WO2020042870A1 - Procédé et dispositif de production et de régénération de solution de placage pour électrodéposition de cuivre d'acide anodique insoluble - Google Patents

Procédé et dispositif de production et de régénération de solution de placage pour électrodéposition de cuivre d'acide anodique insoluble Download PDF

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WO2020042870A1
WO2020042870A1 PCT/CN2019/099192 CN2019099192W WO2020042870A1 WO 2020042870 A1 WO2020042870 A1 WO 2020042870A1 CN 2019099192 W CN2019099192 W CN 2019099192W WO 2020042870 A1 WO2020042870 A1 WO 2020042870A1
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electrolytic
plating
anode
cathode
acidity
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PCT/CN2019/099192
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English (en)
Chinese (zh)
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叶涛
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叶涛
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Priority to CN201980055803.8A priority Critical patent/CN112714803B/zh
Priority to TW108130113A priority patent/TWI707067B/zh
Publication of WO2020042870A1 publication Critical patent/WO2020042870A1/fr

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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the technical field of acid copper electroplating, and particularly relates to a method and a device for producing a plating solution or a plating rehydration solution in an insoluble anode acid copper plating process.
  • Electroplating is the process of plating a thin layer of other metal or alloy on the metal surface by using the principle of an electrolytic cell.
  • the existing acid copper sulfate electroplating copper process can be mainly divided into two processes: soluble anode and insoluble anode.
  • Soluble anodized copper electroplating refers to the type of process in which the anode will gradually dissolve during the electrochemical reaction of electroplating.
  • a common soluble anode material is phosphor copper.
  • copper ions in the plating solution are reduced to metallic copper on the surface of the cathode plating to achieve electroplating, and the copper ions in the plating solution are continuously consumed; at the same time, the copper metal on the phosphorous copper as the anode is dissolved into copper ions. Thereby, the copper ion of the plating solution is supplemented.
  • phosphorous copper is used instead of metallic copper as the soluble anode.
  • the reason is that the surface of the metallic copper anode is easily oxidized by the oxidizing substance in the plating solution to copper oxide or cuprous oxide during the electroplating process, resulting in metal.
  • the dissolution speed of the copper anode is not uniform, which causes the composition of the plating solution to be unstable, which in turn affects the quality of the plating.
  • phosphorous copper as a soluble anode can improve the defect of uneven anode dissolution speed to a certain extent, when using a phosphorous copper anode, the problem of unstable anode quality caused by anodic polarization and uneven current distribution is easy to occur; another On the one hand, phosphorous copper is relatively expensive. During its production and use, toxic phosphorus-containing wastewater is generated, which enters the human body and is extremely harmful to the liver and other organs. In order to achieve the wastewater discharge target, it is necessary to increase the cost of electroplating waste liquid treatment.
  • insoluble anodized copper electroplating process is just the opposite, which refers to the electroplating process in which the anode does not occur or a small amount of dissolution occurs during the electroplating reaction.
  • Common insoluble anodes are titanium, conductive graphite, platinum and lead alloys coated with precious metal oxides.
  • the first common acidic copper plating process using insoluble anodes uses an aqueous solution of copper sulfate and sulfuric acid as the plating solution.
  • Water reacts at the anode to generate hydrogen ions and oxygen. Copper ions in the plating solution are reduced to metal at the cathode. copper.
  • the sulfuric acid concentration in the electroplating solution is getting higher and higher. Therefore, during the electroplating process, copper oxide needs to be continuously added. On the one hand, it reacts with the sulfuric acid in the electroplating solution to supplement the copper ions lost in the electroplating solution.
  • the equivalent amount of sulfuric acid is correspondingly consumed to suppress the continuous increase of sulfuric acid concentration in the plating solution.
  • Another common acid copper plating process using an insoluble anode is to add iron ions on the basis of a plating solution whose main component is copper sulfate and an aqueous sulfuric acid solution.
  • the electrochemical reaction on the anode is the oxidation of divalent iron ions to trivalent iron ions. Copper ions are reduced to metallic copper at the cathode.
  • the ferrous ion is used to continuously corrode the copper metal outside the electroplating system to supplement the copper ion concentration of the electroplating solution.
  • This process can reduce the amount of oxygen dissolved in the plating solution, and avoid the problem of degradation of the plating quality caused by oxygen.
  • the metal copper on the cathode plating is etched back, which destroys the formed plating layer, and then affects the plating quality.
  • the first object of the present invention is to provide a method for producing a plating solution or a plating rehydration solution in an insoluble anode acid copper plating process.
  • the production method has low cost, and the prepared solution can be used as a plating solution or a plating rehydration solution or a finished sulfuric acid. Copper solution to suit many different needs.
  • a second object of the present invention is to provide a device for realizing the production method of a plating solution or a plating rehydration solution suitable for the above-mentioned insoluble anode acid copper plating process.
  • a method for producing a plating solution or a plating rehydration solution in an insoluble anode acid copper plating process includes the following steps:
  • An electrolytic cell is provided, and the electrolytic cell is separated into an electrolytic anode region and an electrolytic cathode region by using an electrolytic cell membrane, and the electrolytic cell membrane is used to prevent cations from passing through to prevent the cations from passing between the electrolytic anode region and the electrolytic cathode region.
  • the anolyte is composed of an aqueous solution of at least one of sulfuric acid and copper sulfate, and the composition in terms of mass percentage is:
  • the rest is water, and the total mass percentage of the solute in the anolyte is not less than 0.03%;
  • a metal electrode containing a copper element is used as an electrolytic anode, and the electrolytic anode is immersed in the anolyte; a conductor is used as an electrolytic cathode, and the electrolytic cathode is immersed in the cathode electrolysis Liquid
  • an electroplating solution or electroplating rehydration solution suitable for insoluble anode acid copper electroplating is separately produced to provide a plating solution required for the production of insoluble anode acid copper electroplating, and / or by adding the electroplating liquid in the electroplated copper production in a timely manner.
  • the method of electroplating to maintain the concentration of copper ions in the electroplating solution that can continuously plate copper can not only ensure good electroplating quality, but also simple operation, without using complicated and large equipment, and without expensive chemicals as raw materials.
  • the cost of electroplated copper is reduced, which significantly improves the processability and cost performance of the electroplated copper production.
  • the role of the electrolytic cell membrane in step (1) of the present invention is to prevent cations from passing through, so as to prevent free exchange of cations between the electrolytic anode region and the electrolytic cathode region, and at the same time, allow the charge to be electrolyzed in the electrolysis process during the electrolysis.
  • a transition is made between the anode region and the electrolytic cathode region.
  • the electrolytic cell membrane may use an anion exchange membrane and / or a bipolar membrane.
  • the catholyte is composed of an aqueous solution of at least one of sulfuric acid, sulfate, carbonic acid, and an inorganic base, and the total mass percentage of the solute in the catholyte is 0.1 to 40%. At least one of said catholytes contains sulfuric acid.
  • the catholyte is water or an aqueous solution of an electrolyte
  • the electrolyte may be any electrolyte
  • the anolyte needs to contain sulfuric acid.
  • the anolyte prepared in step (2) of the present invention may be prepared by using component raw materials, or it may be a plating solution derived from an insoluble anode acid copper electroplating process production line.
  • the copper ion concentration in the anolyte can reach different predetermined values, so that solutions for different uses such as electroplating solution, electroplating rehydration solution or finished copper sulfate solution can be obtained:
  • the predetermined value is equal to the concentration of copper ions in the plating solution required on the insoluble anode acid copper electroplating process production line.
  • the obtained solution can be directly used as the initial plating solution for the insoluble anode acid copper electroplating process, or it can be used as a plating rehydration solution. Add directly to the plating solution during the plating process to quickly replenish the copper ions lost during the plating process;
  • the predetermined value is any value other than zero, and the obtained solution can be used as one of the raw materials for the initial plating solution for the preparation of the insoluble anode acid copper plating process;
  • the predetermined value is greater than the concentration of copper ions in the plating solution required on the insoluble anode acid copper electroplating process production line.
  • the resulting solution can be directly added to the plating solution as a plating replenishment during the plating process to quickly supplement the plating process. Lost copper ions;
  • the predetermined value is equal to the concentration of copper ions in the finished copper sulfate solution, and the obtained solution can be used as a finished copper sulfate solution.
  • the working principle of the present invention In the electrolytic cell, the metal copper on the anode becomes copper ions and dissolves in the anolyte, and the hydrogen ions on the cathode become hydrogen to escape the electrolytic cell.
  • the specific electrochemical reaction that occurs is as follows :
  • hydroxide ions and / or carbonate ions in the catholyte and / or inorganic base anions in the catholyte can enter the electrolytic anode through the anion exchange membrane.
  • the zone is combined with hydrogen ions in the anolyte to generate water to consume sulfuric acid in the anolyte.
  • the sulfate radical originally belonging to the sulfuric acid in the anolyte and the anode electrochemically generated copper ions form copper sulfate.
  • the hydroxide ions generated by the cathode electrochemical reaction combine with the hydrogen ions in the catholyte to generate water to consume the sulfuric acid in the catholyte.
  • the catholyte originally belongs to the sulfate ion of sulfuric acid. Copper sulfate can be formed by anion exchange membrane entering the electrolytic anode area and the copper ions electrochemically generated by the anode.
  • the preparation of the anolyte can also use water as the electrolyte first, and then apply an electrolytic voltage higher than the working setting
  • the electrolysis is performed by passing the sulfate in the catholyte through the anion exchange membrane and the copper ions generated on the anode to form a copper sulfate electrolyte. Because water itself has a weaker ionization capacity, ion transfer can also occur at higher electrolytic voltages to achieve electrochemical reactions.
  • the bipolar membrane is a special ion exchange membrane, it is a negative and positive composite membrane made of a cation exchange membrane and an anion exchange membrane.
  • anion and cation exchange water (H 2 O) between the composite layer film dissociate into hydrogen ions (H +) and hydroxide ions (OH -), respectively by an anion exchange membrane and the cation exchange membrane, as H + and OH - ions.
  • H + hydrogen ions
  • OH - hydroxide ions
  • the present invention adopts a bipolar membrane as an electrolytic cell diaphragm
  • the characteristics of the bipolar membrane that can be hydrolyzed to H + and OH - under the action of a direct-current electric field can be used directly as water as a catholyte.
  • You can also use the electrolytic solution of the electrolyte as the catholyte, which can effectively improve the electrical efficiency and reduce the electrolytic voltage. Because the solutions on both sides of the bipolar membrane are not connected, the selected electrolyte can be dissolved in water to generate ions. There is no limit.
  • the sulfate in the catholyte according to the present invention is a strong electrolyte salt of sulfuric acid, that is, a water-soluble sulfate, including potassium sulfate, sodium sulfate, copper sulfate, iron sulfate, aluminum sulfate, ferrous sulfate, titanium sulfate, and ammonium sulfate.
  • a water-soluble sulfate including potassium sulfate, sodium sulfate, copper sulfate, iron sulfate, aluminum sulfate, ferrous sulfate, titanium sulfate, and ammonium sulfate.
  • cadmium sulfate, magnesium sulfate, manganese sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, nickel sulfate, and zinc sulfate and there is no limitation on the ratio of various sulfates.
  • the inorganic base according to the present invention has at least one of hydroxide, carbonate and bicarbonate, including sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and hydrogen carbonate.
  • hydroxide, carbonate and bicarbonate including sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and hydrogen carbonate.
  • potassium, ammonium carbonate, and ammonium bicarbonate, and the ratio of various inorganic bases are not limited.
  • the electrolytic cathode is an acid- and alkali-resistant conductive body, and is preferably composed of a metal and / or graphite.
  • the metal may be titanium, platinum, gold, silver, copper, or iron. Any of the above, or an alloy containing at least one of the above metals, may be a bare metal, or a metal electrode coated with an electrode coating or an inert metal on the surface, or stainless steel, the inert metal Including but not limited to platinum and gold, the inert metals that can be used when the catholyte does not contain sulfuric acid also include titanium and silver.
  • the electrolytic anode according to the present invention contains other metallic elements and / or insoluble impurities other than copper, it can still achieve the purpose of electrolytically generating copper sulfate. However, it may cause other metal ion impurities and / or insoluble solid impurities in the anolyte obtained from the electrolysis. When it is used as a plating solution or a plating replenisher for electroplating, it may cause power consumption and the plating layer to contain metals other than copper. Impurities, problems such as uneven and uneven plating, affect production efficiency or plating quality. At this time, it is usually necessary to increase filtration or other means to reduce impurities in the resulting anolyte to ensure that it can achieve better plating quality when used in electroplating.
  • the electrolytic anode used contains other metallic elements and / or insoluble impurities, the less the better, the copper anode is preferred for the electrolytic anode in the present invention.
  • the present invention is associated with an insoluble anode acid copper electroplating process production line, and adjusts the electrolytic current of step (5) according to the present invention according to the dynamic change of process parameters on the insoluble anode acid copper electroplating process production line.
  • control the turning on or off of the electrolytic power source of the present invention or dynamically change the process parameters of the electrolytic process in step (5) of the present invention, or adjust the size of the plating current on the insoluble anode acid copper electroplating process production line, or Control the turning on / off of the electroplating power supply on the insoluble anode acid copper electroplating process production line, so that the process parameters of the plating rehydration obtained by the present invention can be matched with the process parameters of the insoluble anode acid copper electroplating process production line, or can make the production line
  • the copper ions in the electroplating solution can be replenished in time.
  • the process parameters include copper ion concentration, sulfuric acid concentration, working time, and workload.
  • the present invention when the present invention is associated with an insoluble anodic acid copper electroplating process production line, that is, the anolyte according to the present invention is directly derived from the insoluble anodic acid copper electroplating process production line and / Or electroplating waste liquid, after the step (5) turns on the electrolytic power to start the electrolytic reaction, the copper ion concentration of the anolyte and / or the copper ion concentration of the plating solution on the insoluble anode acid copper electroplating process line of the present invention is performed Detect and adjust the size of the electrolytic current and / or the plating current on the production line according to the detection result, or turn on / off the electrolytic power and / or the plating power on the production line according to the present invention.
  • the specific operations are as follows:
  • the copper ion concentration of the anolyte and / or the plating solution on the production line of the present invention is less than or equal to a set value, increase the electrolytic current or turn on the electrolytic power to promote the electrolytic reaction of the present invention and / or reduce the The plating current is used to reduce the copper ion consumption rate of the plating solution, until the copper ion concentration of the anolyte and / or the copper ion concentration of the plating solution on the production line is restored to the set value, the electrolytic current is reduced or shut down Electrolytic power, and / or increased plating current.
  • the copper ion concentration of the anolyte and / or the plating solution on the production line it can be detected indirectly by detecting the specific gravity value and / or the photoelectric colorimetric value and / or the redox potential of the anolyte.
  • the copper ion concentration of the anolyte and / or the copper ion concentration of the plating solution The greater the specific gravity of the measured anolyte and / or the plating solution on the production line, or the darker the color, or the higher the redox potential, the higher the concentration of copper ions.
  • the concentration of sulfuric acid and / or sulfate and / or carbonic acid and / or inorganic alkali in the catholyte is detected. And adding sulfuric acid and / or sulfate and / or water and / or carbon dioxide to the electrolytic cathode area according to the detection result, so as to adjust the sulfuric acid and / or sulfate and / or carbonic acid and / or inorganic in the catholyte
  • the concentration of alkali is maintained within the set value:
  • sulfuric acid and / or sulfate and / or carbonic acid and / or carbonate or bicarbonate inorganic base concentration in the catholyte is less than or equal to a set value
  • sulfuric acid or Its aqueous solution and / or sulfate or its aqueous solution and / or carbon dioxide or when the concentration of the catholyte due to evaporation of water is greater than or equal to a set value
  • water is added to the electrolytic cathode area until the cathode is electrolyzed
  • the concentration of sulfuric acid and / or sulfate and / or inorganic base of the liquid returns to the set value.
  • the sulfuric acid concentration of the catholyte can be indirectly detected by detecting the acidity value and / or specific gravity value of the catholyte;
  • the pH and / or specific gravity of the catholyte can be used to indirectly detect the sulfate and / or carbonic acid and / or of the catholyte Inorganic alkali concentration; in the process of detecting the concentration of the inorganic alkali and / or carbonic acid in the carbonic acid and / or bicarbonate of the catholyte, the carbonation of the catholyte can be detected indirectly by detecting the electrolytic cell pressure of the present invention.
  • Base and / or bicarbonate inorganic base component and / or carbonic acid are examples of the electrolytic cell pressure of the present invention.
  • the separator is an anion exchange membrane
  • the electrolytic reaction proceeds, part of the carbonate and / or Bicarbonate ions enter the electrolytic anode zone through the diaphragm and react with hydrogen ions in the anolyte to generate water and carbon dioxide.
  • the pH of the catholyte also rises due to the increase in hydroxide ion concentration As the concentration of hydroxide ions in the catholyte increases, the proportion of hydroxides in the anions passing through the anion exchange membrane becomes larger and larger.
  • the present invention passes oxygen into the anolyte, and the oxygen may be derived from the oxygen generated at the electrolytic anode and / or an external oxygen source and / or air.
  • the purpose of passing oxygen into the anolyte is to accelerate the increase of the copper ion concentration in the anolyte.
  • the principle is that oxygen oxidizes part of the metal copper in the electrolytic anode to copper oxide, and the generated copper oxide and sulfuric acid The reaction produces copper sulfate, which does not affect the progress of the electrolytic reaction while increasing the copper ion concentration.
  • the more oxygen is passed in the faster the copper ion concentration increases, so the oxygen inflow is not particularly limited.
  • the electrolytic anode according to the present invention contains copper oxide. Similar to the above principle, the copper oxide in the electrolytic anode reacts with sulfuric acid to generate copper sulfate, which accelerates the increase of the copper ion concentration in the anolyte.
  • an insoluble electrolytic anode may be provided at the bottom of the electrolytic anode area.
  • metallic copper sink to the bottom of the electrolytic anode region will fall electrolytic insoluble anode surface
  • metallic copper is directly subjected to the insoluble anode current electrolytic reaction takes place, Cu-2e - ⁇ Cu 2+ , whereby a solid The copper sludge is converted into copper ions and dissolved in the anolyte.
  • the insoluble anode electrolytic oxygen generation reaction will occur, 2H 2 O + 2e - ⁇ O 2 + 4H +, to reach in the anolyte
  • the conductor is resistant to sulfuric acid or copper sulfate during the electrolytic process, it can be used as the insoluble electrolytic anode, such as common titanium coated with precious metal oxides, conductive graphite, platinum, gold, metals plated with platinum or gold, etc.
  • Electrolytic anode As long as the conductor is resistant to sulfuric acid or copper sulfate during the electrolytic process, it can be used as the insoluble electrolytic anode, such as common titanium coated with precious metal oxides, conductive graphite, platinum, gold, metals plated with platinum or gold, etc. Electrolytic anode.
  • the electrolytic current of the electrolytic anode is higher than the electrolytic current of the insoluble electrolytic anode at the bottom of the electrolytic anode region, so as to reduce unnecessary power consumption when there is little or no metallic copper falling on the surface of the insoluble electrolytic anode.
  • the anolyte having a copper ion concentration higher than that of the plating solution is added to the plating tank on the production line by detecting the copper ion concentration and / or acid concentration in the plating solution and / or according to the time setting.
  • the concentration of copper ions in the plating solution can be correspondingly reflected by its specific gravity value and / or redox potential value and / or colorimetric value, and the acid concentration in the plating solution can be correspondingly reflected by its acidity value and / or pH value. .
  • the electroplating tank on the production line and / or the electrolytic anode area and / or the electrolytic cathode area of the present invention by monitoring the liquid level of the electroplating tank on the production line and / or the electrolytic anode area and / or the electrolytic cathode area of the present invention, the electroplating tank on the production line and / or the electrolytic anode area of the present invention and / Or add electrolytic water to the cathode area of the electrolyte or the corresponding plating solution or the aqueous solution of the components contained in the electrolyte.
  • the separator may also use two layers of anion exchange membranes, or when a bipolar membrane is used as the separator, the separator may be formed by a double layer A combination of a polar membrane and an anion exchange membrane, wherein the anion exchange membrane is located on the side of the anion exchange membrane in the bipolar membrane, the two anion exchange membranes or a bipolar membrane and a
  • the combination of two anion exchange membranes allows an electrolytic buffer zone to be formed between the electrolytic anode region and the electrolytic cathode region to prevent hydroxide ions generated on the electrolytic cathode and / or anions of the original inorganic base of the catholyte from passing through.
  • the anion exchange membrane is in contact with the copper ions of the anolyte, or the hydroxide ions generated on the bipolar membrane are in direct contact with the copper ions of the anolyte, thereby preventing the diaphragm from being easily blocked by the generated copper slurries without this electrolytic buffer.
  • the electrolytic buffer contains a buffer electrolyte, and the buffer electrolyte is an aqueous solution containing no copper ions but containing sulfuric acid.
  • the reason that the electrolytic buffer is not provided in the electrolytic cell is likely to cause the copper mud to block the diaphragm.
  • the diaphragm uses an anion exchange membrane and the catholyte is neutral or alkaline, hydroxide ions and / or The anion of the original inorganic base of the catholyte can enter the electrolytic anode region through the anion exchange membrane; when the membrane is a bipolar membrane, hydroxide ions generated on the bipolar membrane will directly enter the electrolytic anode region.
  • the hydroxide ion or the anion of the inorganic base Once the hydroxide ion or the anion of the inorganic base enters the electrolytic anode zone, it will react with copper ions and generate copper sludge such as copper hydroxide on the separator, thereby accumulating copper sludge and causing the diaphragm to be blocked, affecting the progress of the electrolytic reaction.
  • the diaphragm When the diaphragm is blocked by the copper mud in a large area, the diaphragm must be replaced. It can be seen that the problem of clogging the diaphragm with copper sludge will cause the service life of the diaphragm to decrease and increase production costs virtually.
  • an electrolytic buffer is provided between the electrolytic anode area and the electrolytic cathode area, so that hydroxide ions and / or anions of inorganic bases react with sulfuric acid in the buffer electrolyte before entering the electrolytic anode area.
  • the separator is a combination of a bipolar membrane and an anion exchange membrane and the anion exchange membrane is on the side of the anion exchange membrane in the bipolar membrane
  • the buffer electrolyte is free of free hydrogen
  • the ionic aqueous solution can also achieve the purpose of the present invention, that is, it can still produce electroplating rehydration, etc., but it can not play the role of the electrolytic buffer, that is, there may still be the phenomenon that the copper mud blocks the diaphragm. This is because the buffer electrolyte does not contain free hydrogen ions.
  • the hydroxide ions generated on the bipolar membrane cannot be consumed in the electrolytic buffer, and will continue to enter the electrolytic anode area through the anion exchange membrane.
  • the copper ions react and form copper sludge deposits such as copper hydroxide on the anion exchange membrane.
  • the pH value and / or the acidity value and / or the specific gravity value of the buffer electrolyte are detected, and the buffer electrolyte is electrolyzed according to the detection result.
  • the present invention can further make the following improvements:
  • the present invention is connected to the electroplated copper production line and combined into a whole production, that is, the electrolytic cell and the solution in the electroplating production line of the present invention form a controllable circulating flow system, and the preferred method is in the electroplated copper production process.
  • the anode After detecting that the anolyte in the electrolytic cell of the present invention reaches or exceeds a set value, and the plating solution on the electroplating production line needs to supplement the copper ion content, the anode can be electrolyzed by the related equipment control
  • the electrolyte is directly added to the plating tank, and at the same time, a medium amount of the plating solution is transferred to the electrolytic anode region of the electrolytic cell of the present invention as an anolyte to increase the copper ion concentration, thus forming a recycling cycle for electroplating and electrolytic regeneration. system.
  • the electrolytic cell membrane uses an anion exchange membrane
  • the catholyte contains sulfate
  • the electrolytic reaction proceeds
  • the sulfate ion in the catholyte will pass through the anion exchange membrane and enter the electrolytic anode zone, resulting in a continuous decrease in the sulfate ion concentration in the catholyte, and the sulfate ion concentration in the anolyte Keep rising.
  • the reduction of sulfate ions in the catholyte means the reduction of conductive ions, which increases the resistance of the electrolyte and further reduces the electrical efficiency. To avoid this, it is necessary to supplement the sulfate ion in the catholyte. At this time, if the method of directly adding sulfuric acid / sulfate to the catholyte is used to supplement the number of sulfate ions, the total amount of sulfate ions in the entire electrolysis and electroplating system will be increased, thereby destroying the overall balance of the electrolysis and electroplating reactions.
  • an acidity balance cathode area is separated in the electrolytic anode area, and the acidity balance cathode area faces the electrolytic cathode area using a separator as a separator.
  • the acidity-balanced cathode region contains acidity-balanced catholyte.
  • the acidity-balanced catholyte is an inorganic alkaline aqueous solution with a mass percentage of 0.5 to 35%; when the acidity When a bipolar membrane is used as the separator in the balanced cathode region, the acidity balanced catholyte is an aqueous solution of water and / or electrolyte in a mass percentage; the acidity balanced electrolysis system includes an acidity balanced cathode region disposed in the acidity balanced cathode region.
  • the acidity balanced anode and the acidity balanced cathode are both insoluble electrodes, preferably composed of metal and / or graphite.
  • the metal surface of the insoluble electrode may be covered with a protective coating or an inert metal, and the metal is preferably titanium or platinum.
  • the inert metal includes, but is not limited to, platinum and gold
  • the solution contacted by the acidity balance electrode does not contain Inert metals that can be used in sulfuric acid include titanium and silver.
  • the acidity balance electrolysis system will cause the water in the electrolytic solution of the present invention to undergo an electrolytic reaction, generate hydrogen at the acidity balance cathode, and generate oxygen and hydrogen ions at the acidity balance anode.
  • Sulfate ions in the anolyte are affected by the electric field gravity of the acidity balance anode and pass through the anion exchange membrane into the electrolytic cathode area, and combine with hydrogen ions generated by water electrolysis to form sulfuric acid, thereby improving the sulfate of the catholyte concentration.
  • the catholyte can also be prepared by preparing the anolyte and adding it to the electrolytic cell.
  • the cathode electrolysis zone first uses water as the electrolyte, and then applies an acid equilibrium electrolysis voltage higher than the working balance to the acid balance electrolysis system for electrolysis, so that the sulfate in the anolyte passes through the anion exchange membrane and the acidity balance anode to produce The hydrogen ions form sulfuric acid to complete. Because water itself has a weaker ionization capacity, ion transfer can also occur at higher electrolytic voltages to achieve electrochemical reactions.
  • the present invention can also detect the concentration of the inorganic base of the acidity-balanced catholyte and perform inorganic alkali and / or the acidity-balanced catholyte according to the detection result. Carbon dioxide is added or the acidity balance catholyte is replaced with a new one.
  • the diaphragm of the acidity balance cathode area uses a bipolar membrane, the liquid level of the acidity balance catholyte can be detected and the acidity balance can be adjusted according to the detection result. Add catholyte to water, or replace the catholyte with a new acidity balance:
  • the diaphragm of the acidity balanced cathode region uses an anion membrane and the concentration of the inorganic base in the acidity balanced catholyte is lower than the initial value, an inorganic base and / or carbon dioxide is added to the acidity balanced catholyte until the acidity is balanced.
  • the concentration of each component in the catholyte is restored to the initial value, or the catholyte is replaced with a new acidity balance.
  • the detection of the concentration of the inorganic alkali in the acidity-balanced catholyte can also be reflected correspondingly by detecting the pH value and / or the acidity value and / or the specific gravity value of the acidity-balanced catholyte.
  • the invention relates to a production device for an insoluble anode acid copper plating electroplating bath or a plating rehydration process, which is characterized in that it includes an electrolytic device, which is mainly composed of an electrolytic cell, an electrolytic anode, an electrolytic cathode, and an electrolytic power source. And the electrolytic cathode are respectively connected to a positive electrode and a negative electrode of the electrolytic power source, wherein:
  • the electrolytic cell is provided with an electrolytic cell membrane, and the electrolytic cell is divided into an electrolytic anode region and an electrolytic cathode region, and the electrolytic anode region and the electrolytic cathode region are respectively used for containing an anolyte and a catholyte;
  • the electrolytic anode is a soluble electrolytic anode, the electrolytic anode contains a copper element (corresponding to a method main item), and the electrolytic anode is disposed in the electrolytic anode area, and the Copper electrolysis is copper ions, used to increase the copper ion concentration in the anolyte;
  • the electrolytic cathode is a conductor, and the electrolytic cathode is disposed in the electrolytic cathode region.
  • the present invention can further improve the following:
  • the present invention can add a current regulator to the electrolytic power supply, or use the current regulator that comes with the power supply itself to adjust the output current of the electrolytic power supply, or control the on / off of the electrolytic power supply.
  • the output current of the electrolytic power supply can affect the rate of increase of the copper ion concentration in the anolyte during the electrolytic reaction. The larger the output current, the faster the increase of the copper ion concentration; otherwise, the smaller the output current, the copper ion concentration The slower the rate of increase.
  • Connect the current regulator to the detection device of the electrolyte or plating solution and set the set value of the relevant detection index which can automatically control the current regulator pair according to the dynamic index detected by the detection device for the electrolyte or plating solution in real time. Regulating operation of output current of electrolytic power supply.
  • the electrolytic cell membrane according to the present invention uses an anion exchange membrane and / or a bipolar membrane.
  • the electrolytic anode containing copper element according to the present invention may be an electrolytic anode containing metallic copper, or an electrolytic anode containing both metallic copper and copper oxide.
  • an electrolytic solution stirring device may be added to the electrolytic anode area and / or the electrolytic cathode area; the electrolytic solution stirring device may use the electrolyte reflux liquid to stir. Any one of the agitating device, a blade stirring device, and a pneumatic stirring device, or any combination thereof.
  • the electrolyte reflux liquid stirring device includes a liquid outlet pipe, a pump, and a return pipe. A device in which an electrolyte is passed into a gas to cause the electrolyte to flow.
  • the invention can also provide a hydrogen efflux system above the electrolytic cathode area, which is used to suck the hydrogen generated by the electrolytic reaction in the electrolytic cathode area to avoid the safety hazard caused by the accumulation of hydrogen.
  • the hydrogen exhaust system can be a general exhaust system or a simple exhaust pipe.
  • the electrolytic anode region according to the present invention is connected to the electroplating tank of the insoluble anode acid copper electroplating process by pipes, so that when the copper ion concentration of the anolyte reaches a predetermined value, or When the copper ion concentration of the plating solution is lower than the set value of the insoluble anodic acid copper electroplating process, the anolyte can be directly added as a plating solution to a plating bath of the insoluble anodic acid copper electroplating process, or the electroplating The plating solution in the tank flows into the electrolytic anode region.
  • the electrolytic anode area is connected to the electroplating tank through a pump and a pipe and / or an overflow port, and a diaphragm and / or a filtering device is provided at the place where the electrolytic anode area is connected to the electroplating tank, in order to remove the plating solution and / Or copper sludge that may be present in the electrolyte and / or impurities brought during the use of the electrode.
  • a level gauge, a hydrometer, an acidity meter, a redox potentiometer, and a photoelectric colorimeter are provided in the plating tank on the production line and / or the electrolytic anode area and / or the electrolytic cathode area according to the present invention.
  • one or more detection devices in the pH meter to detect corresponding parameters in the plating bath and / or the anolyte and / or catholyte of the present invention in the plating bath.
  • the electrolytic solution detection device is connected to an automatic feeding controller, and the automatic feeding controller can be based on time and / or the detection result of the plating solution and / or the electrolytic solution detection device and / or the present invention.
  • Control of the electrolytic cell pressure by adding an anolyte to the electroplating solution, and / or adding an electroplating solution and / or raw materials and / or water to the anolyte, and / or electrolyzing to the cathode Add raw materials and / or carbon dioxide and / or water to the solution.
  • the diaphragm uses two layers of anion exchange membrane or a combined diaphragm composed of a bipolar membrane and a layer of anion exchange membrane in the electrolytic anode region and the electrolytic cathode region.
  • An electrolytic buffer is separated from the electrolytic buffer.
  • the electrolytic buffer contains a copper ion-free and sulfuric acid-containing aqueous solution as an electrolytic buffer.
  • a stirring device and / or a buffer detection device may be provided in the electrolytic buffer zone.
  • the buffer detection device includes one or more of a pH meter, an acidity meter, and a hydrometer, and is used for measuring
  • the buffer solution in the electrolytic buffer described above is used to detect one or more indicators.
  • the buffer detection device can be further connected to an automatic feeding controller, and the automatic feeding controller can control the supplementation of sulfuric acid and / or the electrolytic buffer according to the detection result of the buffer detection device. Or a solution containing sulfuric acid.
  • an acidity balanced cathode region is separated in the electrolytic anode region, and the acidity
  • the balance cathode area faces the electrolytic cathode area using an anion exchange membrane as a partition, and an acidity balance electrolysis system is provided at the same time, so that during the electroplating production, the electrolytic cell of the present invention is connected with the electroplating tank on the production line to form a circulating flow system.
  • the concentration of sulfate ions in the catholyte is increased, while maintaining the stability of the electrolyte components , Reduce the resistance of the electrolyte.
  • the acidity balance electrolysis system is mainly composed of the acidity balance cathode area, an acidity balance cathode provided in the acidity balance cathode area, and an acidity balance anode provided in the electrolytic cathode area, and an acidity balance
  • the power source is composed of the acidity balanced cathode and the acidity balanced anode, which are respectively connected to the negative electrode and the positive electrode of the acidity balanced power source.
  • a plurality of detection devices such as a stirring device and / or a pH meter and / or an acidity meter and / or a specific gravity meter may be further provided for the acidity-balanced cathode.
  • the acidity balance catholyte in the zone is tested for one or more indicators.
  • a supplementary liquid addition tank and / or a carbon dioxide source, and an automatic feeding controller may be further added, wherein the supplementary liquid addition tank and the acidity are added.
  • the balance cathode area pipeline is connected and a supplementary liquid pump is provided on the pipeline.
  • the carbon dioxide source is connected to the acidity balance cathode area pipeline and a gas valve is provided on the pipeline between the two to control the flow of carbon dioxide gas.
  • the automatic feeding controller is respectively connected to the detection device in the acidity balance cathode zone, a make-up liquid pump and / or a carbon dioxide source gas valve, and controls the supplement according to the detection result of the detection device
  • the flow of the liquid pump and / or the carbon dioxide source gas valve is either on / off.
  • a hydrometer and / or an acidity meter and / or a pH meter may be provided in the electrolytic cathode region, and the acidity balance may be controlled according to the detection results of the hydrometer and / or the acidity meter and / or the pH meter.
  • the power and / or electrolytic power is either on or off.
  • the present invention has the following beneficial effects:
  • the present invention provides a plating solution required for the production of insoluble anode acid copper electroplating by separately producing a plating solution or a plating rehydration solution suitable for the insoluble anode acid copper electroplating process, and / or by providing the electroplating in the electroplated copper production in a timely manner.
  • the method of adding electroplating liquid to maintain the concentration of copper ions in the electroplating solution that can sustain copper plating can not only ensure good electroplating quality, but also simple operation, without using complicated and large equipment, and without expensive chemicals as raw materials.
  • the cost of the electroplated copper is reduced, thereby overcoming the shortcomings of the prior art, and significantly improving the processability and cost performance of the electroplated copper production, which is conducive to implementation and application in actual production;
  • the present invention can also produce an initial electroplating bath or produce an electroplating bath.
  • Raw materials can also produce finished copper sulfate solution for direct sale, with various uses;
  • the present invention can be connected with the insoluble anode acid copper electroplating process production line to form a plating and electrolytic regeneration recycling system.
  • the produced plating rehydration liquid is controlled according to the process requirements and real-time conditions of the insoluble anode acid copper electroplating process production line.
  • the addition amount can automatically control the copper ion replenishing speed in the plating solution, thereby ensuring that the plating can obtain a high-quality copper layer;
  • an electrolytic buffer zone can be provided between the electrolytic anode region and the electrolytic cathode region of the electrolytic reaction, thereby avoiding the problem that the copper sludge is generated on the diaphragm and causing the diaphragm to be blocked, thereby improving the service life of the diaphragm;
  • the sulfate ion in the catholyte can be increased without increasing the total sulfate ion concentration in the electrolyte. Increased concentration reduces the resistance of the electrolyte while maintaining the stability of the electrolyte components;
  • the parameters of the electrolyte of the present invention or / and the plating solution on the production line can be tested, and the plating or / and The size of the electrolytic current of the invention, or the control of the electroplating on the production line, and / or the turning on or off of the electrolytic power source of the invention, enables the electrolytic production of the plating rehydration solution of the invention and the insoluble anode acid copper electroplating process production line to achieve a continuous, Stable plating production.
  • FIG. 1 is a schematic diagram of a production apparatus for a plating solution or a plating rehydration solution in an insoluble anode acid copper plating process according to Examples 1-2 and 13-14 of the present invention.
  • FIG. 2 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for the insoluble anode acid copper electroplating process in Examples 3 and 17 of the present invention.
  • FIG. 3 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 4 of the present invention.
  • FIG. 4 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 5 of the present invention.
  • FIG. 5 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 6 of the present invention.
  • FIG. 6 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 7 of the present invention.
  • FIG. 7 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 8 of the present invention.
  • FIG. 8 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 9 of the present invention.
  • FIG. 9 is a schematic structural diagram of an electrolytic cell used in Examples 9, 10, 15, and 16 of the present invention.
  • FIG. 10 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for an insoluble anode acid copper electroplating process according to Embodiment 10 of the present invention.
  • FIG. 11 is a schematic diagram of an electroplating and electrolytic regeneration recycling system for the insoluble anode acid copper electroplating process in Examples 11 and 12 of the present invention.
  • FIG. 12 is a schematic structural diagram of an electrolytic cell used in Examples 11 and 12 of the present invention.
  • the copper sulfate used is preferably copper sulfate produced by Changzhou Hairun Chemical; sulfuric acid, copper oxide, potassium sulfate, iron sulfate, aluminum sulfate, ferrous sulfate, ammonium sulfate, cadmium sulfate, sulfuric acid Magnesium, manganese sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, nickel sulfate, zinc sulfate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, carbonic acid Ammonium hydrogen is preferably a product produced by Guangzhou Chemical Reagent Factory; metal copper used is preferably metal copper produced by Changsha Tianjiu Metal Materials Co., Ltd .; sodium sulfate used is preferably sodium sulfate produced by Jiuzhong Chemical Company; titanium sulfate used
  • this is a basic embodiment of a production device for a plating solution or a plating rehydration solution suitable for an insoluble anode acid copper plating process, which is an electrolytic device mainly composed of an electrolytic cell, an electrolytic anode 4, an electrolytic cathode 5 and
  • the electrolytic power source 6 and the electrolytic cell diaphragm 3 are composed of the electrolytic anode 4 and the electrolytic cathode 5 respectively connected to the positive electrode and the negative electrode of the electrolytic power source 6, wherein:
  • the electrolytic cell membrane 3 divides the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1, and the electrolytic anode region 2 and the electrolytic cathode region 1 are respectively used for containing an anolyte and a catholyte;
  • the electrolytic cell membrane 3 uses an anion exchange membrane.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 Use an anion exchange membrane to separate the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1;
  • Step 2 Prepare anolyte and catholyte separately
  • Step 3 The anolyte prepared in step 2 is poured into the electrolytic anode zone 2 and the catholyte is prepared and poured into the electrolytic cathode zone 1;
  • Step 4 Connect the electrolytic anode 4 with the positive electrode of the electrolytic power source 6 and immerse it in the anolyte, connect the electrolytic cathode 5 with the negative electrode of the electrolytic power source 6 and immerse it in the catholyte;
  • Step 5 Turn on the electrolytic power 6 to perform the electrolytic operation, set the copper ion predetermined value according to the copper ion concentration required for the plating solution, and take out the anolyte when the copper ion concentration in the anolyte reaches a predetermined value. , Used as the initial acid copper sulfate electroplating bath in the ordinary electroplating tank 12 without a diaphragm;
  • Step 6 After the electroplating using the initial acidic copper sulfate electroplating solution described in Step 5, the electroplated cathode 14 (ie, the cathode plating) is taken out; the electroplated cathode 14 is cleaned with water and dried with hot air; and a computer is used The surface of the plating layer was observed under a microscope, and the observation results are recorded in Table-1.
  • the electroplated cathode 14 ie, the cathode plating
  • Embodiment 2 is also a production device of a plating solution or a plating rehydration solution suitable for the insoluble anodic acid copper electroplating process of the present invention.
  • the composition of the electrolytic device is the same as that of Example 1, except that the anolyte and catholyte are different. The ratio is different.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 Set up three electrolytic cells as shown in FIG. 1.
  • the electrolytic cell membrane 3 uses an anion exchange membrane to divide the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1.
  • Step 2 Prepare anolyte and catholyte separately
  • Step 3 The anolyte prepared in step 2 is poured into the electrolytic anode zone 2 and the catholyte is prepared and poured into the electrolytic cathode zone 1;
  • a plating solution is prepared and poured into a common plating tank 12 without a diaphragm
  • Step 4 Connect the electrolytic anode 4 with the positive electrode of the electrolytic power source 6 and immerse it in the anolyte, connect the electrolytic cathode 5 with the negative electrode of the electrolytic power source 6 and immerse it in the catholyte;
  • the insoluble plating anode 13 and the plating cathode 14 are respectively connected to the positive electrode and the negative electrode of a plating power source and are immersed in the plating solution;
  • Step 5 Turn on the electrolytic power supply 6 to perform the electrolytic operation of the present invention, and simultaneously start the production of electroplated copper.
  • the plating test time is set to 5 hours.
  • manual detection When the copper ion concentration in the anolyte according to the present invention is equal to or higher than the copper ion concentration required by the plating solution, and the copper ion concentration of the plating solution is lower than the set value, the anolyte is added as a plating supplement liquid to the plating In the tank 12, the copper ion concentration of the plating solution is restored to or exceeds a set value, thereby stabilizing the copper ion concentration of the plating solution;
  • Step 6 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • FIG. 2 shows one of the embodiments in which the electroplating solution or / and electroplating rehydration production device of the present invention is connected to an insoluble anode acid copper electroplating process production line.
  • the electroplating solution or / and electroplating rehydration production device of the present invention uses an electrolytic device.
  • the electrolytic device is composed of an electrolytic cell, two electrolytic anodes 4, two electrolytic cathodes 5, three electrolytic cell membranes 3, an electrolytic power source 6, an electrolytic solution stirring device 16, and two hydrogen effluent systems 11.
  • An electrolytic anode 4 and two electrolytic cathodes 5 are connected to the positive and negative electrodes of the electrolytic power source 6, respectively:
  • Three electrolytic cell membranes 3 divide the electrolytic cell into four electrolytic regions, and place the electrolytic anode 4 and the electrolytic cathode 5 in the four electrolytic regions, respectively, to form two electrolytic anode regions 2 and two electrolytic cathode regions. 1, and the electrolytic anode area 2 and the electrolytic cathode area 1 are arranged adjacent to each other, and the electrolytic anode area 2 and the electrolytic cathode area 1 are respectively used for containing the anolyte and the catholyte; the electrolytic cell membrane 3 uses an anion exchange membrane ;
  • the electrolyte stirring device 16 adopts an electrolyte reflux liquid stirring device, which includes a liquid outlet pipe, a pump, and a return pipe; the hydrogen outflow system 11 uses a general exhaust system, and two exhaust ports are respectively arranged at Above two electrolytic cathode zones 1.
  • This embodiment is associated with an electroplating tank 12 produced by insoluble anode acid copper electroplating.
  • the electroplating tank 12 is provided with an insoluble electroplating anode 13 and an electroplating cathode 14 (that is, a cathode plating part).
  • An exhaust fan is provided directly above the electroplating anode 13 System 15, the air outlet of the exhaust pipe of the system is introduced into the anolyte of the present invention, so that oxygen generated during the electroplating process is introduced into the anolyte, so that it is supplemented to the anolyte as an oxygen source in.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 2, the electrolytic cell is divided into an electrolytic anode region 2 and an electrolytic cathode region 1 by using an electrolytic cell diaphragm 3.
  • the electrolytic anode region 22 is provided with an electrolyte reflux liquid stirring device, and the electrolytic cathode 5
  • a hydrogen efflux system 11 is arranged above to lead the hydrogen generated on the electrolytic cathode 5 out of the electrolytic system;
  • Step 2 Prepare an anolyte and a catholyte separately; prepare a plating solution and pour it into an ordinary plating tank 12 without a diaphragm;
  • Step 3 The anolyte prepared in step 2 is poured into the electrolytic anode zone 2 and the catholyte is prepared and poured into the electrolytic cathode zone 1;
  • Step 4 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; insoluble plating
  • the anode 13 and the electroplated cathode 14 are respectively connected to the positive electrode and the negative electrode of the electroplating power source and are immersed in the electroplating solution.
  • An extraction fan system 15 is provided directly above the electroplated anode 13, and an air outlet of an exhaust pipe of the extraction fan system 15 Introduced into the anolyte;
  • Step 5 Turn on the electrolytic power supply 6, apply electricity to perform the electrolytic operation, and start the plating operation at the same time.
  • Set the plating test time to 5 hours.
  • the electrolytic current is adjusted by the copper ion concentration of the electrolytic solution, and supplemental sulfuric acid is added to the electrolytic anode zone 2 according to the measured anolyte sulfuric acid concentration, and an anolyte with a volume of 5% plating solution is added to the plating tank 12 every 1 hour;
  • Step 6 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • the electroplating solution or / and electroplating rehydration production device of the present invention is connected to an insoluble anode acid copper electroplating process production line.
  • the electroplating solution or / and electroplating rehydration production device of the present invention uses an electrolytic device It is mainly composed of an electrolytic cell, an electrolytic anode 4, an electrolytic cathode 5, an electrolytic power source 6, a stirring device 16 and an electrolytic cell diaphragm 3.
  • the electrolytic anode 4 and the electrolytic cathode 5 are respectively connected to the positive electrode and the negative electrode of the electrolytic power source 6, among them:
  • the electrolytic cell membrane 3 divides the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1, and the electrolytic anode region 2 and the electrolytic cathode region 1 are respectively used for containing an anolyte and a catholyte;
  • the electrolytic cell diaphragm 3 uses an anion exchange membrane; the stirring device 16 is placed in the electrolytic anode area 2 and the electrolytic cathode area 1, and the stirring device 16 placed in the electrolytic anode area 2 uses a paddle agitator.
  • the stirring device 16 in the electrolytic cathode zone 1 is a reflux liquid stirring device.
  • a hydrogen effluent system 11 is provided above the electrolytic cathode region 1 for drawing hydrogen generated on the cathode out of the electrolytic system.
  • This embodiment is associated with an electroplating tank 12 produced by insoluble anode acid copper electroplating.
  • the electroplating tank 12 is provided with an insoluble electroplating anode 13 and an electroplating cathode 14 (that is, a cathode plating part); the electroplating tank 12 is provided with an overflow port 20 and It is connected to the relay groove 19.
  • An automatic feeding controller 17 is connected to the electrolytic anode area 2, the electrolytic cathode area 1 and the plating tank 12 to detect parameters in the anolyte, catholyte and electroplating solution; the automatic feeding controller 17 is also connected to the electrolytic power source 6 In order to control the size of the electrolytic current and the on / off of the electrolytic power source 6.
  • the two supplementary liquid addition tanks 18 are connected to the electrolytic cathode zone 1 described above, and the pump connected to the supplementary liquid addition tank 18 is connected to an automatic feeding controller 17, and the on / off of the pump is controlled by the automatic feeding controller 17 To achieve automatic feeding.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 3, the electrolytic cell is divided into an electrolytic anode region 2 and an electrolytic cathode region 1 by using an electrolytic cell diaphragm 3.
  • a stirring device 16 is provided at the bottom of the electrolytic anode region 2. The stirring device 16 is stirred by a paddle. There is also a stirring device 16 in the electrolytic cathode zone 1. The stirring device 16 uses a reflux liquid stirring device.
  • a hydrogen efflux system 11 is arranged above the electrolytic cathode zone 1 to lead the hydrogen generated on the cathode out of the electrolytic system.
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2.
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; insoluble plating
  • the anode 13 and the plating cathode 14 are respectively connected to a positive electrode and a negative electrode of a plating power source with a current regulator and are immersed in the plating solution;
  • Step 4 Use the automatic feeding controller 17 to perform parameter measurement on the specific gravity of the plating solution, the photoelectric colorimetric value of the anolyte, the acidity of the catholyte, and the specific gravity of the catholyte, and set according to the obtained values. Electrolysis During the process, the current of the electroplating tank 12 and the electrolytic cell are adjusted or shut down according to the specific gravity of the plating solution and the photoelectric colorimetric value of the anolyte, respectively.
  • Step 5 Set the electroplating test time to 5 hours. During the electroplating process, the acidity of the plating solution is manually detected, and the anolyte is added to the plating tank 12 according to the acidity of the plating solution obtained by the detection.
  • Step 6 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • FIG. 4 shows one of the embodiments of the electroplating solution or / and electroplating rehydration production device of the present invention connected to an insoluble anode acid copper electroplating process production line.
  • Embodiment 5 is different from Embodiment 4 in that:
  • the stirring device 16 placed in the electrolytic anode zone 2 is a reflux liquid stirring device
  • a supplementary liquid addition tank 18 is connected to the electrolytic cathode region 1; another supplemental liquid addition tank 18 is connected to the electrolytic anode region 2;
  • the electrolytic anode region 2 is connected to the plating tank 12, and a pump is further provided between the electrolytic anode region 2 and the plating tank 12, and the pump is connected to the automatic feeding controller 17;
  • the electroplating tank 12 is provided with an overflow port 20, which is connected to a relay tank 19.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 4, an anion exchange membrane is used to divide the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1.
  • the anode region and the cathode region of the electrolytic tank are respectively provided with an electrolyte reflux liquid stirring device.
  • a hydrogen efflux system 11 is arranged above the cathode of the electrolytic cell to lead the hydrogen generated on the cathode out of the electrolytic system.
  • the electrolytic anode area 2 is connected to a pump by a pipe, and the outlet of the pump is connected to the pipe by a pipe without a diaphragm.
  • the electroplating tank 12 is connected, and the electroplating tank 12 is provided with an overflow port 20 and is connected to the relay tank 19;
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2, prepare the catholyte and pour it into the electrolytic cathode zone 1, prepare the plating solution and pour it into the plating tank 12;
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; insoluble plating
  • the anode 13 and the plating cathode 14 are respectively connected to a positive electrode and a negative electrode of a plating power source and are immersed in the plating solution;
  • Step 4 Using the automatic feeding controller 17, the specific gravity of the plating solution, the redox potential of the plating solution, the photoelectric colorimetric value of the plating solution, the specific gravity value of the anolyte, the level of the anolyte, and the catholyte
  • the pH value is measured by parameters and set according to the obtained values.
  • the anolyte is automatically added to the plating tank 12 according to the specific gravity value, redox potential value, and photoelectric colorimetric value of the plating solution obtained during the test.
  • the specific gravity value of the anolyte obtained through the test is to adjust the current of the electrolytic cell or shut down, and the supplemental sulfuric acid aqueous solution is added to the electrolytic anode zone 2 according to the level of the anolyte obtained from the test.
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • this is one of the embodiments related to the insoluble anode acid copper electroplating process production line.
  • the difference between embodiment 6 and embodiment 5 lies in:
  • the bottom of the electrolytic anode zone 2 is provided with an insoluble electrolytic anode 23 connected to a power source;
  • the plating tank 12 is divided into a plating tank anode region and a plating tank cathode region by a plating diaphragm 21;
  • a fresh water source 25 is connected to the anode area of the electroplating tank and the cathode area of the electroplating tank 12 respectively, and a pump is connected between the clean water source 25 and the anode area of the electroplating tank and between the clean water source 25 and the cathode area of the electroplating tank.
  • Each pump is connected to the automatic feeding controller 17, so that the automatic feeding controller 17 is used to control the supply of fresh water to the anode area and the cathode area of the plating tank;
  • the supplementary liquid adding tank 18 connected to the electrolytic anode zone 2 is replaced by a fresh water source 25;
  • a filtering device 22 is further connected between the plating tank 12 and the anode area;
  • a carbon dioxide source 26 is connected to the electrolytic cathode region 1.
  • a gas valve 27 is connected between the carbon dioxide source 26 and the electrolytic cathode region 1.
  • the gas valve 27 is connected to an automatic dosing controller 17, so that the dosing of carbon dioxide is controlled by the automatic dosing controller 17. ;
  • the cathode area of the electroplating tank 12 is further provided with an overflow port 20, which allows the electroplating and overflow in the cathode area of the electroplating tank to the electrolytic anode area 2, and the overflow port 20 and the electrolytic anode area 2 There is also a diaphragm 24 therebetween.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 5, the electrolytic cell membrane 3 of the present invention uses an anion exchange membrane to divide the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1.
  • the electroplating copper production line uses a plating cell 12 with a membrane 24.
  • the electrolytic anode zone 2 and the electrolytic cathode zone 1 of the present invention are respectively provided with an electrolyte reflux liquid stirring device.
  • a hydrogen efflux system 11 is provided above the electrolytic cathode 5 in the electrolytic cathode zone 1 to lead the hydrogen generated on the cathode out of the electrolytic system.
  • the electrolytic anode area 2 is connected to a pump by a pipeline, the pump outlet is connected by a pipeline, the outlet of the pipeline is placed in the cathode area of a plating tank, and a filtering device 22 is installed on the pipeline;
  • the cathode area of the electroplating tank is provided with an overflow port 20 and is connected to the electrolytic anode area 2 by a pipeline, and the pipeline is provided with a diaphragm 24;
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2, prepare the catholyte and pour it into the electrolytic cathode zone 1, prepare the plating solution and pour it into the anode zone and the cathode zone of the plating bath;
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte, the electrolysis A titanium anode is provided at the bottom of the anode region 2 and is connected to the positive electrode of the electrolytic power source 6; the insoluble plating anode 13 and the plating cathode 14 are respectively connected to the positive electrode and the negative electrode of the plating power source and immersed in the plating solution;
  • Step 4 Using the automatic feeding controller 17, the acidity of the catholyte, the specific gravity of the anolyte, the pH of the catholyte, the level of the anode zone of the plating bath, the level of the cathode zone of the plating bath, and electrolysis
  • the level of the anode zone 2, the level of the electrolytic cathode zone 1, and the pressure of the electrolytic cell are measured and set according to the obtained data.
  • the acidity value of the cathode plating solution obtained automatically is automatically added to the cathode region of the plating tank.
  • the anolyte is poured, the current of the electrolytic cell is automatically adjusted or shut down according to the specific gravity value of the anolyte obtained from the test, and the water is automatically added to the anode area of the electroplating tank according to the liquid level of the anode area of the electroplating tank. Automatically add water to the cathode area of the electroplating tank according to the liquid level obtained in the detection of the electroplating tank, and automatically add water to the electrolytic anode area 2 according to the level of the electrolytic anode area 2 obtained from the test.
  • the liquid level in the cathode area 1 is automatically added to the electrolytic cathode area 1 by adding an inorganic alkaline aqueous solution, and the dioxin is automatically added to the electrolytic cathode area 1 according to the electrolytic cell pressure in the electrolytic cell. Turn on the power, turn on the electricity for electrolytic operation, and start the plating operation at the same time, set the plating test time to 5 hours;
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • this is one of the embodiments of the present invention related to the insoluble anode acid copper electroplating process production line.
  • the difference between embodiment 7 and embodiment 5 lies in:
  • the electrolytic cell is divided into an electrolytic anode region 2, an electrolytic cathode region 1, and an electrolytic buffer region 7 by an electrolytic cell membrane 3, and the electrolytic buffer region 7 is located between the electrolytic anode region 2 and the electrolytic cathode region 1;
  • a fresh water source 25 is connected to the electrolytic cathode region 1, and a clear water source 25 is also provided between the electrolytic cathode region 1 and the electrolytic cathode region 1.
  • a gas valve 27, and the automatic feeding controller 17 is connected to the gas valve 27, so that the automatic feeding controller 17 is used to control adding water to the electrolytic cathode zone 1;
  • the overflow port 20 of the plating tank 12 is connected to the electrolytic anode region 2;
  • An oxygen source 28 is also connected to the electrolytic anode region 2.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 6, the electrolytic cell is divided into an electrolytic anode region 2, an electrolytic buffer region 7, and an electrolytic cathode region 1 by using an anion exchange membrane.
  • the anode region and the cathode region of the electrolytic cell are respectively provided with electrolyte reflux.
  • a hydrogen efflux system 11 is provided above the cathode of the electrolytic cell to lead the hydrogen generated on the cathode out of the electrolytic system.
  • the electrolytic anode area 2 is connected to a pump by a pipe, and the pump outlet is connected to the pump by a pipe.
  • An ordinary electroplating tank 12 without a diaphragm is connected.
  • the electroplating tank 12 is provided with an overflow port 20 and is connected to the electrolytic anode region 2 so that the electrolytic anode region 2 and the electroplating tank 12 form a closed cycle.
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2. Prepare the catholyte and pour it into the electrolytic cathode zone 1. Prepare the buffer electrolyte and pour it into the electrolytic buffer zone 7. Prepare the plating solution and pour it into the plating tank. 12 in
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; insoluble plating
  • the anode 13 and the plating cathode 14 are respectively connected to a positive electrode and a negative electrode of a plating power source and are immersed in the plating solution;
  • Step 4 Use the automatic feeding controller 17 to set and detect the specific gravity of the electroplating solution, the specific gravity of the anolyte, and the specific gravity of the catholyte, and automatically adjust the specific gravity of the electroplating solution according to the specific gravity of the electroplating solution.
  • the anolyte is added to the plating tank 12, and the current of the electrolytic cell is automatically adjusted or shut down according to the specific gravity of the anolyte obtained from the test.
  • the anolyte is automatically added to the electrolytic cathode zone 1 according to the specific gravity of the anolyte obtained from the test.
  • Replenish clean water turn on the power, apply electricity for electrolytic operation, and start the plating operation at the same time, set the plating test time to 5 hours; continue to add oxygen to the electrolytic anode zone 2, and check the acidity value of the buffer electrolyte every 1 hour and Adding sulfuric acid to the electrolytic buffer 7 to supplement the sulfuric acid component in the buffer electrolyte;
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • Embodiment 8 As shown in FIG. 7, this is one of the embodiments related to the insoluble anode acid copper electroplating process production line.
  • Embodiment 7 The difference between Embodiment 8 and Embodiment 7 is that:
  • the electrolysis buffer 7 is also provided with a stirring device 16 which adopts a paddle agitator;
  • a supplementary liquid addition tank 18 connected to the electrolytic buffer 7 is provided.
  • a pump is also connected between the electrolytic buffer 7 and the supplementary liquid addition tank 18, and the pump is connected to the automatic feeding controller 17, so that the automatic feeding controller 17 According to the parameters detected by the electrolytic buffer zone 7, the control unit adds a supplementary liquid to the electrolytic buffer zone 7.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 7, the electrolytic cell is divided into an electrolytic anode region 22, an electrolytic buffer region 7, and an electrolytic cathode region 11 using an anion exchange membrane.
  • the stirring device 16 uses an electrolyte reflux liquid stirring device.
  • a hydrogen efflux system 1111 is provided above the electrolytic cathode 55 to lead the hydrogen generated on the electrolytic cathode 5 out of the electrolytic system.
  • the electrolytic anode area 22 is connected to a pump by a pipe, and the liquid outlet of the pump is connected by a pipe to an ordinary electroplating tank 1222 without a diaphragm.
  • the electroplating tank 12 is provided with an overflow port 20 and is connected to the electrolytic anode region 2. Making the electrolytic anode region 2 and the plating tank 12 form a closed cycle;
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2. Prepare the catholyte and pour it into the electrolytic cathode zone 1. Prepare the buffer electrolyte and pour it into the electrolytic buffer zone 7. Prepare the plating solution and pour it into the plating tank. 12 in
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; insoluble plating
  • the anode 13 and the plating cathode 14 are respectively connected to a positive electrode and a negative electrode of a plating power source and are immersed in the plating solution;
  • Step 4 Use the automatic feeding controller 17 to set and detect the specific gravity of the plating solution, the specific gravity of the anolyte, the pH of the catholyte, the pH and specific gravity of the buffer electrolyte, and automatically detect
  • the specific gravity value of the obtained electroplating solution is automatically added to the plating tank 12 with anolyte, and the current of the electrolytic regeneration tank is automatically adjusted or shut down according to the specific gravity of the anolyte obtained, and the catholyte is automatically obtained according to the detection.
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • the electroplating solution or electroplating rehydration production device of the present invention uses an electrolysis device, which is mainly composed of an electrolytic cell and an electrolytic anode. 4.
  • An electrolytic cathode 5, an electrolytic power source 6, a stirring device 16 and an electrolytic cell diaphragm 3, the electrolytic anode 4 and the electrolytic cathode 5 are respectively connected to a positive electrode and a negative electrode of the electrolytic power source 6, wherein:
  • the electrolytic cell membrane 3 divides the electrolytic cell into an electrolytic anode region 2 and an electrolytic cathode region 1, and the electrolytic anode region 2 and the electrolytic cathode region 1 are respectively used for containing an anolyte and a catholyte;
  • the electrolytic cell diaphragm 3 uses an anion exchange membrane; the stirring device 16 is placed in the electrolytic anode area 2 and the electrolytic cathode area 1, the stirring device 16 is a uniform reflux liquid stirring device; and the hydrogen is provided above the electrolytic cathode area 1
  • the exhaust system 11 leads the hydrogen generated on the cathode out of the electrolytic system;
  • An electrolytic cell diaphragm 3 is also used in the electrolytic anode region 2 to separate an acidity balanced cathode region 8.
  • the acidity balanced cathode region 8 is provided with an acidity balanced cathode 10
  • the electrolytic cathode region 1 is provided with an acidity balanced anode 9.
  • Said acidity balance anode 9 and acidity balance cathode 10 are respectively connected to the positive electrode and the negative electrode of another electrolytic power source 6;
  • the automatic feeding controller 17 detects the values in the electroplating tank 12, the electrolytic anode area 2, and the acidity balance cathode area 8, respectively, so as to control the addition operation and the size of the electrolytic current and the on / off of the electrolytic power supply 6;
  • the electrolytic anode area 2 is connected to the electroplating tank 12.
  • the electroplating anode 13 and the electroplating cathode 14 are provided in the electroplating tank 12, and a pump is provided between the electrolytic anode area 2 and the electroplating tank 12.
  • the pump is connected to the automatic feeding controller 17. So as to control the on / off of the pump through the automatic feeding controller 17;
  • the plating tank 12 is provided with an overflow port 20, and the overflow port 20 is connected to the electrolytic anode region 2;
  • a carbon dioxide source 26 is connected to the acidity-balanced cathode region 8, and a gas valve 27 is connected between the carbon dioxide source 26 and the acidity-balanced cathode region 8.
  • the gas valve 27 is connected to the automatic dosing controller 17 so as to pass the automatic dosing controller. 17 Control the increase of carbon dioxide.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIGS. 8 and 9, the electrolytic cell is divided into an electrolytic anode region 2, an acidity balanced cathode region 8, and an electrolytic cathode region 1 using an anion exchange membrane.
  • the electrolytic anode region 2 and the electrolytic cathode region 1 are respectively set There is a liquid stirring liquid stirring device.
  • a hydrogen efflux system 11 is arranged above the electrolytic cathode 5 to lead the hydrogen generated on the cathode out of the electrolytic system.
  • the electrolytic anode area 2 is connected to a pump by a pipeline.
  • the port is connected by a pipe to an ordinary electroplating tank 12 without a diaphragm.
  • the electroplating tank 12 is provided with an overflow port 20 and is connected to the electrolytic anode region 2 so that the electrolytic anode region 2 and the electroplating tank 12 are formed. Closed loop
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2, prepare the catholyte and pour it into the electrolytic cathode zone 1, prepare 10 acidity balance cathodes and pour into the acidity balance cathode zone 8, prepare the plating solution and pour Into the plating tank 12;
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; balance the acidity
  • the anode 9 is connected to the positive electrode of the acid-balanced power source and is immersed in the catholyte
  • the acidity-balanced cathode 10 is connected to the negative electrode of the acid-balanced power source and immersed in the acid-balanced cathode 10 solution
  • the insoluble plating anode 13 and the plating cathode 14 are respectively connected with The positive electrode and the negative electrode of the plating power source are connected and immersed in the plating solution;
  • Step 4 The automatic feeding controller 17 is used to set and detect the redox potential of the electroplating solution, the specific gravity value of the anolyte, and the specific gravity of the electrolyte of the cathode 10 electrolyte.
  • the redox potential value is automatically added to the electroplating tank 12 and the anolyte is automatically added.
  • the current of the electrolytic cell is adjusted or shut down according to the specific gravity of the anolyte obtained from the test, and the specific gravity of the electrolyte of the cathode 10 is automatically balanced according to the acidity obtained from the test.
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • the plating tank 12 is not provided with an overflow port 20;
  • the automatic feeding controller 17 detects the values in the electroplating tank 12 and the electrolytic anode area 2 respectively, so as to control the addition operation and the size of the electrolytic current and the on / off of the electrolytic power source 6;
  • the electrolytic anode region 2 is connected to the plating tank 12 to form a circulation loop, and the two pumps between the electrolytic anode region 2 and the plating tank 12 are connected to an automatic feeding controller 17.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIGS. 9 and 10, the electrolytic cell is divided into an electrolytic anode zone 2, an electrolytic cathode zone 1, and an acidity balanced cathode zone 8 using an anion exchange membrane.
  • the electrolytic anode zone 2 and the electrolytic cathode zone 1 are respectively provided with There is an electrolyte reflux liquid stirring device.
  • a hydrogen efflux system 11 is arranged above the electrolytic cathode 5 to lead the hydrogen generated on the cathode out of the electrolytic system.
  • the electrolytic anode area 2 and a common electroplating tank 12 without a diaphragm are composed of two pipes. Being connected, the pipelines are respectively provided with pumps with opposite fluid directions, so that the electrolytic anode region 2 and the electroplating tank 12 form a closed cycle;
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2, prepare the catholyte and pour it into the electrolytic cathode zone 1, prepare 10 acidity balance cathodes and pour into the acidity balance cathode zone 8, prepare the plating solution and pour Into the plating tank 12;
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; balance the acidity
  • the anode 9 is connected to the positive electrode of the acid-balanced power source and is immersed in the catholyte
  • the acidity-balanced cathode 10 is connected to the negative electrode of the acid-balanced power source and immersed in the acid-balanced cathode 10 solution
  • the insoluble plating anode 13 and the plating cathode 14 are respectively connected with The positive electrode and the negative electrode of the plating power source are connected and immersed in the plating solution;
  • Step 4 Use the automatic feeding controller 17 to set and detect the photoelectric colorimetric value of the electroplating solution and the specific gravity value of the anolyte, and automatically send the electroplating bath to the electroplating tank according to the photoelectric colorimetric value of the electroplating solution 12 Add the anolyte and start the pump that adds the electroplating solution to the electrolytic anode zone 2 at the same time, and automatically adjust or shut down the current of the electrolytic cell according to the specific gravity value of the anolyte obtained by detection; turn on the power, Turn on the electrolytic electrode and the acid balance electrode in turn to perform the electrolytic operation, and start the plating operation at the same time, set the plating test time to 5 hours;
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • the components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acidity balanced cathode 10, acidity balanced anode 9, and acidity balanced cathode 10 described in Example 10 are shown in Table-1 below.
  • Figures 11 and 12 show one of the embodiments of the present invention related to the insoluble anode acid copper electroplating process production line. The difference between embodiment 11 and embodiment 9 lies in:
  • an electrolytic cell diaphragm 3 is also used to separate an acidity balanced cathode area 8 and the electrolytic anode area 2 is placed between the electrolytic cathode area 1 and the acidity balanced cathode area 8, and the electrolytic anode area 2 and the electrode cathode area 2.
  • the stirring device 16 is provided in each of the acidity balanced cathode regions 8, and the stirring devices 16 each adopt an electrolyte reflux liquid stirring device;
  • the acidity balance cathode region 8 is further connected with a supplementary liquid addition tank 18, and a pump is arranged between the supplemental liquid addition tank 18 and the acidity balance cathode region 8, and the pump is connected to the automatic feeding controller 17 so that The feeding controller 17 controls the addition of the supplementary liquid;
  • the acidity balance cathode zone 8 is also provided with an overflow port 20, which is connected to a relay tank 19;
  • the automatic feeding controller 17 detects the values in the electroplating tank 12, the electrolytic anode zone 2, the electrolytic cathode zone 1, and the acidity balance cathode zone 8, respectively, so as to control the operation of the feeding operation and the size of the electrolytic current and the on / off of the electrolytic power source 6.
  • the method is suitable for producing a plating solution or a plating rehydration solution for an insoluble anode acid copper plating process, and includes the following steps:
  • Step 1 As shown in FIG. 11 and FIG. 12, the electrolytic cell is divided into an electrolytic anode region 2, an electrolytic cathode region 1, and an acidity balance cathode region 8 using an anion exchange membrane, the electrolytic anode region 2, the electrolytic cathode region 1, and the acidity.
  • Equilibrium cathode zone 8 is provided with an electrolyte reflux liquid stirring device.
  • the acidity balanced cathode zone 8 is provided with an overflow port 20 and is connected to a relay tank 19 through a pipeline.
  • the electrolytic cathode 5 A hydrogen efflux system 11 is arranged above to lead the hydrogen generated on the cathode out of the electrolytic system.
  • the electrolytic anode area 2 is connected to a pump by a pipe, and the pump outlet is connected to a common electroplating tank 12 without a diaphragm by a pipe.
  • the electroplating tank 12 is provided with an overflow port 20 and is connected to the electrolytic anode region 2 so that the electrolytic anode region 2 and the electroplating tank 12 form a closed cycle;
  • Step 2 Prepare the anolyte and pour it into the electrolytic anode zone 2, prepare the catholyte and pour it into the electrolytic cathode zone 1, prepare 10 acidity balance cathodes and pour into the acidity balance cathode zone 8, prepare the plating solution and pour Into the plating tank 12;
  • Step 3 Connect the electrolytic anode 4 to the positive electrode of the electrolytic power source 6 with a current regulator and immerse it in the anolyte, connect the electrolytic cathode 5 to the negative electrode of the electrolytic power source 6 and immerse it in the catholyte; balance the acidity
  • the anode 9 is connected to the positive electrode of the acid-balanced power source and is immersed in the catholyte
  • the acidity-balanced cathode 10 is connected to the negative electrode of the acid-balanced power source and immersed in the acid-balanced cathode 10 solution
  • the insoluble plating anode 13 and the plating cathode 14 are respectively connected with The positive electrode and the negative electrode of the plating power source are connected and immersed in the plating solution;
  • Step 4 The automatic feeding controller 17 is used to set and detect the specific gravity of the plating solution, the specific gravity of the anolyte, the acidity of the catholyte, and the pH value of the acid balance 10 cathode.
  • the specific gravity value of the obtained electroplating solution is automatically added to the plating bath 12, and the current of the electrolytic bath is automatically adjusted or shut down according to the specific gravity value of the anolyte obtained.
  • the acidity value controls the turning on and off of the acid balance power supply; automatically adds fresh acidity balance cathode 10 liquid to supplement the inorganic alkali raw material according to the pH value of the acidity balance cathode 10 liquid obtained from the detection, and simultaneously adds carbon dioxide; Perform electrolytic operation and start plating at the same time, set the plating test time to 5 hours;
  • Step 5 Take out the electroplated cathode 14 after setting the plating time; wash the electroplated cathode 14 with water and blow dry with hot air; observe the plating surface with a computer microscope, and record the observation results in Table-1 .
  • the components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acidity balanced cathode 10, acidity balanced anode 9, and acidity balanced cathode 10 described in Example 11 are shown in Table-1 below.
  • Embodiment 12 As shown in FIG. 11 and FIG. 12, the apparatus of Embodiment 12 and the production method of the plating solution or the plating rehydration liquid suitable for the insoluble anode acid copper plating process are the same as those of Embodiment 11.
  • Step 5 After setting the plating time, take out the electroplated cathode 14; wash the electroplated cathode 14 with water and blow dry with hot air; and observe the plating surface with a computer microscope, and record the observation results in Table-1.
  • the components or materials of the anolyte, catholyte, electrolytic anode 4, electrolytic cathode 5, acidity balanced cathode 10, acidity balanced anode 9, and acidity balanced cathode 10 described in Example 12 are shown in Table-1 below.
  • the devices of Examples 13 and 14 and the production method of the plating solution or the plating rehydration solution suitable for the insoluble anode acid copper plating process are the same as those of the embodiment 1.
  • the acidity and specific gravity of the catholyte are measured manually every 15 minutes, and a 50% wt sulfuric acid aqueous solution is added to the electrolytic cathode zone 1 according to the measured results.
  • the anolyte becomes a copper sulfate product after being concentrated and dried.
  • the devices of Examples 15 and 16 and the method for producing a plating solution or a plating rehydration solution suitable for an insoluble anode acid copper plating process are the same as those of Example 10.
  • the acidity-balanced cathode region 8 is composed of a bipolar membrane; an automatic feeding controller 17 is used to perform parameters on the photoelectric colorimetric value of the plating solution, the specific gravity value of the anolyte, and the liquid level of the acid-balanced cathode 10 solution. Set and test, automatically add anolyte to the plating tank 12 according to the photoelectric colorimetric value of the plating solution obtained at the same time, and start the pump that adds the plating solution to the electrolytic anode zone 2 at the same time.
  • the specific gravity value of the electrolyte adjusts the current of the electrolytic cell or shuts down, and automatically adds water to the acidity balanced cathode area 8 according to the level of the acidity balanced cathode 10 liquid obtained by the detection; when the power is turned on, the electrolytic electrode is simultaneously Power on the acid balance electrode for electrolytic operation and start the plating operation at the same time. Set the plating test time to 5 hours.
  • the plating cathode 14 is taken out; the plating cathode 14 is washed with clean water and dried with hot air; and the surface of the plating layer is observed using a computer microscope, and the observation results are recorded in Table-1.
  • Example 17 As shown in Fig. 2, the device of Example 17 and the production method of the electroplating solution or electroplating rehydration solution suitable for the insoluble anodic acid copper electroplating process are the same as those of Example 3.
  • the electrolytic cell is divided into an electrolytic anode area 2 and an electrolytic cathode area 1 by using a bipolar membrane.
  • the copper ion concentration and sulfuric acid concentration of the anolyte and the catholyte level are detected manually.
  • the electrolytic current is adjusted by the copper ion concentration of the electrolytic solution, and supplementary sulfuric acid is added to the electrolytic anode area 2 according to the measured sulfuric acid concentration of the anolyte, and water is supplied to the electrolytic cathode area 1 according to the measured level of the catholyte.
  • the device of Embodiment 18 and the production method of the plating solution or plating rehydration liquid suitable for the insoluble anode acid copper plating process are the same as those of Embodiment 7.
  • the electrolytic cell is divided into an electrolytic anode zone 2, an electrolytic buffer zone 7, and an electrolytic cathode zone 1.
  • the electrolytic anode zone 2 and the electrolytic buffer zone 7 are separated by an anion exchange membrane.
  • the electrolytic buffer zone 7 and the electrolytic cathode Zones 1 are separated by a bipolar membrane.
  • the quality of the plating layer is bright, uniform, and flat. It can be seen that the electroplating fluid or electroplating fluid obtained by the present invention can Meet the use of insoluble anode acid copper plating process.

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Abstract

L'invention porte sur un procédé de production de la solution d'électrodéposition ou de la solution de supplément d'électrodéposition dans un procédé d'électrodéposition de cuivre d'acide d'anode insoluble, comprenant les étapes suivantes consistant à : 1) fournir une cellule électrolytique et utiliser une membrane cellulaire électrolytique (3) pour séparer la cellule électrolytique en une zone d'anode électrolytique (2) et une zone de cathode électrolytique (1) ; 2) préparer respectivement un électrolyte anodique et un électrolyte cathodique ; 3) ajouter l'électrolyte anodique à la zone d'anode électrolytique (2), et ajouter l'électrolyte cathodique dans la zone de cathode électrolytique (1) ; 4) immerger une anode électrolytique (4) dans l'électrolyte anodique, et immerger une cathode électrolytique (5) dans l'électrolyte cathodique ; et 5) connecter l'anode électrolytique (4) et de la cathode électrolytique (5) à une électrode positive et à une électrode négative d'une alimentation électrique électrolytique (6), connecter l'alimentation électrique électrolytique (6) pour effectuer une réaction électrolytique, et extraire l'électrolyte anodique lorsque la concentration d'un ion cuivre dans l'électrolyte anodique atteint une valeur prédéterminée. L'invention concerne également un dispositif de mise en œuvre le procédé de production approprié pour la solution d'électrodéposition ou la solution de supplément d'électrodéposition dans un procédé d'électrodéposition de cuivre d'acide d'anode insoluble.
PCT/CN2019/099192 2018-08-27 2019-08-05 Procédé et dispositif de production et de régénération de solution de placage pour électrodéposition de cuivre d'acide anodique insoluble WO2020042870A1 (fr)

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TW108130113A TWI707067B (zh) 2018-08-27 2019-08-22 不溶性陽極酸性電鍍銅製程的電鍍液或電鍍補液的生產方法和裝置

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113818055A (zh) * 2020-08-28 2021-12-21 叶涛 一种不溶性阳极的酸性电镀铜镀液或电镀补充液的成分调整方法及装置
CN114192771A (zh) * 2021-12-07 2022-03-18 北京有研粉末新材料研究院有限公司 一种具有超低松装密度的海石花状电解铜粉及其制备方法
WO2023196284A1 (fr) * 2022-04-04 2023-10-12 Applied Materials, Inc. Systèmes et procédés d'électroplacage à concentrations en ions métalliques accrues
WO2024078627A1 (fr) * 2022-10-14 2024-04-18 叶涛 Procédé et appareil d'optimisation de processus de placage de cuivre anodique insoluble intégré à la dissolution de cuivre électrolytique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112553665A (zh) * 2020-11-13 2021-03-26 扬昕科技(苏州)有限公司 电镀方法
CN112981504A (zh) * 2021-02-05 2021-06-18 隽美经纬电路有限公司 一种聚酰亚胺薄膜电解镀铜设备及其使用方法
CN114908364B (zh) * 2022-06-15 2024-01-05 昆明理工大学 一种离子膜电解法连续制备硫酸铜晶体的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2269241Y (zh) * 1996-08-05 1997-12-03 柯建信 半渗透式离子析出装置
JP2001089900A (ja) * 1999-09-20 2001-04-03 Shimonoseki Mekki Kk 不溶性陽極を使用するめっき方法及びその装置
CN101935862A (zh) * 2010-08-17 2011-01-05 苏州铨笠电镀挂具有限公司 一种阳离子发生装置
CN101962796A (zh) * 2010-08-17 2011-02-02 苏州铨笠电镀挂具有限公司 一种可持续补充镀液中金属阳离子的方法
CN202072769U (zh) * 2011-04-29 2011-12-14 郑州大学 一种制备四甲基氢氧化铵的双膜电解装置

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA703750B (en) * 1969-06-06 1971-01-27 Australian Iron And Steel Ltd Addition of metal ions to plating bath
US5480516A (en) * 1993-05-12 1996-01-02 Sterling Pulp Chemicals, Ltd. Electrolytic production of acid
JPH10121297A (ja) * 1996-10-16 1998-05-12 Nippon Riironaale Kk 不溶性陽極を用いた電気銅めっき装置及びそれを使用する銅めっき方法
IT1318545B1 (it) * 2000-05-31 2003-08-27 De Nora Elettrodi Spa Cella di elettrolisi per il ripristino della concentrazione di ionimetallici in processi di elettrodeposizione.
CN101307446A (zh) * 2007-05-17 2008-11-19 先丰通讯股份有限公司 蚀刻废液的回收技术及其装置
JP2012237050A (ja) * 2011-05-10 2012-12-06 Uingu:Kk 不溶性陽極を用いた硫酸銅めっき方法とそのための装置
WO2018103621A1 (fr) * 2016-12-05 2018-06-14 叶旖婷 Procédé de dépôt électrolytique de cuivre acide utilisant une anode insoluble et équipement associé
CN107641821B (zh) * 2017-09-14 2019-06-07 上海新阳半导体材料股份有限公司 一种硫酸铜电镀液、其制备方法和应用及电解槽
JP2024016297A (ja) * 2020-12-04 2024-02-07 ディップソール株式会社 酸性めっきシステム及びアノードセル

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2269241Y (zh) * 1996-08-05 1997-12-03 柯建信 半渗透式离子析出装置
JP2001089900A (ja) * 1999-09-20 2001-04-03 Shimonoseki Mekki Kk 不溶性陽極を使用するめっき方法及びその装置
CN101935862A (zh) * 2010-08-17 2011-01-05 苏州铨笠电镀挂具有限公司 一种阳离子发生装置
CN101962796A (zh) * 2010-08-17 2011-02-02 苏州铨笠电镀挂具有限公司 一种可持续补充镀液中金属阳离子的方法
CN202072769U (zh) * 2011-04-29 2011-12-14 郑州大学 一种制备四甲基氢氧化铵的双膜电解装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113818055A (zh) * 2020-08-28 2021-12-21 叶涛 一种不溶性阳极的酸性电镀铜镀液或电镀补充液的成分调整方法及装置
CN114192771A (zh) * 2021-12-07 2022-03-18 北京有研粉末新材料研究院有限公司 一种具有超低松装密度的海石花状电解铜粉及其制备方法
CN114192771B (zh) * 2021-12-07 2024-05-31 北京有研粉末新材料研究院有限公司 一种具有超低松装密度的海石花状电解铜粉及其制备方法
WO2023196284A1 (fr) * 2022-04-04 2023-10-12 Applied Materials, Inc. Systèmes et procédés d'électroplacage à concentrations en ions métalliques accrues
WO2024078627A1 (fr) * 2022-10-14 2024-04-18 叶涛 Procédé et appareil d'optimisation de processus de placage de cuivre anodique insoluble intégré à la dissolution de cuivre électrolytique

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