CN116685721A

CN116685721A - Optimization process and device for insoluble anodic acidic sulfate electroplated copper

Info

Publication number: CN116685721A
Application number: CN202180084378.2A
Authority: CN
Inventors: 叶涛; 叶旖婷
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-12-31
Filing date: 2021-12-30
Publication date: 2023-09-01
Also published as: TWI806328B; TW202229649A; US20240060202A1; WO2022143860A1

Abstract

The invention discloses an optimization process of insoluble anode acid sulfate electroplated copper, which comprises an electroplating bath, an electroplating power supply, an insoluble anode and an acid sulfate copper plating electroplating solution which is used as an electroplating solution, wherein the electroplating solution is characterized in that: adopting a plate-shaped insoluble anode which is made of titanium material covered with a coating and is in a net shape or provided with a hollowed-out structure, and additionally arranging at least one liquid suction pipe/port on the surface of the insoluble anode, which is opposite to the cathode, so that electroplating liquid can flow in an overflow or/and electric liquid suction mode of the liquid suction pipe/port; and (3) switching on an electroplating power supply to carry out electroplating production operation, and sucking away the electroplating liquid through overflow of the liquid suction pipe/port or/and in a power mode, so that the electroplating liquid in the electroplating tank forms liquid flow to the liquid suction pipe/port, and correspondingly, adding the electroplating liquid into the electroplating tank to maintain the quantity of the electroplating liquid in the electroplating tank until the electroplating is completed and the plated piece is taken out. The process can effectively improve the uniformity of the electroplated metal copper layer and improve the electroplating quality.

Description

Optimization process and device for insoluble anodic acidic sulfate electroplated copper

Technical Field

The invention belongs to the field of copper electroplating processes, and particularly relates to an optimization process and device for insoluble anode acid sulfate copper electroplating.

Background

Copper electroplating is one of the most common processes in the electroplating industry. Generally, to plate nickel, gold, silver, tin metal layers on the surfaces of various metal pieces, an intermediate copper layer is needed to be plated in advance to improve the bonding force of the outer surface plating layers; in addition, copper metal plating processes are also common in the circuit board industry in manufacturing processes.

The existing acid sulfate copper plating process is a plating process using sulfuric acid and copper sulfate as main components of a plating solution thereof, and can be divided into two different processes according to a soluble anode and an insoluble anode. The soluble anode copper electroplating process adopts phosphor copper as a soluble anode material; the insoluble anode copper plating process refers to an electroplating process in which the anode does not generate or generates little dissolution in the electroplating reaction process, namely, an insoluble anode material is adopted, and an insoluble titanium-based coating anode is commonly adopted in the prior art.

The anodic electrochemical reaction formulas of the two acid sulfate copper electroplating processes are as follows:

(1) Soluble anode copper electroplating process

Cu-2e ^- →Cu ²⁺

(2) Insoluble anode copper electroplating process

Compared with the soluble anode copper electroplating process, the insoluble anode copper electroplating process generates hydrogen ions and oxygen by the electrolytic reaction of water on the anode, copper ions in the electroplating solution are reduced to metallic copper at the cathode, and the cathode plating piece is electroplated with a more uniform, flat and compact copper metal plating layer due to the stable anode external dimension and controllable and stable electroplating solution component state in the electroplating process; besides direct current plating, the insoluble anode copper plating process can be applied to pulse plating, and the production efficiency can be greatly improved by increasing the anode current density.

Meanwhile, as technological development has been fully advanced into 5G electrical communication in recent years, demands of the market for precision circuit boards are increasing, wherein demands for aspect ratio values of copper plated through holes (i.e., hole length to hole diameter ratio of through holes) in multilayer circuit boards are also increasing, so that an insoluble anodic copper plating process has been promoted in the current circuit board processing production to improve the production quality and production efficiency of copper plating of circuit board products.

When double-sided electroplating is carried out on a circuit board with a larger aspect ratio value of a copper plated through hole, the cathode plating piece is converted into an electrolytic anode copper dissolving reaction by utilizing the back pulse of a power supply in the existing insoluble anode copper electroplating process; therefore, the uniformity and flatness of the plating layer can be optimized, the dispersion capacity of the plating solution can be improved, the binding force of the plating layer can be improved, and the copper plating layer with the through holes can be well penetrated.

However, the existing insoluble anode copper plating process still has the following disadvantages:

1. oxygen bubbles are generated on the anode in the electroplating process and can be distributed between the anode and the cathode plating piece, so that a barrier for blocking electroplating current is formed, the uniformity of discharge is affected, and the uniformity of a plating layer is reduced. Meanwhile, oxygen bubbles generated in the electroplating process in the conventional vertical electroplating process can form a bubble layer with a certain gradient from bottom to top on the surface of the anode, so that current is further unevenly distributed, and the quality of a plated part in vertical electroplating is seriously affected.

Aiming at the problem of vertical electroplating, the solution of the prior art adopts a horizontal electroplating mode, so that the influence caused by blocking a barrier by a bubble layer is reduced to the greatest extent, but the horizontal electroplating equipment has more complicated structure and very limited space in an electroplating bath, so that the plated part can only be a thin plate generally and cannot meet the electroplated copper production of products with different external dimensions.

2. In the reverse pulse electroplating process, when the original insoluble anode is converted into a cathode under the action of reverse pulse, the polarity conversion of the insoluble anode can enable the surface of the insoluble anode to generate hydrogen evolution reaction, so that titanium oxide on the surface of a titanium substrate of the insoluble titanium-based coating anode is changed into titanium hydride, and the coating of the insoluble anode is fallen to cause anode damage.

3. In the existing insoluble anode copper electroplating process, an organic electroplating additive, namely a brightening additive, is usually required to be added into a plating solution so as to enable a plated part to obtain a smoother and cleaner plating layer. The anode used in the insoluble anode copper plating process is coated with a noble metal coating on the surface, and the coating has a catalytic effect on the decomposition reaction of the electroplating additive and can directly decompose the electroplating additive in the plating solution. In addition, some nascent oxidants accelerate the decomposition and destruction of plating additives when the insoluble anode is subjected to acidic copper plating operations. Therefore, the existing insoluble anode is used in the electrolytic copper plating process, and the consumption of the electroplating additive is far greater than the normal consumption in the soluble anode electrolytic copper plating process. The plating additive is additionally consumed resulting in increased production costs.

In view of the foregoing, although insoluble anodes have advantages of flat plating and high efficiency over soluble anodes in electrolytic copper plating processes, there is still a need for process optimization.

Disclosure of Invention

The first object of the present invention is to provide an optimized process for insoluble anodic acidic sulfate copper plating, which can effectively improve the uniformity of a copper layer plated on a plated article and improve the plating quality.

The second object of the present invention is to provide an optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating.

The first object of the invention is achieved by the following technical scheme:

an optimization process of insoluble anode acid sulfate electroplated copper comprises an electroplating bath, an electroplating power supply, an insoluble anode and an acid sulfate copper plating electroplating solution as an electroplating solution, wherein the electroplating part is used as a cathode, and the optimization process is characterized in that:

(1) Adopting a plate-shaped insoluble anode which is made of titanium material covered with a coating and is net-shaped or provided with a hollowed-out structure, and then installing the insoluble anode and the cathode in a plating bath; at least one liquid suction pipe/port is additionally arranged on the side of the insoluble anode, which is opposite to the cathode, so that the electroplating liquid can flow in an overflow or/and electric liquid suction mode through the liquid suction pipe/port;

(2) And (3) switching on an electroplating power supply to carry out electroplating production operation, and sucking the electroplating liquid through overflow of the liquid suction pipe/port or/and in a power mode, so that the electroplating liquid in the electroplating tank forms liquid flow flowing to the liquid suction pipe/port, and correspondingly, adding the electroplating liquid into the electroplating tank to maintain the amount of the electroplating liquid in the electroplating tank until the electroplating is completed and the plated piece is taken out.

The insoluble anode adopts a reticular or hollowed-out plate-shaped structure, so that the insoluble anode is provided with holes with two through sides, and is matched with at least one liquid suction pipe/port arranged on the side of the anode facing away from the cathode, and liquid near the insoluble anode generates liquid flow far away from the cathode and passing through the holes of the anode in a overflowing and/or power mode, so that oxygen bubbles generated on the surface of the anode in the electroplating process can pass through holes formed by meshes or hollowed-out structures of the insoluble anode along with the liquid flow, and are discharged and released by a region between the anode and a cathode plating piece, thereby being beneficial to reducing the accumulation of oxygen on the surface of the side of the anode facing the cathode in the electroplating process to form an oxygen bubble shielding layer, and further improving the electroplating uniformity and the electroplating efficiency of the plating piece.

Preferably, the pipette/port uses a motive force to create a flow of liquid near the insoluble anode away from the cathode and through the anode aperture, the motive force being a pump that pressurizes the drain and/or negative pressure pipette.

The re-addition of the plating solution into the plating tank to maintain the plating solution amount in the plating tank may be a new plating solution or a plating replacement solution, or may be a reflux system.

The reflux system adopted by the invention mainly comprises a pump and a connecting pipeline, one end of the reflux system is connected with a liquid suction pipe/port, the other end of the reflux system is communicated with the electroplating bath, and electroplating liquid sucked by the liquid suction pipe/port is refluxed into the electroplating bath by the reflux system, so that liquid flow of the electroplating liquid in the electroplating bath to the liquid suction pipe/port at the anode is formed, and the reflux system is circulated and reciprocated. The reflux system can be constructed by connecting a connecting pipe to the plating tank on the basis of the liquid near the insoluble anode being pumped by the above-mentioned pipette/port to generate a flow of liquid away from the cathode and through the pores of the anode.

The method is applicable to vertical plating and horizontal plating; can be matched with a common direct current power supply or a back pulse power supply. Particularly, when the method is applied to vertical electroplating, the technical problem that an oxygen bubble forms a current blocking shielding layer on the surface of the anode facing the cathode in the prior art can be effectively solved, so that the insoluble anode can realize good electroplating effect in vertical electroplating equipment with simple structure and easy maintenance.

The invention can be improved as follows:

the side of the insoluble anode facing the cathode is additionally provided with at least one liquid spraying pipe/port, the liquid spraying pipe/port is connected with an externally connected liquid spraying pipeline and is used for spraying liquid towards the anode, and the liquid spraying pipe/port is matched with the liquid sucking pipe/port to generate more stable and controllable liquid flow far away from the cathode near the insoluble anode, so that bubbles generated on the anode in the electroplating process can smoothly pass through a pore of the insoluble anode to leave an area between the anode and a cathode plating piece, and the liquid spraying pipeline is a pipeline with a pump, the other end of the pipeline is communicated with a container filled with electroplating liquid, and continuous electroplating liquid is provided for the liquid spraying of the liquid spraying pipe/port.

Preferably, the liquid spraying pipe/opening is arranged at the bottom of the electroplating bath on the side of the insoluble anode facing the cathode, so that the liquid spraying pipe/opening and the liquid sucking pipe/opening are matched to generate liquid flow from bottom to top, bubbles generated on the anode are sucked away from the cathode as soon as possible through the pores of the insoluble anode, and meanwhile, the phenomenon that the current distribution of the electroplating liquid is influenced due to the fact that the electroplating liquid in the area between the anode and the cathode plating piece generates vortex is avoided.

The invention can also adopt the improvement of the feed structure of the insoluble anode, and a feed circuit is preferably arranged at two sides of the horizontal side of the insoluble anode, so that the current density difference between the upper part and the lower part of the insoluble anode is reduced, and the conductivity of the gas-liquid mixture between the gas-evolving electrode and the cathode region tends to be uniform. The method overcomes the defect that the electroplating current distribution of the electroplating solution is extremely uneven because the upper part of the anode is more concentrated with the electroanalysis bubbles due to the higher current density than the lower part of the anode in the upper feeding mode.

The invention can further add a gas-liquid separator in the reflux pipe system, so that the liquid suction pipe discharges the gas-liquid mixture fluid sucked from the electroplating bath into the gas-liquid separator through a connecting pipeline. The gas-liquid separator is a device which leads oxygen bubbles generated on the anode in the electroplating process and electroplating liquid to be drained into a larger space, so that the flow rate of the liquid is slowed down and gas in the liquid escapes. The gas-liquid mixture is separated in the gas-liquid separator to release gas, and then the liquid is led back to the electroplating tank again for circulating flow.

Preferably, the oxygen separated out in the gas-liquid separator is collected and reused.

The plating tank may be divided into two regions, namely an anode plating tank region and a cathode plating tank region, by a plating tank separator, and the plating solutions in the two plating tank regions may be the same or different. Namely, the electroplating solution in the anode electroplating bath area is anode electroplating solution, in particular to aqueous solution containing inorganic acid and/or inorganic salt, or acidic sulfate copper plating electroplating solution is adopted; the plating solution in the cathode plating bath zone is an acidic sulfate copper plating solution. In the electroplating process, the insoluble anode and the cathode plating piece are respectively arranged in the anode electroplating bath area and the cathode electroplating bath area in a separated mode. In this preferred embodiment, the pipette/port described in the present invention is disposed in the anode plating bath zone, since the bubbles are only present in the anode bath zone between the two electrodes, and a flow of liquid is only generated in the anode bath zone away from the cathode and through the anode aperture. If a liquid spraying pipe/opening is further arranged on the side of the insoluble anode facing the cathode, the liquid spraying pipe/opening is also positioned in the anode plating bath area.

The plating bath separator is used for separating oxygen and hydroxyl radicals generated on the anode from the plating solution in the area near the cathode plating piece so as to reduce the possibility that the oxygen and hydroxyl radicals enter the acidic copper plating solution near the cathode plating piece to chemically react with the plating additive, thereby reducing the extra loss of the plating additive in the acidic copper plating solution. Meanwhile, the concentrated pumping and exhausting of oxygen generated on the surface of the anode in the electroplating process are facilitated.

Preferably, the plating bath separator is at least one selected from the group consisting of a cation exchange membrane, an anion exchange membrane, a bipolar membrane, a reverse osmosis membrane, a filter cloth, an ultrafiltration membrane, a ceramic filter plate, and a PE filter plate.

When the cation exchange membrane is selected as the plating bath separator, with the progress of electrochemical reaction, copper ions of the acidic sulfate copper plating bath in the cathode plating bath region are reduced to metallic copper on the surface of the cathode plating member, and cations in the plating bath in the anode plating bath region enter the cathode plating bath region through the plating bath separator.

When the plating bath separator is an anion exchange membrane, with the progress of electrochemical reaction, copper ions of the acid sulfate copper plating bath in the cathode plating bath region are reduced to metallic copper on the surface of the cathode plating member, and at the same time anions of the acid sulfate copper plating bath in the cathode plating bath region enter the anode plating bath region through the plating bath separator.

When the ultrafiltration membrane and/or the ceramic filter plate and/or the PE filter plate and/or the filter cloth are/is selected for the electroplating bath partition, along with the progress of electrochemical reaction, copper ions of the acidic sulfate copper plating electroplating solution in the cathode electroplating bath region are reduced to metallic copper on the surface of a cathode plating part, meanwhile, part of cations in the electroplating solution in the anode electroplating bath region can enter the cathode electroplating bath region through small holes of the electroplating bath partition, and part of anions of the acidic sulfate copper plating electroplating solution in the cathode electroplating bath region can also enter the anode electroplating bath region through small holes of the electroplating bath partition.

When the bipolar membrane is independently selected as the plating bath separator, along with the progress of electrochemical reaction, copper ions of the acidic sulfate copper plating solution in the cathode plating bath region are reduced to metallic copper on the surface of the cathode plating piece, and meanwhile, the bipolar membrane generates hydrogen ions through the electrolytic reaction of water and enters the cathode plating bath region.

When the reverse osmosis membrane is selected as the plating bath separator, the copper ions of the acidic sulfate copper plating solution in the cathode plating bath area are reduced to metallic copper on the surface of the cathode plating member as the electrochemical reaction proceeds. If hydrogen ions are present in the plating solution in the anodic plating bath section, the hydrogen ions also pass through the plating bath partition into the cathodic plating bath section.

Preferably, the anodic plating solution is a solution of sulfuric acid and/or copper sulfate. More preferably, the anodic plating solution is a sulfuric acid solution.

When the gas-liquid separator is additionally arranged in the reflux pipe system, the liquid suction pipe/port discharges the gas-liquid mixture fluid sucked from the anode plating bath area into the gas-liquid separator through the connecting pipeline, and after the gas-liquid mixture is separated in the gas-liquid separator to release gas, the liquid of the gas-liquid mixture is led back to the anode plating bath area again to circularly flow.

As an improved embodiment of the present invention, the anode plating tank zone is in the form of an anode box and is installed in the plating tank to separate the anode plating tank zone and the cathode plating tank zone, which is specifically: the anode box is in a cubic box shape, the insoluble anode is positioned in the anode box, the surface of the anode box facing the cathode plating piece is a plating bath partition, the internal space of the anode box is an anode plating bath area, and the space in the plating bath and outside the anode box is a cathode plating bath area. In this preferred embodiment, the pipette/port according to the invention is arranged on the anode cartridge, in particular in the spatial position or cartridge wall of the side of the insoluble anode facing away from the cathode; in addition, a liquid spray pipe/port can be arranged in the anode box, and the liquid spray pipe/port is particularly positioned in the area between the side of the insoluble anode facing the cathode and the adjacent box wall in the anode box. Preferably, the liquid ejected from the liquid ejecting pipe/port in the anode box is taken from the liquid in the gas-liquid separator.

Preferably, the periphery of the anode box, which faces the cathode, is provided with a liquid spraying pipe for spraying electroplating liquid to the cathode, so that the electroplating liquid can flow into the deep part of the holes of the cathode plating piece, and the electroplating liquid in the holes can be updated in a supplementing manner, thereby improving the electroplating quality of the deep part of the holes of the plating piece.

More preferably, when a plurality of anode boxes are arranged, the spraying action of the liquid spraying pipe outside the anode boxes is controlled by a program according to time and/or flow, and the time difference and/or the flow difference are used for avoiding the mutual opposite collision of liquid flows sprayed by the anode boxes at the two sides of the cathode plating piece at the same time, so that the optimization of the plating solution filling effect is realized.

The invention can also be provided with a back pulse protection screen on the insoluble anode, wherein the back pulse protection screen is in any electrode structure form which is favorable for discharging, such as uncoated titanium bulges or raised meshes, strips and the like, arranged on the surface of the anode facing the cathode, and is directly connected with the titanium substrate of the insoluble anode. The shape of the bulge can be a convex point shape, a spike shape and a vertical strip shape; the raised net and the raised strip can be net or strip fixed on the support leg end of the anode facing the cathode, or net or strip formed by connecting the upper part of any raised object, and the plane formed by the net or strip is parallel or basically parallel to the anode surface.

The structure of the insoluble anode is modified in a targeted way, and when the reverse pulse power supply is adopted as an electroplating process, the process quality advantage of the insoluble anode can be effectively exerted. The principle of the anti-pulse protection screen is that titanium has unidirectional conduction threshold metal characteristics in the electrochemical reaction of electrolyte water solution, namely when the exposed titanium metal of the anti-pulse protection screen is used as an anode to carry out the electrochemical reaction of the electrolyte water solution, an oxide layer is generated on the surface of the titanium metal and is difficult to participate in the electrochemical reaction, but the titanium metal can normally participate in the discharge when being used as a cathode to carry out the electrochemical reaction, so that the anti-pulse protection screen hardly participates in the reaction when being used as an anode to carry out the electrochemical reaction of electroplating, but the titanium anode body coated with the coating carries out the main electrochemical reaction of electroplating; however, when the original plating piece is converted into anode for electrolytic copper dissolution after the reverse pulse pole-changing phase of the power supply, the insoluble anode is converted into cathode, and the reverse pulse protection screen participates in electrochemical reaction for discharging. Because the back pulse protection screen protrudes from the surface of the insoluble anode and is closer to the cathode plating piece in distance, according to the electric field potential difference principle, the back pulse protection screen can more effectively attract electroplating current and lead main current to flow from the titanium base material in the insoluble anode after passing through the back pulse protection screen. The hydrogen evolution reaction will occur directly on the back pulse protection screen rather than primarily on the surface of the insoluble anode coating as in the prior art. Therefore, the back pulse protection screen can effectively reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode coating, thereby effectively prolonging the service life of the insoluble anode. When the back pulse protection screen is provided with protrusions, the more the protrusions are, the more uniformly distributed the protrusions are, and the better the protection effect on the insoluble anode coating is.

The invention can further add the setting frame at the edge of the insoluble anode, and the insoluble anode is connected with the setting frame, which is helpful for enhancing the straight mechanical rigidity of the insoluble anode and reducing the influence of discharge non-uniformity caused by anode deformation. The thickness of the shaping frame is larger than the thickness of the insoluble anode and/or the width of the shaping frame is larger than the width of the non-porous part of the insoluble anode and/or the mechanical rigidity of the shaping frame is higher than the mechanical rigidity of the insoluble anode and/or the mechanical rigidity of the insoluble anode is reinforced by a stable structure.

The shaping frame can be made of any material which is positive, insoluble, heat-resistant, acid-resistant and high in rigidity.

When the insoluble anode is provided with the back pulse protection screen and the shaping frame is made of bare titanium or coated titanium, the back pulse protection screen can be independently connected with the titanium of the shaping frame or simultaneously connected with the titanium of the shaping frame except for the scheme of directly connecting with the titanium base material of the insoluble anode. As the thicker electric conductor has smaller resistance, the shaping frame in the preferred scheme can lead the whole current of the insoluble anode to be reasonably distributed during electroplating, and can lead the main current to be led into the shaping frame for bypass in the reverse pulse electrolysis process, thereby further protecting the surface coating of the insoluble anode.

Preferably, the shaping frame is made of conductive material, and the shaping frame is connected with the positive electrode of the electroplating power supply through the titanium substrate of the insoluble anode, or is simultaneously connected with the titanium substrate of the insoluble anode and the positive electrode of the electroplating power supply, or is connected with the positive electrode of the reverse pulse electroplating power supply.

More preferably, the shaping frame is made of bare titanium, and the shaping frame is connected with the positive electrode of the electroplating power supply through the titanium substrate of the insoluble anode, or is connected with the titanium substrate of the insoluble anode and the positive electrode of the electroplating power supply at the same time, or is connected with the positive electrode of the reverse pulse electroplating power supply, so that the insoluble anode can be combined for improving the feed structure.

The invention can be improved as follows: and adding a supplementary solution or electroplating raw material into the electroplating tank according to the analysis result of the component concentration of the electroplating solution in the electroplating process so as to maintain the stability of the proportion of each component in the electroplating solution.

The invention can be improved as follows: the electroplating bath can be directly connected with the electroplating liquid regeneration device or connected with the electroplating liquid regeneration device through the transfer bath to form a controllable recycling system arranged according to the process, and the controllable recycling system is used for supplementing an electroplating copper source, so that the environment-friendly clean production is realized, and the production cost is reduced.

The invention can be improved as follows: the side of the insoluble anode, which is opposite to the cathode, is connected with a conductor communicated with the anode of the electroplating power supply, and the bypass current of the conductor is utilized to increase the uniformity of discharge during the insoluble anode electroplating, so that the electroplating quality of a plated piece is improved. The electric conductor can be a conductive plate or a conductive net, and meanwhile, the conductive plate or the conductive net is connected with the shaping frame, so that the insoluble anode can be discharged more uniformly during electroplating.

Preferably, the conductive plate is an uncoated titanium plate with a net-shaped or hollow structure, or the conductive net is an uncoated titanium net.

The invention can be further changed into that the back pulse protection screen is arranged on the electric conductor, and then the back pulse protection screen passes through meshes or hollow structures of the insoluble anode to extend out of the surface of the insoluble anode towards the cathode. The method comprises the following two connection modes:

the anti-pulse protection screen is welded with a titanium substrate of an anode when passing through the insoluble anode, and can shunt anti-pulse current along a conductor and the titanium substrate of the insoluble anode respectively through a protruding part during electroplating so as to reduce hydrogen evolution phenomenon on the insoluble anode.

The anti-pulse protection screen net does not conduct electricity when passing through the insoluble anode, and current passing through the insoluble anode can be reduced when in anti-pulse electroplating, so that hydrogen evolution phenomenon is further reduced.

Preferably, the back pulse protection screen is not connected with the insoluble anode in a conductive way, and the insoluble anode and/or the shaping frame are/is connected with the conductive plate or the conductive screen by welding through a titanium plate or a titanium screen.

More preferably, the shaping frame is welded with the conductive plate or the conductive net by using a titanium plate or a titanium net for peripheral edge sealing. This allows the insoluble anode to draw a more uniform current during electroplating and allows the main current to be shunted through the reverse pulse guard net, the sizing frame and/or the conductive plate (net) as the insoluble anode is turned to the cathode during reverse pulse operation, further reducing the hydrogen evolution reaction of the insoluble anode.

The invention can be improved by installing at least one liquid suction pipe/port on the side of the conducting plate or the conducting net facing away from the cathode when the insoluble anode is provided with the back pulse protection screen net, the shaping frame and the conducting plate or the conducting net; the insoluble anode and the conductive plate or the conductive net are connected by sealing edges between the two through a shaping frame made of titanium plate materials, so that the main liquid flow of the liquid spraying pipe/port carries the bubbles separated by the anode and can intensively pass through the through holes on the insoluble anode and the through holes on the conductive plate or the conductive net behind the insoluble anode, and the bubbles are pushed into the liquid spraying pipe/port to be sucked and flow out.

Preferably, the insoluble anode with the back pulse protection net, the shaping frame, the electric conductor and the insoluble anode assembly of the liquid suction pipe/port and the liquid spraying pipe/port are installed in the anode box to be used as an anode groove zone box type assembly.

The invention can be improved as follows: when the cathode plating piece needs to be plated in a plurality of directions or the plating areas of the surfaces in different directions are different, one power supply can be used for connecting two or more insoluble anodes, and the insoluble anodes are reasonably distributed at the periphery of the plating piece for electrochemical reaction of plating; two or more power supplies and a plurality of insoluble anodes can be selected to be commonly connected with a cathode plating piece for electroplating under the arrangement of reasonable positions; and two or more electroplating power supplies and one or more insoluble anodes respectively connected with each power supply can be also arranged according to the required electrochemical reaction quantity, and under the condition of electroplating by commonly connecting cathode electroplating workpieces, the current intensity output by each electroplating power supply can be accurately regulated according to the electroplating surface areas and the technological requirements of the electroplated parts in different directions so as to improve the electroplating quality of the electroplated parts.

The second object of the invention is achieved by the following technical scheme:

An optimizing device of insoluble anode acid sulfate electroplated copper comprises an electroplating bath, an insoluble anode, a cathode serving as a plating piece and an electroplating power supply, and is characterized in that: the electroplating bath is also internally provided with at least one liquid suction pipe/port, and the liquid suction pipe/port is positioned on the surface of the insoluble anode, which is opposite to the cathode, and is used for generating liquid flow in the electroplating bath in an overflow or/and electric liquid suction mode of passing through the liquid suction pipe/port;

the insoluble anode is a titanium material covered with a coating, and is in a net shape or a plate shape with a hollowed-out structure;

the positive electrode and the negative electrode of the electroplating power supply are respectively connected with the insoluble anode and the plating piece serving as the cathode in the electroplating process.

The invention can be improved as follows: the device of the invention adopts a reflux system, which mainly comprises a power source and a connecting pipeline, one end of the reflux system is connected with a liquid suction pipe/port, the other end is communicated with a plating bath, and the reflux system is utilized to reflux the plating solution sucked by the liquid suction pipe/port into the plating bath again, so as to form liquid flow of the plating solution in the plating bath to the liquid suction pipe/port at the anode, and the liquid flow is circulated and reciprocated. The reflux system may be configured by connecting a connecting conduit to the plating cell based on the use of power to the pipette/port to create a flow of liquid near the insoluble anode away from the cathode and through the anode aperture.

The invention can be improved as follows: the electroplating bath is characterized in that at least one liquid spraying pipe/port is arranged in the electroplating bath, the liquid spraying pipe/port is arranged in a region space between two electrodes on the side of the insoluble anode facing the cathode, the liquid spraying pipe/port is externally connected with a liquid spraying pipeline for spraying liquid to the anode, the liquid spraying pipeline is matched with the liquid spraying pipe/port to generate more stable and controllable liquid flow far away from the cathode near the insoluble anode, the liquid spraying pipeline is a pipeline with a pump, the other end of the pipeline is communicated with a container filled with electroplating liquid, and the pipeline can also be directly connected with a reflux system connected with the liquid spraying pipe/port, so that continuous electroplating liquid is provided for liquid spraying of the liquid spraying pipe/port.

Preferably, the spray pipe/port is installed at the bottom of the plating tank on the side of the insoluble anode facing the cathode and sprays liquid toward the insoluble anode.

The invention can be improved as follows: the liquid suction pipe/port is connected with the gas-liquid separator through a connecting pipeline, the gas-liquid separator is a larger container device, and when oxygen bubbles generated on the anode in the electroplating process are drained to the gas-liquid separator together with the electroplating liquid, the larger space is utilized to slow down the flow rate of the liquid so as to lead the gas to escape. The gas-liquid separator can be communicated with the electroplating bath through a pump and a connecting pipeline to form a reflux system, and the liquid treated by the released gas is discharged back to the electroplating bath for circulating flow.

The invention can be improved as follows: and arranging an electroplating bath separator in the electroplating bath, and separating the electroplating bath into an anode electroplating bath area and a cathode electroplating bath area.

Preferably, the separation of the anode plating cell region and the cathode plating cell region is performed by installing an anode box in the plating cell: the anode box is in a cube box shape, the insoluble anode is positioned in the anode box, the surface of the anode box facing the cathode plating piece is a plating bath partition, the internal space of the anode box is an anode plating bath area, and the rest of the plating bath areas except the anode box are cathode plating bath areas. The liquid suction pipe/port is arranged on the anode box, in particular on the space or box wall of the side of the anode box opposite to the insoluble anode and facing away from the cathode; in addition, a liquid spray pipe/port can be arranged in the anode box, and the liquid spray pipe/port is particularly positioned in the area between the side of the insoluble anode facing the cathode and the adjacent box wall in the anode box.

Preferably, the liquid outlet of the gas-liquid separator is connected with the liquid spraying pipeline and the liquid spraying pipe/port, namely a pump is arranged on a connecting pipeline of the gas-liquid separator and the liquid spraying pipe/port, so that the reflux pipeline and the liquid spraying pipeline are combined into a whole, and the anode electroplating liquid is quickly guided into the gas-liquid separator through the liquid suction pipe/port to be separated from gas and liquid under the action of the pushing force of the pump and the bubble penetrating through the structural pore of the insoluble anode.

The invention can be improved as follows: the periphery of the outer side edge of the surface of the anode box facing the cathode plating piece is provided with liquid injection pipes, and each liquid injection pipe is internally provided with a flow regulator so as to regulate the injection effect of the cathode plating liquid.

More preferably, a plurality of anode boxes can be arranged in one plating tank, and the spraying action of the liquid spraying pipes arranged outside the anode boxes can be controlled through a program, so that the phenomenon that the spraying pipes arranged on the anode boxes are flushed with spraying liquid during the action and the filling optimization cannot be realized is avoided.

The insoluble anode can be further provided with a back pulse protection screen which is an uncoated titanium bulge arranged on the surface of the insoluble anode facing the cathode plating piece, the bulge is directly connected with a titanium substrate of the insoluble anode, and the bulge can be in a convex point shape, a spike shape, a vertical strip shape or any electrode structure form which is connected with any shape structure and is beneficial to discharge, such as a net shape or a strip shape.

The invention can be improved as follows: the edge of the insoluble anode is also provided with a shaping frame.

Preferably, the shaping frame is made of bare titanium, and is connected with the positive electrode of the electroplating power supply through the titanium substrate of the insoluble anode, or is connected with the titanium substrate of the insoluble anode and the positive electrode of the electroplating power supply at the same time.

The invention can be improved as follows: the surface of the insoluble anode, which is opposite to the cathode, is provided with a conductor communicated with the anode of the electroplating power supply, so that the discharge of the insoluble anode is uniform. Preferably, the electric conductor is a titanium plate with a net-shaped or hollow structure, namely a conductive net or a conductive plate.

The invention can be improved as follows: the insoluble anode is improved in feed structure, and feed circuits are preferably arranged at two sides of the level of the polar plate of the insoluble anode, so that the conductivity of the gas-liquid mixture between the gas-evolving electrode and the cathode region tends to be uniform, and the defect that the gas-evolving electrode forms a gradient bubble layer in the traditional top-down feed mode is overcome.

The invention can be improved as follows: the insoluble anode with the back pulse protection net, the shaping frame and the electric conductor and the insoluble anode components of the liquid suction pipe/port and the liquid spraying pipe/port are arranged in the anode box with the liquid spraying pipe to be used as an anode groove area assembly, so that the electroplating equipment is more compact.

The invention can be improved as follows: when the plating surface areas of the plating parts in all directions are inconsistent, a power supply and two or more insoluble anodes with more than two numbers can be adopted as a plating process system reasonably distributed around the cathode; two or more electroplating power sources and two or more insoluble anodes can be arranged on the periphery of the cathode plating piece according to the process requirements to form an electroplating system of the common cathode plating piece. The working states between the power supplies are controlled by a program according to the technological requirements, so that the cathode plating piece can meet the electroplating quality requirements.

The invention can be improved as follows: in order to meet the quality requirement of the pore plating of the cathode plating piece, a reverse pulse plating power supply and a reverse pulse plating process can be adopted to better exert the performance and the function of the insoluble anode to improve the plating quality and efficiency.

The invention can be improved as follows: the stirring device is arranged in the electroplating bath to help the concentration of each component of the electroplating solution to be evenly distributed. The stirring device is any one stirring device or any combination of stirring devices of a reflux liquid stirring device, a leaf stirring device and a pneumatic stirring device, the reflux liquid stirring device comprises a liquid outlet pipe, a pump and a reflux pipe, and the pneumatic stirring device is equipment which can introduce gas into the electroplating liquid to enable the electroplating liquid to flow.

The invention can be improved as follows: and a current regulator is additionally arranged on the electroplating power supply, or the electroplating power supply with the current regulator is adopted for regulating the output current of the electroplating power supply, or controlling the on/off of the electroplating power supply.

The invention can be improved as follows: and a detection device is arranged in the electroplating bath and comprises one or more of a liquid level meter, a hydrometer, an acidometer, an oxidation-reduction potentiometer, a photoelectric colorimeter, a pH meter and a thermometer, and is used for detecting corresponding technological parameters of liquid in the electroplating bath.

Preferably, the detecting device is connected with an automatic detecting and feeding controller, and the automatic detecting and feeding controller can control the process according to time and/or the detecting result of the detecting device: and adding a replenishing solution of the electroplating solution and/or chemical raw materials and/or clean water into the electroplating tank, and/or controlling the starting or stopping of an electroplating power supply or the current.

The invention can be improved as follows: and a filtering device is connected with the electroplating bath through a pipeline so as to remove copper sludge possibly existing in the electroplating solution and/or impurities brought in the use process of the electrode.

The invention can be improved as follows: and a tail gas pumping and exhausting system is arranged above the electroplating tank so as to pump out gas generated on the anode and/or the cathode in the electroplating process, and avoid accumulation to ensure safe production.

The invention can be improved as follows: the electroplating bath is connected with an electroplating liquid regeneration device through a pipeline and a pump to form electroplating copper source supplementing controllable recycling system equipment arranged according to the process.

The invention can be improved as follows: a temporary storage tank connected with the electroplating tank is additionally arranged and used for temporarily storing liquid flowing out of the electroplating tank and/or liquid to be added into the electroplating tank and/or carrying out other chemical reactions on the electroplating liquid.

The invention can be improved as follows: a temperature cold-heat exchanger is installed in the electroplating tank and/or the gas-liquid separator to stabilize the temperature of the electroplating solution.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the invention, the plate-shaped structural material with a net-shaped or hollow structure is adopted as the insoluble anode, and the liquid suction pipe/port is arranged in the direction of the insoluble anode back to the cathode, so that the problem that the electroplating uniformity is affected due to the formation of an oxygen bubble shielding layer by accumulation of oxygen on the surface of the anode in the prior art can be effectively solved, the plating layer is more uniform and flat, and the electroplating quality is remarkably improved; and the liquid spraying pipe/port arranged at the bottom of the plating bath on the side of the insoluble anode facing the cathode is matched with the liquid sucking pipe/port to generate liquid flow from bottom to top and away from the cathode, so that bubbles generated on the anode enter the liquid sucking pipe/port as soon as possible through the pores of the insoluble anode, and meanwhile, the phenomenon that the current distribution of the plating solution is influenced due to the fact that the plating solution in the area between the anode and the cathode plating piece generates vortex is avoided.

The method can obtain uniform and high-quality plating layers in a vertical plating mode, so that the method can be popularized to the traditional vertical plating process, and the process problem that the plating parts with irregular shapes are difficult to overcome in an insoluble anode horizontal plating line can be avoided.

2. The sizing frame is arranged at the edge of the insoluble anode, so that the leveling mechanical rigidity of the insoluble anode can be effectively enhanced, the discharge non-uniformity phenomenon caused by anode deformation is reduced, the quality of a plated part is improved, and a product with high flatness and uniformity is obtained;

in addition, the invention further provides a bare titanium material or a titanium material shaping frame coated with a coating, which is connected with the titanium base material and/or the back pulse protection screen of the anode body, or a conductor is arranged on the surface of the insoluble anode, which is opposite to the cathode, so that the discharge uniformity of the insoluble anode during electroplating can be effectively increased, and the coating protection effect and the electroplating quality can be improved.

3. The back pulse protection screen is arranged on the surface of the insoluble anode facing the cathode plating piece, so that the condition that a coating on the surface of the insoluble anode is damaged due to hydrogen evolution reaction can be effectively reduced in the back pulse process, the service life of the insoluble anode is prolonged, and the production cost is reduced;

the invention is provided with the naked titanium material or the titanium material shaping frame coated with the coating, and when the shaping frame is connected with the titanium base material of the insoluble anode and/or the back pulse protection screen and/or the positive electrode of the electroplating back pulse power supply, the shaping frame can effectively lead the main current into the shaping frame to bypass in the back pulse electrolysis process, thereby further improving the protection effect of the coating on the surface of the insoluble anode and reducing the damage of the insoluble anode.

Therefore, the process of the invention can effectively ensure the through quality of the copper plated through hole, namely better electroplating quality, greatly reduce the damage of the insoluble anode and prolong the service life of the insoluble anode in the back pulse electroplating process.

4. According to the invention, the liquid spraying pipe is arranged outside the anode box to spray the electroplating liquid to the plated piece, so that the electroplating liquid flows into the small holes of the cathode plated piece, and the plating liquid in the holes is updated in a supplementing manner, so that the through-hole penetrating quality of the plated piece is further improved.

5. According to the invention, when the electroplating bath is divided into the anode electroplating bath area and the cathode electroplating bath area by adopting the electroplating bath separator, the extra loss of the electroplating additive of the acid copper electroplating solution can be effectively reduced, so that the production cost is reduced; wherein the consumption rate of the electroplating additive in the process of the invention is 1/3 of that of the prior art.

6. The insoluble anode with the back pulse protection net, the shaping frame, the conducting plate or the conducting net, the insoluble anode component of the liquid suction pipe/port and the liquid spraying pipe/port are arranged in the anode box to be used as an anode groove zone box type assembly, and a plurality of insoluble anodes are reasonably connected at the periphery of the plating piece, so that the problems of uneven discharge and hydrogen evolution of the anode are solved, and the electroplating quality of the external irregular plating piece is improved.

7. The device can be matched with the electroplating liquid regeneration device for use, the electroplating tank is connected with the electroplating liquid regeneration device, and a circulating recycling system for supplementing the electroplating copper source is formed by combining a control system, so that the pollution of phosphorus copper is reduced, the green clean production is realized, and meanwhile, the production cost is reduced.

Drawings

The invention is further illustrated by the following figures.

FIG. 1 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 1 of the present invention;

FIG. 2 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 2 of the present invention;

FIG. 3 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 3 of the present invention;

FIG. 4 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 4 of the present invention;

FIG. 5 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 5 of the present invention;

FIG. 6 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 6 of the present invention;

FIG. 7 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 7 of the present invention;

FIG. 8 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 8 of the present invention;

FIG. 9 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 9 of the present invention;

FIG. 10 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 10 of the present invention;

FIG. 11 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 11 of the present invention;

FIG. 12 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 12 of the present invention;

FIG. 13 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 13 of the present invention;

FIG. 14 is an insoluble anodic acidic copper plating apparatus of comparative example 1 of the prior art;

FIG. 15 is a view showing an insoluble anodic acidic copper plating apparatus of comparative example 2 of the prior art;

FIG. 16 is an optimized apparatus for insoluble anodic acidic sulfate copper plating according to example 14 of the present invention;

FIG. 17 is an optimized apparatus for insoluble anodic acidic sulfate plating copper according to example 15 of the present invention.

FIG. A is a schematic diagram of an insoluble anode in example 1 of the present invention;

FIG. B is a schematic view of an insoluble anode in example 2 of the present invention;

FIG. C is a schematic view of an insoluble anode in example 3 of the present invention;

FIG. D is a schematic diagram of an insoluble anode in example 4 of the present invention;

FIG. E is a schematic diagram of an insoluble anode in example 5 of the present invention;

FIG. F is a schematic diagram of an insoluble anode in example 6 of the present invention;

FIG. G is a schematic view showing the structure of insoluble anode cartridges in examples 7 and 11 of the present invention;

FIG. H is a schematic view showing the structure of an insoluble anode cartridge in example 8 of the present invention;

FIG. J is a schematic view showing the structure of insoluble anode cartridges in examples 9 and 12 of the present invention;

fig. K is a schematic view showing the structure of the insoluble anode cartridge in examples 10 and 13 of the present invention.

Reference numerals: 1-insoluble anode, 1-1-insoluble anode hollowed-out hole, 2-liquid suction pipe/port, 3-feeder line installation hole, 4-cathode plating piece, 5-plating tank, 6-plating power supply, 7-acid sulfate copper plating solution, 8-gas-liquid separator, 9-liquid reflux circulation pipeline, 10-liquid spray pipe/port, 11-plating tank separator, 12-anode tank plating solution, 13-anode box, 14-liquid spray pipe, 15-back pulse protection screen, 16-shaping frame, 17-conductor (bar, screen), 18-fixing device, 19-back pulse plating power supply, 20-plating solution regeneration device, 21-detection device, 22-liquid circulation pipe, 23-corrosion-resistant pump, 24-stirring device, 25-gas suction hood, 26-28-plating additive, 29-variable frequency pump, 30-pumped liquid flow regulator, 31-copper metal block, 32-temporary storage tank, 33-solid-liquid separation filter, 34-automatic detection feed controller, 35-flowmeter, 36-temperature heat exchanger, 37-39-titanium overflow buffer basket, and 39-titanium buffer basket.

Detailed Description

The invention is further illustrated by the following specific examples.

In the examples described below, the copper sulfate used was a commercially available copper sulfate product; the sulfuric acid used is preferably a product produced by Guangzhou chemical reagent plant; the titanium-based coating electroplating anode and the electroplating tank are products produced by the manufacturing company of high environmental protection equipment in the bergamot market; the electroplating cathode is preferably a commercially available pure copper plate and a copper plate with small holes; the ion exchange membrane used is preferably an ion exchange membrane produced by membrane International; the bipolar membrane is preferably produced by national first technology; ultrafiltration membranes, filter cloth, ceramic filter plates, PE filter plates and reverse osmosis membranes are commercial products; the microscope used is preferably a computer microscope produced by Guangzhou optical instruments factory; the electroplating power supply and the back pulse electroplating power supply are products produced by Guangzhou, ishiku, guangxi, and Guangxi electroplating equipment factories; the acid copper plating additive is a product produced by the high-power group company in the city of bergamot. In addition to the above, the person skilled in the art may choose, according to routine choice, other products having similar properties to the above-mentioned products listed in the present invention, all of which achieve the object of the present invention.

Example 1

As shown in fig. 1, an embodiment of an optimizing apparatus for insoluble anodic acidic sulfate copper plating comprises a plating tank 5, an insoluble anode 1, a pipette 2, a cathode plating member 4, a plating power supply 6, and a gas-liquid separator 8, wherein:

a liquid suction pipe 2 is arranged in the plating bath 5, and the liquid suction pipe 2 is positioned on one surface of the insoluble anode 1, which is opposite to the cathode plating piece 4; the liquid suction pipe 2 is connected with the gas-liquid separator 8 through a connecting pipeline, the other end of the gas-liquid separator 8 is connected with the electroplating bath through a pipeline and a pump 23, and the liquid suction pipe 2 is used for separating and releasing gas from the gas-liquid mixture sucked from the electroplating bath through the connecting pipeline, and then the liquid is led back to the electroplating bath again for circulating flow.

The insoluble anode 1 is a titanium material coated with a coating, the structure is a plate-shaped object with a hollowed through hole, and a feeder line is arranged in a feeder line from a feeder line mounting hole at the upper part of an anode plate for feeding from above;

the positive and negative poles of the plating power supply 6 are connected to the insoluble anode 1 and the cathode plating member 4, respectively, during the plating process.

The cathode plating 4 is a flat copper plate.

An optimization method of insoluble anodic acid copper plating, comprising the following steps:

(1) Preparing a plating solution according to the specification of Table-1, and pouring the plating solution into a plating tank;

(2) The insoluble anode device is arranged in the electroplating bath, a liquid suction pipe is arranged on one surface of the insoluble anode, which is opposite to the cathode, the anode of the electroplating power supply is connected with the insoluble anode, and the cathode of the electroplating power supply is connected with the cathode plating piece;

(3) Putting a proper amount of electroplating additive into the electroplating solution, switching on an electrolysis power supply, and performing electroplating production operation by taking the acid copper plating electroplating solution as the electroplating solution;

(4) After the electroplating is completed, taking out the cathode plating piece; cleaning the cathode plating piece by using clear water and drying by using hot air; and the surface of the plating was observed using a computer microscope, and the observed results are recorded in table-1.

In the electroplating process, the structure of the insoluble anode is matched with a liquid suction pipe arranged on one surface of the anode, which is opposite to the cathode, liquid near the insoluble anode generates liquid flow which is opposite to the cathode and passes through the pores of the anode through overflow, and oxygen bubbles generated on the surface of the anode are discharged and released along with the liquid flow which passes through the pores formed by the structure of the insoluble anode and is sent to the direction away from the cathode.

COD of the plating solution was detected before and after the plating operation, the consumption of the plating additive by the process was preliminarily determined by the values of the changes before and after, and the results were recorded in Table-2.

Example 2

As shown in fig. 2, an example of an optimized apparatus for insoluble anodic acidic sulfate plating copper, which is different from the apparatus of example 1 in that:

the insoluble anode 1 has a structure shown in a figure B, the insoluble anode is a titanium net covered with a coating, a shaping frame 16 made of titanium material covered with the coating is welded around the four sides of the insoluble anode, and feeder lines are arranged from feeder line mounting holes at two horizontal sides of the anode plate for structural improvement.

The electroplating operation was performed using the procedure of the insoluble anodic acidic copper plating optimization method described in example 1 according to the parameters specified in table-1, and the results are recorded in table-1.

Example 3

As shown in fig. 3, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises a plating tank 5, an insoluble anode 1, a cathode plating member 4, a plating power supply 6, a gas-liquid separator 8, and a solid-liquid separation filter 33, wherein:

the plating tank 5 is internally provided with a liquid suction port 2, a liquid spraying pipe 10, a leaf stirring device 24.2 and a pneumatic stirring device 24.1, wherein the liquid suction port 2 is arranged on the wall of the plating tank 5 and is positioned on one surface of the insoluble anode 1, which is opposite to the cathode plating piece 4, the liquid spraying pipe 10 is arranged in the two-pole area space of one surface of the insoluble anode 1, which faces the cathode plating piece 4, the liquid suction port 2 is connected with a gas-liquid separator 8 through a pipeline and a pump, and the gas-liquid separator 8 filters the liquid after gas separation treatment through a liquid backflow circulation pipeline 9 and a filtering device 33, and then flows back into the plating tank 5 from the liquid spraying pipe 10.

The insoluble anode 1 is a titanium material covered with a coating, the insoluble anode 1 is a plate with hollowed through holes, a shaping frame 16 made of bare titanium material is welded around four sides of the insoluble anode 1, a back pulse protection screen 15 is arranged on the insoluble anode 1 and the shaping frame 16, the back pulse protection screen 15 is a spike-shaped uncoated titanium material, and a feeder line installation hole at the upper part of an anode plate is provided with a feeder line for structural improvement of feeding from top.

The positive and negative electrodes of the plating power supply 6 are connected to the insoluble anode 1 and the cathode plating member 4, respectively, during the plating process.

The cathode plating piece 4 is a flat copper plate.

The electroplating operation was performed using the procedure of the insoluble anodic acidic copper plating optimizing method described in example 1 according to each of the parameters specified in table-1, and the results are recorded in tables-1 and-2.

In the electroplating process, the hollow structure of the insoluble anode is matched with a liquid suction port arranged on one surface of the anode, which is opposite to the cathode, and liquid near the insoluble anode is enabled to generate liquid flow which is opposite to the cathode and passes through pores of the anode by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to the direction away from the cathode along with the liquid flow which passes through the pores formed by the hollow structure of the insoluble anode, and are discharged to a gas-liquid separator for release, and the liquid separated from the released gas in the gas-liquid separator is led back to the electroplating bath for circulation flow.

Example 4

As shown in fig. 4, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises a plating tank 5, an insoluble anode 1, a pipette 2, a cathode plating member 4, a reverse pulse plating power supply 19, a gas-liquid separator 8, wherein:

the electroplating bath 5 is provided with a liquid suction pipe 2 and a liquid spray pipe 10, the liquid suction pipe 2 is positioned on one surface of the insoluble anode 1 facing away from the cathode plating piece 4, and the liquid spray pipe 10 is arranged in the two-pole area space of one surface of the insoluble anode 1 facing the cathode plating piece 4; the liquid suction pipe 2 is connected with the gas-liquid separator 8 through a pipeline and a pump 23, and the gas-liquid separator 8 returns the treated liquid to the electroplating tank through a liquid return circulation pipeline 9;

as shown in the graph D, the insoluble anode is a titanium plate coated with a coating and having a hollowed-out structure. The insoluble anode 1 is provided with a back pulse protection screen 15 on the surface facing the cathode plating piece, the back pulse protection screen is an uncoated titanium bulge directly connected with the titanium base material of the insoluble anode 1, the bulge is in a needle-punched shape and a strip shape, and the top ends of the bulges are connected through a screen wire to form a protection screen; the back of the insoluble anode 1 away from the cathode is connected with an electric conductor 17, and the electric conductor 17 is a conductive rod. The structure improvement of feeding from above is made by arranging a feeder line into a feeder line from the feeder line mounting hole at the upper part of the insoluble anode 1.

The cathode plating piece 4 is a flat copper plate with a small through hole;

the positive and negative poles of the reverse pulse plating power supply 19 are connected to the insoluble anode 1 and the cathode plating member 4, respectively, during the plating process.

According to each of the parameters specified in Table-1, the procedure of the optimization method for insoluble anodic acid copper plating described in example 1 was used for the plating operation, and the results were recorded in Table-1; COD of the plating solution was detected before and after the plating operation, the consumption of the plating additive by the process was preliminarily determined from the change data before and after, and the results were recorded in Table-2.

In the electroplating process, the hollow structure of the insoluble anode is matched with the liquid suction pipe arranged on one surface of the anode facing the cathode and the liquid spraying pipe arranged on one surface of the insoluble anode facing the cathode, and liquid near the insoluble anode is enabled to generate liquid flow which is far away from the cathode and passes through pores of the anode by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to the direction far away from the cathode along with the liquid flow through the pores formed by the hollow structure of the insoluble anode and are discharged to a gas-liquid separator to be released, and the liquid separated from the released gas in the gas-liquid separator is led back to the electroplating tank again to be circulated. In the reverse pulse electrolysis process, the reverse pulse protection screen net can effectively reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode coating.

Example 5

As shown in fig. 5, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises a plating tank 5, an insoluble anode 1, a pipette 2, a cathode plating member 4, and a reverse pulse plating power supply 19, wherein:

the plating tank 5 is provided with a plating tank separator 11 to divide it into an anode plating tank region and a cathode plating tank region, and the plating tank separator 11 is specifically a combination of an ultrafiltration membrane and a filter cloth. A liquid suction pipe 2 and a liquid spray port 10 are arranged in the anode plating bath area; the liquid spraying pipe 10 is arranged at the bottom of the anode plating bath area on the surface of the insoluble anode 1 facing the cathode plating piece 4 and is connected with one surface of the anode plating bath area far away from the cathode plating bath area through a pipeline and a pump 23.1; the liquid suction pipe 2 is provided with 2 liquid suction ports and is positioned on the surface of the insoluble anode 1, which is opposite to the cathode plating piece 4; the liquid suction pipe 2 is connected with a pumping pipe 23.2 to drain the liquid with bubbles to a position far away from the cathode plating piece 4 in the anode plating bath area for releasing gas;

as shown in fig. E, the insoluble anode 1 located in the anode plating bath zone is a coated titanium mesh; the edge of the periphery of the insoluble anode 1 is welded with a shaping frame 16 with an edge, and the shaping frame 16 is made of bare titanium; the conductor 17 is a net-shaped conductor with a bypass structure, the periphery of which is welded with the shaping frame 16 by using a titanium net, and the conductor 17 is positioned on one surface of the insoluble anode 1, which is opposite to the cathode plating piece 4; the mounting structure of the shaping frame 16 and the electric conductor 17 is that one surface of the insoluble anode 1, which is opposite to the cathode plating part 4, is used as a panel frame to be welded at the periphery in a sealing way, and the three are formed into a square box with two surfaces communicated with meshes and are electrically connected. The electric conductor 17 is provided with a back pulse protection screen 15 which is arranged and welded on the electric conductor 17; the back pulse protection screen 15 is a non-coated titanium spike that passes through and is not in contact with the mesh of the insoluble anode 1. The upper part of the insoluble anode 1 is provided with a feeder line mounting hole, and a feeder line is arranged in the feeder line mounting hole to carry out structural improvement of upper feed.

The cathode plating piece 4 is a flat copper plate with small holes in the cathode plating bath area;

(1) Preparing electroplating solutions according to the specification of the table-1, and pouring the anode electroplating solution and the cathode electroplating solution into an anode electroplating bath area and a cathode electroplating bath area respectively;

(2) The insoluble anode device is arranged in the electroplating bath, a liquid suction pipe is arranged on one surface of the insoluble anode, which is opposite to the cathode, the anode of the electroplating power supply is connected with the insoluble anode, and the cathode of the electroplating power supply is connected with a plating piece;

(3) Adding a proper amount of electroplating additive into the cathode electroplating solution, and switching on an electrolysis power supply to carry out electroplating production operation;

In the electroplating process, the net structure of the insoluble anode is matched with a liquid suction pipe arranged on one surface of the anode facing away from the cathode and a liquid spraying pipe arranged on the bottom of one surface of the insoluble anode facing the cathode, and liquid near the insoluble anode is enabled to generate liquid flow which is far away from the cathode and passes through meshes of an anode body and conductive meshes by adopting power, so that oxygen bubbles generated on the surface of the anode can more intensively pass through meshes of the insoluble anode and the conductive body along with the liquid flow and are sent to the direction far away from the cathode for release. Under the condition of reverse pulse electrolysis, the spike of the reverse pulse protection screen net is not contacted with the insoluble anode, so that reverse pulse current is returned to the conductor from the spike tip and led away from the bypass, the electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the electrode transfer can be effectively reduced, and the coating of the insoluble anode is prevented from falling off. The design of the electrolytic cell separator can also effectively reduce the loss of electroplating additives.

Example 6

As shown in fig. 6, the optimizing apparatus of the insoluble anodic acidic sulfate plating copper of the present example is different from the apparatus of example 5 in that:

plating cell separator 11 is specifically a combination of PE filter plates and ceramic filter plates.

The nozzle of the spray pipe 10 is designed into a flat horn mouth shape, the spray pipe 10 is arranged at the bottom of an anode plating bath zone on one surface of the insoluble anode 1 facing the cathode plating piece 4, and the spray pipe 10 is connected with one surface of the anode plating bath zone far away from the cathode plating bath zone through a pipeline and a pump 23.1. The mouth of the liquid suction pipe 2 is in a horn mouth shape and is positioned at the position of one surface of the insoluble anode 1, which is away from the cathode plating piece 4; the liquid suction pipe 2 is connected with a pumping pipe 23.2 to drain the liquid with bubbles to a position far away from the cathode plating piece 4 in the anode plating bath area for releasing gas;

as shown in fig. F, the insoluble anode 1 in the anode plating bath area is a hollow through-hole titanium plate covered with a coating; the peripheral edge of the insoluble anode 1 is welded with a sealed shaping frame 16, and the shaping frame 16 is made of bare titanium; the conductor 17 is a titanium plate with hollowed through holes, the periphery of the conductor is welded with the shaping frame 16, and the conductor 17 is positioned on one surface of the insoluble anode 1, which is opposite to the cathode plating piece 4; the insoluble anode 1 is electrically connected with the shaping frame 16 and the conductor 17, and the three are connected into a square box with two hollow through holes on two sides and titanium plates communicated and other four closed sides. The conductor 17 is also provided with a protective screen net 15 as a back pulse, and is arranged and welded on the conductor 17; the back pulse protection screen 15 is a non-coated titanium spike passing through the hollowed-out through hole of the insoluble anode 1 and not contacting with the same. The upper part of the insoluble anode 1 is provided with a feeder line installation hole, and a feeder line is arranged in the feeder line installation hole for structural improvement.

The procedure of the insoluble anodic acidic copper plating optimizing method described in example 5 was used for the plating operation according to each parameter specified in Table-1, and the results were recorded in Table-1.

In the electroplating process, the hollow structure of the insoluble anode is matched with the horn liquid suction pipe arranged on one surface of the anode facing the cathode and the flat horn liquid spray pipe arranged on the bottom of one surface of the insoluble anode facing the cathode, and liquid near the insoluble anode is enabled to generate liquid flow which is far away from the cathode and passes through the insoluble anode and the conductor hollow through holes by adopting power, so that oxygen bubbles generated on the surface of the anode can be more intensively released along with the liquid flow in the direction of being far away from the cathode after passing through the insoluble anode hollow through holes. Under the condition of reverse pulse electrolysis, the spike of the reverse pulse protection screen net is not contacted with the insoluble anode, so that reverse pulse current is returned to the conducting plate from the spike tip and led away from the bypass, the electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the electrode transfer can be effectively reduced, and the coating of the insoluble anode is prevented from falling off. The design of the electrolytic cell separator can also effectively reduce the loss of electroplating additives.

Example 7

As shown in fig. 7, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises an electroplating tank 5, an anode box 13, a cathode plating member 4, a gas-liquid separator 8, and a reverse pulse electroplating power supply 19, wherein:

an anode box 13 is arranged in the electroplating bath 5, and an electroplating bath separator 11 is arranged on one surface of the anode box 13 facing the cathode plating piece 4, wherein the electroplating bath separator 11 is specifically a cation exchange membrane; the internal space of the anode box 13 is an anode plating bath area, and the space outside the anode box 13 in the plating bath 5 is a cathode plating bath area.

As shown in fig. G, the anode cartridge 13 is connected to the pipette 2 and has a liquid ejection port 10 provided therein; the liquid suction pipe 2 is provided with 4 liquid suction ports which are arranged in the anode box 13 and are positioned on one surface of the insoluble anode 1 facing away from the cathode plating piece 4, and the liquid spray ports 10 are positioned on one surface of the insoluble anode 1 facing the cathode plating piece 4; the liquid suction pipe 2 is connected with the pump 23 and the gas-liquid separator 8 through a pipeline, the gas-liquid separator 8 is connected with the liquid spraying port 10 through the liquid reflux circulation pipeline 9, and the liquid after the gas release treatment is refluxed into the anode box 13;

the insoluble anode 1 of the embodiment is of a structure shown in a figure D and is a titanium plate coated with a coating and provided with a hollowed-out structure; the insoluble anode 1 is provided with a reverse pulse protection screen 15 on the surface facing the cathode plating piece, the reverse pulse protection screen 15 is an uncoated titanium bulge directly connected with the titanium base material of the insoluble anode 1, and the top ends of the bulges are connected into an electrified net shape by using titanium wires; the insoluble anode 1 is connected with the positive electrode of a reverse pulse electroplating power supply 19 in the electroplating process; the back of the insoluble anode 1 away from the cathode is connected with an electric conductor 17, and the electric conductor 17 is a conductive rod. The upper part of the insoluble anode 1 is provided with a feeder line installation hole, and a feeder line is arranged in the feeder line installation hole for structural improvement. The anode assembly described above is mounted in an anode cartridge 13, as shown in figure G.

The cathode plating part 4 is a flat copper plate with small holes in the cathode plating bath area and is connected with the negative electrode of the reverse pulse plating power supply 19.

In the electroplating process, a liquid suction pipe arranged on one surface of the insoluble anode in the anode box, which is opposite to the cathode direction, and a liquid spraying port arranged on the bottom of one surface of the insoluble anode, which faces to the cathode, in the anode box are matched, liquid near the insoluble anode is enabled to generate liquid flow which is opposite to a plating part, which is far away from the cathode and passes through anode pores by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to a gas-liquid separator along with the liquid flow to be discharged and released, and the liquid after gas release flows back to the anode box again. In the reverse pulse electrolysis process, the reverse pulse protection screen net can effectively reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the pole transfer, and avoid the falling of the coating of the insoluble anode. The anode cartridge design with the cell separator is effective in reducing the loss of plating additives.

Example 8

As shown in fig. 8, the optimizing apparatus of the insoluble anodic acidic sulfate plating copper of the present example is different from the apparatus of example 7 in that:

the plating bath separator 11 is specifically a combination of a reverse osmosis membrane and a filter cloth;

as shown in fig. H, the anode box 13 is connected with a pipette 2 and a liquid spraying pipe 10, the nozzle of the pipette 2 is in a big horn shape, and the liquid spraying pipe 10 is provided with a plurality of nozzles which are arranged in parallel.

The anode assembly which is the same as that of the embodiment 5 is adopted in the embodiment, and comprises an insoluble anode 1, an electric conductor 17, a shaping frame 16 and a back pulse protection screen 15, wherein a feeder line installation hole is formed in the upper part of the insoluble anode 1, a feeder line is arranged in the feeder line installation hole, the structure is improved, the structure is shown in a figure E, and the anode assembly is arranged in an anode box 13, as shown in a figure H. During the electroplating process, the insoluble anode 1 is connected to the positive electrode of the reverse pulse plating power supply 19.

The cathode plating part 4 is a flat copper plate with small holes, is arranged in a cathode plating tank area and is connected with the negative electrode of the reverse pulse plating power supply 19 in the plating process.

In the electroplating process, the anode box structure shown in the figure H is adopted, and liquid near the insoluble anode is enabled to generate liquid flow which is far away from the cathode plating piece and passes through meshes of the insoluble anode and the electric conductor by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to the gas-liquid separator to be discharged along with the liquid flow through the meshes of the insoluble anode and the electric conductor, and the liquid after gas release is refluxed to the anode box again. In the reverse pulse electrolysis process, the reverse pulse protection screen net can effectively reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the pole transfer, and avoid the falling of the coating of the insoluble anode. The anode cartridge design with the cell separator effectively isolates the plating bath additive from contact with the anode to reduce its loss.

Example 9

As shown in fig. 9, the optimizing apparatus of insoluble anodic acidic sulfate plating copper of the present embodiment is different from the apparatus of embodiment 7 in that it further comprises a liquid ejection tube 14; and:

the plating bath separator 11 is specifically a combination of an anion exchange membrane and a filter cloth;

as shown in fig. J, the anode box 13 is connected with the pipette 2 and the liquid spraying pipe 10, in the anode box 13, the pipe orifice of the pipette 2 is in a big horn shape, and the liquid spraying pipe 10 is provided with a plurality of pipe orifices arranged in parallel. The liquid suction pipe 2 is connected with the pump 23.1 and the gas-liquid separator 8 through a pipeline, the gas-liquid separator 8 is connected with the liquid spraying pipe 10 through the liquid reflux circulation pipeline 9, and the treated liquid is refluxed into the anode box 13; the liquid jet pipe 14 is arranged at the periphery edge of the anode box 13, which faces the cathode plating piece 4, and the liquid jet pipe 14 is connected with the cathode plating bath area through a pipeline and a pump 23.2 so as to spray liquid towards the cathode plating piece 4.

The anode assembly which is the same as that of the embodiment 6 is adopted in the embodiment, and comprises an insoluble anode 1, an electric conductor 17, a shaping frame 16 and a back pulse protection screen 15, wherein a feeder line installation hole is formed in the upper part of the insoluble anode 1, a feeder line is arranged in the feeder line installation hole, the structure is shown in a figure F, and the anode assembly is installed in an anode box 13, as shown in a figure J. During the electroplating process, the insoluble anode 1 is connected to the positive electrode of the reverse pulse plating power supply 19.

The cathode plating part 4 is a flat copper plate with a plurality of small holes, is arranged in a cathode plating tank area and is connected with the negative electrode of the reverse pulse plating power supply 19 in the plating process.

The procedure of the insoluble anodic acidic copper plating optimizing method described in example 5 was used for the plating operation according to each parameter specified in Table-1, and the results were recorded in Table-1. COD detection was performed on the cathode plating solution before and after the plating operation, the consumption of the plating additive by the process was preliminarily determined based on the data change before and after the operation, and the results were recorded in Table-2.

In the electroplating process, the anode box structure shown in the figure J is adopted, and liquid near the insoluble anode is enabled to generate liquid flow which is far away from the cathode plating piece and passes through the hollow through holes of the insoluble anode and the conductor by adopting power, so that oxygen bubbles generated on the surface of the anode pass through the hollow through holes of the insoluble anode and the conductor along with the liquid flow to be sent to the gas-liquid separator for discharging and releasing, and the liquid after separating and releasing gas is refluxed to the anode box again. In the reverse pulse electrolysis process, the reverse pulse protection screen net can effectively reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the pole transfer, and avoid the falling of the coating of the insoluble anode. The liquid spraying pipe outside the anode box sprays the electroplating liquid to the cathode plating piece through the pump, so that the electroplating liquid is poured into the small holes of the cathode plating piece, and the electroplating liquid in the holes is updated in a supplementing mode. Additionally, the design of the anode box with the plating bath separator can effectively isolate the electroplating solution additive from the anode to reduce the loss of the electroplating solution additive.

Example 10

As shown in fig. 10, the optimizing apparatus of insoluble anodic acidic sulfate copper plating of the present embodiment is different from the apparatus of embodiment 7 in that it further comprises a liquid ejecting pipe 14; and:

plating bath separator 11 is specifically a combination of bipolar membrane and filter cloth;

as shown in fig. K, the anode box 13 is internally connected with the liquid suction pipe 2 and is internally provided with a liquid spraying port 10, the liquid suction pipe 2 is provided with 4 pipe ports in the anode box 13, the liquid spraying port 10 is positioned on one side of the insoluble anode 1 facing away from the cathode plating piece 4, and the liquid spraying port 10 is positioned on one side of the insoluble anode 1 facing the cathode plating piece 4. The liquid suction pipe 2 is connected with the pump 23.1 and the gas-liquid separator 8 through a pipeline, the gas-liquid separator 8 is connected with the liquid spraying port 10 through the liquid backflow circulating pipeline 9, and the treated liquid is backflow to the anode box 13. The liquid jet pipe 14 is arranged at the periphery edge of the anode box 13, which faces the cathode plating piece 4, and the liquid jet pipe 14 is connected with the cathode plating bath area through a pipeline and a pump 23.2 so as to spray liquid towards the cathode plating piece 4.

The anode assembly of the embodiment, which is the same as that of the embodiment 3, comprises an insoluble anode 1, a shaping frame 16 and a back pulse protection screen 15, wherein a feeder line mounting hole is formed in the upper part of the insoluble anode 1, and a feeder line is arranged in the insoluble anode for structural improvement, the structure is shown in a figure C, and the anode assembly is arranged in an anode box 13, as shown in a figure K. During the electroplating process, the insoluble anode 1 is connected to the positive electrode of the reverse pulse plating power supply 19.

In the electroplating process, the anode box structure shown in the figure K is adopted, and liquid near the insoluble anode is enabled to generate liquid flow which is far away from the cathode and passes through the hollow through holes of the anode by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to the gas-liquid separator along with the liquid flow to be discharged and released, and the liquid after separating and releasing gas is returned to the anode box again. In the reverse pulse electrolysis process, the reverse pulse protection screen net can reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the pole inversion, and avoid the falling of the coating of the insoluble anode. The liquid spraying pipe outside the anode box sprays the electroplating liquid to the cathode plating piece through a pump, so that the electroplating liquid flows into the small holes of the cathode plating piece to make the plating liquid in the holes updated in a supplementing way. Additionally, the design of the anode box with the plating bath separator can effectively isolate the electroplating solution additive from the anode to reduce the loss of the electroplating solution additive.

Example 11

As shown in fig. 11, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises a plating tank 5, an anode box 13, a cathode plating member 4, a plating power supply 6, and a gas-liquid separator 8, wherein:

three anode boxes 13 are arranged in the electroplating bath 5, wherein the surfaces of the anode boxes 13 facing the cathode plating piece 4 are all electroplating bath partitions 11, and the electroplating bath partitions 11 are specifically cation exchange membranes; the internal space of the anode box 13 is an anode plating bath area, and the space outside the anode box 13 in the plating bath 5 is a cathode plating bath area.

As shown in fig. G, each anode cartridge 13 is connected with a pipette 2 and a liquid ejection port is provided therein, and the structure is the same as that of the anode cartridge 13 of embodiment 7. The liquid suction pipe 2 of each anode box 13 is respectively connected with a pump and then connected with the gas-liquid separator 8; the gas-liquid separator 8 above the plating liquid level is connected to the liquid ejecting port 10 of each anode cartridge 13 through the liquid return circulation pipe 9, and returns the liquid subjected to the outgas treatment to each anode cartridge 13.

The cathode plating bath area is provided with a detection device 21 and a stirring device 24, wherein the detection device 21 comprises a gravimeter, a photoelectric colorimeter and an acidometer, and the stirring device 24 is a reflux liquid stirring device. The cathode plating bath area is connected with an overflow buffer tank 38, a pump 23.4, a filter 33.1, a plating solution regeneration device 20, a liquid flow regulator 30 with a pump and a filter 33.2 in turn as a circulation loop; the catholyte in the catholyte tank is overflowed into overflow buffer tank 38 and pumped 23.4 through filter 33.1 back to the plating solution regenerator 20. Wherein the feeding action of the flow regulator 30 with pumping liquid is controlled by an automatic detection and feeding controller 34 according to the result measured by the detection device 21, so that the cathode plating liquid is supplemented by the copper source. A tail gas pumping and exhausting system 25 is arranged above the electroplating tank 5;

The anode assembly of this embodiment, which is the same as that of embodiment 4, comprises an insoluble anode 1, an electric conductor 17 and a back pulse protection screen 15, wherein the upper part of the insoluble anode 1 is provided with a feeder line mounting hole, and a feeder line is arranged in the feeder line mounting hole to make structural improvement, the structure is shown in a figure D, and the anode assembly is arranged in an anode box 13, as shown in a figure G. During the electroplating process, the insoluble anode 1 is connected to the positive electrode of the electroplating power supply 19.

The cathode plating member 4 is a flat copper plate, is arranged in the cathode plating bath area, and is connected with the negative electrode of the plating power supply 19 in the plating process.

In the electroplating process, a liquid suction pipe arranged on one surface of the insoluble anode in the anode box, which is away from the cathode, is matched with a liquid spraying opening arranged on the bottom of one surface of the insoluble anode, which faces the cathode, in the anode box, and liquid near the insoluble anode is enabled to generate liquid flow which is away from the cathode and passes through pores of the insoluble anode by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to a gas-liquid separator along with the liquid flow to be released as gas, and the liquid after releasing the gas flows back into the anode box again. The anode box with the electroplating bath separator can separate the cathode and anode electrolyte and effectively reduce the loss of electroplating additives. The gas discharged from the gas-liquid separator can be further processed after being collected.

Example 12

As shown in fig. 12, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises a plating tank 5, an anode box 13, a cathode plating member 4, a gas-liquid separator 8, and a reverse pulse plating power supply 19, wherein:

six anode boxes 13 are arranged in the electroplating bath 5, one surface of the anode box 13 facing the cathode plating piece 4 is provided with an electroplating bath separator 11, and the electroplating bath separator 11 is a combination of an anion exchange membrane and filter cloth; the internal space of the anode box 13 is an anode plating bath area, and the rest space outside the anode box 13 in the plating bath 5 is a cathode plating bath area. The cathode plating bath area is provided with a detection device 21, the detection device 21 comprises a liquid level meter, an oxidation-reduction potentiometer, a photoelectric colorimeter, a pH meter and a thermometer, and the detection device 21 is connected with an automatic detection feeding controller 34 to control the liquid level, temperature adjustment, power supply output current of the plating bath, detect the plating solution concentration, plating time and other technological parameters, so that the plating is carried out according to the technological requirements.

Anode cartridge 13 as shown in fig. J, the anode cartridge 13 is connected with a pipette 2 and a liquid ejecting tube 10, and the structure of the anode cartridge 13 is the same as that of example 9. The liquid suction pipes 2 in the anode boxes 13 are respectively connected with a pump 23 through pipelines and then connected with a temporary storage groove 32; wherein pumps 23.1, 23.2, 23.3 pump liquid into the temporary storage tank 32.1 and pumps 23.4, 23.5, 23.6 pump liquid into the temporary storage tank 32.2. The liquid of the two temporary storage tanks is led into the gas-liquid separator 8 through the pump 23.7 and the pipeline with bubbles, and the metal copper 31 is stored in the gas-liquid separator 8; the method is to make full use of sulfuric acid and oxygen in the anodic plating solution to participate in the chemical reaction of copper metal to prepare the copper sulfate solution. The anode plating solution is subjected to chemical reaction in the gas-liquid separator 8, and after the gas is released in the gas-liquid separator 8, the anode plating solution is led to the liquid spraying pipe 10 of each anode box 13 through the pump 23.8 and the liquid reflux circulating pipeline 9, and the liquid is pumped into the anode boxes 13. The periphery of each anode box 13 facing the outside of the cathode plating piece 4 is respectively provided with a liquid injection pipe 14, and the liquid injection pipes 14 are connected with the cathode plating bath area so as to control the liquid injection towards the cathode plating piece 4 through the action of a program.

The anode assembly which is the same as that of the embodiment 6 is adopted in the embodiment, and comprises an insoluble anode 1, an electric conductor 17, a shaping frame 16 and a back pulse protection screen 15, wherein a feeder line installation hole is formed in the upper part of the insoluble anode 1, a feeder line is arranged in the feeder line installation hole, the structure is shown in a figure F, and the anode assembly is installed in an anode box 13, as shown in a figure J. During the electroplating process, the insoluble anode 1 is connected to the positive electrode of the electroplating power supply 19.

The cathode plating member 4 is a flat copper plate with a plurality of small holes, is arranged in a cathode plating tank area, and is connected with the negative electrode of the plating power supply 19 in the plating process.

The procedure for optimizing the acid copper plating described in example 1 was repeated according to the parameters specified in Table-1, and the results were recorded in Table-1.

In the electroplating process, the liquid near the insoluble anode in the anode box is enabled to generate liquid flow which is away from the cathode and passes through the anode pores by adopting power, so that oxygen bubbles generated on the surface of the anode are sent to two temporary storage tanks along with the liquid flow and then pumped into the gas-liquid separator to participate in the chemical reaction of copper metal. The solution is pumped back again into the respective anode cartridge after releasing the gas in the gas-liquid separator. In the reverse pulse electrolysis process, the reverse pulse protection screen net can reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the pole inversion, and avoid the falling of the coating of the insoluble anode. The liquid spraying pipe outside the anode box sprays the electroplating liquid to the cathode plating piece through the pump, so that the electroplating liquid flows into the small holes of the cathode plating piece to make the electroplating liquid in the holes updated in a supplementing way, and the electroplating liquid is stirred at the same time. In the electroplating process, the cathode plating piece can move in one direction in parallel or move back and forth in two directions in parallel so as to obtain a more uniform plating layer. In addition, the anode box with the plating bath separator prevents the plating catholyte from entering the anode plating bath area, so that the loss of plating additives can be effectively reduced, and the anode plating solution with bubbles in the anode box is conveniently collected and used for participating in the copper metal chemical reaction of the temporary storage tank to prepare more copper sulfate solution.

Example 13

As shown in fig. 13, the optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating of the present embodiment comprises an electroplating tank 5, an anode box 13, a cathode plating member 4, a gas-liquid separator 8, and two reverse pulse electroplating power sources 19, wherein:

six anode boxes 13 are arranged in the electroplating bath 5, one surface of the anode box 13 facing the cathode plating piece is provided with an electroplating bath separator 11, and the electroplating bath separator 11 is a combination of a bipolar membrane and filter cloth; the internal space of the anode box 13 is an anode plating bath region, and the space of the plating bath 5 except for the anode box 13 is a cathode plating bath region. The cathode plating bath area is provided with a detection device 21, the detection device 21 comprises a liquid level meter, a specific gravity meter and an acidometer, the detection device 21 is connected with an automatic detection feeding controller 34, and the automatic detection feeding controller 34 controls the electroplating current and parameters of the plating solution in the process and alarms according to the data measured by the detection device 21.

The structure of the anode boxes 13 is the same as that of the embodiment 10, as shown in fig. K, each anode box 13 is respectively connected with a liquid suction pipe 2 and a liquid spraying hole 10 is arranged in each anode box 13, the liquid suction pipe 2 is provided with 4 pipe orifices in the anode boxes 13, the liquid spraying holes 10 are positioned on the surface of the insoluble anode 1 facing away from the cathode plating piece 4, and the liquid spraying holes 10 are positioned on the surface of the insoluble anode 1 facing the cathode plating piece 4. The liquid suction pipe 2 is connected with a gas-liquid separator 8 through a pipeline, and overflowed liquid is led into the liquid suction pipe for gas release separation. The liquid released from the gas-liquid separator 8 is pumped by a pump 23.1 to flow back into the circulation pipe 9 through the solid-liquid separation filter 33, and the liquid return circulation pipe 9 is connected to the liquid spraying port 10 in each anode box 13 to return the liquid after the gas release treatment to the anode box 13. The liquid injection pipe 14 is arranged at the periphery edge of the anode box 13, which faces the cathode plating piece 4, the liquid injection pipe 14 is connected with the cathode plating bath area through a pipeline and a pump 23.2, and the injection action of the liquid injection pipe 14 performs the action of spraying liquid towards the cathode plating piece 4 through a set program of the automatic detection feeding controller 34.

The anode assembly of the embodiment, which is the same as that of the embodiment 3, comprises an insoluble anode 1, a shaping frame 16 and a back pulse protection screen 15, wherein a feeder line mounting hole is formed in the upper part of the insoluble anode 1, and a feeder line is arranged in the insoluble anode for structural improvement, the structure is shown in a figure C, and the anode assembly is arranged in an anode box 13, as shown in a figure K.

The cathode plating member 4 is a flat copper plate with a plurality of small holes and is arranged in the cathode plating bath area.

In the electroplating process, the titanium substrate of the insoluble anode 1 is respectively connected with the anodes of two corresponding reverse pulse electroplating power supplies 19, and the four cathode plating pieces 4 are commonly connected with the cathodes of the two reverse pulse electroplating power supplies.

In the electroplating process, the liquid near the insoluble anode in the anode box is enabled to generate liquid flow which is far away from the cathode and passes through the anode pores by adopting power to enable oxygen bubbles generated on the surface of the anode to be sent to the gas-liquid separator along with the liquid flow for gas discharge and release, and the liquid after gas release is reflowed to each anode box of the electroplating bath again. In the electroplating reverse pulse electrolysis process, the reverse pulse protection screen net can reduce electrochemical hydrogen evolution reaction on the surface of the insoluble anode during the transfer of the electrode, and avoid the falling of the coating of the insoluble anode. The liquid spraying pipe outside the anode box sprays the electroplating liquid to the cathode plating piece through a pump, so that the electroplating liquid flows into the small holes of the cathode plating piece to make the plating liquid in the holes updated in a supplementing way. When electroplating is carried out, the cathode plating piece moves in parallel in a one-way or two-way back and forth manner in the electroplating bath, and the output current value of each electroplating power supply is adjusted according to the quality requirement of the cathode electroplating process, so that better cathode plating is obtained. In addition, the design of a plurality of anode boxes with plating bath partitions can effectively reduce the loss of plating additives.

Example 14

Referring to FIG. 16, a basic embodiment of an optimizing apparatus for insoluble anodic acidic sulfate plating copper according to the present invention comprises a plating tank 5, an insoluble anode 1, a pipette 2, a cathode plating member 4, and a plating power source 6, wherein:

the plating tank 5 is provided with a liquid suction pipe 2, the liquid suction pipe 2 is positioned on one surface of the insoluble anode 1, which is opposite to the cathode plating piece 4, and the insoluble anode 1 is a titanium net coated with a coating.

The insoluble anode 1 is a titanium material coated with a coating, the structure is a plate with hollowed through holes, and a feeder line is arranged from a feeder line mounting hole at the upper part of an anode plate for structural improvement.

The cathode plating piece 4 is a flat copper plate.

Example 15

As shown in fig. 17, the optimizing apparatus of the insoluble anodic acidic sulfate plating copper of the present example is different from the apparatus of example 1 in that:

the reverse pulse plating power supply 19 is adopted to replace the plating power supply 6;

As shown in fig. C, the insoluble anode 1 is a titanium material covered with a coating, the structure is a plate-shaped object with hollowed through holes, a shaping frame 16 is welded around four sides, and the shaping frame 16 is made of a non-conductive material; discharge spines are arranged on the insoluble anode 1 and in the shaping frame 16 as a back pulse protection screen 15, and a feeder line is arranged from a feeder line mounting hole at the upper part of the anode plate for structural improvement.

The positive electrode and the negative electrode of the reverse pulse plating power supply 19 are respectively connected with the insoluble anode 1 and the cathode plating member 4 during the plating process.

The cathode plating piece 4 is a flat copper plate.

Comparative example 1

Referring to FIG. 14, an apparatus for acid sulfate plating copper using an insoluble anode of the prior art comprises a plating tank 5, an insoluble anode 1, a cathode plate 4, and a reverse pulse plating power supply 19.

The electrolytic cell 5 is fitted with an insoluble anode 14 and a cathode plating 4.

The insoluble anode 1 is coated titanium material, and the cathode plating part 4 is a flat copper plate with a plurality of small holes.

The insoluble anode 1 is connected to the positive electrode of the reverse pulse plating power supply 19, and the cathode plating member 4 is connected to the negative electrode of the power supply 19.

The reverse pulse plating power supply 19 was turned on to perform plating operation according to the parameters specified in Table-1, and the results are recorded in Table-1. COD detection was performed on the cathode plating solution before and after the plating operation, the consumption of the plating additive by the process was preliminarily determined based on the data change before and after the operation, and the results were recorded in Table-2.

In the comparative example, a large number of bubbles exist in the electroplating solution between the cathode plating piece and the insoluble anode to influence the electric field current distribution, and the hydrogen evolution reaction on the surface of the insoluble anode coating is serious under the condition of back pulse, so that the plating layer is uneven and the anode coating is damaged and falls off due to the two factors.

Comparative example 2

As shown in FIG. 15, an insoluble anodic acidic copper plating apparatus of the comparative example of the prior art of the present invention. Which is different from the apparatus of comparative example 1 in that it further includes a plating bath partition 11, a stirring device 24, and a titanium basket 39.

The electrolytic tank 5 is provided with a titanium basket 39, an insoluble anode 1 is arranged in the titanium basket, a neutral filter membrane 11 is wrapped on the periphery of the titanium basket 39, an inner space surrounded by the titanium basket 39 and the neutral filter membrane 11 is an anode electroplating bath area, and the rest space in the electroplating tank is a cathode electroplating bath area; the plating tank 5 is also provided with a stirring device 24 and a cathode plating member 4.

The insoluble anode 1 and titanium basket 39 are connected to the positive electrode of the reverse pulse plating power supply 19, and the cathode plating member 4 is connected to the negative electrode of the reverse pulse plating power supply 19.

The stirring device 24 was turned on according to the parameters specified in Table-1, and the reverse pulse plating power supply 19 was turned on to perform the plating operation, and the results are recorded in Table-1.

In the comparative example, the electric field current distribution is affected by a large number of bubbles in the electroplating solution between the cathode and the anode, and the hydrogen evolution reaction on the surface of the anode coating is serious under the condition of back pulse. These two factors lead to uneven plating and damaged and detached anode coating.

The process conditions of the examples and comparative examples of the present invention are:

(1) the electroplating current was 2A/dm ² ；

(2) When the back pulse power supply works, the forward current is 2A/dm ² The back pulse current was 6A/dm ² The time ratio of the forward current to the reverse pulse current is 20:1;

(3) electroplating time is 40 minutes, and the temperature is 30 ℃; (4) the acidic copper plating bath comprises:

CuSO ₄ 200g/L

H ₂ SO ₄ 60g/L

Cl ^- 70g/L

commercial high-strength card copper plating additive 9mg/L.

The method for identifying the plating state and uniformity comprises the following steps:

after the electroplating operation is finished, slicing and polishing the cathode plating piece subjected to the electroplating operation from top to bottom at three uniform points, and observing and measuring the thickness of the sliced plating layer by adopting a microscope; for a cathode plating piece with a small hole, the state in the hole and the copper plating condition are observed; the results of the measurements and the conclusions drawn are shown in Table-1.

The identification method of anode coating state comprises the following steps:

after the electroplating operation, observing the anode coating with naked eyes, and testing whether the coating falls off by adopting a brush lightly brushing layer; the conclusions are shown in Table-1.

The method for identifying consumption condition of electroplating brightening agent comprises the following steps:

detecting the COD value of the electroplating solution or the cathode electroplating solution by adopting a national standard COD detection method before and after the electroplating operation, and evaluating the consumption condition of the electroplating brightening agent by the variation difference of the COD values of the electroplating solution or the cathode electroplating solution before and after the electroplating operation; the conclusions are shown in Table-2.

TABLE-1

TABLE-2

As can be seen from Table-1 above, the quality of the plated layers obtained by electroplating in examples 1 to 15 of the present invention and comparative examples 1 to 2 of the prior art were compared: the three-point (upper, middle, lower) thickness data measured for the plating layers obtained in examples 1-15 were more average and superior to comparative example 1. Wherein, in examples 2-13, the shaping frame or the conductor playing the role of a feeder line and the connection point thereof are arranged, the overall thickness of the plating layer obtained by electroplating is consistent, and the surface is flat and small Kong Dutong is consistent. In comparative examples 1 and 2, the plating solution was affected by bubbles during the plating operation, and the plating surface was rough and uneven in thickness, and the plating through in the pinholes was also unsatisfactory. Thus, the plating layer obtained by the process is more uniform and smoother, and the through hole penetrating quality is higher. After the invention improves the insoluble anode copper plating process of gassing, the plating quality can be effectively improved, and the requirements of the plating industry on high-quality products can be met.

As can be seen from Table-1 above, examples 4 to 10, examples 12 to 13, and example 15 of the present invention, which also employ a reverse pulse plating power supply, were compared with comparative examples 1 to 2 of the prior art as anode coating conditions: the insoluble anodes of the embodiments 4 to 10, the embodiments 12 to 13 and the embodiment 15 are all provided with the back pulse protection screen, wherein the insoluble anode coating is complete and does not fall off after the electroplating operation of the embodiments 4 to 10 and the embodiments 12 to 13 is finished, and the upper position of the insoluble anode coating slightly falls off after the electroplating operation is finished due to the lack of a bypass design in the embodiment 15; the insoluble anodes of comparative examples 1 and 2 were free of the back pulse protection screen to protect the insoluble anode coating, and the coating was significantly removed by light brushing with a brush after the plating operation was completed. Therefore, when the insoluble anode is provided with the reverse pulse protection screen, the electrochemical hydrogen evolution reaction on the surface of the insoluble anode coating can be effectively reduced, so that the service life of the insoluble anode is prolonged.

Since the electroplating additive used in the industry is an organic compound, the consumption condition can be correspondingly reflected by the change of the COD value of the electroplating solution, namely, the faster the COD value of the electroplating solution is reduced, the faster the consumption speed of the electroplating additive in the electroplating solution is indicated. As can be seen from Table-2 above, examples 9 and 10 in which the plating tank of the invention was provided with the plating tank separator were compared with comparative example 1, and examples 1 and 4 in which the plating tank separator was not provided in the plating tank: the COD values of the cathode plating solutions measured before and after the plating operation in example 9 and example 10 were different by not more than 80mg/L, respectively, which proves that the loss of the plating additive was small. The COD values of the plating solutions measured before and after the plating operation in comparative example 1, example 1 and example 4 were each different by 200mg/L or more, indicating that the amount of the plating additive loss was large. It has been demonstrated that the plating bath of the present invention provides effective savings in the use of plating additives when a plating bath divider is provided.

Further, comparative example 1 of the prior art is most similar to the basic arrangement of examples 9 and 10 of the present invention. However, examples 9 and 10 were superior to comparative example 1 in terms of plating uniformity, pinhole plating, anode coating state, and consumption of plating additive.

The present invention may be summarized in other specific forms without departing from the spirit or essential characteristics thereof. The above-described embodiments of the present invention are to be considered in all respects only as illustrative and not restrictive. Therefore, any minor modifications, equivalent changes and modifications made to the above embodiments according to the essential technology of the present invention fall within the scope of the present invention.

Claims

An optimization process of insoluble anode acid sulfate electroplated copper comprises an electroplating bath (5), an electroplating power supply (6), an insoluble anode (1) and an acid sulfate copper plating electroplating solution serving as an electroplating solution, wherein a plating part is used as a cathode (4), and the optimization process is characterized in that:

1) Adopting a plate-shaped insoluble anode (1) which is made of titanium material covered with a coating and is net-shaped or provided with a hollowed-out structure, and then installing the insoluble anode (1) and the cathode (4) in a plating bath; at least one liquid suction pipe/port (2) is additionally arranged on the side of the insoluble anode (1) facing away from the cathode (4), so that the electroplating liquid can flow through overflow of the liquid suction pipe/port (2) or/and electric liquid suction mode;

2) And (3) switching on an electroplating power supply (6) to perform electroplating production operation, and sucking the electroplating liquid through overflow of the liquid suction pipe/port (2) or/and in a power mode, so that the electroplating liquid in the electroplating tank (5) forms liquid flow to the liquid suction pipe/port (2), and correspondingly, adding the electroplating liquid into the electroplating tank (5) to maintain the amount of the electroplating liquid in the electroplating tank (5) until the electroplating is completed and the plated piece is taken out.
The optimization process of insoluble anodic acid sulfate electrolytic copper plating according to claim 1, characterized in that at least one liquid spraying pipe/port (10) is added on the side of the insoluble anode (1) facing the cathode (4), and the liquid spraying pipe/port (10) is connected with an external liquid spraying pipeline for spraying liquid towards the anode, and is matched with the liquid sucking pipe/port (2), so that a more stable and controllable liquid flow far away from the cathode (2) is generated near the insoluble anode (1).
The optimizing process of insoluble anodic acidic sulfate electrolytic copper plating according to claim 2, wherein a gas-liquid separator (8) is added, and the liquid suction pipe/port (2) discharges the gas-liquid mixture fluid sucked out from the plating tank (5) into the gas-liquid separator (8) through a connecting pipe; the gas-liquid mixture is separated in a gas-liquid separator (8) to release gas, and then the liquid is led back to the electroplating tank (5) again for circulating flow.
An optimised process for insoluble anodic acid sulphate electrolytic copper plating according to claim 3 characterised in that the plating bath (5) is divided into two regions, an anodic plating bath region and a cathodic plating bath region, by a plating bath divider (11); the electroplating solution in the anode electroplating bath area is anode electroplating solution, in particular to aqueous solution containing inorganic acid and/or inorganic salt, or acidic sulfate copper plating electroplating solution is adopted; the electroplating solution in the cathode electroplating bath area is acidic sulfate copper plating electroplating solution; in the electroplating process, the insoluble anode (1) and the cathode (4) are respectively arranged in the anode electroplating bath area and the cathode electroplating bath area in an isolated manner; the liquid suction pipe/port (2) and the liquid spraying pipe/port (10) are arranged in the anode plating bath area.
The process for optimizing the anodic acid sulfate plating copper according to claim 4, characterized in that the anodic plating bath zone takes the form of an anodic cartridge (13) and is installed in the plating bath (5) to separate the anodic plating bath zone from the cathodic plating bath zone, in particular: the anode box (13) is in a cubic box shape, the insoluble anode (1) is positioned in the anode box (13), the surface of the anode box (13) facing the cathode plating piece (4) is provided with a plating bath separator (11), the internal space of the anode box (13) is an anode plating bath area, and the space in the plating bath (5) and outside the anode box (13) is a cathode plating bath area; the liquid suction pipe/port (2) is arranged on the anode box (13), and is particularly positioned on the space or box wall of the side of the insoluble anode (1) facing away from the cathode (4) in the anode box (13); in addition, the liquid jet pipe/port (10) is located in the anode box (13) in the area between the side of the insoluble anode (1) facing the cathode (4) and the adjacent box wall.
The optimizing process of insoluble anode acid sulfate electrolytic copper plating according to any one of claims 1 to 5, characterized in that a setting frame (16) is added at the edge of the insoluble anode, and the setting frame (16) is made of a material having positive insolubility, heat resistance, acid resistance and high rigidity.
The optimization process of insoluble anodic acid sulfate electroplated copper according to claim 6, wherein the surface of the insoluble anode (1) facing away from the cathode (4) is connected with an electrical conductor (17) in communication with the positive electrode of the electroplating power supply (6).
The optimization process of insoluble anodic acidic sulfate electrolytic copper plating according to claim 7, wherein the insoluble anode (1) and/or the shaping frame (16) and/or the conductor (17) are provided with a back pulse protection screen (15) on the side facing the cathode (4), and the back pulse protection screen (15) is an uncoated titanium bump or a bump mesh/strip.
The optimization process of insoluble anodic acidic sulfate electrolytic copper plating according to claim 8, characterized in that when a back pulse protection screen (15) is provided on the insoluble anode (1), the back pulse protection screen (15) is an uncoated titanium bump or a raised mesh/strip provided on the side of the anode (1) facing the cathode (4) and is directly connected with the titanium substrate of the insoluble anode (1); when the back pulse protection screen (15) is arranged on the shaping frame (16) and the shaping frame (16) is made of bare titanium or coated titanium, the back pulse protection screen (15) is connected with the titanium base material of the insoluble anode (1) except for the scheme of direct connection, or is connected with the titanium material of the shaping frame (16) singly or simultaneously; when the back pulse protection screen (15) is arranged on the electric conductor (17), the back pulse protection screen (15) penetrates through the mesh or hollow structure of the insoluble anode (1) to extend out of the surface of the insoluble anode (1) towards the cathode (4).
The optimization process for insoluble anodic acidic sulfate electrolytic copper plating according to claim 9, wherein the shape of the projections is a convex dot shape, a spike shape, a vertical bar shape; the raised net or strip is fixed on the surface of the insoluble anode (1) and/or the shaping frame (16) and/or the conductor (17) facing the cathode (4) and extends to the supporting leg end of the cathode (17), or is formed by interconnecting the upper parts of the raised matters, and the plane formed by the net or strip is parallel or basically parallel to the surface of the anode (1).
An optimization device of insoluble anode acid sulfate electroplated copper comprises an electroplating bath (5), an insoluble anode (1), a cathode (4) serving as a plating piece and an electroplating power supply (6), and is characterized in that: the electroplating bath is also internally provided with at least one liquid suction pipe/port (2), and the liquid suction pipe/port (2) is positioned on the side of the insoluble anode (1) facing away from the cathode and is used for generating liquid flow in the electroplating bath (5) in an overflow or/and electric liquid suction mode of the liquid suction pipe/port (2);

the insoluble anode (1) is a titanium material coated with a coating, and is in a net shape or a plate shape with a hollowed-out structure;

The positive electrode and the negative electrode of the electroplating power supply (6) are respectively connected with the insoluble anode (1) and a plating piece serving as the cathode (4) in the electroplating process.
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 11, wherein: at least one liquid spraying pipe/opening (10) is arranged in the electroplating bath (5), the liquid spraying pipe/opening (10) is arranged in a region space between two electrodes on the side of the insoluble anode (1) facing the cathode (4), and the liquid spraying pipe/opening (10) is externally connected with a liquid spraying pipeline for spraying liquid to the anode (1); the device adopts a reflux system, which mainly comprises a power source and a connecting pipeline, wherein one end of the reflux system is connected with a liquid suction pipe/port (2), the other end of the reflux system is communicated with a liquid spraying pipe/port (10), and electroplating liquid sucked by the liquid suction pipe/port (2) is refluxed into the electroplating bath (5) by using the reflux system, so that liquid flow of the electroplating liquid in the electroplating bath (5) flowing to the liquid suction pipe/port (2) at the anode is formed.
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 12, wherein: the liquid suction pipe/port (2) is connected with the gas-liquid separator (8) through a connecting pipeline; the gas-liquid separator (8) is also communicated with the electroplating bath (5) through a pump and a connecting pipeline to form a reflux system, and the liquid treated by the released gas is discharged back to the electroplating bath (5) for circulating flow.
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 13, wherein: a plating tank separator (11) is arranged in the plating tank (5), and the plating tank (5) is divided into an anode plating tank area and a cathode plating tank area.
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 14, wherein: the anode plating tank area and the cathode plating tank area are separated in a mode of installing an anode box (13) in the plating tank (5): the anode box (13) is in a cubic box shape, the insoluble anode (1) is positioned in the anode box (13), the surface of the anode box (13) facing the cathode (4) is provided with an electroplating bath separator (11), the internal space of the anode box (13) is an anode electroplating bath area, and the rest spaces except the anode box in the electroplating bath are cathode electroplating bath areas; the liquid suction pipe/port (2) is arranged on the anode box (13), in particular on the space or box wall of the side of the anode box (13) opposite to the insoluble anode (1) and facing away from the cathode (4); in addition, a liquid spraying pipe/port (10) is arranged in the anode box (13), and the liquid spraying pipe/port is particularly positioned in the area between the side of the insoluble anode (1) facing the cathode (4) and the adjacent box wall in the anode box (13).
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 15, wherein: the periphery of the outer side surface of the anode box facing the cathode plating piece is provided with liquid injection pipes (14), and each liquid injection pipe (14) is internally provided with a flow regulator so as to regulate the injection effect of the cathode plating liquid.
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 16, wherein: the insoluble anode (1) is also provided with a back pulse protection screen (15), the back pulse protection screen (15) is an uncoated titanium protrusion arranged on the surface of the insoluble anode (1) facing the cathode (4), the protrusion is directly connected with the titanium substrate of the insoluble anode (1), and the protrusion is in a convex point shape, a spike shape, a vertical strip shape or a net shape/strip shape connected with the structure of the shape.
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 17, wherein: the edge of the insoluble anode (1) is also provided with a shaping frame (16).
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 18, wherein: the surface of the insoluble anode (1) facing away from the cathode (4) is provided with a conductor (17) communicated with the positive electrode of the electroplating power supply (6).
The optimizing apparatus for insoluble anodic acidic sulfate electrolytic copper plating according to claim 19, wherein: an insoluble anode assembly with the back pulse protection net (15), the shaping frame (16) and the electric conductor (17) as well as a liquid suction pipe/port (2) and a liquid spraying pipe/port (10) is arranged in an anode box (13) with a liquid spraying pipe (14) to be used as an anode cell area assembly.