4-10 and embodiments 12-13 were in perfect condition after electroplating, and the anode coating in embodiment 15 had its upper part slightly fell off after light brushing due to the lack of bypass design; whereas the insoluble anode in comparative examples 1-2 were provided without a reverse-pulse protective screen which protects anode coating, the coating after electroplating obviously fell off when it was brushed lightly. It can be summarized that the insoluble anode of the present disclosure provided with a reverse-pulse protective screen can effectively reduce the electrochemical formation of hydrogen on the surface of the insoluble anode coating, thus extending the service life of the insoluble anode.
[0305] Since the electroplating additives used in the industry are organic compounds, their consumption can be reflected by the change in the COD value of the electroplating solution, i.e., the faster the COD value of the electroplating solution decreases, the faster the electroplating additives in the electroplating solution are consumed. As shown in Table 2 above, when comparing embodiment 9 and embodiment 10, in which the electroplating cell was provided with a electroplating cell divider, with comparative example 1, embodiment 1 and embodiment 4, in which the electroplating cell is not provided with a electroplating cell divider: in embodiment 9 and embodiment 10, the difference between the COD values of the catholyte before and after electroplating were not exceed 80 mg/L, indicating a small consumption of electroplating additives. In comparative example 1, embodiment 1 and embodiment 4, the difference between the COD values of the electroplating solution before and after electroplating were more than 200 mg/L, indicating a large consumption of electroplating additives. It can be proved that the electroplating cell of the present disclosure provided with an electroplating cell divider can effectively save electroplating additives.
[0306] Furthermore, the basic setup of Comparative Example 1 of the prior art was the most similar to that of Embodiment 9 and Embodiment 10 of the present disclosure. However, both Embodiment 9 and Embodiment 10 were superior to Comparative Example 1 in terms of electroplating uniformity, small hole electroplating quality, anode coating condition, and consumption of electroplating additives.
[0307] The present disclosure may be outlined in other specific forms that do not contradict the spirit or the main features of the present disclosure. The aforementioned embodiments are the preferred embodiments of the present invention. They do not intend to limit the scope of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.