WO2022143860A1 - 不溶性阳极酸性硫酸盐电镀铜的优化工艺及装置 - Google Patents

不溶性阳极酸性硫酸盐电镀铜的优化工艺及装置 Download PDF

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WO2022143860A1
WO2022143860A1 PCT/CN2021/142832 CN2021142832W WO2022143860A1 WO 2022143860 A1 WO2022143860 A1 WO 2022143860A1 CN 2021142832 W CN2021142832 W CN 2021142832W WO 2022143860 A1 WO2022143860 A1 WO 2022143860A1
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electroplating
anode
insoluble
cathode
liquid
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PCT/CN2021/142832
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English (en)
French (fr)
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叶涛
叶旖婷
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叶涛
叶旖婷
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Priority to CN202180084378.2A priority Critical patent/CN116685721A/zh
Priority to US18/270,494 priority patent/US20240060202A1/en
Publication of WO2022143860A1 publication Critical patent/WO2022143860A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/04—Removal of gases or vapours ; Gas or pressure control
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating

Definitions

  • the invention belongs to the field of electroplating copper technology, and particularly relates to an optimized process and device for electroplating copper with insoluble anodic acid sulfate.
  • Electroplating copper is one of the most common processes in the electroplating industry. Generally speaking, if nickel, gold, silver and tin metal layers are to be plated on the surface of various types of metal parts, an intermediate copper layer needs to be pre-plated to improve the bonding force of the outer coating; in addition, the circuit board industry Copper metal electroplating is also common in the production process.
  • the existing acid sulfate copper electroplating process is an electroplating process with sulfuric acid and copper sulfate as the main components of the electroplating solution, which can be divided into two different processes according to the soluble anode and the insoluble anode.
  • the soluble anodic copper plating process uses phosphorous copper as the soluble anode material; the insoluble anodic copper plating process refers to the electroplating process in which the anode does not dissolve or a very small amount of dissolution occurs during the electroplating reaction process, that is, the insoluble anode material is used, which is common in the prior art.
  • An insoluble titanium-based coated anode is used.
  • the insoluble anodic copper plating process produces hydrogen ions and oxygen through the electrolysis of water on the anode, and the copper ions in the electroplating solution are reduced to metallic copper at the cathode.
  • the stable anode shape and the controllable and stable composition state of the electroplating solution enable a more uniform, flat and dense copper metal coating to be electroplated on the cathode plating parts; and in addition to DC electroplating, the insoluble anode copper electroplating process can also be applied to pulse electroplating.
  • the production efficiency can also be greatly improved by increasing the anode current density.
  • the reverse pulse of the power supply is used in the existing insoluble anodic copper electroplating process to convert the cathode plated parts into electrolytic anodic copper-dissolving reaction; this can not only achieve optimization
  • Oxygen bubbles are generated on the anode during the electroplating process, and the bubbles will be distributed between the anode and cathode plating parts, thereby forming a barrier to hinder the electroplating current, affecting the uniformity of discharge, thereby reducing the uniformity of the coating.
  • the oxygen bubbles generated during the electroplating process will form a certain gradient of bubble layers on the anode surface from bottom to top, which will further lead to uneven current distribution, thus seriously affecting the quality of vertical electroplating.
  • the solution in the prior art is to use horizontal electroplating to minimize the influence of the bubble layer hindering the barrier.
  • the structure of the horizontal electroplating equipment is more complicated, and the space in the electroplating tank is very limited. , so the plated parts are usually only thin plates, which cannot meet the production of electroplated copper for products with different dimensions.
  • organic electroplating additives namely bright additives
  • organic electroplating additives are usually added to the plating solution to obtain a smoother and smoother coating on the plated parts. Since the surface of the anode used in the insoluble anodic copper electroplating process is coated with a precious metal coating, 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.
  • some new oxidants will accelerate the decomposition and damage of the plating additives.
  • the consumption of the electroplating additives is far greater than the normal consumption in the soluble anode copper electroplating process.
  • Plating additives are additionally consumed resulting in increased production costs.
  • insoluble anodes have the advantages of flat coating and high efficiency compared with soluble anodes in copper electroplating process, process optimization is still necessary.
  • the first object of the present invention is to provide an optimized process for insoluble anodic acid sulfate copper electroplating, which can effectively improve the uniformity of the electroplated metal copper layer on the plated parts and improve the electroplating quality.
  • the second object of the present invention is to provide an optimized device for electroplating copper with insoluble anodic acid sulfate.
  • An optimized process for insoluble anodic acid sulfate copper electroplating comprising an electroplating tank, an electroplating power source, an insoluble anode, and a plating piece as a cathode and an acid sulfate copper electroplating solution as the electroplating solution, characterized in that:
  • the material is coated titanium and the shape is a mesh or a plate with a hollow structure as the insoluble anode, and then the insoluble anode and the cathode are installed in the electroplating tank; and in the At least one pipette/port is added on the side of the insoluble anode facing away from the cathode, so that the electroplating solution can generate liquid flow through the overflow of the pipette/port or/and by means of electrodynamic suction;
  • the insoluble anode of the present invention adopts a net-like or hollowed-out plate-like structure, so that it has pores that pass through on both sides, and is matched with the at least one pipette/port provided on the side of the anode facing away from the cathode direction,
  • the liquid near the insoluble anode is caused to flow away from the cathode and through the pores of the anode by overflow and/or dynamic means, so that the oxygen bubbles generated on the surface of the anode during the electroplating process can pass through the mesh of the insoluble anode with the liquid flow.
  • the pores formed by the hollow structure are taken away from the area between the anode and the cathode plating part for efflux release, which helps to reduce the accumulation of oxygen on the surface of the anode facing the cathode during the electroplating process to form an oxygen bubble shielding layer, Thereby, the electroplating uniformity and electroplating efficiency of the plated parts are improved.
  • the pipette/port uses a power to generate a flow of liquid near the insoluble anode away from the cathode and through the pores of the anode, the power being a pumping of pressurized drainage and/or suction of negative pressure.
  • adding the electroplating solution into the electroplating tank to maintain the amount of electroplating liquid in the electroplating tank can be by adding a new electroplating solution or an electroplating replenishing solution, or using a reflow system.
  • the backflow system adopted in the present invention is mainly composed of a pump and a connecting pipe, one end of which is connected to a suction pipe/port, and the other end is connected to an electroplating tank, and the electroplating solution sucked by the liquid suction pipe/port is used to flow back into the electroplating by using the backflow system.
  • the liquid flow of the electroplating solution in the electroplating tank to the suction pipe/port at the anode is formed, and the cycle is reciprocated.
  • the return system can be constructed by adding a connecting pipe to the electroplating tank on the basis of the above-mentioned suction pipe/port using a pump to make the liquid near the insoluble anode generate a liquid flow away from the cathode and through the anode pores.
  • the method of the invention is suitable for both vertical electroplating and horizontal electroplating; it can be used in combination with ordinary direct current power supply and reverse pulse power supply. Especially when the method of the present invention is applied to vertical electroplating, it can effectively solve the technological problem that oxygen bubbles form a current blocking shielding layer on the surface of the anode facing the cathode in the prior art, so that the insoluble anode has a simple structure and is easy to maintain. Good electroplating effect can also be achieved in the vertical electroplating equipment.
  • the present invention can do the following improvements:
  • At least one liquid spray pipe/port is added on the side of the insoluble anode facing the cathode, and the liquid spray pipe/port is connected with an external liquid spray pipeline for spraying liquid toward the anode, and is connected with the suction pipe/port
  • a more stable and controllable liquid flow away from the cathode is generated near the insoluble anode, so that the bubbles generated on the anode during the electroplating process can smoothly pass through the pores of the insoluble anode and leave the area between the anode and the cathode plating.
  • the liquid spray pipeline is a pipeline with a pump connected to the container containing the electroplating liquid at the other end, and provides a continuous flow of electroplating liquid for the liquid spray pipe/port spraying liquid.
  • the liquid spray pipe/port is arranged at the bottom of the electroplating tank on the side of the insoluble anode facing the cathode, so that the liquid spray pipe/port and the suction pipe/port cooperate to produce a downward
  • the liquid flow on the anode can make the bubbles generated on the anode be sucked away from the cathode through the pores of the insoluble anode as soon as possible, and at the same time avoid the eddy current of the electroplating solution in the area between the anode and the cathode plating piece and affect the current distribution of the electroplating solution.
  • the present invention can also improve the feeding structure of the insoluble anode. It is preferable to set the feeding lines from the horizontal sides of the insoluble anode to reduce the current density difference between the upper and lower parts of the insoluble anode, so that the gas evolution electrode and the cathode area can be improved.
  • the conductivity of the gas-liquid mixture tends to be uniform. This overcomes the disadvantage that the current density of the upper part of the anode is higher than that of the lower part of the feeding method, so that the electrolytic bubbles are more concentrated in the upper part of the anode, resulting in extremely uneven plating current distribution of the electroplating solution.
  • a gas-liquid separator can be further added to the return piping system, so that the liquid suction pipe discharges the gas-liquid mixture fluid sucked from the electroplating tank into the gas-liquid separator through the connecting pipe.
  • the gas-liquid separator is a device for draining the oxygen bubbles generated on the anode during the electroplating process together with the electroplating solution to a larger space, so that the liquid flow rate is slowed down and the gas escapes. After the gas-liquid mixture is separated in the gas-liquid separator to release the gas, its liquid is drawn back into the electroplating tank for circulating flow again.
  • the oxygen separated out in the gas-liquid separator is collected and reused.
  • the electroplating tank can also be separated into two areas, an anode plating tank area and a cathode plating tank area, with an electroplating tank separator, and the electroplating solutions in the two electroplating tank areas can be the same, or can be different. That is, the electroplating solution in the anodic electroplating tank area is an anodic electroplating solution, specifically an aqueous solution containing inorganic acids and/or inorganic salts, or an acidic sulfate copper plating electroplating solution; the electroplating solution in the cathode electroplating tank area is Acid sulfate copper plating bath.
  • the insoluble anode and cathode plating parts are isolated and placed in the anode plating tank area and the cathode plating tank area, respectively.
  • the pipette/port of the present invention is arranged in the anode plating tank area, and only in the anode tank area is generated away from the cathode and penetrates through flow through the anode pores. If a liquid spray pipe/port is further provided on the side of the insoluble anode facing the cathode, the liquid spray pipe/port is also located in the anodizing bath area.
  • the function of the electroplating tank separator is to separate the oxygen and hydroxyl radicals generated on the anode from the electroplating solution in the vicinity of the cathode plating piece, so as to reduce the entry of oxygen and hydroxyl radicals into the acid copper plating electroplating solution near the cathode plating piece.
  • the chance of chemical reaction with electroplating additives is reduced, thereby reducing the additional loss of electroplating additives in acid copper plating baths.
  • the electroplating tank separator is selected from at least one of cation exchange membrane, anion exchange membrane, bipolar membrane, reverse osmosis membrane, filter cloth, ultrafiltration membrane, ceramic filter plate and PE filter plate.
  • the cation exchange membrane When the cation exchange membrane is used as the separator of the electroplating tank, with the progress of the electrochemical reaction, the copper ions in the acid sulfate copper plating solution in the cathode electroplating tank area are reduced to metallic copper on the surface of the cathode plating piece At the same time, the cations in the electroplating solution in the anodic electroplating tank area will enter the cathode electroplating tank area through the electroplating tank partition.
  • the anion exchange membrane When the anion exchange membrane is used as the separator of the electroplating tank, with the progress of the electrochemical reaction, the copper ions in the acid sulfate copper plating solution in the cathode electroplating tank area are reduced to metallic copper on the surface of the cathode plating piece At the same time, the anions of the acid sulfate copper plating solution in the cathodic electroplating tank area will enter the anode electroplating tank area through the electroplating tank separator.
  • the acid sulfate in the cathode electroplating tank area The copper ions of the copper-plating electroplating solution are reduced to metallic copper on the surface of the cathode plating part, and at the same time, some cations in the electroplating solution in the anodizing bath area will enter the cathode electroplating through the small holes of the electroplating bath partition. In the tank area, some anions of the acid sulfate copper plating solution in the cathodic electroplating tank area also enter into the anode plating tank area through the small holes of the electroplating tank separator.
  • the electroplating tank separator is a bipolar membrane alone
  • the copper ions in the acid sulfate copper plating solution in the cathode electroplating tank area are reduced to metallic copper on the surface of the cathode plating piece
  • the electrolysis reaction of water occurs inside the bipolar membrane to generate hydrogen ions and enter into the cathode electroplating tank area.
  • the reverse osmosis membrane When the reverse osmosis membrane is used as the separator of the electroplating tank, with the progress of the electrochemical reaction, the copper ions in the acid sulfate copper plating solution in the cathode electroplating tank area are reduced to metallic copper on the surface of the cathode plating piece . If there are hydrogen ions in the electroplating solution in the anode plating tank, the hydrogen ions will also enter the cathode plating tank through the plating tank separator.
  • 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.
  • the liquid suction pipe/port discharges the gas-liquid mixture fluid sucked out from the anode plating tank area into the gas-liquid separator through the connecting pipe, and the gas-liquid separator is discharged. After the liquid mixture is separated in the gas-liquid separator to release the gas, the liquid of the liquid mixture is led back to the anode plating tank again for circulating flow.
  • the anode plating tank area adopts the form of an anode box and is installed in the plating tank to separate the anode plating tank area and the cathode plating tank area, which is specifically: the The anode box is in the shape of a cube-shaped box, and the insoluble anode is located in the anode box.
  • the side of the anode box facing the cathode plating part is the electroplating tank partition.
  • the inner space of the anode box is the anode plating tank area.
  • the electroplating tank The space outside the middle and anode boxes is the cathode plating tank area.
  • the pipette/port of the present invention is arranged on the anode box, specifically on the space position or the box wall of the side of the insoluble anode facing away from the cathode in the anode box; in addition, the The anode box can also be provided with a liquid spray pipe/port, which is specifically located in the area between the side of the insoluble anode facing the cathode and the adjacent box wall in the anode box.
  • the liquid sprayed from the liquid spray pipe/port in the anode box is taken from the liquid in the gas-liquid separator.
  • liquid spray pipes are installed on the periphery of the anode box facing the cathode side, for spraying the electroplating solution to the cathode, so that the electroplating solution can pour into the depth of the pores of the cathode plating parts, so that the inside of the pores
  • the electroplating solution can be supplemented and updated to improve the electroplating quality in the pore depth of the plated part.
  • the spray action of the liquid injection pipe outside the anode box is program-controlled according to time and/or flow, and the time difference and/or flow difference is used to avoid anodes on both sides of the cathode plating piece.
  • the liquid streams sprayed by both sides of the box at the same time collide with each other, so as to achieve the optimization of the effect of the plating solution.
  • a reverse pulse protection screen can also be provided on the insoluble anode, and the reverse pulse protection screen is an uncoated titanium protrusion or a raised mesh arranged on the side of the anode facing the cathode.
  • Any electrode structure that is beneficial to discharge, such as objects, strips, etc., is directly connected to the titanium substrate of the insoluble anode.
  • the shape of the protrusions can be in the shape of bumps, spikes, and vertical strips; the raised meshes and strips can be supports extending toward the cathode on the side of the anode facing the cathode.
  • a mesh or strip fixed at the foot end, or a mesh or strip formed by interconnecting with the upper part of any of the above-mentioned protrusions, the plane formed by the mesh or strip is parallel to the anode surface or basically parallel.
  • the above structure of the insoluble anode is modified in a targeted manner, and the process quality advantage of the insoluble anode of the present invention can be more effectively exerted when the reverse pulse power supply is used as the electroplating process.
  • the anti-pulse protective screen protects the insoluble anode in the process of anti-pulse electrolysis.
  • the exposed titanium metal of the protective screen When the exposed titanium metal of the protective screen is used as the anode for the electrochemical reaction of the electrolyte aqueous solution, an oxide layer will be formed on the surface and it is difficult to participate in the electrochemical reaction, but when it is used as the cathode for the electrochemical reaction, it can normally participate in the discharge characteristics, which makes the setting
  • the insoluble anode with the anti-pulse protective screen is used as the anode for electroplating electrochemical reaction, the anti-pulse protective screen hardly participates in the reaction, but the main electroplating is carried out by the coated titanium anode body.
  • the reverse pulse protection screen participates in the electrochemical reaction and discharges . Since the reverse pulse protection screen protrudes from the surface of the insoluble anode and is closer to the cathode plating piece in distance, according to the principle of electric field potential difference, it can more effectively attract the electroplating current and make the main current pass through the reverse pulse protection screen. The current is then directed from the titanium substrate in the insoluble anode.
  • the hydrogen evolution reaction occurs directly on the back pulse protection screen, rather than mainly on the surface of the insoluble anode coating as in the prior art.
  • the reverse pulse protection screen can effectively reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode coating, thereby effectively prolonging the service life of the insoluble anode.
  • the anti-pulse protection screen is a protrusion, the more the protrusions are, the more uniform the distribution is, the better the protection effect of the insoluble anode coating is.
  • a setting frame can be further added to the edge of the insoluble anode, and the connection of the setting frame to the insoluble anode helps to enhance its straight mechanical rigidity and reduce the influence of uneven discharge caused by anode deformation.
  • the thickness of the sizing frame is greater than the thickness of the insoluble anode and/or its width is greater than the width of the non-porous portion of the insoluble anode and/or its mechanical rigidity is greater than that of the insoluble anode and/or is reinforced by a stabilizing structure Mechanical rigidity of the insoluble anode.
  • the shaping frame can be any material with positive insolubility, heat and acid resistance and strong rigidity.
  • the anti-pulse protective screen is in addition to the titanium base of the insoluble anode.
  • the anti-pulse protective screen can also be connected with the titanium material of the setting frame alone, or connected with both at the same time. Since the thicker the conductor, the smaller the resistance, the sizing frame in this preferred solution can not only make a reasonable current distribution of the overall current of the insoluble anode during electroplating, but also introduce the main current into the sizing frame during the reverse pulse electrolysis process. The frame is bypassed to further protect the surface coating of the insoluble anode.
  • the sizing frame is made of conductive material, and the sizing frame is connected to the positive electrode of the electroplating power source through the titanium base material of the insoluble anode, or is simultaneously connected to the titanium base material of the insoluble anode and the positive electrode of the electroplating power source. Connected to or connected to the positive pole of the reverse pulse electroplating power supply.
  • the shaping frame is made of exposed titanium material, and the shaping frame is connected to the positive electrode of the electroplating power supply through the titanium base material of the insoluble anode, or is simultaneously connected to the titanium base material of the insoluble anode and the anode of the electroplating power supply.
  • the positive electrode is connected, or connected with the positive electrode of the reverse pulse electroplating power supply, which can be combined with the insoluble anode to improve the feeding structure.
  • the present invention can make the following improvements: in the electroplating process, supplementary solution or electroplating raw materials are added to the electroplating tank according to the analysis result of the component concentration of the electroplating solution, so as to maintain the stability of each component ratio in the electroplating solution.
  • the electroplating tank can be connected with the electroplating solution regeneration device directly or through a transfer tank to form a controllable recycling system set according to the process, which can be used as a supplement for the electroplating copper source, which helps to achieve green Cleaner production and lower production costs.
  • the present invention can make the following improvements: the side of the insoluble anode facing away from the cathode is connected with a conductor that communicates with the positive electrode of the electroplating power supply, and the bypass current of the conductor is used to increase the uniformity of discharge during electroplating of the insoluble anode, thereby improving the plated parts plating quality.
  • the conductor can be a conductive plate or a conductive mesh, and the conductive plate or the conductive mesh is connected to the shaping frame, so that the insoluble anode can be more uniformly discharged during electroplating.
  • the conductive plate is an uncoated titanium plate with a mesh or hollow structure, or the conductive mesh is an uncoated titanium mesh.
  • the anti-pulse protective screen can be further arranged on the conductor, and then the anti-pulse protective screen can be extended from the surface of the insoluble anode to the cathode through the mesh or hollow structure of the insoluble anode.
  • the anti-pulse protective screen can be extended from the surface of the insoluble anode to the cathode through the mesh or hollow structure of the insoluble anode.
  • the anti-pulse protective screen is welded and connected to the titanium substrate of the anode when passing through the insoluble anode, and during electroplating, the anti-pulse current can be shunted along the conductor and the titanium substrate of the insoluble anode through the protruding part, respectively. To reduce the occurrence of hydrogen evolution on the insoluble anode.
  • the reverse pulse protection screen does not conduct conductive connection when passing through the insoluble anode, and can reduce the current passing through the insoluble anode during reverse pulse electroplating, thereby further reducing its hydrogen evolution phenomenon.
  • the anti-pulse protection screen and the insoluble anode are not conductively connected, and the insoluble anode and/or the shaping frame and the conductive plate or the conductive mesh are connected by welding using a titanium plate or a titanium mesh.
  • a titanium plate or a titanium mesh is used to seal the surrounding edges between the shaping frame and the conductive plate or the conductive mesh by welding.
  • the current released by the insoluble anode during electroplating is more uniform, and when the insoluble anode is converted into a cathode during the operation of the reverse pulse, its main current passes through the reverse pulse protection net, sizing frame and/or conductive plate (mesh)
  • the bypass shunt enables to further reduce the hydrogen evolution reaction of the insoluble anode.
  • the present invention can be improved as follows: when the insoluble anode is provided with the reverse pulse protection screen, the setting frame and the conductive plate or conductive mesh, at least one suction absorber is installed on the side of the conductive plate or conductive mesh facing away from the cathode. liquid pipe/port; and the insoluble anode and the conductive plate or the conductive mesh are connected by a setting frame made of titanium plate as a sealing edge between the two, so that the main liquid flow of the liquid spray pipe/port carries the energy of the bubbles formed by the anode. Concentrate through the through holes on the insoluble anode and the through holes on the conductive plate or conductive mesh behind it, and are pushed into the pipette/mouth to attract outflow.
  • the insoluble anode with the reverse pulse protection net, the sizing frame, the electrical conductor and the insoluble anode assembly with the suction pipe/port and the liquid spray pipe/port are installed in the anode box as the anode cell box formula assembly.
  • the invention can make the following improvements: when the cathode plating part needs to be electroplated in multiple directions or the electroplating area of the surface in different directions is not equal, one power supply can be used to connect two or more insoluble anodes, and distribute them reasonably Electrochemical reaction of electroplating is performed on the surrounding position of the plated part; two or more power sources and multiple insoluble anodes can also be used to connect the cathode plated parts for electroplating in a reasonable position; The amount of reaction is to set two or more electroplating power sources and each power source is connected to one or more of the insoluble anodes. In the case of a common cathode electroplating workpiece for electroplating, the electroplating surface area and process in different directions of the plated parts are determined. It is required to precisely adjust the current intensity output by each electroplating power supply to improve the electroplating quality of the plated parts.
  • An optimization device for insoluble anodic acid sulfate electroplating copper comprising an electroplating tank, an insoluble anode, a cathode used as a plating piece, and an electroplating power supply, characterized in that: the electroplating tank is further provided with at least one pipette/port, The pipette/port is located on the side of the insoluble anode facing away from the cathode, and is used to make the electroplating solution flow in the electroplating tank through the overflow of the pipette/port or/and the electrokinetic suction method;
  • the insoluble anode is a titanium material covered with a coating, and its shape is a mesh or a plate with a hollow structure;
  • the positive electrode and the negative electrode of the electroplating power supply are respectively connected with the insoluble anode and the plated part as the cathode during the electroplating process.
  • the device of the present invention adopts a return system, which is mainly composed of a power source and a connecting pipe, one end of which is connected to a suction pipe/port, and the other end is connected to an electroplating tank.
  • the electroplating solution sucked by the mouth flows back into the electroplating tank, forming a liquid flow from the electroplating solution in the electroplating tank to the suction pipe/port at the anode, and the cycle is reciprocated.
  • the backflow system can be constructed on the basis of the above-mentioned suction pipe/port using power to make the liquid near the insoluble anode generate a liquid flow away from the cathode and through the pores of the anode, plus a connecting pipe to communicate with the electroplating tank.
  • the electroplating tank is provided with at least one liquid spray pipe/port, and the liquid spray pipe/port is arranged in the area space between the two electrodes on the side of the insoluble anode facing the cathode , the spray pipe/port is connected to a liquid spray pipeline for spraying liquid to the anode, and cooperates with the liquid suction pipe/port to generate a more stable and controllable liquid flow away from the cathode near the insoluble anode.
  • the liquid spray pipeline is a pipeline with a pump connected to the container containing the electroplating solution at the other end, and can also be directly connected to the above-mentioned return system connecting the suction pipe/port to provide a continuous flow of liquid for the liquid spray pipe/port. electroplating solution.
  • the liquid spray pipe/port is installed at the bottom of the electroplating tank on the side of the insoluble anode facing the cathode and sprays liquid toward the insoluble anode.
  • the present invention can make the following improvements: the suction pipe/port is connected with the gas-liquid separator through a connecting pipe, and the gas-liquid separator is a larger container device, when the liquid generated on the anode during the electroplating process is removed After the oxygen bubbles are drained to the gas-liquid separator together with the electroplating solution, the larger space is used to slow down the liquid flow rate and cause the gas to escape.
  • the gas-liquid separator can also be communicated with the electroplating tank through a pump and a connecting pipe to form a return system, and the liquid treated by releasing the gas is discharged back into the electroplating tank for circulating flow.
  • the present invention can be improved as follows: an electroplating tank separator is arranged in the electroplating tank to separate the electroplating tank into an anode plating tank area and a cathode plating tank area.
  • the anode plating tank area and the cathode plating tank area are separated by installing an anode box in the plating tank: the anode box is a cube-shaped box, the insoluble anode is located in the anode box, and the anode box is located in the anode box.
  • the side of the box surface facing the cathode plating member is the electroplating tank partition, the inner space of the anode box is the anode plating tank area, and the remaining space in the electroplating tank except the anode box is the cathode plating tank area.
  • the suction pipe/port is arranged on the anode box, specifically on the space or box wall of the anode box on the side of the anode box facing away from the cathode relative to the insoluble anode;
  • the liquid pipe/port in particular, is located in the area of the anode box between the side of the insoluble anode facing the cathode and the adjacent box wall.
  • the liquid outlet of the gas-liquid separator is connected with the liquid spray pipeline and the liquid spray pipe/port, that is, a pump is installed on the connecting pipe between the gas-liquid separator and the liquid spray pipe/port, so that the The return pipeline and the liquid spray pipeline are combined into one, so that the anodic plating solution is quickly drained into the gas-liquid separator through the suction pipe/port with the air bubbles through the structural pores of the insoluble anode under the driving force of the pump.
  • a pump is installed on the connecting pipe between the gas-liquid separator and the liquid spray pipe/port, so that the The return pipeline and the liquid spray pipeline are combined into one, so that the anodic plating solution is quickly drained into the gas-liquid separator through the suction pipe/port with the air bubbles through the structural pores of the insoluble anode under the driving force of the pump.
  • the present invention can make the following improvements: the outer side edge of the side of the anode box facing the cathode plating part is equipped with liquid spray pipes, and each liquid spray pipe is equipped with a flow regulator, so as to be used for the discharge of the cathode plating solution. Adjustment of spray effect.
  • a plurality of anode boxes can also be set in one electroplating tank, and the spraying action of the liquid injection pipe arranged outside the anode box can be controlled by a program, so as to avoid the injection pipe installed on the anode box during the operation. Jet liquid hedges and does not achieve optimal filling.
  • the insoluble anode of the present invention may also be provided with a back-pulse protection screen, and the back-pulse protection screen is an uncoated titanium protrusion disposed on the side of the insoluble anode facing the cathode plating piece.
  • the protrusion is directly connected to the titanium substrate of the insoluble anode, and its shape can be a bump, a spike, a vertical strip, or any electrode structure that is conducive to discharge, such as a mesh or strip connected to the above-mentioned arbitrary shape structure. form.
  • the present invention can be improved as follows: the edge of the insoluble anode is also provided with a shaping frame.
  • the sizing frame selects exposed titanium material, and is connected with the positive electrode of the electroplating power supply through the titanium base material of the insoluble anode, or is connected with the titanium base material of the insoluble anode and the positive electrode of the electroplating power supply at the same time.
  • the present invention can be improved as follows: the side of the insoluble anode facing away from the cathode is installed with a conductor connected to the positive electrode of the electroplating power supply, so that the discharge is uniform.
  • the conductor is a titanium plate with a mesh or hollow structure, that is, a conductive mesh or a conductive plate.
  • the present invention can make the following improvements: by adopting the improvement of the power feeding structure of the insoluble anode, it is preferable to set the feeding lines from the horizontal sides of the polar plates of the insoluble anode, so that the gas-liquid mixture between the gas-emission electrode and the cathode area is The conductivity tends to be uniform, thus overcoming the disadvantage of forming a gradient bubble layer in the gassing electrode due to the traditional top-down feeding method.
  • the present invention can be improved as follows: the insoluble anode assembly with the reverse pulse protection net, the sizing frame, the electrical conductor, the suction pipe/port, the liquid spray pipe/port is installed on the insoluble anode assembly with the liquid spray pipe
  • the anode box is used as an anode tank assembly to make the electroplating equipment more compact.
  • the present invention can make the following improvements: when the electroplating surface areas of the plated parts are inconsistent in all directions, one power supply and two or more insoluble anodes can be used as the electroplating process system reasonably distributed around the cathode; Two or more electroplating power sources and two or more insoluble anodes are arranged around the cathode plating parts to form a common cathode plating part electroplating system. The working state between the power sources is controlled according to the process requirements, so that the cathode plating parts can meet the plating quality requirements.
  • the present invention can make the following improvements: in order to meet the quality requirements for pore electroplating of cathode plating parts, a reverse pulse electroplating power source can be used, and a reverse pulse electroplating process can be used to better exert the performance and function of the insoluble anode of the present invention to improve Plating quality and efficiency.
  • the present invention can be improved as follows: a stirring device is arranged in the electroplating tank to assist the uniform distribution of the concentration of each component of the electroplating solution.
  • the stirring device is any one of a reflux liquid stirring device, a blade stirring device, and a pneumatic stirring device or any combination thereof.
  • the reflux liquid stirring device includes a liquid outlet pipe, a pump, and a return pipe.
  • the pneumatic stirring device is a device that can pass gas into the electroplating solution to make the electroplating solution flow.
  • the present invention can make the following improvements: add a current regulator to the electroplating power supply, or adopt an electroplating power supply with its own current regulator to adjust the output current size of the electroplating power supply, or control the opening/closing of the electroplating power supply. or shut down.
  • a detection device is provided in the electroplating tank, including one or more of a liquid level meter, a hydrometer, an acidity meter, an oxidation-reduction potentiometer, a photoelectric colorimeter, a pH meter and a thermometer , used to detect the corresponding process parameters of the liquid in the electroplating bath.
  • the detection device is connected to an automatic detection and feeding controller, and the automatic detection and feeding controller can perform process control according to the time and/or the detection result of the detection device: adding electroplating to the electroplating tank liquid replenishment and/or chemical raw materials and/or clean water, and/or control the start or stop of the electroplating power supply or the magnitude of the current.
  • the present invention can be improved as follows: a filter device is arranged to be connected with the electroplating tank through a pipeline, so as to remove the copper mud that may exist in the electroplating solution and/or the impurities brought during the use of the electrode.
  • the present invention can be improved as follows: a tail gas extraction system is arranged above the electroplating tank to extract the gas generated on the anode and/or the cathode during the electroplating process to avoid accumulation and ensure safe production.
  • the present invention can be improved as follows: the electroplating tank is connected with the electroplating solution regeneration device through pipelines and pumps to form the electroplating copper source supplementary controllable recycling system equipment set according to the process.
  • the present invention can be improved as follows: a temporary storage tank connected to the electroplating tank is added to temporarily store the liquid flowing out of the electroplating tank and/or the liquid to be added to the electroplating tank, and/or for the electroplating liquid to carry out other chemical reactions.
  • the present invention can be improved as follows: a temperature-cooling heat exchanger is installed in the electroplating tank and/or the gas-liquid separator to stabilize the temperature of the electroplating solution.
  • the present invention has the following beneficial effects:
  • the present invention can effectively overcome the accumulation of oxygen on the surface of the anode in the prior art by using a mesh or a plate-shaped structural material with a hollow structure as the insoluble anode, and setting a suction pipe/port in the direction of the insoluble anode facing away from the cathode.
  • the method of the present invention can also obtain a uniform and high-quality coating in the vertical electroplating method, so it can be extended to the traditional vertical electroplating process, and therefore, it can avoid that the irregularly shaped plated parts are difficult to overcome in the insoluble anode horizontal electroplating line process issues.
  • a shaping frame is arranged at the edge of the insoluble anode, which can effectively enhance the flat mechanical rigidity of the insoluble anode, reduce the uneven discharge caused by the deformation of the anode, improve the quality of the plated parts, and obtain high flatness and uniformity. product;
  • the present invention is further provided with a bare titanium material or a coated titanium material shaping frame connected to the titanium base material of the anode body and/or the anti-pulse protection screen, or the side of the insoluble anode facing away from the cathode is provided with It can effectively increase the uniformity of the discharge of the insoluble anode during electroplating, thereby improving the coating protection effect and electroplating quality.
  • a reverse pulse protection screen is set on the side of the insoluble anode surface facing the cathode plating part, which can effectively reduce the situation that the coating on the surface of the insoluble anode is damaged due to hydrogen evolution reaction during the reverse pulse process, thereby prolonging the insolubility.
  • Anode service life reduce production costs;
  • the present invention is provided with an exposed titanium material or a titanium material forming frame covered with a coating, when it is connected with the titanium base material of the insoluble anode and/or the reverse pulse protection screen and/or the positive electrode of the electroplating reverse pulse power supply, it can effectively In the process of reverse pulse electrolysis, the main current is introduced into the setting frame for bypassing, thereby further improving the protection effect of the surface coating on the insoluble anode and reducing the damage of the insoluble anode.
  • the process of the present invention can not only effectively ensure the penetration quality of the copper-plated through holes, that is, better electroplating quality, but also greatly reduce the damage of the insoluble anode and prolong the service life of the insoluble anode during the reverse pulse electroplating process.
  • a liquid spray pipe is arranged outside the anode box to spray the electroplating solution to the plated parts, so that the electroplating solution pours into the inside of the small holes of the cathode plated parts, so that the plating solution inside the pores is supplemented and updated, thereby further improving the transmission efficiency of the plated parts. Hole penetration quality.
  • the present invention can effectively reduce the extra loss of the electroplating additives of the acid electroplating copper electroplating solution when the electroplating tank is separated into an anode electroplating tank area and a cathode electroplating tank area by using the electroplating tank separator, thereby reducing the production cost; wherein, The consumption rate of the electroplating additive in the process of the present invention is 1/3 of the prior art.
  • the present invention installs the insoluble anode with the anti-pulse protection net, the shaping frame, the conductive plate or the conductive net and the insoluble anode assembly of the suction pipe/port and the liquid spray pipe/port in the anode box as a
  • the box-type assembly in the anode tank area, and multiple insoluble anodes are reasonably connected around the plated parts, which not only solves the problems of uneven anode discharge and hydrogen evolution, but also improves the electroplating quality of the irregular-shaped plated parts.
  • the device of the present invention can be used in conjunction with the electroplating solution regeneration device.
  • the electroplating tank is connected with the electroplating solution regeneration device, and a recycling system supplemented by the electroplating copper source is formed through the combination of the control system, which helps to reduce phosphorus. Copper pollution achieves green and clean production while reducing production costs.
  • Fig. 1 is the optimization device of the insoluble anodic acid sulfate copper electroplating of the embodiment of the present invention 1;
  • Fig. 2 is the optimization device of the insoluble anodic acid sulfate copper electroplating of the embodiment 2 of the present invention
  • Fig. 3 is the optimization device of insoluble anodic acid sulfate copper electroplating according to Embodiment 3 of the present invention.
  • Fig. 4 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 4 of the present invention
  • Fig. 5 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 5 of the present invention.
  • Fig. 6 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 6 of the present invention.
  • Fig. 7 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 7 of the present invention.
  • Fig. 8 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 8 of the present invention.
  • Fig. 9 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 9 of the present invention.
  • Fig. 10 is the optimization device of insoluble anodic acid sulfate copper electroplating according to the embodiment 10 of the present invention.
  • Fig. 11 is the optimized device of insoluble anodic acid sulfate copper electroplating according to Example 11 of the present invention.
  • Fig. 12 is the optimization device of insoluble anodic acid sulfate copper electroplating according to Example 12 of the present invention.
  • Fig. 13 is the optimization device of insoluble anodic acid sulfate copper electroplating according to Example 13 of the present invention.
  • Fig. 14 is the insoluble anodic acid copper electroplating device of the prior art comparative example 1;
  • Fig. 15 is the insoluble anodic acid copper electroplating device of the prior art comparative example 2;
  • Example 16 is an optimized device for copper electroplating with insoluble anodic acid sulfate in Example 14 of the present invention
  • FIG. 17 is an optimized device for copper electroplating with insoluble anodic acid sulfate in Example 15 of the present invention.
  • Figure A is a schematic diagram of an insoluble anode in Example 1 of the present invention.
  • Figure B is a schematic diagram of an insoluble anode in Example 2 of the present invention.
  • Figure C is a schematic diagram of an insoluble anode in Example 3 of the present invention.
  • Figure D is a schematic diagram of an insoluble anode in Example 4 of the present invention.
  • Figure E is a schematic diagram of an insoluble anode in Example 5 of the present invention.
  • Figure F is a schematic diagram of an insoluble anode in Example 6 of the present invention.
  • Figure G is a schematic diagram of the structure of the insoluble anode box in Examples 7 and 11 of the present invention.
  • Figure H is a schematic diagram of the structure of the insoluble anode box in Example 8 of the present invention.
  • Figure J is a schematic diagram of the structure of the insoluble anode box in Examples 9 and 12 of the present invention.
  • Figure K is a schematic diagram of the structure of the insoluble anode box in Examples 10 and 13 of the present invention.
  • the copper sulfate used is a commercially available copper sulfate product;
  • the sulfuric acid used is preferably a product produced by Guangzhou Chemical Reagent Factory;
  • the used titanium-based coating electroplating anode and electroplating tank are Foshan Yegao Products produced by Environmental Protection Equipment Manufacturing Co., Ltd.;
  • the electroplating cathodes used are preferably commercially available pure copper plates and copper plates with small holes;
  • the ion exchange membranes used are preferably ion exchange membranes produced by Membrane International Corporation;
  • the bipolar used The membrane is preferably a bipolar membrane produced by Guochu Technology;
  • the ultrafiltration membrane, filter cloth, ceramic filter plate, PE filter plate and reverse osmosis membrane are commercially available commodities;
  • the microscope used is preferably a computer microscope produced by Guangzhou Optical Instrument Factory;
  • the electroplating power supply and reverse pulse electroplating power supply used are products produced by Guangzhou Panyu Guangxing Electroplating Equipment Factory;
  • FIG. 1 it is an example of an optimized device for insoluble anodic acid sulfate copper electroplating, which includes an electroplating tank 5 , an insoluble anode 1 , a liquid suction pipe 2 , a cathode plating part 4 , an electroplating power source 6 , and a gas-liquid separator 8 ,in:
  • the electroplating tank 5 is provided with a liquid suction pipe 2, and the liquid suction pipe 2 is located on the side of the insoluble anode 1 facing away from the cathode plating part 4; One end is connected with the electroplating tank through a pipeline and a pump 23, so that the liquid suction pipe 2 through the connecting pipeline will separate the gas-liquid mixture sucked out of the electroplating tank in the gas-liquid separator to release the gas, and then the liquid will be led back to the place again. Circulating flow in the electroplating tank.
  • Figure A is a titanium material covered with a coating, and the structure is a plate with hollow through holes, and the feeder installation hole on the upper part of the anode plate is set into the feeder line as a slave. feed up;
  • the positive and negative electrodes of the electroplating power source 6 are respectively connected to the insoluble anode 1 and the cathode plating member 4 during the electroplating process.
  • the cathode plating member 4 is a flat copper plate.
  • An optimized method for insoluble anodic acid copper electroplating including the following steps:
  • the insoluble anode device is installed in the electroplating tank, and the suction pipe is arranged on the side of the insoluble anode facing away from the cathode, the positive electrode of the electroplating power supply is connected with the insoluble anode, and the negative electrode of the electroplating power supply is connected with the cathode plating part;
  • the structure of the insoluble anode cooperates with the pipette arranged on the side of the anode facing away from the cathode.
  • the liquid near the insoluble anode generates a liquid flow away from the cathode and passing through the pores of the anode, so that the The oxygen bubbles generated on the surface of the anode flow through the pores formed by the structure of the insoluble anode and are sent to the direction away from the cathode to be discharged and released.
  • the COD of the plating solution is detected before and after the electroplating operation, and the consumption of the electroplating additives by the process is preliminarily judged by the change value before and after, and the results are recorded in Table-2.
  • the structure of the insoluble anode 1 is shown in Figure B.
  • the insoluble anode is a titanium mesh covered with a coating, and the welding material around the four sides of the insoluble anode is a setting frame 16 of a coated titanium material.
  • the feeder installation hole is set into the feeder line for structural improvement.
  • the optimized device for insoluble anodic acid sulfate copper electroplating in this embodiment includes an electroplating tank 5 , an insoluble anode 1 , a cathode plating member 4 , an electroplating power source 6 , a gas-liquid separator 8 , and a solid-liquid separator.
  • Filter 33 where:
  • the electroplating tank 5 is provided with a liquid suction port 2, a liquid spray pipe 10, a leaf stirring device 24.2 and a pneumatic stirring device 24.1, and the liquid suction port 2 is arranged on the wall of the electroplating tank 5, and is located in the insoluble anode 1 facing away from the cathode plating piece 4.
  • the liquid spray pipe 10 is installed in the space of the bipolar region on the side of the insoluble anode 1 facing the cathode plating member 4, the liquid suction port 2 is connected to the gas-liquid separator 8 through a pipeline and a pump, and the gas-liquid separator 8 is circulated through the liquid backflow.
  • the pipeline 9 and the filtering device 33 return the liquid after the gassing treatment to the electroplating tank 5 from the liquid spraying pipe 10 after filtering.
  • the structure of the insoluble anode 1 is shown in Figure C.
  • the insoluble anode 1 is a titanium material covered with a coating.
  • a back-pulse protection screen 15 is installed on the anode 1 and on the setting frame 16.
  • the back-pulse protection screen 15 is a thorn-shaped uncoated titanium material, and is set into the feeder line from the feeder installation hole on the upper part of the anode plate to serve as a slave. Structural improvement of the upper feed.
  • the positive and negative electrodes of the electroplating power source 6 are connected to the insoluble anode 1 and the cathode plating member 4, respectively, during the electroplating process.
  • the cathode plating member 4 is a flat copper plate.
  • the hollow structure of the insoluble anode is matched with the liquid suction port arranged on the side of the anode facing away from the cathode.
  • the oxygen bubbles generated on the surface are sent to the direction away from the cathode through the pores formed by the hollow structure of the insoluble anode with the liquid flow, and are discharged to the gas-liquid separator for release. Return to the plating tank for circulating flow.
  • the optimized device for insoluble anodic acid sulfate copper electroplating in this embodiment includes an electroplating tank 5, an insoluble anode 1, a liquid suction pipe 2, a cathode plating member 4, a reverse pulse electroplating power source 19, a gas-liquid Separator 8, where:
  • the electroplating tank 5 is provided with a liquid suction pipe 2 and a liquid spray pipe 10, the liquid suction pipe 2 is located on the side of the insoluble anode 1 facing away from the cathode plating member 4, and the liquid spray pipe 10 is installed on the two poles of the insoluble anode 1 facing the cathode plating member 4 side.
  • the suction pipe 2 is connected to the gas-liquid separator 8 through the pipeline and the pump 23, and the gas-liquid separator 8 returns the treated liquid to the electroplating tank through the liquid return circulation pipeline 9;
  • the insoluble anode is a coated titanium plate with a hollow structure.
  • the insoluble anode 1 is provided with a reverse pulse protection screen 15 on the side facing the cathode plating piece, and the reverse pulse protection screen is an uncoated titanium protrusion directly connected to the titanium substrate of the insoluble anode 1, and the shape of the protrusion is
  • the structure is needle-punched and strip-shaped, and the top end is connected by mesh to form a protective net cover; a conductor 17 is connected to the back of the insoluble anode 1 away from the cathode, and the conductor 17 is a conductive rod.
  • the feeder installation hole on the upper part of the insoluble anode 1 is set into the feeder line to improve the structure of feeding power from above.
  • the cathode plating part 4 is a flat copper plate with small through holes
  • the positive and negative electrodes of the reverse pulse electroplating power source 19 are respectively connected to the insoluble anode 1 and the cathode plating member 4 during the electroplating process.
  • Example 1 According to the parameters specified in Table-1, the steps of the optimization method for insoluble anodic acid copper electroplating described in Example 1 were used to carry out the electroplating operation, and the results were recorded in Table-1; the plating solution was tested for COD before and after the electroplating operation. , through the change data before and after to preliminarily judge the consumption of electroplating additives by the process, and record the results in Table-2.
  • the hollow structure of the insoluble anode cooperates with the suction pipe arranged on the side of the anode facing away from the cathode, and the liquid spray pipe arranged on the side of the insoluble anode facing the cathode, so that the liquid near the insoluble anode is generated by using power. Facing the liquid flow away from the cathode and passing through the anode pores, the oxygen bubbles generated on the anode surface are sent to the direction away from the cathode through the pores formed by the insoluble anode hollow structure with the liquid flow, and are discharged into the gas-liquid separator for release. The liquid after separation and release of gas in the gas-liquid separator is led back to the electroplating tank for circulating flow again.
  • the reverse pulse protection screen can effectively reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode coating.
  • the optimized device for insoluble anodic acid sulfate copper electroplating includes an electroplating tank 5, an insoluble anode 1, a pipette 2, a cathode plating member 4, and a reverse pulse electroplating power source 19, wherein:
  • the electroplating tank 5 is provided with an electroplating tank separator 11 to separate it into an anode electroplating tank area and a cathode electroplating tank area, and the electroplating tank partition 11 is specifically a combination of an ultrafiltration membrane and a filter cloth.
  • the anode plating tank area is provided with a liquid suction pipe 2 and a liquid spray port 10; the liquid spray pipe 10 is installed at the bottom of the anodized plating tank area on the side of the insoluble anode 1 facing the cathode plating part 4, and is connected to the electrode away from the cathode through the pipeline and the pump 23.1.
  • the anode plating tank area of the electroplating tank area is connected on one side; the suction pipe 2 is provided with two liquid suction ports and is located on the side of the insoluble anode 1 facing away from the cathode plating part 4; the suction pipe 2 is connected with a pump 23.2 The pipeline, the liquid with bubbles is drained to the anode plating tank area away from the cathode plating part 4 to release the gas;
  • the insoluble anode 1 located in the anodizing tank area is a titanium mesh covered with a coating; the periphery of the insoluble anode 1 is also welded with a shaping frame 16 for edge sealing, and the shaping frame 16 is made of exposed titanium. ;
  • Conductor 17 is a reticulated bypass structure conductor with titanium mesh and sizing frame 16 welded around it, and conductor 17 is located on the side of insoluble anode 1 facing away from cathode plating 4; sizing frame 16 and conductor 17
  • the installation structure of the insoluble anode 1 is that the side of the insoluble anode 1 facing away from the cathode plating member 4 is used as a plate frame and welded around the edges.
  • the conductor 17 is provided with an anti-pulse protective screen 15, which is mounted and welded on the conductor 17; the anti-pulse protective screen 15 is an uncoated titanium spike that passes through the mesh hole of the insoluble anode 1 and does not contact with it.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder line is set through it for structural improvement of feeding power from above.
  • the cathode plating part 4 is a flat copper plate with small holes in the cathode plating tank area;
  • the positive and negative electrodes of the reverse pulse electroplating power source 19 are respectively connected to the insoluble anode 1 and the cathode plating member 4 during the electroplating process.
  • An optimized method for insoluble anodic acid copper electroplating including the following steps:
  • the mesh structure of the insoluble anode is matched with the suction pipe arranged on the side of the anode facing away from the cathode, and the liquid spray pipe arranged at the bottom of the side of the insoluble anode facing the cathode, and the liquid near the insoluble anode is generated by using power.
  • the oxygen bubbles generated on the anode surface can be more concentrated with the liquid flow through the insoluble anode and the mesh of the conductor, and sent to the direction away from the cathode freed.
  • the optimized device for insoluble anodic acid sulfate copper electroplating of the present embodiment is different from the device of embodiment 5 in that:
  • the electroplating tank separator 11 is specifically a combination of a PE filter plate and a ceramic filter plate.
  • the nozzle of the liquid spray pipe 10 is designed in the shape of a flat bell mouth, and is installed at the bottom of the anodizing tank area on the side of the insoluble anode 1 facing the cathode plating part 4.
  • the anodizing bath areas are connected on one side.
  • the mouth of the suction pipe 2 is in the shape of a bell mouth and is located on the side of the insoluble anode 1 facing away from the cathode plating part 4; the suction pipe 2 drains the liquid with bubbles to the anode plating through the pipeline connected with the pump 23.2 Gas is released in the tank area away from the cathode plating part 4;
  • the insoluble anode 1 located in the anodizing tank area is a hollow through-hole titanium plate covered with a coating; the edge of the insoluble anode 1 is also welded with a setting frame 16 for edge sealing.
  • the material of the setting frame 16 It is a bare titanium material;
  • the conductor 17 is a bypass structure conductor with a titanium plate with hollow through holes and the four peripheries are welded with the setting frame 16, and the conductor 17 is located on the side of the insoluble anode 1 facing away from the cathode plating part 4;
  • the insoluble anode 1 is electrically connected to the shaping frame 16 and the conductor 17, and the three are connected to form a square box with two sides of the hollow through-hole titanium plate connected and the other four sides sealed.
  • the conductor 17 is also provided with an anti-pulse protection screen 15, which is installed and welded on the conductive plate 17; the anti-pulse protection screen 15 is an uncoated titanium material that passes through the hollow through holes of the insoluble anode 1 and does not contact with it. spikes.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder line is set through it for structural improvement.
  • the cathode plating part 4 is a flat copper plate with small holes in the cathode plating tank area;
  • the positive and negative electrodes of the reverse pulse electroplating power source 19 are respectively connected to the insoluble anode 1 and the cathode plating member 4 during the electroplating process.
  • the hollow structure of the insoluble anode is matched with the horn pipette arranged on the side of the anode facing away from the cathode, and the flat horn pipette arranged at the bottom of the side of the insoluble anode facing the cathode.
  • the liquid generates a liquid flow away from the cathode and through the hollow through holes of the insoluble anode and the conductor, so that the oxygen bubbles generated on the surface of the anode can be released more concentratedly with the liquid flow through the hollow through holes of the insoluble anode and sent to the direction away from the cathode.
  • the spikes of the reverse-pulse protective screen are not in contact with the insoluble anode, so the reverse-pulse current is returned from the needle stick tip to the conductive plate and led away from the bypass, which can effectively reduce the insoluble anode.
  • the electrochemical hydrogen evolution reaction occurs on the surface when the pole is turned to prevent the coating of the insoluble anode from peeling off.
  • the design of the cell separator can also effectively reduce the loss of electroplating additives.
  • the optimized device for insoluble anodic acid sulfate copper electroplating in this embodiment includes an electroplating tank 5, an anode box 13, a cathode plating member 4, a gas-liquid separator 8, and a reverse pulse electroplating power source 19, wherein :
  • An anode box 13 is provided in the electroplating tank 5, and the side of the anode box 13 facing the cathode plating member 4 is provided with an electroplating tank partition 11, and the electroplating tank partition 11 is specifically a cation exchange membrane; the inner space of the anode box 13 is an anode In the electroplating tank area, the space outside the anode box 13 in the electroplating tank 5 is the cathode electroplating tank area.
  • the anode box 13 is connected with a liquid suction pipe 2 and a liquid spray port 10 is arranged in it;
  • the liquid suction pipe 2 has four liquid suction ports in the anode box 13 and located in the insoluble anode 1 facing away from the cathode plating part 4 side, the liquid spray port 10 is located on the side of the insoluble anode 1 facing the cathode plating part 4;
  • the suction pipe 2 is connected with the pump 23 and the gas-liquid separator 8 through the pipeline, and the gas-liquid separator 8 is connected with the liquid return circulation pipeline 9 through the pipeline.
  • the liquid ejection port 10 is connected, and the liquid after the gas release treatment is returned to the anode box 13;
  • the insoluble anode 1 in this embodiment has the structure shown in Figure D, which is a titanium plate with a hollowed-out structure covered with a coating; the insoluble anode 1 is provided with a reverse pulse protection screen 15 on the side facing the cathode plating piece, and the reverse pulse protection screen 15 is a Uncoated titanium protrusions directly connected to the titanium base of the insoluble anode 1, and connected to the top of each protrusion using titanium wires to form an open grid; the insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power supply 19 during the electroplating process ; Connect the conductor 17 on the back of the insoluble anode 1 away from the cathode, and the conductor 17 is a conductive rod.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder line is inserted through it for structural improvement.
  • the above-mentioned anode assembly is installed in the anode box 13, as shown in Fig. G.
  • the cathode plating member 4 is a flat copper plate with small holes in the cathode plating tank area, and is connected to the negative electrode of the reverse pulse plating power source 19 .
  • the suction pipe arranged on the side of the insoluble anode facing away from the cathode in the anode box cooperates with the liquid spray port arranged at the bottom of the side facing the cathode of the insoluble anode in the anode box.
  • the liquid flow away from the cathode plating part and passing through the pores of the anode makes the oxygen bubbles generated on the anode surface pass through the pores formed by the structure of the insoluble anode with the liquid flow and are sent to the gas-liquid separator for discharge and release.
  • the liquid is returned to the anode box again.
  • the reverse pulse protection screen can effectively reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode when the electrode is turned, and prevent the coating of the insoluble anode from falling off.
  • the anode box design with cell divider can effectively reduce the loss of plating additives.
  • the optimized device for insoluble anodic acid sulfate copper electroplating of the present embodiment is different from the device of embodiment 7 in that:
  • the electroplating tank separator 11 is specifically a combination of reverse osmosis membrane and filter cloth;
  • the anode box 13 is connected with a liquid suction pipe 2 and a liquid spray pipe 10, the nozzle of the liquid suction pipe 2 is in the shape of a large trumpet, and the liquid spray pipe 10 is provided with a plurality of nozzles arranged in parallel.
  • This embodiment uses the same anode assembly as that of Embodiment 5, including an insoluble anode 1, a conductor 17, a setting frame 16, and a back-pulse protection screen 15.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder circuit is set therefrom.
  • the structure is shown in Figure E, and the anode assembly is installed in the anode box 13, as shown in Figure H.
  • the insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power source 19 .
  • the cathode plating member 4 is a flat copper plate with small holes, which is arranged in the cathode plating tank area, and is connected with the negative electrode of the reverse pulse plating power source 19 during the plating process.
  • this embodiment adopts the anode box structure as shown in Figure H.
  • the liquid near the insoluble anode generates a liquid flow away from the cathode plating piece and passing through the insoluble anode and the conductor mesh, so that the anode is formed.
  • the oxygen bubbles generated on the surface flow through the insoluble anode and the mesh of the conductor and are sent to the gas-liquid separator to be discharged and released, and the liquid after the gas is released is returned to the anode box again.
  • the reverse pulse protection screen can effectively reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode when the electrode is turned, and prevent the coating of the insoluble anode from falling off.
  • the anode box design with cell divider effectively isolates the bath additives from contact with the anode to reduce its loss.
  • the optimized device for insoluble anodic acid sulfate copper electroplating of the present embodiment is different from the device of embodiment 7 in that it also includes a liquid injection pipe 14; and:
  • the electroplating tank separator 11 is specifically a combination of anion exchange membrane and filter cloth
  • the anode box 13 is connected with a liquid suction pipe 2 and a liquid spray pipe 10.
  • the nozzle of the liquid suction pipe 2 is in the shape of a large trumpet, and the liquid spray pipe 10 is provided with a plurality of parallel arranged Nozzle.
  • the suction pipe 2 is connected with the pump 23.1 and the gas-liquid separator 8 through the pipeline, and the gas-liquid separator 8 is connected with the liquid spray pipe 10 through the liquid return circulation pipeline 9, and the treated liquid is returned to the anode box 13;
  • the box 13 facing the cathode plating member 4 is provided with a liquid injection pipe 14 along the periphery.
  • the liquid injection pipe 14 is connected to the cathode plating tank area through pipes and a pump 23.
  • This embodiment adopts the same anode assembly as in Embodiment 6, including an insoluble anode 1, a conductor 17, a setting frame 16, and a back-pulse protection screen 15.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder circuit is set therefrom.
  • the structure is shown in Figure F, and the anode assembly is installed in the anode box 13, as shown in Figure J.
  • the insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power source 19 .
  • the cathode plating member 4 is a flat copper plate with a plurality of small holes, is arranged in the cathode plating tank area, and is connected with the negative electrode of the reverse pulse plating power source 19 during the plating process.
  • the electroplating operation was carried out using the steps of the optimization method for insoluble anodic acid copper electroplating described in Example 5, and the results were recorded in Table-1.
  • the cathodic plating solution is tested for COD, and the consumption of the electroplating additives is preliminarily determined according to the data changes before and after the operation, and the results are recorded in Table-2.
  • this embodiment adopts the anode box structure as shown in Figure J.
  • the liquid near the insoluble anode generates a liquid flow away from the cathode plating member and passing through the hollow through holes of the insoluble anode and the conductor.
  • the oxygen bubbles generated on the surface of the anode pass through the hollow through holes of the insoluble anode and the conductor with the liquid flow and are sent to the gas-liquid separator for discharge and release, and the liquid after separation and release of gas is returned to the anode box again.
  • the reverse pulse protection screen can effectively reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode when the electrode is turned, and prevent the coating of the insoluble anode from falling off.
  • the liquid injection pipe outside the anode box sprays the electroplating solution to the cathode plating part by pumping, so that the electroplating solution pours into the inside of the small hole of the cathode plating part, and the plating solution in the hole is replenished and renewed.
  • the anode box design with the plating tank divider can effectively isolate the plating solution additives from contacting the anode to reduce its loss.
  • the optimized device for insoluble anodic acid sulfate copper electroplating in this embodiment is different from the device in Embodiment 7 in that it also includes a liquid injection pipe 14; and:
  • the electroplating tank separator 11 is specifically a combination of bipolar membrane and filter cloth
  • the anode box 13 is connected with a liquid suction pipe 2 and has a liquid spray port 10 therein.
  • the liquid suction pipe 2 has four nozzles in the anode box 13, which are located in the insoluble anode 1 facing away from the cathode plating
  • the liquid spray port 10 is located on the side of the insoluble anode 1 facing the cathode plating member 4 .
  • the liquid suction pipe 2 is connected to the pump 23.1 and the gas-liquid separator 8 through a pipeline, and the gas-liquid separator 8 is connected to the liquid ejection port 10 through a liquid return circulation pipeline 9 to return the treated liquid to the anode box 13.
  • a liquid injection pipe 14 is installed on the periphery of the anode box 13 facing the cathode plating member 4 .
  • the liquid injection pipe 14 is connected to the cathode plating tank area through pipes and a pump 23.
  • the same anode assembly as in Embodiment 3 is used, including an insoluble anode 1, a shaping frame 16, and a back-pulse protection screen 15.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder line is inserted through it for structural improvement.
  • the anode assembly is installed in the anode box 13, as shown in Figure K.
  • the insoluble anode 1 is connected to the positive electrode of the reverse pulse electroplating power source 19 .
  • the cathode plating member 4 is a flat copper plate with a plurality of small holes, is arranged in the cathode plating tank area, and is connected with the negative electrode of the reverse pulse plating power source 19 during the plating process.
  • the electroplating operation was carried out using the steps of the optimization method for insoluble anodic acid copper electroplating described in Example 5, and the results were recorded in Table-1.
  • the cathodic plating solution is tested for COD, and the consumption of the electroplating additives is preliminarily determined according to the data changes before and after the operation, and the results are recorded in Table-2.
  • this embodiment adopts the anode box structure as shown in Figure K.
  • the liquid near the insoluble anode generates a liquid flow away from the cathode and passing through the hollow through holes of the anode, so that the oxygen bubbles generated on the anode surface are generated.
  • the liquid flow through the hollow through hole of the insoluble anode it is sent to the gas-liquid separator to be discharged and released, and the liquid after separation and release of gas is returned to the anode box again.
  • the reverse pulse protection screen can reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode when the electrode is turned, and prevent the coating of the insoluble anode from falling off.
  • the liquid spray tube outside the anode box sprays the electroplating solution to the cathode plating piece through the pump, so that the electroplating solution pours into the inside of the small hole of the cathode plating piece, so that the plating solution inside the hole is replenished and renewed.
  • the anode box design with plating tank divider can effectively isolate the plating solution additives from contact with the anode to reduce its loss.
  • the optimized device for insoluble anodic acid sulfate copper electroplating includes an electroplating tank 5, an anode box 13, a cathode plating member 4, an electroplating power source 6, and a gas-liquid separator 8, wherein:
  • anode boxes 13 in the electroplating tank 5 there are three anode boxes 13 in the electroplating tank 5, and the side of the anode box 13 facing the cathode plating part 4 is an electroplating tank partition 11, and the electroplating tank partition 11 is specifically a cation exchange membrane; the inner space of the anode box 13 is an anode plating The tank area, the space other than the anode box 13 in the electroplating tank 5 is the cathode electroplating tank area.
  • each anode box 13 is connected with a liquid suction pipe 2 and a liquid ejection port is arranged in it, which is the same as that of the anode box 13 of the seventh embodiment.
  • the suction pipes 2 of each anode box 13 are respectively connected with a pump, and then connected with the gas-liquid separator 8;
  • the liquid ejection port 10 is connected, and the liquid that has been degassed is returned to each anode box 13.
  • a detection device 21 and a stirring device 24 are arranged in the cathode electroplating tank area.
  • the detection device 21 includes a hydrometer, a photoelectric colorimeter, and an acidity meter.
  • the stirring device 24 is a reflux liquid stirring device.
  • the cathode electroplating tank area is connected with the overflow buffer tank 38, the pump 23.4, the filter 33.1, the electroplating solution regeneration device 20, the pump liquid flow regulator 30 and the filter 33.2 in sequence as a circulating loop; The liquid overflowing into the overflow buffer tank 38 is pumped 23.4 through the filter 33.1 and then pumped back to the electroplating liquid regeneration device 20.
  • a tail gas extraction system 25 is arranged above the electroplating tank 5;
  • the same anode assembly as in Embodiment 4 is used, including an insoluble anode 1, a conductor 17, and a back-pulse protection screen 15.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder line is inserted into it for structural improvement.
  • the anode assembly is installed in the anode box 13, as shown in Figure G.
  • the insoluble anode 1 and the electroplating power source 19 are connected positively.
  • the cathode plating member 4 is a flat copper plate, located in the cathode plating tank area, and connected to the negative electrode of the electroplating power source 19 during the electroplating process.
  • the suction pipe on the side facing away from the cathode of the insoluble anode in the anode box cooperates with the liquid spray port at the bottom of the side facing the cathode of the insoluble anode in the anode box, and the liquid near the insoluble anode is generated by using power.
  • the liquid flow away from the cathode and passing through the pores of the insoluble anode causes the oxygen bubbles generated on the anode surface to be sent to the gas-liquid separator with the liquid flow for gas release, and the liquid after the gas is released is returned to the anode box again.
  • the anode box design with electroplating tank divider can separate the anolyte and anolyte, and can effectively reduce the loss of electroplating additives.
  • the gas discharged from the gas-liquid separator can be collected and further processed.
  • the optimized device for insoluble anodic acid sulfate copper electroplating in the present embodiment includes an electroplating tank 5, an anode box 13, a cathode plating member 4, a gas-liquid separator 8, and a reverse pulse electroplating power source 19, wherein :
  • the electroplating tank 5 is provided with six anode boxes 13, and the side of the anode box 13 facing the cathode plating member 4 is an electroplating tank partition 11, and the electroplating tank partition 11 is a combination of an anion exchange membrane and a filter cloth; the interior of the anode box 13 The space is the anode plating tank area, and the remaining space outside the anode box 13 in the plating tank 5 is the cathode plating tank area.
  • the cathode electroplating tank area is provided with a detection device 21.
  • the detection device 21 includes a liquid level meter, a redox potentiometer, a photoelectric colorimeter, a pH meter and a thermometer.
  • the detection device 21 is connected to the automatic detection and feeding controller 34 to control the liquid level of the plating tank. , temperature adjustment, power output current, detection of plating solution concentration, plating time and other process parameters, so that electroplating is carried out according to process requirements.
  • the structure of the anode box 13 is shown in FIG. J.
  • the anode box 13 is connected with a liquid suction pipe 2 and a liquid spray pipe 10 , and the structure of the anode box 13 is the same as that of Embodiment 9.
  • the suction pipes 2 in each anode box 13 are respectively connected with a pump 23 through the pipeline, and then connected with the temporary storage tank 32; wherein the pumps 23.1, 23.2, 23.3 pump the liquid into the temporary storage tank 32.1, and the pump 23.4, 23.5, 23.6 send the liquid to the temporary storage tank 32.2.
  • the liquid of the two temporary storage tanks is led to the gas-liquid separator 8 with air bubbles through the pump 23.7 and the pipeline, and the metal copper 31 is stored in the gas-liquid separator 8; this method is to make full use of the sulfuric acid in the anode plating solution. and oxygen to participate in the chemical reaction of copper metal to obtain copper sulfate solution.
  • the anodic plating solution is chemically reacted in the gas-liquid separator 8, and the gas is released in the gas-liquid separator 8 and then drained to the liquid spray pipe 10 of each anode box 13 through the pump 23.8 and the liquid return circulation pipeline 9, and the liquid is discharged.
  • the pump flows into the anode box 13 .
  • Each anode box 13 is provided with liquid injection pipes 14 on the periphery of the outer side facing the cathode plating member 4 .
  • This embodiment adopts the same anode assembly as in Embodiment 6, including an insoluble anode 1, a conductor 17, a setting frame 16, and a back-pulse protection screen 15.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder circuit is set therefrom.
  • the structure is shown in Figure F, and the anode assembly is installed in the anode box 13, as shown in Figure J.
  • the insoluble anode 1 and the electroplating power source 19 are connected positively.
  • the cathode plating member 4 is a flat copper plate with a plurality of small holes, is arranged in the cathode plating tank area, and is connected to the negative electrode of the electroplating power source 19 during the electroplating process.
  • the liquid near the insoluble anode in the anode box is powered to generate a liquid flow away from the cathode and through the anode pores, so that the oxygen bubbles generated on the anode surface are sent to the two temporary storage tanks with the liquid flow. Then it is pumped into the gas-liquid separator to participate in the chemical reaction of copper metal. In the gas-liquid separator the solution after releasing the gas is pumped back into the individual anode boxes again.
  • the reverse pulse protection screen can reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode when the electrode is turned, and prevent the coating of the insoluble anode from falling off.
  • the liquid spray tube outside the anode box sprays the electroplating solution to the cathode plating piece through the pump, so that the electroplating solution pours into the inside of the small hole of the cathode plating piece, so that the plating solution inside the pores is replenished and updated, and the plating solution is also stirred.
  • the cathode plating parts can be moved in parallel in one direction or in two directions in parallel to obtain a more uniform coating.
  • the anode box with the electroplating tank separator prevents the electroplating catholyte from entering the anode plating tank area, which can effectively reduce the loss of electroplating additives and facilitate the collection of the anodic plating solution with bubbles in the anode box for the copper participating in the temporary storage tank.
  • Metal chemical reaction to produce more copper sulfate solution can effectively reduce the loss of electroplating additives and facilitate the collection of the anodic plating solution with bubbles in the anode box for the copper participating in the temporary storage tank.
  • the optimized device for insoluble anodic acid sulfate copper electroplating in this embodiment includes an electroplating tank 5 , an anode box 13 , a cathode plating piece 4 , a gas-liquid separator 8 , and two reverse pulse electroplating power sources 19 ,in:
  • the electroplating tank 5 is provided with six anode boxes 13, and the side of the anode box 13 facing the cathode plating piece is an electroplating tank partition 11, and the electroplating tank partition 11 is a combination of a bipolar membrane and a filter cloth; the inner space of the anode box 13 It is an anode plating tank area, and the space other than the anode box 13 in the plating tank 5 is a cathode plating tank area.
  • the cathode electroplating tank area is provided with a detection device 21.
  • the detection device 21 includes a liquid level gauge, a hydrometer and an acidity meter.
  • the detection device 21 is connected to the automatic detection and feeding controller 34. The data is used to control and alarm the electroplating current control and bath parameters in the process.
  • each anode box 13 is respectively connected with a liquid suction pipe 2 and has a liquid spray port 10 therein.
  • the nozzle is located on the side of the insoluble anode 1 facing away from the cathode plating member 4
  • the liquid spray port 10 is located on the side of the insoluble anode 1 facing the cathode plating member 4 .
  • the suction pipes 2 are all connected to the gas-liquid separator 8 through pipes, and the overflowing liquid is drained into them for release gas separation.
  • the degassed liquid in the gas-liquid separator 8 flows back into the circulation pipe 9 through the solid-liquid separation filter 33 using the pump 23.1.
  • the gas-treated liquid is returned to the anode box 13 .
  • a liquid injection pipe 14 is installed on the periphery of the anode box 13 facing the cathode plating part 4.
  • the liquid injection pipe 14 is connected to the cathode plating tank area through a pipeline and a pump 23.2.
  • the injection action of the liquid injection pipe 14 is automatically detected and fed.
  • the setting program of the controller 34 performs the operation of spraying the liquid toward the cathode plating material 4 .
  • the same anode assembly as in Embodiment 3 is used, including an insoluble anode 1, a shaping frame 16, and a back-pulse protection screen 15.
  • the upper part of the insoluble anode 1 is provided with a feeder installation hole, and a feeder line is inserted through it for structural improvement.
  • the anode assembly is installed in the anode box 13, as shown in 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 tank area.
  • the titanium base material of the insoluble anode 1 is respectively connected to the positive poles of the two reverse pulse electroplating power sources 19 arranged correspondingly, and the four cathode plating pieces 4 are commonly connected to the cathodes of the two reverse pulse electroplating power sources.
  • the liquid near the insoluble anode in the anode box generates a liquid flow away from the cathode and through the pores of the anode through the use of power to spray the solution from the liquid nozzle, so that the oxygen bubbles generated on the anode surface are sent to the anode with the liquid flow.
  • the gas is discharged and released in the gas-liquid separator, and the liquid after the gas is released is returned to each anode box of the electroplating tank again.
  • the reverse pulse protection screen can reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode when the pole is turned, and prevent the coating of the insoluble anode from falling off.
  • the liquid spray tube outside the anode box sprays the electroplating solution to the cathode plating piece through the pump, so that the electroplating solution pours into the inside of the small hole of the cathode plating piece, so that the plating solution inside the hole is replenished and renewed.
  • the cathode plating parts move in parallel in one or two directions in the electroplating tank, and according to the quality requirements of the cathode electroplating process, the respective output current values of the electroplating power sources are adjusted to obtain better cathode plating.
  • multiple anode box designs with plating tank dividers can effectively reduce the loss of plating additives.
  • FIG. 16 it is a basic embodiment of an optimized device for insoluble anodic acid sulfate copper electroplating according to the present invention, which includes an electroplating tank 5, an insoluble anode 1, a liquid pipette 2, a cathode plating member 4, and an electroplating power source 6, wherein:
  • a liquid suction pipe 2 is arranged in the electroplating tank 5, and the liquid suction pipe 2 is located on the side of the insoluble anode 1 facing away from the cathode plating member 4, and the insoluble anode 1 is a titanium mesh covered with a coating.
  • the structure of the insoluble anode 1 is shown in Figure A, which is a titanium material covered with a coating, and the structure is a plate with hollow through holes, and the feeder installation hole on the upper part of the anode plate is set into the feeder line as a structure. Improve.
  • the positive and negative electrodes of the electroplating power source 6 are respectively connected to the insoluble anode 1 and the cathode plating member 4 during the electroplating process.
  • the cathode plating member 4 is a flat copper plate.
  • the optimized device for insoluble anodic acid sulfate copper electroplating of the present embodiment is different from the device of embodiment 1 in that:
  • the insoluble anode 1 is a titanium material coated with a coating, and the structure is a plate with hollow through holes.
  • a shaping frame 16 is welded around the four sides, and the shaping frame 16 is a non-conductive material; on the insoluble anode 1 Discharge spikes are installed in the sizing frame 16 as a back-pulse protection screen 15, and the feeder line is set into the feeder line from the feeder installation hole on the upper part of the anode plate for structural improvement.
  • the positive and negative electrodes of the reverse pulse electroplating power source 19 are respectively connected to the insoluble anode 1 and the cathode plating member 4 during the electroplating process.
  • the cathode plating member 4 is a flat copper plate.
  • FIG. 14 it is a prior art device for electroplating copper with insoluble anodic acid sulfate, which includes an electroplating tank 5 , an insoluble anode 1 , a cathode plating member 4 , and a reverse pulse electroplating power source 19 .
  • the electrolytic cell 5 is equipped with an insoluble anode 14 and a cathode plating member 4 .
  • the insoluble anode 1 is a titanium material covered with a coating
  • the cathode plating member 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 electroplating power source 19 , and the cathode plating member 4 is connected to the negative electrode of the power source 19 .
  • FIG. 15 it is an insoluble anodic acid copper electroplating device according to the prior art comparative example of the present invention.
  • the difference from the device of Comparative Example 1 is that it also includes a plating tank partition 11 , a stirring device 24 , and a titanium basket 39 .
  • the electrolytic cell 5 is equipped with a titanium basket 39, the titanium basket is equipped with an insoluble anode 1, the titanium basket 39 is surrounded by a neutral filter membrane 11, and the inner space surrounded by the titanium basket 39 and the neutral filter membrane 11 is an anode plating tank area, The remaining space in the electroplating tank is a cathode electroplating tank area; a stirring device 24 and a cathode plating member 4 are also installed in the electroplating tank 5 .
  • the insoluble anode 1 is a titanium material covered with a coating
  • the cathode plating member 4 is a flat copper plate with a plurality of small holes.
  • the insoluble anode 1 and the titanium basket 39 are connected to the positive electrode of the reverse pulse electroplating power source 19 , and the cathode plating member 4 is connected to the negative electrode of the reverse pulse power source 19 .
  • the stirring device 24 was turned on, and the reverse pulse electroplating power supply 19 was turned on to carry out the electroplating operation, and the results were recorded in Table-1.
  • the electroplating current is 2A/dm 2 ;
  • the forward current is 2A/dm 2
  • the reverse pulse current is 6A/dm 2
  • the time ratio of forward current and reverse pulse current is 20:1;
  • the electroplating time is 40 minutes and the temperature is 30°C;
  • 4 The acid copper plating solution includes:
  • Gaoli brand copper plating additive 9mg/L Commercially available Gaoli brand copper plating additive 9mg/L.
  • the cathodic plated parts that have undergone the electroplating operation are sliced and polished from top to bottom at three even positions, and the sliced coating is observed and thickness measured with a microscope; for the cathodic plated parts with small holes, It is also necessary to observe the state of the hole and the copper plating; the measured results and the conclusions drawn are shown in Table-1.
  • the COD value of the electroplating solution or the cathodic electroplating solution is detected by the national standard COD detection method before and after the electroplating operation, respectively, and the consumption of the electroplating brightener is evaluated by the difference in the COD value of the electroplating solution or electroplating catholyte solution before and after electroplating. ;
  • the conclusions drawn are shown in Table-2.
  • the plating layer obtained by the process of the present invention is more uniform and flat, and the penetration quality of the through hole is higher. It is illustrated that the invention can effectively improve the electroplating quality after improving the gas evolution insoluble anodic copper electroplating process and meet the requirements of the electroplating industry for high-quality products.
  • Example 15 of the present invention which also use the reverse pulse electroplating power supply, and the prior art comparative examples 1 to 2 are compared:
  • the insoluble anodes of Examples 4 to 10, Examples 12 to 13, and Example 15 of the present invention are all provided with a reverse pulse protection screen.
  • the layers were all intact and did not fall off.
  • Example 15 of the present invention lacked a bypass design, so after the electroplating operation was completed, the upper part of the insoluble anode coating slightly fell off after light brushing; while the insoluble anodes of Comparative Examples 1 to 2 had no reverse pulse protection screen.
  • the insoluble anode of the present invention can effectively reduce the electrochemical hydrogen evolution reaction on the surface of the insoluble anode coating when the reverse pulse protection screen is provided, thereby prolonging the service life of the insoluble anode.
  • Example 9 and Example 10 the difference between the COD values of the cathodic electroplating solutions measured before and after the electroplating operation is no more than 80 mg/L, which proves that the loss of electroplating additives is small.
  • Comparative Example 1, Example 1 and Example 4 the COD values of the electroplating solutions measured before and after the electroplating operation were all different by more than 200 mg/L, indicating that the loss of electroplating additives was large. Therefore, it can be proved that the electroplating tank separator of the present invention can effectively save the materials used for electroplating additives.
  • Comparative Example 1 is most similar to the basic settings of Examples 9 and 10 of the present invention. However, Example 9 and Example 10 are better than Comparative Example 1 in terms of coating uniformity, small hole plating through, anode coating state, and consumption of electroplating additives.

Abstract

本发明公开一种不溶性阳极酸性硫酸盐电镀铜的优化工艺，包括电镀槽、电镀电源、不溶性阳极以及以镀件为阴极，以酸性硫酸盐镀铜电镀液作为电镀液，其特征在于：采用材质为覆有涂层的钛材、且形状为网状或者带镂空结构的板状作为不溶性阳极，并在不溶性阳极背向阴极的那一面增设至少一个吸液管/口，以使电镀液通过吸液管/口的溢流或/和电动吸液方式产生液流；接通电镀电源进行电镀生产作业，同时通过吸液管/口的溢流或/和采用动力的方式吸走电镀液，使电镀槽中的电镀液形成流向吸液管/口的液流，相应地再添加电镀液进入电镀槽中以维持电镀槽内的电镀液体量，直到完成电镀将镀件取出。该工艺能有效提高电镀金属铜层的均匀性，提高电镀质量。

Description

不溶性阳极酸性硫酸盐电镀铜的优化工艺及装置 技术领域
本发明属于电镀铜工艺领域，具体涉及不溶性阳极酸性硫酸盐电镀铜的优化工艺和装置。
背景技术
电镀铜是电镀工业中最常见的工序之一。通常而言，若要在多种类的金属件其表面镀上镍、金、银、锡金属层，都需要先预镀上一中间铜层以改善其外表镀层的结合力；此外，线路板行业在生产制程中也常见到铜金属电镀工序。
现有的酸性硫酸盐电镀铜工艺是以硫酸和硫酸铜为其电镀液主成分的电镀工艺，其可以根据可溶性阳极和不溶性阳极分为两种不同的工艺。可溶性阳极电镀铜工艺采用磷铜作为可溶性阳极材料；而不溶性阳极电镀铜工艺则指在电镀反应过程中阳极不发生或发生极少量溶解的电镀工艺,，即采用不溶性阳极材料，现有技术中普遍采用不溶性钛基涂层阳极。
两种酸性硫酸盐电镀铜工艺的阳极电化学反应式如下：
(1)可溶性阳极电镀铜工艺
Cu-2e -→Cu 2+
(2)不溶性阳极电镀铜工艺
Figure PCTCN2021142832-appb-000001
与可溶性阳极电镀铜工艺相比，不溶性阳极电镀铜工艺在阳极上发生水的电解反应生成氢离子和氧气，电镀液中的铜离子在阴极处被还原成金属铜，由于在电镀过程中有较稳定的阳极外形尺寸和可控、稳定的电镀液成分状态，使得在阴极镀件电镀出更加均匀平整密致的铜金属镀层；而且除了直流电镀以外不溶性阳极电镀铜工艺也能适用于脉冲电镀，还能够通过增加阳极电流密度使生产效率得到大幅提高。
与此同时，由于近年科技发展已全面步入5G电气通信，市场对精密线路板的需求越来越大，其中对多层线路板中镀铜通孔的纵横比值(即通孔的孔长与孔径的比值)的要求也日益提高，因此，目前线路板加工生产中已开始推广不溶性阳极电镀铜工艺，以提升线路板产品电镀铜的生产质量和生产效率。
对于镀铜通孔其纵横比值较大的线路板进行双面电镀时，现有的不溶性阳极电镀铜工艺中利用电源的反脉冲使阴极镀件转作电解阳极溶铜反应；如此不仅能实现优化镀层的均匀性和平整性、改善镀液分散能力和提高镀层结合力，而且还能使具有通孔的镀铜层得到良好的贯通效果。
然而，现有的不溶性阳极电镀铜工艺中仍存有下列缺点：
1.电镀过程中阳极上产生氧气泡，该气泡会分布于阳极和阴极镀件之间，从而形成阻碍电镀电流的屏障，影响放电的均匀性，从而降低镀层的均匀性。同时，常规采用垂直电镀工艺时电镀过程中产生的氧气泡会在阳极表面从下至上形成一定梯度的气泡层而进一步导致电流分布不均，因此严重影响垂直电镀的镀件质量。
针对上述垂直电镀的问题，现有技术的解决方法是采用水平电镀的方式，使得最大限度地降低气泡层阻碍屏障所带来的影响，但是水平电镀设备结构更为复杂，电镀槽内空间很局限，因此镀件通常只能是薄板，不能满足不同外形尺寸产品的电镀铜生产。
2.在反脉冲电镀过程中，当原来的不溶性阳极在反向脉冲的作用下转变为阴极时，不溶性阳极所发生的极性转变会令其表面出现析氢反应，使得不溶性钛基涂层阳极的钛基材表面的氧化钛变为氢化钛，导致不溶性阳极的涂层脱落造成阳极损坏。
3.现有的不溶性阳极电镀铜工艺中，镀液里通常需要加入有机的电镀添加剂，即光亮添加剂，来使镀件获得更为平整光洁的镀层。而由于不溶性阳极电镀铜工艺中所使用的阳极其表面涂覆有贵金属涂层，所述涂层对电镀添加剂的分解反应具有催化作用，能够直接对镀液中的电镀添加剂进行分解。另外，不溶性阳极进行酸性镀铜作业时，一些新生的氧化剂会加速对电镀添加剂的分解破坏。所以，在电镀铜工艺中使用现有的不溶性阳极，其电镀添加剂的消耗量远远大于可溶性阳极电镀铜工艺中的正常用量。电镀添加剂被额外地消耗导致生产增加成本。
综上所述，尽管在电镀铜工艺中不溶性阳极与可溶性阳极相比，有镀层平整和效率高的优势，但仍有必要进行工艺优化。
发明内容
本发明的第一个目的在于提供一种不溶性阳极酸性硫酸盐电镀铜的优化工艺，该工艺能有效提高镀件上电镀金属铜层的均匀性，提高电镀质量。
本发明的第二个目的在于提供一种不溶性阳极酸性硫酸盐电镀铜的优化装置。
本发明的第一个目的通过以下技术方案实现：
一种不溶性阳极酸性硫酸盐电镀铜的优化工艺，包括电镀槽、电镀电源、不溶性阳极以及以镀件为阴极，以酸性硫酸盐镀铜电镀液作为电镀液，其特征在于：
(1)采用材质为覆有涂层的钛材、且形状为网状或者带镂空结构的板状作为不溶性阳极，然后将所述不溶性阳极和所述阴极安装在电镀槽中；并在所述不溶性阳极背向阴极的那一面增设至少一个吸液管/口，以使电镀液通过该吸液管/口的溢流或/和电动吸液方式产生液流；
(2)接通电镀电源进行电镀生产作业，同时，通过所述吸液管/口的溢流或/和采用动力的方式吸走电镀液，使电镀槽中的电镀液形成流向吸液管/口的液流，相应地，再添加电镀液进入电镀槽中以维持电镀槽内的电镀液体量，直到完成电镀将镀件取出。
本发明所述的不溶性阳极采用网状或者带镂空的板状结构，使其具备两面贯通的孔隙，与所述设置在阳极背向阴极方向的那一面的至少一个吸液管/口相配合，通过溢流和/或采用动力的方式令不溶性阳极附近的液体产生远离阴极并穿过阳极孔隙的液流，从而使得电镀过程中阳极表面产生的氧气泡能随液流穿过不溶性阳极的网孔或镂空结构所形成的孔隙，被带离阳极与阴极镀件之间的区域作外排释放，这样有助于减少电镀过程中氧气在阳极面向阴极那一面的表面聚积而形成氧气泡屏蔽层，从而提高镀件的电镀均匀性和电镀效率。
优选地，所述吸液管/口采用动力使不溶性阳极附近的液体产生远离阴极并穿过阳极孔隙的液流，所述的动力为加压引流和/或负压吸液的泵浦。
本发明所述的再添加电镀液进入电镀槽中以维持电镀槽内的电镀液体量，可以是另外添加新的电镀液或者电镀补液，也可以是采用回流系统。
本发明采用的回流系统主要由泵浦和连接管道组成，其一端连接吸液管/口，另一端连通电镀槽，利用该回流系统使由吸液管/口吸走的电镀液再回流入电镀槽中，形成电镀槽内的电镀液流向阳极处的吸液管/口的液流，循环往复。所述回流系统可以在上述吸液管/口采用泵浦使不溶性阳极附近的液体产生远离阴极并穿过阳极孔隙的液流的基础上加上连接管道连通电镀槽而构成。
本发明的方法既适用于垂直电镀，也适用于水平电镀；既能与普通的直流电源配合使用，也能与反脉冲电源匹配使用。特别是将本发明的方法应用于垂直电镀时，能有效地解决现有工艺中氧气泡在阳极面向阴极的那一面的表面上形成电流阻碍屏蔽层的工艺问题，使不溶性阳极在结构简单容易维护的垂直电面镀设备中也能实现良好的 电镀效果。
本发明可以做以下改进：
在所述不溶性阳极面向阴极的那一面增设至少一个喷液管/口，该喷液管/口与外接的喷液管路相连，用以朝向阳极喷液，与所述的吸液管/口配合，在不溶性阳极附近产生更稳定可控的远离阴极的液流，从而更好地令电镀过程中阳极上产生的气泡顺利穿过不溶性阳极的孔隙离开阳极与阴极镀件之间的区域，所述喷液管路为另一端连通装有电镀液的容器的具有泵浦的管路，为喷液管/口喷液提供源源不断的电镀液。
优选地，所述的喷液管/口设置在所述不溶性阳极面向阴极的那一面的电镀槽底部，从而使所述喷液管/口和所述的吸液管/口配合产生从下而上的液流，令阳极上产生的气泡尽快通过不溶性阳极的孔隙被吸走远离阴极，同时避免阳极与阴极镀件之间区域的电镀液产生涡流而影响电镀液的电流分布。
本发明还可以采用对所述的不溶性阳极进行馈电结构改进，优选从不溶性阳极的水平两旁边设入馈电线路，减少不溶性阳极的上部和下部的电流密度差，使析气电极与阴极区域间的气液混合液的电导率趋向均匀一致。这克服了从上馈电方式因阳极上部电流密度较下部大而令电析气泡更加集中于阳极上部，导致电镀液的电镀电流分布极不均匀的缺点。
本发明还可以进一步在回流管系中增设气液分离器，使所述的吸液管通过连接管道将从电镀槽吸出的气液混合物流体排入到气液分离器中。所述的气液分离器是将电镀过程中阳极上产生的氧气泡连同电镀液一起被引流到较大的空间，令液体流速减慢致使其中气体逸出的装置。所述气液混合物在气液分离器中作分离释放气体后其液体再次被引回流到所述电镀槽中作循环流动。
优选地，对所述气液分离器中所析出的氧气收集再利用。
本发明还可以将所述电镀槽用电镀槽分隔物将其分隔开为阳极电镀槽区和阴极电镀槽区两个区域，在所述二电镀槽区中的电镀液可以是相同的，也可以是不同的。即所述阳极电镀槽区中的电镀液为阳极电镀液，具体为含有无机酸和/或无机盐的水溶液，或者采用酸性硫酸盐镀铜电镀液；所述阴极电镀槽区中的电镀液为酸性硫酸盐镀铜电镀液。电镀过程中，所述不溶性阳极和阴极镀件分别隔离置于所述阳极电镀槽区和阴极电镀槽区中。在此优选方案中，由于气泡仅存在于两极之间的阳极槽区范围内，本发明所述的吸液管/口设置在阳极电镀槽区内，仅在阳极槽区内产生远离阴极并穿过阳极孔隙的液流。若进一步在所述不溶性阳极面向阴极的那一面设置喷液管/口 时，所述喷液管/口也位于阳极电镀槽区内。
所述的电镀槽分隔物作用在于对阳极上所生成的氧气和羟基自由基与阴极镀件附近区域的电镀液进行分隔，以减少氧气和羟基自由基进入阴极镀件附近的酸性镀铜电镀液中与电镀添加剂发生化学反应的机会，从而降低酸性镀铜电镀液中电镀添加剂的额外损耗。同时，也有利于实现电镀过程中阳极表面所产生的氧气得到集中抽排。
优选地，所述的电镀槽分隔物选自阳离子交换膜、阴离子交换膜、双极膜、反渗透膜、滤布、超滤膜、陶瓷滤板和PE滤板中的至少一种。
当所述的电镀槽分隔物单独选用阳离子交换膜时，随着电化学反应的进行，所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的铜离子在阴极镀件表面被还原为金属铜，同时所述阳极电镀槽区中的电镀液中的阳离子会通过所述电镀槽分隔物进入到所述阴极电镀槽区中。
当所述的电镀槽分隔物单独选用阴离子交换膜时，随着电化学反应的进行，所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的铜离子在阴极镀件表面被还原为金属铜，同时所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的阴离子会通过所述电镀槽分隔物进入到所述阳极电镀槽区中。
当所述的电镀槽分隔物单独选用超滤膜和/或陶瓷滤板和/或PE滤板和/或滤布时，随着电化学反应的进行，所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的铜离子在阴极镀件表面被还原为金属铜，同时所述阳极电镀槽区中的电镀液中的部分阳离子会通过所述电镀槽分隔物的小孔进入到所述阴极电镀槽区中，所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的部分阴离子也会通过所述电镀槽分隔物的小孔进入到所述阳极电镀槽区中。
当所述的电镀槽分隔物单独选用双极膜时，随着电化学反应的进行，所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的铜离子在阴极镀件表面被还原为金属铜，同时所述的双极膜内部发生水的电解反应生成氢离子并进入到所述阴极电镀槽区中。
当所述的电镀槽分隔物单独选用反渗透膜时，随着电化学反应的进行，所述阴极电镀槽区中酸性硫酸盐镀铜电镀液的铜离子在阴极镀件表面被还原为金属铜。若所述阳极电镀槽区中电镀液存在有氢离子，所述氢离子也会通过所述电镀槽分隔物进入到所述阴极电镀槽区中。
优选地，所述的阳极电镀液为硫酸和/或硫酸铜的溶液。更优选地，所述的阳极电镀液为硫酸溶液。
本发明若在回流管系中增设气液分离器时，所述的吸液管/口通过连接管道将从阳极电镀槽区吸出的气液混合物流体排入到气液分离器中，所述气液混合物在气液分离器中作分离释放气体后，其液体再次被引回流到所述阳极电镀槽区中作循环流动。
作为本发明一种改进的实施方式，所述阳极电镀槽区采用阳极盒的形式并安装在所述的电镀槽中以对阳极电镀槽区和阴极电镀槽区作分隔，其具体为：所述阳极盒为立方体型盒状，不溶性阳极位于阳极盒中，所述阳极盒面朝向阴极镀件的那一面为电镀槽分隔物，所述阳极盒的内部空间为阳极电镀槽区，所述电镀槽中、阳极盒以外的空间为阴极电镀槽区。在此优选方案中，本发明所述的吸液管/口设置在所述阳极盒上，具体位于阳极盒内所述不溶性阳极背向阴极的那一面的空间位置或者盒壁上；另外，所述阳极盒内还可以设置有喷液管/口，具体位于阳极盒内所述不溶性阳极面向阴极那一面与相邻盒壁之间的区域中。优选地，所述阳极盒内喷液管/口喷出的液体取自于所述气液分离器中的液体。
优选地，在所述阳极盒朝向阴极那一面外的四周边沿装设有液体喷射管，用于向阴极喷射电镀液，从而使电镀液能够涌入阴极镀件的孔隙深处，令孔隙内部的电镀液能得到补充更新，以此提高镀件的孔隙深处的电镀质量。
更优选地，当设置有多个阳极盒时，所述阳极盒外的液体喷射管的喷射动作根据时间和/或流量进行程序控制，利用时间差和/或流量差来避免阴极镀件两侧阳极盒双方同时喷射的液流相互对射冲撞，从而实现镀液灌孔效果的最优化。
本发明还可以在所述的不溶性阳极上设有反脉冲保护屏网，所述反脉冲保护屏网为设置在阳极面向阴极那一面上的无涂层钛材凸起物或凸起的网状物、条状物等任意有利于放电的电极结构形式，且与不溶性阳极的钛基材直接连接。所述凸起物的形状可以是凸点状、尖刺状、竖条状；所述的凸起的网状物和条状物则可以是在阳极面向阴极那一面上伸向阴极方向的支持脚端固定的网状物或者条状物，或者是与上述任意凸起物上部相互连接形成的网状物或者条状物，所述网状物或条状物构成的平面与阳极面平行或者基本平行。
上述这种对不溶性阳极的结构有针对性地进行改造，在采用反脉冲电源作电镀工艺时，更能有效地发挥本发明所述不溶性阳极的工艺质量优势。所述的反脉冲保护屏网在反脉冲电解过程中对不溶性阳极起保护作用，其原理是利用钛在电解质水溶液电化学反应中具有单向导电的阀值金属特性，即利用所述的反脉冲保护屏网裸露的钛金属作为阳极进行电解质水溶液的电化学反应时，其表面会有氧化层生成而难以参与电 化学反应，但作为阴极进行电化学反应时却能正常参与放电的特性，使得设置有所述反脉冲保护屏网的不溶性阳极作为阳极进行电镀电化学反应时，所述的反脉冲保护屏网几乎不参加反应，而是由所述覆有涂层的钛材阳极本体进行主要的电镀的电化学反应；但当电源反脉冲换极相后，原镀件转作阳极电解溶铜时，所述的不溶性阳极转作为阴极时，则所述反脉冲保护屏网参与电化学反应进行放电。由于所述反脉冲保护屏网从不溶性阳极表面凸出而在距离上更加接近阴极镀件，所以根据电场电位差原理，其更加能有效地吸引电镀电流并使主电流通过反脉冲保护屏网后再从所述不溶性阳极里的钛基材中导流。析氢反应会直接在所述反脉冲保护屏网上发生，而非如现有技术主要发生在不溶性阳极涂层的表面。因此所述的反脉冲保护屏网能有效地减少不溶性阳极涂层表面的电化学析氢反应，从而有效地延长不溶性阳极的使用寿命。当所述的反脉冲保护屏网为凸起物时，所述凸起物的数量越多、分布越均匀，对所述不溶性阳极涂层的保护效果越好。
本发明还可以进一步在所述的不溶性阳极的边沿增设定型框，所述不溶性阳极连接上所述定型框有助于增强其平直机械刚性，减少因阳极变型带来的放电不均匀的影响。所述定型框的厚度大于所述不溶性阳极厚度和/或其宽度大于所述不溶性阳极无孔隙部位的宽度和/或其机械刚性高于所述不溶性阳极的机械刚性和/或通过稳定结构来加强所述不溶性阳极的机械刚性。
所述的定型框可以采用任意具有阳性不溶性、耐热耐酸且刚性较强的材料。
当本发明所述的不溶性阳极设置有反脉冲保护屏网且所述的定型框为裸露钛材或者覆有涂层的钛材时，所述的反脉冲保护屏网除了与不溶性阳极的钛基材直接连接的方案外，也可以单独与所述定型框的钛材连接，或者同时与两者连接。由于导电体越粗电阻越小，使得此优选方案中的定型框除了在电镀时能使不溶性阳极的整体电流作合理的电流分布之外，还能在反脉冲电解过程中将主电流接引入定型框中作旁路引走，进一步保护不溶性阳极的表面涂层。
优选地，所述的定型框选用导电材料，且所述定型框通过所述不溶性阳极的钛基材与电镀电源的正极相连接，或同时与所述不溶性阳极的钛基材和电镀电源的正极相连接，或与反脉冲电镀电源的正极相连接。
更优选地，所述的定型框选用裸露钛材，且所述定型框通过所述不溶性阳极的钛基材与电镀电源的正极连接，或同时与所述不溶性阳极的钛基材和电镀电源的正极相连接，或与反脉冲电镀电源的正极相连接，能够结合不溶性阳极作馈电结构的改进。
本发明可以作以下改进：电镀过程中根据对电镀液的成分浓度的分析结果向电镀槽中加投补充液或者电镀原料，以维持电镀液中各成分比例的稳定。
本发明可以作以下改进：所述的电镀槽可以直接或者通过中转槽与电镀液再生装置相连接，形成按工艺设置的可控循环回用系统，作电镀铜源补充，这有助于实现绿色清洁生产和降低生产成本。
本发明可以作以下改进：所述不溶性阳极背向阴极的那一面连接有与电镀电源正极连通的导电体，利用导电体的旁路电流来增加不溶性阳极电镀时放电的均匀性，从而提高镀件的电镀质量。所述的导电体可以是导电板或者导电网，同时所述导电板或者导电网与所述定型框相连接，能使该不溶性阳极在电镀时放电更为均匀。
优选地，所述导电板为无涂层的带网状或者镂空结构的钛板，或者所述导电网为无涂层的钛网。
本发明还可以进一步改为将所述的反脉冲保护屏网设置在所述的导电体上，然后将反脉冲保护屏网穿过不溶性阳极的网孔或镂空结构伸出不溶性阳极表面朝向阴极。其中具体有以下两种连接方式：
⑴所述的反脉冲保护屏网在穿过不溶性阳极时与阳极的钛基材焊接相连，在电镀时能使反脉冲电流通过凸出的部分分别沿导电体和不溶性阳极的钛基材分流，以减少在不溶性阳极上发生析氢现象。
⑵所述的反脉冲保护屏网在穿过不溶性阳极时不作导电连接，在反脉冲电镀时更能减少通过所述不溶性阳极的电流，从而进一步减少其析氢现象。
优选地，所述反脉冲保护屏网与所述不溶性阳极不作导电连接，且所述不溶性阳极和/或定型框与所述导电板或者导电网之间使用钛板或钛网作焊接相连。
更优选地，所述定型框与导电板或者导电网之间使用钛板或钛网作四周封边相焊连接。这样既能使电镀时所述不溶性阳极放出电流更为均匀，并且在反脉冲的工作期间当不溶性阳极转变为阴极时，其主电流通过反脉冲保护网、定型框和/或导电板(网)的旁路分流，使进一步减少所述不溶性阳极的析氢反应。
本发明可以作以下改进，当不溶性阳极带有所述反脉冲保护屏网、定型框和导电板或导电网时，在所述导电板或导电网背向阴极的方向的那一面安装至少一个吸液管/口；而且所述不溶性阳极与导电板或导电网通过钛板材质的定型框作两者之间的密封边连接，使喷液管/口的主液流携带着阳极所析气泡能集中通过不溶性阳极上的通孔及其背后的导电板或导电网上的通孔，被推引到吸液管/口中吸引流出。
优选地，将带有所述反脉冲保护网、定型框、导电体的不溶性阳极和吸液管/口、喷液管/口的不溶性阳极组件安装在所述的阳极盒中作为阳极槽区盒式总成。
本发明可以作以下改进：当阴极镀件需要在多个方向进行电镀或者其在不同方向表面的电镀面积不等时，可采用一个电源接上两个或两个以上的不溶性阳极，并合理分布在镀件周边的位置上作电镀的电化学反应；也可以选用两个或多个电源以及多个不溶性阳极在合理位置的布置下共接阴极镀件作电镀；还也可以根据要求的电化学反应量设置两个或两个以上的电镀电源及各电源各自连接上一个或一个以上的所述不溶性阳极，在共接阴极电镀工件进行电镀的情况下，根据镀件不同方向的电镀表面积和工艺要求对各电镀电源输出的电流强度大小进行精确调节，以提高镀件的电镀质量。
本发明的第二个目的通过以下技术方案实现：
一种不溶性阳极酸性硫酸盐电镀铜的优化装置，包括电镀槽、不溶性阳极、作为镀件的阴极、电镀电源，其特征在于：所述的电镀槽内还设置有至少一个吸液管/口，所述吸液管/口位于所述不溶性阳极背向阴极的那一面，用于使电镀液通过该吸液管/口的溢流或/和电动吸液方式在电镀槽内产生液流；
所述的不溶性阳极为覆有涂层的钛材，其形状为网状或者带镂空结构的板状；
所述的电镀电源的正极和负极在电镀过程中分别与所述的不溶性阳极和作为阴极的镀件连接。
本发明可以作以下改进：本发明的装置采用回流系统，其主要由动力源和连接管道组成，其一端连接吸液管/口，另一端连通电镀槽，利用该回流系统使由吸液管/口吸走的电镀液再回流入电镀槽中，形成电镀槽内的电镀液流向阳极处的吸液管/口的液流，循环往复。所述回流系统可以在上述吸液管/口采用动力使不溶性阳极附近的液体产生远离阴极并穿过阳极孔隙的液流的基础上加上连接管道连通电镀槽而构成。
本发明可以作以下改进：所述的电镀槽内设置有至少一个喷液管/口，所述喷液管/口设置在所述不溶性阳极面向阴极的那一面的两电极之间的区域空间内，该喷液管/口外接一喷液管路，用于向阳极喷液，与所述的吸液管/口配合，在不溶性阳极附近产生更稳定可控的远离阴极的液流，所述喷液管路为另一端连通装有电镀液的容器的具有泵浦的管路，也可以直接与上述连接吸液管/口的回流系统连接，为喷液管/口喷液提供源源不断的电镀液。
优选地，所述喷液管/口安装在所述不溶性阳极面向阴极的那一面的电镀槽底部并向着所述不溶性阳极作喷液。
本发明可以作以下改进：所述的吸液管/口通过连接管道与气液分离器相连接，所述的气液分离器是一个较大的容器装置，当将电镀过程中阳极上产生的氧气泡连同电镀液一起引流到气液分离器后，利用其较大的空间令液体流速减慢致使其中气体逸出。所述气液分离器还可以再通过泵浦和连接管道与电镀槽连通构成回流系统，将释放气体处理后的液体排回到电镀槽中作循环流动。
本发明可以作以下改进：在所述的电镀槽中设置电镀槽分隔物，将电镀槽分隔开为阳极电镀槽区和阴极电镀槽区。
优选地，所述阳极电镀槽区和阴极电镀槽区的分隔采用在电镀槽中安装阳极盒的方式来进行分隔：所述阳极盒为立方体型盒状，不溶性阳极位于阳极盒中，所述阳极盒面朝向阴极镀件的那一面为电镀槽分隔物，所述阳极盒的内部空间为阳极电镀槽区，所述电镀槽中除阳极盒以外的其余空间为阴极电镀槽区。所述的吸液管/口设置在所述阳极盒上，具体位于阳极盒相对所述不溶性阳极背向阴极的那一面的空间或盒壁上；另外，所述阳极盒内还可以设置有喷液管/口，具体位于阳极盒内所述不溶性阳极面向阴极的那一面与相邻盒壁之间的区域中。
优选地，所述气液分离器的出液口与所述喷液管路和喷液管/口连接，即所述气液分离器与喷液管/口的连接管道上安装泵浦，使所述回流管道与喷液管路合二为一，使阳极电镀液受泵浦的推动作用力带着气泡穿透不溶性阳极的结构孔隙通过吸液管/口快速地引流到气液分离器中作气液分离。
本发明可以作以下改进：所述的阳极盒朝向阴极镀件的那一面的外侧面边沿四周装设有液体喷射管，并且各液体喷射管中装置有流量调节器，以便作向阴极电镀液的喷射效果的调节。
更优选地，还可以在一个电镀槽中设置多个阳极盒，在所述阳极盒外设置的液体喷射管的喷射动作可以通过程序进行控制，以避免阳极盒上安装的喷射管在动作期间的喷射液体对冲而不能实现灌孔最优化。
本发明所述的不溶性阳极上还可以设有反脉冲保护屏网，所述反脉冲保护屏网是设置在不溶性阳极面向阴极镀件的那一面上的无涂层钛材凸起物，所述凸起物与不溶性阳极的钛基材直接连接，其形状可以是凸点状，尖刺状，竖条状，或与上述任意形状结构连接的网状或者条状等任意有利于放电的电极结构形式。
本发明可以作以下改进：所述的不溶性阳极的边沿处还设置有定型框。
优选地，所述的定型框选用裸露钛材，并通过所述不溶性阳极的钛基材与电镀电 源正极作连接，或者同时与所述不溶性阳极的钛基材以及电镀电源正极作连接。
本发明可以作以下改进：所述不溶性阳极背向阴极的那一面安装连接有与电镀电源正极连通的导电体，使其放电均匀。优选所述导电体为带网状或者镂空结构的钛板，即导电网或者导电板。
本发明可以作以下改进：采用对所述的不溶性阳极进行馈电结构改进，优选从不溶性阳极的极板水平两旁边设入馈电线路，使析气电极与阴极区域间的气液混合液其电导率趋向均匀一致，从而克服了传统的从上而下的馈电方式令析气电极形成有梯度的气泡层缺点。
本发明可以作以下改进：将带有所述反脉冲保护网、定型框、导电体的不溶性阳极和吸液管/口、喷液管/口的不溶性阳极组件安装在所述带液体喷射管的阳极盒中作为阳极槽区总成，使电镀设备更为紧凑。
本发明可以作以下改进：当镀件的各方向的电镀表面积不一致时，可采用一个电源和两个或多个以上数目的不溶性阳极作绕围阴极合理分布的电镀工艺系统；也可以根据工艺要求采用两个或多个电镀电源和两个或多个不溶性阳极布置在阴极镀件周边而组成一个共阴极镀件的电镀系统。电源之间的工作状态按工艺要求作程序控制，使阴极镀件能满足电镀质量要求。
本发明可以作以下改进：为能达到对阴极镀件孔隙电镀的质量要求，可采用反脉冲式电镀电源，应用反脉冲电镀工艺以更好的发挥本发明所述不溶性阳极的性能和作用来提高电镀质量和效率。
本发明可以作以下改进：在电镀槽中设置搅拌装置，以助电镀液各组分的浓度均匀分布。所述的搅拌装置为回流液体搅拌装置、叶搅拌装置、气动搅拌装置中任一种搅拌装置或它们的任意组合，所述回流液体搅拌装置包括出液管、泵浦、回流管，所述气动搅拌装置为可向所述电镀液通入气体使电镀液发生流动的设备。
本发明可以作以下改进：对所述的电镀电源增设电流调节器，或者采用自带电流调节器的电镀电源，用于所述电镀电源的输出电流大小调节，或控制所述电镀电源的开启/或关停。
本发明可以作以下改进：在所述的电镀槽内设置检测装置，包括液位计、比重计、酸度计、氧化还原电位计、光电比色计、pH计和温度计中的一种或多种，用于检测电镀槽中液体的相应工艺参数。
优选地，所述的检测装置连接一自动检测投料控制器，所述的自动检测投料控制 器能根据时间和/或所述检测装置的检测结果来进行工艺控制：对所述电镀槽加投电镀液的补充液和/或化学原料和/或清水，和/或对电镀电源的启动或者关停或者电流大小进行控制。
本发明可以作以下改进：设置过滤装置通过管道与所述电镀槽连接，以便除去电镀液中可能存在的铜泥和/或电极使用过程中带来的杂质。
本发明可以作以下改进：在所述电镀槽的上方设置尾气抽排系统，以抽走电镀过程中阳极和/或阴极上产生的气体，避免积聚以确保安全生产。
本发明可以作以下改进：所述电镀槽通过管道和泵浦与电镀液再生装置相连接，形成按工艺设置的电镀铜源补充可控循环回用系统设备。
本发明可以作以下改进：增设与电镀槽连接的暂存槽，用于暂存从所述电镀槽中流出的液体和/或准备加入所述电镀槽的液体，和/或用于电镀液进行其它的化学反应。
本发明可以作以下改进：在所述电镀槽和/或气液分离器中装设有温度冷热交换器，以稳定电镀液温度。
与现有技术相比，本发明具有以下有益效果：
1.本发明通过采用网状或者带镂空结构的板状结构材料作为不溶性阳极，并在不溶性阳极背向阴极的方向设置吸液管/口，能有效克服现有技术中因阳极表面的氧气聚积形成氧气泡屏蔽层而影响电镀均匀性的问题，使镀层更加均匀、平整，显著提高电镀质量；而且设置在不溶性阳极面向阴极那一面的电镀槽底部的喷液管/口，与吸液管/口配合产生从下而上且远离阴极的液流，令阳极上产生的气泡尽快通过不溶性阳极的孔隙进入吸液管/口中，同时避免阳极与阴极镀件之间区域的电镀液产生涡流而影响电镀液的电流分布。
本发明的方法在垂直电镀方式中也能获得均匀高质量的镀层，因此可以推广到传统的垂直电镀工艺中使用，也因此能够避免外型不规则的镀件在不溶性阳极水平电镀线中难以克服的工艺问题。
2.本发明在不溶性阳极边沿处设置定型框，能有效增强所述不溶性阳极的平整机械刚性，减少因阳极变型带来的放电不均匀现象，提高镀件质量，获得平整度和均匀度高的产品；
而且本发明进一步设置与所述阳极本体的钛基材和/或反脉冲保护屏网连接的裸露钛材或者覆有涂层的钛材定型框，或者在不溶性阳极背向阴极的那一面设有导电体，能够有效增加不溶性阳极在电镀时放电的均匀性从而提高涂层保护效果和电镀质量。
3.本发明在不溶性阳极面朝向阴极镀件的那一面上设置反脉冲保护屏网，能够在反脉冲过程中有效减少不溶性阳极表面的涂层因析氢反应而导致被破坏的情况，从而延长不溶性阳极使用寿命，降低生产成本；
而且本发明设置有裸露钛材或者覆有涂层的钛材定型框，其与不溶性阳极的钛基材和/或反脉冲保护屏网和/或电镀反脉冲电源的正极连接时，能有效在反脉冲电解过程中将主电流接引入定型框中作旁路引走，从而进一步提高对不溶性阳极表面涂层保护效果，减少不溶性阳极的损坏。
因此，采用本发明的工艺，能够在反脉冲电镀过程中，既有效保证镀铜通孔的贯通质量，即较好的电镀质量，也大大减少不溶性阳极的损坏，延长不溶性阳极使用寿命。
4.本发明在阳极盒外设有液体喷射管向镀件喷射电镀液，使电镀液涌入阴极镀件的小孔内部，令孔隙内部的镀液得到补充更新，从而进一步提高镀件的通孔贯通质量。
5.本发明在采用电镀槽分隔物将电镀槽分隔开为阳极电镀槽区和阴极电镀槽区时，能有效减少酸性电镀铜电镀液的电镀添加剂的额外损耗，从而降低生产成本；其中，本发明工艺中电镀添加剂的消耗速度为现有技术的1/3。
6.本发明将带有所述反脉冲保护网、定型框、导电板或导电网的不溶性阳极和吸液管/口、喷液管/口的不溶性阳极组件安装在所述的阳极盒中作为阳极槽区盒式总成，且在镀件周边合理连接多个不溶性阳极，这不仅解决了阳极放电不均和析氢的问题，而且提高了外型不规则镀件的电镀质量。
7.本发明装置能与电镀液再生装置配合使用，将所述的电镀槽与电镀液再生装置作连接，通过控制系统的结合来构成电镀铜源补充的循环回用系统，有助于减少磷铜污染实现绿色清洁生产，同时又降低生产成本。
附图说明
以下通过附图对本发明作进一步的说明。
图1为本发明实施例1的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图2为本发明实施例2的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图3为本发明实施例3的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图4为本发明实施例4的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图5为本发明实施例5的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图6为本发明实施例6的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图7为本发明实施例7的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图8为本发明实施例8的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图9为本发明实施例9的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图10为本发明实施例10的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图11为本发明实施例11的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图12为本发明实施例12的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图13为本发明实施例13的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图14为现有技术比较例1的不溶性阳极酸性电镀铜装置；
图15为现有技术比较例2的不溶性阳极酸性电镀铜装置；
图16为本发明实施例14的不溶性阳极酸性硫酸盐电镀铜的优化装置；
图17为本发明实施例15的不溶性阳极酸性硫酸盐电镀铜的优化装置。
图A为本发明实施例1中不溶性阳极的示意图；
图B为本发明实施例2中不溶性阳极的示意图；
图C为本发明实施例3中不溶性阳极的示意图；
图D为本发明实施例4中不溶性阳极的示意图；
图E为本发明实施例5中不溶性阳极的示意图；
图F为本发明实施例6中不溶性阳极的示意图；
图G为本发明实施例7和11中不溶性阳极盒结构的示意图；
图H为本发明实施例8中不溶性阳极盒结构的示意图；
图J为本发明实施例9和12中不溶性阳极盒结构的示意图；
图K为本发明实施例10和13中不溶性阳极盒结构的示意图。
附图标记：1-不溶性阳极，1-1-不溶性阳极上的镂空孔，2-吸液管/口，3-馈线安装孔，4-阴极镀件，5-电镀槽，6-电镀电源，7-酸性硫酸盐镀铜电镀液，8-气液分离器，9-液体回流循环管道，10-喷液管/口，11-电镀槽分隔物，12-阳极槽电镀液，13-阳极盒，14-液体喷射管，15-反脉冲保护屏网，16-定型框，17-导电体(棒、网板)，18-固定装置，19-反脉冲电镀电源，20-电镀液再生装置，21-检测装置，22-液体循环管，23-耐腐蚀泵浦，24-搅拌装置，25-抽气罩，26～28-电镀添加剂，29-变频泵，30-带泵浦液体流量调节器，31-铜金属块，32-暂存槽，33-固液分离过滤器，34-自动检测投料控制器，35-流量计，36-温度冷热交换器，37-阳极涂层，38-溢出缓冲槽，39-钛篮。
具体实施方式
以下通过具体的实施例对本发明作进一步的说明。
在下述实施例中，所使用的硫酸铜为市售的硫酸铜产品；所使用的硫酸优选为广州化学试剂厂生产的产品；所使用的钛基涂层电镀阳极和电镀槽为佛山市业高环保设备制造有限公司生产的产品；所使用的电镀阴极优选为市售的纯铜板和带小孔铜板块；所使用的离子交换膜优选为膜国际公司生产的离子交换膜；所使用的双极膜优选为国初科技生产的双极膜；超滤膜、滤布和陶瓷滤板、PE滤板及反渗透膜为市售商品；所使用的显微镜优选为广州光学仪器厂生产的电脑显微镜；所使用的电镀电源和反脉冲电镀电源为广州市番禺广兴电镀设备厂生产产品；酸性镀铜电镀添加剂为佛山市高力集团公司生产的产品。除上述列举的之外，本领域技术人员根据常规选择，也可以选择其他具有与本发明列举的上述产品具有相似性能的产品，均可以实现本发明的目的。
实施例1
如图1所示，为不溶性阳极酸性硫酸盐电镀铜的优化装置的实施例，其包括电镀槽5，不溶性阳极1，吸液管2，阴极镀件4，电镀电源6，气液分离器8，其中：
电镀槽5里设置有吸液管2，吸液管2位于不溶性阳极1背向阴极镀件4的一面；吸液管2通过连接管道与气液分离器8相连接，气液分离器8另一端通过管道和泵浦23与电镀槽相连接，使的吸液管2通过连接管道将从电镀槽吸出的气液混合物在气液分离器中作分离释放气体后其液体再次被引回流到所述电镀槽中作循环流动。
不溶性阳极1的结构如图A所示，其为覆有涂层的钛材，结构为带镂空通孔的板状物，且从阳极极板的上部的馈线安装孔设入馈电线路作从上馈电；
电镀电源6的正极和负极在电镀过程中分别与不溶性阳极1和阴极镀件4相连接。
阴极镀件4为一块平整铜板。
不溶性阳极酸性电镀铜的优化方法，包括以下步骤：
(1)根据表-1指定的电镀液进行准备，将电镀液倒入电镀槽中；
(2)将不溶性阳极装置安装在电镀槽中，并在不溶性阳极背向阴极的一面设置吸液管，将电镀电源的正极与不溶性阳极连接，将电镀电源的负极与阴极镀件连接；
(3)往电镀液中投入适量的电镀添加剂，接通电解电源，以酸性镀铜电镀液作为电镀液进行电镀生产作业；
(4)电镀完成后，将阴极镀件取出；使用清水清洗所述阴极镀件并利用热风吹干；并使用电脑显微镜观察镀层表面，将观察的结果记录于表-1中。
电镀过程中，由不溶性阳极的结构与设置在阳极背向阴极方向一面的吸液管相配合，通过溢流使不溶性阳极附近的液体产生背向远离阴极并穿过阳极孔隙的液流，使的阳极表面产生的氧气泡随液流穿过不溶性阳极其结构所形成的孔隙送往远离阴极的方向外排释放。
在电镀的作业前后对镀液进行COD的检测，通过前后的变化数值来初步判断工艺对电镀添加剂的消耗状况，将结果记录于表-2中。
实施例2
如图2所示，为不溶性阳极酸性硫酸盐电镀铜的优化装置的实施例，其与实施例1的装置的不同之处在于：
不溶性阳极1的结构如图B，不溶性阳极为覆有涂层的钛网，而且不溶性阳极的四边周围焊接材质为覆有涂层的钛材的定型框16，并从阳极极板的水平两旁的馈线安装孔设入馈电线路作结构改进。
根据表-1指定的各参数，采用实施例1所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
实施例3
如图3所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，不溶性阳极1，阴极镀件4，电镀电源6，气液分离器8，固液分离过滤器33，其中：
电镀槽5里设置有吸液口2、喷液管10、叶搅拌装置24.2和气动搅拌装置24.1，吸液口2设在电镀槽5壁上，且位于不溶性阳极1背向阴极镀件4的一面，喷液管10装置在不溶性阳极1面向阴极镀件4的一面的两极区域空间内，吸液口2通过管道和泵浦连接气液分离器8，且气液分离器8通过液体回流循环管道9和过滤装置33将析气处理后的液体经过滤后，从喷液管10回流至电镀槽5中。
不溶性阳极1结构如图C所示，不溶性阳极1为覆有涂层的钛材，结构为带镂空通孔的板状物，四边周围焊接有材质为裸露钛材的定型框16，并且在不溶性阳极1上和定型框16上安装反脉冲保护屏网15，反脉冲保护屏网15为尖刺状的无涂层钛材，从阳极极板的上部的馈线安装孔设入馈电线路作从上馈电的结构改进。
电镀电源6的正极和负极在电镀过程中分别与不溶性阳极1和阴极镀件4相连 接。
所述的阴极镀件4为一块平整铜板。
根据表-1指定的各参数，采用实施例1所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1和表-2中。
电镀过程中，不溶性阳极的镂空结构与设置在阳极背向阴极方向一面的吸液口相配合，通过采用动力令不溶性阳极附近的液体产生背向远离阴极并穿过阳极孔隙的液流，使得阳极表面产生的氧气泡随液流穿过不溶性阳极镂空结构所形成的孔隙送往远离阴极的方向并外排到气液分离器中释放，气液分离器中作分离释放气体后的液体再次被引回流到电镀槽中作循环流动。
实施例4
如图4所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，不溶性阳极1，吸液管2，阴极镀件4，反脉冲电镀电源19，气液分离器8，其中：
电镀槽5设置有吸液管2和喷液管10，吸液管2位于不溶性阳极1背向阴极镀件4的一面，喷液管10装置在不溶性阳极1面向阴极镀件4的一面的两极区域空间内；吸液管2通过管道和泵浦23连接气液分离器8，且所述气液分离器8通过液体回流循环管道9将处理后的液体回流至电镀槽中；
如图D所示，不溶性阳极为覆有涂层带镂空结构的钛板。不溶性阳极1在面向阴极镀件一面设有反脉冲保护屏网15，反脉冲保护屏网为与不溶性阳极1的钛基材直接连接的无涂层钛材凸起物，且凸起物的形状结构为针刺状和条状，在其顶端通过网丝相连接而形成保护网罩；在不溶性阳极1远离阴极的背后连接上导电体17，导电体17为一导电棒。从不溶性阳极1上部的馈线安装孔设入馈电线路作从上馈电的结构改进。
阴极镀件4为带有小通孔的一块平整铜板；
反脉冲电镀电源19的正极和负极在电镀过程中分别与不溶性阳极1和阴极镀件4相连接。
根据表-1指定的各参数，采用实施例1所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中；在电镀的作业前后对镀液进行COD的检测，通过前后的变化数据来初步判断工艺对电镀添加剂的消耗状况，将结果记录于表-2中。
电镀过程中，不溶性阳极的镂空结构与所述设置在阳极背向阴极方向一面的吸液管、设置在不溶性阳极面向阴极的一面的喷液管相配合，通过采用动力令不溶性阳极附近的液体产生背向远离阴极并穿过阳极孔隙的液流，使得阳极表面产生的氧气泡随液流穿过不溶性阳极镂空结构所形成的孔隙送往远离阴极的方向并外排到气液分离器中释放，气液分离器中作分离释放气体后的液体再次被引回流到所述电镀槽中作循环流动。在反脉冲电解过程中，反脉冲保护屏网能有效地减少不溶性阳极涂层表面的电化学析氢反应。
实施例5
如图5所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，不溶性阳极1，吸液管2，阴极镀件4，反脉冲电镀电源19，其中：
电镀槽5中设有电镀槽分隔物11将其分隔开为阳极电镀槽区和阴极电镀槽区，电镀槽分隔物11具体为超滤膜和滤布的组合。阳极电镀槽区设置内有吸液管2和喷液口10；喷液管10装置在不溶性阳极1面向阴极镀件4的一面的阳极电镀槽区底部，并通过管道和泵浦23.1与远离阴极电镀槽区的阳极电镀槽区一面相连接；吸液管2设有2个的吸液口并且位于不溶性阳极1背向阴极镀件4的一面的位置；吸液管2通过连接有泵浦23.2的管道，将带有气泡的液体引流到阳极电镀槽区中远离阴极镀件4处进行释放气体；
如图E所示，位于阳极电镀槽区内的不溶性阳极1为覆有涂层的钛网；不溶性阳极1四周边沿处还焊接有封边的定型框16，定型框16的材质为裸露钛材；导电体17为网状且四周边用钛网与定型框16作焊接的旁路结构导电体，导电体17位于不溶性阳极1在背向阴极镀件4的一面；定型框16与导电体17的安装结构是在不溶性阳极1背向阴极镀件4一面作为板框在四周封边焊接，三者成一个两面相通网孔的方形盒并得到通电连接。导电体17上设有反脉冲保护屏网15，且安装焊接在导电体17上；反脉冲保护屏网15是穿过不溶性阳极1的网孔且与其不接触的无涂层钛材尖刺。不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作从上馈电的结构改进。
阴极镀件4在阴极电镀槽区内，为带有小孔的平整铜板；
反脉冲电镀电源19的正极和负极在电镀过程中分别与不溶性阳极1和阴极镀件4相连接。
不溶性阳极酸性电镀铜的优化方法，包括以下步骤：
(1)根据表-1指定的电镀液进行准备，分别将阳极电镀液和阴极电镀液倒入阳极 电镀槽区和阴极电镀槽区中；
(2)将不溶性阳极装置安装在电镀槽中，并在不溶性阳极背向阴极的一面设置吸液管，将电镀电源的正极与不溶性阳极连接，将电镀电源的负极与镀件连接；
(3)往阴极电镀液中投入适量的电镀添加剂，接通电解电源进行电镀生产作业；
(4)电镀完成后，将阴极镀件取出；使用清水清洗所述阴极镀件并利用热风吹干；并使用电脑显微镜观察镀层表面，将观察的结果记录于表-1中。
电镀过程中，不溶性阳极的网状结构与设置在阳极背向阴极方向一面的吸液管、设置在不溶性阳极面向阴极的一面底部的喷液管相配合，通过采用动力令不溶性阳极附近的液体产生背向远离阴极并穿过阳极本体网孔和导电网孔的液流，使得阳极表面产生的氧气泡更能集中地随液流穿过不溶性阳极和导电体的网孔，送往远离阴极的方向释放。在反脉冲电解的情况下，反脉冲保护屏网的尖刺因与不溶性阳极无接触，故将反脉冲电流从针刺尖端回流到导电体中从旁路引走，能有效地减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。而且电解槽分隔物的设计也能有效地降低电镀添加剂的损耗。
实施例6
如图6所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其与实施例5的装置的不同之处在于：
电镀槽分隔物11具体为PE滤板与陶瓷滤板的组合。
喷液管10的管口设计为扁平喇叭口形状，装置在不溶性阳极1面向阴极镀件4的一面的阳极电镀槽区底部，喷液管10通过管道和泵浦23.1与远离阴极电镀槽区的阳极电镀槽区一面相连接。吸液管2的管口为喇叭口形状，位于不溶性阳极1背向阴极镀件4的一面的位置；吸液管2通过连接有泵浦23.2的管道，将带有气泡的液体引流到阳极电镀槽区中远离阴极镀件4处进行释放气体；
如图F所示，位于阳极电镀槽区内的不溶性阳极1为覆有涂层的镂空通孔钛板；不溶性阳极1四周边沿处还焊接有封边的定型框16，，定型框16的材质为裸露钛材；导电体17为带镂空通孔的钛板且四周边与定型框16作焊接的旁路结构导电体，导电体17位于不溶性阳极1在背向阴极镀件4的一面；使不溶性阳极1与定型框16和导电体17得到通电连接，三者接成一个两面镂空通孔钛板相通而其它四面密闭的方形盒。导电体17上还设有作为反脉冲保护屏网15，且安装焊接在导电板17上；反脉冲保护屏网15是穿过不溶性阳极1的镂空通孔且与其不接触的无涂层钛材尖刺。不溶性 阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进。
阴极镀件4在阴极电镀槽区内，为带有小孔的平整铜板；
反脉冲电镀电源19的正极和负极在电镀过程中分别与不溶性阳极1和阴极镀件4相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
电镀过程中，不溶性阳极的镂空结构与设置在阳极背向阴极方向一面的喇叭吸液管、设置在不溶性阳极面向阴极的一面底部的扁平喇叭喷液管相配合，通过采用动力令不溶性阳极附近的液体产生背向远离阴极并穿过不溶性阳极和导电体镂空通孔的液流，使得阳极表面产生的氧气泡更能集中地随液流穿过不溶性阳极镂空通孔送往远离阴极的方向释放。在反脉冲电解的情况下，反脉冲保护屏网的尖刺因与不溶性阳极无接触，故将反脉冲电流从针刺尖端回流到导电板中从旁路引走，能有效地减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。而且电解槽分隔物的设计也能有效地降低电镀添加剂的损耗。
实施例7
如图7所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，阳极盒13，阴极镀件4，气液分离器8，反脉冲电镀电源19，其中：
电镀槽5中设有一阳极盒13，阳极盒13面朝向阴极镀件4的一面装设有电镀槽分隔物11，该电镀槽分隔物11具体为阳离子交换膜；阳极盒13的内部空间为阳极电镀槽区，在电镀槽5中阳极盒13外的空间为阴极电镀槽区。
如图G所示，阳极盒13连接有吸液管2和其内设置一个喷液口10；吸液管2有4个吸液口在阳极盒13内且位于不溶性阳极1背向阴极镀件4的一面，喷液口10位于不溶性阳极1面向阴极镀件4的一面；吸液管2通过管道与泵浦23和气液分离器8连接，气液分离器8再通过液体回流循环管道9与喷液口10连接，将释气处理后的液体回流至阳极盒13中；
本实施例的不溶性阳极1为图D结构，是覆有涂层带镂空结构的钛板；不溶性阳极1在面向阴极镀件一面设有反脉冲保护屏网15，反脉冲保护屏网15为与不溶性阳极1的钛基材直接连接的无涂层钛材凸起物，并在各凸起物顶端使用钛丝联结为通电网状；不溶性阳极1在电镀过程中与反脉冲电镀电源19正极连接；在不溶性阳极1远离阴极的背后连接上导电体17，导电体17为一导电棒。不溶性阳极1上部设有馈线 安装孔，并从中设入馈电线路作结构改进。上述的阳极组件安装在阳极盒13内，如图G所示。
阴极镀件4在阴极电镀槽区内，为带有小孔的平整铜板，并与反脉冲电镀电源19的负极相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
电镀过程中，设置在阳极盒内不溶性阳极背向阴极方向一面的吸液管、设置在阳极盒内不溶性阳极面向阴极的一面底部的喷液口相配合，通过采用动力令不溶性阳极附近的液体产生背向远离阴极镀件并穿过阳极孔隙的液流，使得阳极表面产生的氧气泡随液流穿过不溶性阳极其结构所形成的孔隙送往气液分离器中外排释放，在将释放气体后的液体再次回流到阳极盒中。在反脉冲电解过程中，反脉冲保护屏网能有效地减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。带有电解槽分隔物的阳极盒设计能有效降低电镀添加剂的损耗。
实施例8
如图8所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其与实施例7的装置的不同之处在于：
电镀槽分隔物11具体为反渗透膜和滤布的组合；
如图H所示，阳极盒13连接有吸液管2和喷液管10，吸液管2的管口呈大喇叭形，喷液管10设有多个平行设置的管口。
本实施例采用与实施例5相同的阳极组件，包括不溶性阳极1、导电体17、定型框16、反脉冲保护屏网15，不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进，结构如图E所示，该阳极组件安装在阳极盒13内，如图H所示。在电镀过程中，不溶性阳极1和反脉冲电镀电源19正极连接。
阴极镀件4为带有小孔的平整铜板，设在阴极电镀槽区内，在电镀过程中与反脉冲电镀电源19的负极作相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
电镀过程中，本实施例采用如图H所示的阳极盒结构，通过采用动力令不溶性阳极附近的液体产生背向远离阴极镀件并穿过不溶性阳极和导电体网孔的液流，使得阳极表面产生的氧气泡随液流穿过不溶性阳极和导电体的网孔送往气液分离器中外排释 放，作释放气体后的液体再次回流到阳极盒中。在反脉冲电解过程中，反脉冲保护屏网能有效地减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。带有电解槽分隔物的阳极盒设计能有效隔离电镀液添加剂与阳极接触以降低其损耗。
实施例9
如图9所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其与实施例7的装置的不同之处在于其还包括液体喷射管14；而且：
电镀槽分隔物11具体为阴离子交换膜和滤布的组合；
如图J所示，阳极盒13连接有吸液管2和喷液管10，在阳极盒13内，吸液管2的管口呈大喇叭形、喷液管10设有多个平行设置的管口。吸液管2通过管道与泵浦23.1和气液分离器8连接，气液分离器8再通过液体回流循环管道9与喷液管10连接，将处理后的液体回流至阳极盒13中；在阳极盒13朝向阴极镀件4一面外的四周边沿装设有液体喷射管14，液体喷射管14与阴极电镀槽区通过管道和泵浦23.2连接，使其朝向阴极镀件4喷液。
本实施例采用与实施例6相同的阳极组件，包括不溶性阳极1、导电体17、定型框16、反脉冲保护屏网15，不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进，结构如图F所示，该阳极组件安装在阳极盒13内，如图J所示。在电镀过程中，不溶性阳极1和反脉冲电镀电源19正极连接。
阴极镀件4为带有多个小孔的平整铜板，设在阴极电镀槽区内，在电镀过程中与反脉冲电镀电源19的负极作相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。在电镀的作业前后对阴极电镀液进行COD检测，根据作业前后的数据变化来初步判定工艺对电镀添加剂的消耗状况，并将结果记录于表-2中。
电镀过程中，本实施例采用如图J所示的阳极盒结构，通过采用动力令不溶性阳极附近的液体产生背向远离阴极镀件并穿过不溶性阳极和导电体的镂空通孔的液流，使得阳极表面产生的氧气泡随液流穿过不溶性阳极和导电体的镂空通孔送往气液分离器中外排释放，作分离释放气体后的液体再次回流到阳极盒中。在反脉冲电解过程中，反脉冲保护屏网能有效地减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。阳极盒外的液体喷射管通过泵浦向阴极镀件喷射电镀 液，使电镀液涌入阴极镀件的小孔内部令孔隙内部的镀液得到补充更新。另外带有电镀槽分隔物的阳极盒设计能有效隔离电镀液添加剂与阳极接触以降低其损耗。
实施例10
如图10所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其与实施例7的装置的不同之处在于还包括液体喷射管14；而且：
电镀槽分隔物11具体为双极膜和滤布的组合；
如图K所示，阳极盒13内连接有吸液管2和其内设有一个喷液口10，吸液管2在阳极盒13内有4个管口，位于不溶性阳极1背向阴极镀件4的一侧，喷液口10位于不溶性阳极1面向阴极镀件4的一侧。吸液管2通过管道与泵浦23.1和气液分离器8连接，气液分离器8再通过液体回流循环管道9与喷液口10连接，将处理后的液体回流至阳极盒13中。在阳极盒13朝向阴极镀件4一面外的四周边沿装设有液体喷射管14，液体喷射管14与阴极电镀槽区通过管道和泵浦23.2连接，使其朝向阴极镀件4喷液。
本实施例采用与实施例3相同的阳极组件包括不溶性阳极1、定型框16、反脉冲保护屏网15，不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进，结构如图C所示，该阳极组件安装在阳极盒13内，如图K所示。在电镀过程中，不溶性阳极1和反脉冲电镀电源19正极连接。
阴极镀件4为带有多个小孔的平整铜板，设在阴极电镀槽区内，在电镀过程中与反脉冲电镀电源19的负极作相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。在电镀的作业前后对阴极电镀液进行COD检测，根据作业前后的数据变化来初步判定工艺对电镀添加剂的消耗状况，并将结果记录于表-2中。
电镀过程中，本实施例采用如图K所示的阳极盒结构，通过采用动力令不溶性阳极附近的液体产生背向远离阴极并穿过阳极镂空通孔的液流，使得阳极表面产生的氧气泡随液流穿过不溶性阳极的镂空通孔送往气液分离器中外排释放，作分离释放气体后的液体再次回流到阳极盒中。在反脉冲电解过程中，反脉冲保护屏网能减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。阳极盒外面的液体喷射管通过泵浦向阴极镀件喷射电镀液，使电镀液涌入阴极镀件的小孔内部令孔隙内部的镀液得到补充更新。另外带有电镀槽分隔物的阳极盒设计能有效隔离电镀 液添加剂与阳极接触以降低其损耗。
实施例11
如图11所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，阳极盒13，阴极镀件4，电镀电源6，气液分离器8，其中：
电镀槽5中设有三个阳极盒13，阳极盒13面朝向阴极镀件4的一面均为电镀槽分隔物11，电镀槽分隔物11具体为阳离子交换膜；阳极盒13的内部空间为阳极电镀槽区，电镀槽5中阳极盒13以外的空间为阴极电镀槽区。
如图G所示，每个阳极盒13连接有吸液管2和其内设置一个喷液口，与实施例7的阳极盒13的结构相同。各个阳极盒13的吸液管2管道分别接有一个泵浦，然后与气液分离器8作连接；处于高于电镀液面的气液分离器8通过液体回流循环管道9与各个阳极盒13的喷液口10连接，将经作释气处理的液体回流至各阳极盒13中。
阴极电镀槽区中设有检测装置21和搅拌装置24，检测装置21包括比重计、光电比色计、酸度计，搅拌装置24为回流液体搅拌装置。阴极电镀槽区依次与溢出缓冲槽38、泵浦23.4、过滤器33.1、电镀液再生装置20、带泵浦液体流量调节器30和过滤器33.2作循环回路连接；阴极电镀槽区中的阴极电镀液溢出到溢出缓冲槽38中被泵浦23.4经过滤器33.1处理后泵送回电镀液再生装置20中。其中带泵浦液体流量调节器30的投料动作由自动检测投控器34根据检测装置21测得的结果发出指令进行控制，使阴极电镀液得到铜源补充。电镀槽5的上方设置有尾气抽排系统25；
本实施例采用与实施例4相同的阳极组件包括不溶性阳极1、导电体17、反脉冲保护屏网15，不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进，结构如图D所示，该阳极组件安装在阳极盒13内，如图G所示。在电镀过程中，不溶性阳极1和电镀电源19正极连接。
阴极镀件4为一块平整铜板，设在阴极电镀槽区内，在电镀过程中与电镀电源19的负极作相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
电镀过程中，阳极盒内的不溶性阳极背向远离阴极方向一面的吸液管和设置在阳极盒内不溶性阳极面向阴极的一面底部的喷液口相配合，通过采用动力令不溶性阳极附近的液体产生背向远离阴极并穿过不溶性阳极孔隙的液流，使得阳极表面产生的氧气泡随液流被送往气液分离器中作气体释放，释放气体后的液体再次回流到阳极盒 中。带有电镀槽分隔物的阳极盒设计能将阴阳电解液作分离，并能有效降低电镀添加剂的损耗。另外对气液分离器中所排出的气体收集后可再进一步处理。
实施例12
如图12所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，阳极盒13，阴极镀件4，气液分离器8，反脉冲电镀电源19，其中：
电镀槽5中设有六个阳极盒13，阳极盒13面朝向阴极镀件4的一面为电镀槽分隔物11，电镀槽分隔物11为阴离子交换膜和滤布的组合；阳极盒13的内部空间为阳极电镀槽区，电镀槽5中阳极盒13以外的余空间为阴极电镀槽区。阴极电镀槽区设有检测装置21，检测装置21包括液位计、氧化还原电位计、光电比色计、pH计和温度计，检测装置21连接自动检测投料控制器34以控制电镀槽的液位、温度调节、电源输出电流，检测镀液浓度、电镀时间等工艺参数，使电镀按工艺要求进行。
阳极盒13结构如图J所示，阳极盒13连接有吸液管2和喷液管10，与实施例9的阳极盒13的结构相同。各阳极盒13中的吸液管2分别通过管道接有一个泵浦23，然后与暂存槽32相连接；其中泵浦23.1、23.2、23.3将液体泵送到暂存槽32.1中，泵浦23.4、23.5、23.6将液体送至暂存槽32.2中。两个暂存槽的液体通过泵浦23.7和管道带着气泡被引至气液分离器8中，而气液分离器8中存有金属铜31；此方法是充分利用阳极电镀液里的硫酸和氧气来参与铜金属的化学反应制得硫酸铜溶液。阳极电镀液在气液分离器8中作化学反应，并于气液分离器8中释放气体后再通过泵浦23.8和液体回流循环管道9引流到各阳极盒13的喷液管10，将液体泵流至阳极盒13内。各阳极盒13朝向阴极镀件4一面外的四周边沿分别装设有液体喷射管14，液体喷射管14与阴极电镀槽区连接，使其通过程序进行动作控制朝向阴极镀件4喷液。
本实施例采用与实施例6相同的阳极组件，包括不溶性阳极1、导电体17、定型框16、反脉冲保护屏网15，不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进，结构如图F所示，该阳极组件安装在阳极盒13内，如图J所示。在电镀过程中，不溶性阳极1和电镀电源19正极连接。
阴极镀件4为带有多个小孔的平整铜板，设在阴极电镀槽区内，在电镀过程中与电镀电源19的负极作相连接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
根据表-1指定的各参数，重复实施例1所述酸性电镀铜的优化方法步骤，并将结 果记录于表-1中。
电镀过程中，通过采用动力令阳极盒中的不溶性阳极附近的液体产生背向远离阴极并穿过阳极孔隙的液流，使得阳极表面产生的氧气泡随液流被送往到两个暂存槽后再泵送入气液分离器中参与铜金属的化学反应。在气液分离器中溶液在释放气体后将其再次泵回到各个阳极盒中。在反脉冲电解过程中，反脉冲保护屏网能减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。阳极盒外面的液体喷射管通过泵浦向阴极镀件喷射电镀液，使电镀液涌入阴极镀件的小孔内部令孔隙内部的镀液得到补充更新，同时也对镀液进行搅拌。电镀过程中，阴极镀件可单向平行移动或者双向来回平行作移动，以获得更均匀的镀层。另外，带有电镀槽分隔物的阳极盒阻止电镀阴极液进入阳极电镀槽区既能有效降低电镀添加剂的损耗，又方便收集阳极盒中带气泡的阳极电镀液，用于参与暂存槽的铜金属化学反应而制得更多的硫酸铜溶液。
实施例13
如图13所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其包括电镀槽5，阳极盒13，阴极镀件4，气液分离器8，两个反脉冲电镀电源19，其中：
电镀槽5中设有六个阳极盒13，阳极盒13面朝向阴极镀件的一面为电镀槽分隔物11，电镀槽分隔物11为双极膜和滤布的组合；阳极盒13的内部空间为阳极电镀槽区，电镀槽5中除阳极盒13以外的空间为阴极电镀槽区。阴极电镀槽区设有检测装置21，检测装置21包括液位计、比重计、酸度计，检测装置21连接自动检测投料控制器34，自动检测投料控制器34根据所述检测装置21测得的数据进行工艺上电镀电流控制和镀液参数的控制和报警。
阳极盒13结构与实施例10相同，如图K所示，各阳极盒13分别连接有吸液管2和其内设有一个喷液口10，吸液管2在阳极盒13内有4个管口，位于不溶性阳极1背向阴极镀件4的一面，喷液口10位于不溶性阳极1面向阴极镀件4的一面。吸液管2均通过管道与气液分离器8连接，将溢出液体引流到其中作释气分离。在气液分离器8中通过释气的液体使用泵浦23.1泵经过固液分离过滤器33回流入循环管道9，液体回流循环管9连接上各阳极盒13中的喷液口10，将释气处理后的液体回流至阳极盒13中。在阳极盒13朝向阴极镀件4一面外的四周边沿装设有液体喷射管14，液体喷射管14与阴极电镀槽区通过管道和泵浦23.2连接，液体喷射管14的喷射动作通过自动检测投料控制器34的设定程序进行朝向阴极镀件4喷液的动作。
本实施例采用与实施例3相同的阳极组件包括不溶性阳极1、定型框16、反脉冲保护屏网15，不溶性阳极1上部设有馈线安装孔，并从中设入馈电线路作结构改进，结构如图C所示，该阳极组件安装在阳极盒13内，如图K所示。
阴极镀件4为带有多个小孔的平整铜板，设在阴极电镀槽区内。
在电镀过程中，不溶性阳极1的钛基材分别和对应设置的两个反脉冲电镀电源19的正极连接，而四个阴极镀件4与两个反脉冲电镀电源的阴极共接。
根据表-1指定的各参数，采用实施例5所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
电镀过程中，通过采用动力使喷液口喷出溶液令阳极盒中的不溶性阳极附近的液体产生背向远离阴极并穿过阳极孔隙的液流，使得阳极表面产生的氧气泡随液流送往气液分离器中作气体外排释放，释放气体后的液体再次回流到电镀槽的各阳极盒中。在电镀反脉冲电解过程中，反脉冲保护屏网能减少不溶性阳极的表面在转极时发生电化学析氢反应，避免不溶性阳极的涂层脱落。阳极盒外面的液体喷射管通过泵浦向阴极镀件喷射电镀液，使电镀液涌入阴极镀件的小孔内部令孔隙内部的镀液得到补充更新。电镀进行时其阴极镀件在电镀槽中作单向或双向来回的平行移动，并且根据阴极电镀工艺质量要求对各个电镀电源进行各自输出电流大小值的调整，以获得更佳的阴极镀层。另外多个带有电镀槽分隔物的阳极盒设计能有效降低电镀添加剂的损耗。
实施例14
如图16所示，为本发明不溶性阳极酸性硫酸盐电镀铜的优化装置的基础实施例，其包括电镀槽5，不溶性阳极1，吸液管2，阴极镀件4，电镀电源6，其中：
电镀槽5里设置有吸液管2，吸液管2位于不溶性阳极1背向阴极镀件4的一面，不溶性阳极1为覆有涂层的钛网。
不溶性阳极1的结构如图A所示，其为覆有涂层的钛材，结构为带镂空通孔的板状物，且从阳极极板的上部的馈线安装孔设入馈电线路作结构改进。
电镀电源6的正极和负极在电镀过程中分别与不溶性阳极1和阴极镀件4相连接。
所述的阴极镀件4为一块平整铜板。
根据表-1指定的各参数，采用实施例1所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
实施例15
如图17所示，为本实施例的不溶性阳极酸性硫酸盐电镀铜的优化装置，其与实施例1的装置的不同之处在于：
采用反脉冲电镀电源19代替电镀电源6；
如图C所示，不溶性阳极1为覆有涂层的钛材，结构为带镂空通孔的板状物，四边周围焊接有定型框16，定型框16为非导电材质；在不溶性阳极1上和定型框16中安装上放电尖刺作为反脉冲保护屏网15，从阳极极板的上部的馈线安装孔设入馈电线路作结构改进。
所述的反脉冲电镀电源19的正极和负极在电镀过程中分别与所述的不溶性阳极1和阴极镀件4相连接。
所述的阴极镀件4为一块平整铜板。
根据表-1指定的各参数，采用实施例1所述不溶性阳极酸性电镀铜优化方法的步骤进行电镀作业，并将结果记录于表-1中。
比较例1
如图14所示，为一种现有技术的不溶性阳极酸性硫酸盐电镀铜的装置，其包括有电镀槽5、不溶性阳极1、阴极镀件4、反脉冲电镀电源19。
电解槽5安装有不溶性阳极14和阴极镀件4。
不溶性阳极1为覆有涂层的钛材，阴极镀件4为带有多个小孔的平整铜板。
不溶性阳极1与反脉冲电镀电源19的正极连接，阴极镀件4与电源19的负极连接。
根据表-1指定的各参数，合上反脉冲电镀电源19进行电镀作业，将结果记录于表-1中。在电镀的作业前后对阴极镀液进行COD检测，根据作业前后的数据变化来初步判定工艺对电镀添加剂的消耗状况，并将结果记录于表-2中。
本对比例因阴极镀件和不溶性阳极间的电镀液中存在大量气泡影响到电场电流分布，并且在反脉冲的情况下不溶性阳极涂层表面析氢反应严重，上述两个因素使得镀层不均匀和阳极涂层受损脱落。
比较例2
如图15所示，为本发明的现有技术对比例的一种不溶性阳极酸性电镀铜装置。其与比较例1的装置的不同之处在于其还包括有电镀槽分隔物11、搅拌装置24、钛篮39。
电解槽5安装有钛篮39，其钛篮内装设有不溶性阳极1，钛篮39外围包有中性滤 膜11，钛篮39和中性滤膜11包围的内部空间为阳极电镀槽区，所述电镀槽中其余空间为阴极电镀槽区；电镀槽5内还安装有搅拌装置24和阴极镀件4。
不溶性阳极1为覆有涂层的钛材，阴极镀件4为带有多个小孔的平整铜板。
不溶性阳极1和钛篮39与反脉冲电镀电源19的正极连接，阴极镀件4与反脉冲电源19的负极连接。
根据表-1指定的各参数，开启搅拌装置24，合上反脉冲电镀电源19进行电镀作业，将结果记录于表-1中。
本对比例因阴、阳极间的电镀液中存在大量气泡影响到电场电流分布，并且在反脉冲的情况下阳极涂层表面析氢反应严重。上述两个因素使到镀层不均匀和阳极涂层受损脱落。
本发明的实施例和对比例的工艺条件为：
①电镀电流为2A/dm 2；
②反脉冲的电源工作时，正向电流为2A/dm 2，反脉冲电流为6A/dm 2，正向电流和反脉冲电流的时间比例为20:1；
③电镀时间40分钟，温度为30℃；④酸性镀铜电镀液包括：
CuSO 4 200g/L
H 2SO 4 60g/L
Cl -70g/L
市售高力牌镀铜电镀添加剂9mg/L。
镀层状态及均匀性的鉴定方法：
电镀作业完成后，对经过电镀作业的阴极镀件从上至下取均匀三点位置进行切片和打磨，并采用显微镜对切片的镀层进行观察和厚度测量；对于带有小孔的阴极镀件，还需观察对孔内状态以及镀铜情况；测得的结果以及得出的结论见表-1。
阳极涂层状态的鉴定方法：
在电镀作业后，用肉眼对阳极涂层进行观察，并采用刷子轻刷涂层测试是否出现涂层脱落现象；得出的结论见表-1。
电镀光亮剂消耗情况的鉴定方法：
分别在电镀作业前以及电镀作业后采用国标COD检测方法对电镀液或者阴极电镀液的COD值进行检测，通过电镀前后电镀液或者电镀阴极液的COD值变化差对电镀光亮剂的消耗情况作出评价；得出的结论见表-2。
表-1
Figure PCTCN2021142832-appb-000002
Figure PCTCN2021142832-appb-000003
Figure PCTCN2021142832-appb-000004
表-2
Figure PCTCN2021142832-appb-000005
由上表-1可见，将本发明实施例1～15与现有技术对比例1～2所电镀所得镀层质量的比较：实施例1～15电镀所得镀层测得的三点(上、中、下)厚度数据更为平均，均优于比较例1。其中，实施例2～13中均设有起到馈线作用的定型框或者导电体及其连接点，电镀所得的镀层整体厚度一致，且表面平整、小孔镀通连贯。而比较例1～2在电镀工作时受气泡影响镀液中的电流分布，所得镀层表面粗糙且厚度不均匀，小孔内的镀通情况也不理想。如此可见，采用本发明工艺得出的镀层更加均匀、平整，通孔贯通质量更高。说明本发明对析气的不溶性阳极电镀铜工艺作改进后，能有效提高电镀质量，满足电镀工业对高质量产品的要求。
由上表-1可见，将同样采用了反脉冲电镀电源的本发明实施例4～10、实施例12～13、实施例15与现有技术对比例1～2作阳极涂层状态比较：本发明实施例4～10、实施例12～13、实施例15的不溶性阳极上均设置有反脉冲保护屏网，其中本发明实施例4～10、实施例12～13电镀作业完成后不溶性阳极涂层均完整无脱落，本发明实施例15因缺少旁路设计所以电镀作业完成后不溶性阳极涂层上部位置轻刷后有轻微脱落；而比较例1～2的不溶性阳极由于没有反脉冲保护屏网对不溶性阳极涂层进行保护，电镀作业完成后用刷子轻刷都有明显的涂层脱落现象。由此可以说明，本发明的不溶性阳极设置有反脉冲保护屏网时能有效减少不溶性阳极涂层表面的电化学析氢反应，从而延长不溶性阳极的使用寿命。
由于业界所采用的电镀添加剂为有机化合物，故其消耗情况可以通过电镀液的COD值变化对应体现，即是，电镀液的COD值下降越快说明电镀液中的电镀添加剂消耗速度越快。由上表-2可见，将本发明电镀槽中设置有电镀槽分隔物的实施例9和实施例10，与比较例1、电镀槽中没有设置电镀槽分隔物的实施例1和实施例4作比较：实施例9和实施例10中电镀作业前后分别测得的阴极电镀液COD值相差不超过80mg/L，证明其电镀添加剂损耗量少。比较例1、实施例1和实施例4中电镀作业前后分别测得的电镀液COD值均相差200mg/L以上，说明其电镀添加剂损耗量大。由此可以证明，本发明的电镀槽中设置有电镀槽分隔物时能有效节省电镀添加剂用料。
此外，现有技术的比较例1与本发明的实施例9和实施例10的基础设置最为相似。然而，实施例9和实施例10无论是镀层均匀度、小孔镀通情况、阳极涂层状态、电镀添加剂的消耗情况都要优于比较例1。
本发明可用其他的不违背本发明的精神或主要特征的具体形式来概述。本发明的上述实施例都只能认为是对本发明的说明而不是限制。因此凡是依据本发明的实质技术对以上实施例所作的任何细微修改、等同变化与修饰，均属于本发明技术方案的范围内。

Claims (20)

  1. 一种不溶性阳极酸性硫酸盐电镀铜的优化工艺，包括电镀槽(5)、电镀电源(6)、不溶性阳极(1)以及以镀件为阴极(4)，以酸性硫酸盐镀铜电镀液作为电镀液，其特征在于：
    1)采用材质为覆有涂层的钛材、且形状为网状或者带镂空结构的板状作为不溶性阳极(1)，然后将所述不溶性阳极(1)和所述阴极(4)安装在电镀槽中；并在所述不溶性阳极(1)背向阴极(4)的那一面增设至少一个吸液管/口(2)，以使电镀液通过该吸液管/口(2)的溢流或/和电动吸液方式产生液流；
    2)接通电镀电源(6)进行电镀生产作业，同时，通过所述吸液管/口(2)的溢流或/和采用动力的方式吸走电镀液，使电镀槽(5)中的电镀液形成流向吸液管/口(2)的液流，相应地，再添加电镀液进入电镀槽(5)中以维持电镀槽(5)内的电镀液体量，直到完成电镀将镀件取出。
  2. 根据权利要求1所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，在所述不溶性阳极(1)面向阴极(4)的那一面增设至少一个喷液管/口(10)，该喷液管/口(10)与外接的喷液管路相连，用以朝向阳极喷液，与所述的吸液管/口(2)配合，在不溶性阳极(1)附近产生更稳定可控的远离阴极(2)的液流。
  3. 根据权利要求2所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，增设气液分离器(8)，使所述的吸液管/口(2)通过连接管道将从电镀槽(5)吸出的气液混合物流体排入到气液分离器(8)中；所述气液混合物在气液分离器(8)中作分离释放气体后其液体再次被引回流到所述电镀槽(5)中作循环流动。
  4. 根据权利要求3所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，将所述电镀槽(5)用电镀槽分隔物(11)将其分隔开为阳极电镀槽区和阴极电镀槽区两个区域；所述阳极电镀槽区中的电镀液为阳极电镀液，具体为含有无机酸和/或无机盐的水溶液，或者采用酸性硫酸盐镀铜电镀液；所述阴极电镀槽区中的电镀液为酸性硫酸盐镀铜电镀液；电镀过程中，所述不溶性阳极(1)和阴极(4)分别隔离置于所述阳极电镀槽区和阴极电镀槽区中；所述的吸液管/口(2)，以及喷液管/口(10)设置在阳极电镀槽区内。
  5. 根据权利要求4所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，所述阳极电镀槽区采用阳极盒(13)的形式并安装在所述的电镀槽(5)中以对阳极电镀槽区和阴极电镀槽区作分隔，其具体为：所述阳极盒(13)为立方体型盒状，不溶性阳极(1)位于阳极盒(13)中，所述阳极盒(13)面朝向阴极镀件(4)的那一面为电镀槽分隔物(11)，所述阳极盒(13)的内部空间为阳极电镀槽区，所述电镀槽(5)中、阳极盒(13)以外的空间为阴极电镀槽区；所述的吸液管/口(2)设置在所述阳极盒(13)上，具体位于阳极盒(13)内所述不溶性阳极(1)背向阴极(4)的那一面的空间或盒壁上；另外，所述喷液管/口(10)位于阳极盒(13)内所述不溶性阳极(1)面向阴极(4)那一面与相邻盒壁之间的区域中。
  6. 根据权利要求1～5任一项所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，在所述的不溶性阳极的边沿增设定型框(16)，所述定型框(16)采用具有阳性不溶性、耐热耐酸且刚性较强的材料。
  7. 根据权利要求6所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，所述不溶性阳极(1)背向阴极(4)的那一面的表面连接有与电镀电源(6)正极连通的导电体(17)。
  8. 根据权利要求7所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，所述的不溶性阳极(1)和/或定型框(16)和/或导电体(17)面向阴极(4)那一面上设有反脉冲保护屏网(15)，所述反脉冲保护屏网(15)为无涂层钛材凸起物或凸起的网状物/条状物。
  9. 根据权利要求8所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，当反脉冲保护屏网(15)设在不溶性阳极(1)上，所述反脉冲保护屏网(15)为设置在阳极(1)面向阴极(4)那一面上的无涂层钛材凸起物或凸起的网状物/条状物，且与不溶性阳极(1)的钛基材直接连接；当反脉冲保护屏网(15)设在定型框(16)上且所述的定型框(16)为裸露钛材或者覆有涂层的钛材时，所述的反脉冲保护屏网(15)除了与不溶性阳极(1)的钛基材直接连接的方案外，或者单独与所述定型框(16)的钛材连接，又或者同时与两者连接；当所述的反脉冲保护屏网(15)设置在所述的导电体(17)上，将反脉冲保护屏网(15)穿过不溶性阳极(1)的网孔或镂空结构伸出不溶性阳极(1)表面朝向阴极(4)。
  10. 根据权利要求9所述的不溶性阳极酸性硫酸盐电镀铜的优化工艺，其特征在于，所述凸起物的形状是凸点状、尖刺状、竖条状；所述的凸起的网状物/条状物则是在不溶性阳极(1)和/或定型框(16)和/或导电体(17)面向阴极(4)那一面上伸向阴极(17)方向的支持脚端固定的网状物或条状物，或者是与上述凸起物上部相互连接形成的网状物或者条状物，所述网状物或者条状物构成的平面与阳极(1)面平行或者基本平行。
  11. 一种不溶性阳极酸性硫酸盐电镀铜的优化装置，包括电镀槽(5)、不溶性阳极(1)、作为镀件的阴极(4)、电镀电源(6)，其特征在于：所述的电镀槽内还设置有至少一个吸液管/口(2)，所述吸液管/口(2)位于所述不溶性阳极(1)背向阴极的那一面，用于使电镀液通过该吸液管/口(2)的溢流或/和电动吸液方式在电镀槽(5)内产生液流；
    所述的不溶性阳极(1)为覆有涂层的钛材，其形状为网状或者带镂空结构的板状；
    所述的电镀电源(6)的正极和负极在电镀过程中分别与所述的不溶性阳极(1)和作为阴极(4)的镀件连接。
  12. 根据权利要求11所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述的电镀槽(5)内设置有至少一个喷液管/口(10)，所述喷液管/口(10)设置在所述不溶性阳极(1)面向阴极(4)的那一面的两电极之间的区域空间内，该喷液管/口(10)外接一喷液管路，用于向阳极(1)喷液；所述装置采用回流系统，其主要由动力源和连接管道组成，其一端连接吸液管/口(2)，另一端连通喷液管/口(10)，利用该回流系统使由吸液管/口(2)吸走的电镀液再回流入电镀槽(5)中，形成电镀槽(5)内的电镀液流向阳极处的吸液管/口(2)的液流。
  13. 根据权利要求12所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述的吸液管/口(2)通过连接管道与气液分离器(8)相连接；所述气液分离器(8)还再通过泵浦和连接管道与电镀槽(5)连通以构成回流系统，将释放气体处理后的液体排回到电镀槽(5)中作循环流动。
  14. 根据权利要求13所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：在所述的电镀槽(5)中设置电镀槽分隔物(11)，将电镀槽(5)分隔开为阳极电 镀槽区和阴极电镀槽区。
  15. 根据权利要求14所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述阳极电镀槽区和阴极电镀槽区的分隔采用在电镀槽(5)中安装阳极盒(13)的方式来进行分隔：所述阳极盒(13)为立方体型盒状，不溶性阳极(1)位于阳极盒(13)中，所述阳极盒(13)面朝向阴极(4)的那一面为电镀槽分隔物(11)，所述阳极盒(13)的内部空间为阳极电镀槽区，所述电镀槽中除阳极盒以外的其余空间为阴极电镀槽区；所述的吸液管/口(2)设置在所述阳极盒(13)上，具体位于阳极盒(13)相对所述不溶性阳极(1)背向阴极(4)的那一面的空间或者盒壁上；另外，所述阳极盒(13)内还设置有喷液管/口(10)，具体位于阳极盒(13)内所述不溶性阳极(1)面向阴极(4)的那一面与相邻盒壁之间的区域中。
  16. 根据权利要求15所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述的阳极盒朝向阴极镀件的那一面的外侧面边沿四周装设有液体喷射管(14)，并且各液体喷射管(14)中装置有流量调节器，以便作向阴极电镀液的喷射效果的调节。
  17. 根据权利要求16所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述的不溶性阳极(1)上还设有反脉冲保护屏网(15)，所述反脉冲保护屏网(15)是设置在不溶性阳极(1)面向阴极(4)的那一面上的无涂层钛材凸起物，所述凸起物与不溶性阳极(1)的钛基材直接连接，并且所述凸起物的形状是凸点状，尖刺状，竖条状，或与上述形状结构连接的网状/条状。
  18. 根据权利要求17所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述的不溶性阳极(1)的边沿处还设置有定型框(16)。
  19. 根据权利要求18所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：所述不溶性阳极(1)背向阴极(4)的那一面安装连接有与电镀电源(6)正极连通的导电体(17)。
  20. 根据权利要求19所述的不溶性阳极酸性硫酸盐电镀铜的优化装置，其特征在于：将带有所述反脉冲保护网(15)、定型框(16)、导电体(17)的不溶性阳极(1)和吸液管/口(2)、喷液管/口(10)的不溶性阳极组件安装在所述带液体喷射管(14)的阳极盒(13)中作为阳极槽区总成。
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