US20130156631A1 - Method of removing oxide film on surface of copper or copper-base alloy and copper or copper-base alloy recovered using the method - Google Patents

Method of removing oxide film on surface of copper or copper-base alloy and copper or copper-base alloy recovered using the method Download PDF

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US20130156631A1
US20130156631A1 US13/714,746 US201213714746A US2013156631A1 US 20130156631 A1 US20130156631 A1 US 20130156631A1 US 201213714746 A US201213714746 A US 201213714746A US 2013156631 A1 US2013156631 A1 US 2013156631A1
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copper
oxide film
pickling solution
base alloy
pickling
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Jyunichi Kumagai
Yoshie Tarutani
Hiroaki Nakayama
Kenzi Okada
Naoki Kato
Kenji Kubota
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority claimed from JP2011274719A external-priority patent/JP5886022B2/ja
Priority claimed from JP2012099274A external-priority patent/JP2013199702A/ja
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Assigned to MITSUBISHI MATERIALS CORPORATION reassignment MITSUBISHI MATERIALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUBOTA, KENJI, TARUTANI, Yoshie, NAKAYAMA, HIROAKI, OKADA, KENZI, KUMAGAI, Jyunichi, KATO, NAOKI
Publication of US20130156631A1 publication Critical patent/US20130156631A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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 present invention relates to a method of removing oxide film on a surface of a copper or copper-base alloy and more specifically relates to a method of removing oxide film on a surface of a copper or copper-base alloy in which a copper or copper-base alloy, to having oxide film formed on a surface thereof, is dipped in a pickling bath to remove the oxide film; and a pickling solution containing the oxide film is electrolyzed in an electrolytic bath so as to recover a high-purity copper or copper-base alloy having superior handleability and to return the electrolyzed pickling solution to the pickling bath for reuse.
  • a copper or copper-base alloy which is subjected to heat treatment such as hot rolling or hot extrusion, is normally pickled or etched in order to remove oxide film or fine defects formed on a surface thereof.
  • a pickling solution or an etchant sulfuric acid, a sulfuric acid-based acid obtained by mixing hydrogen peroxide with sulfuric acid, hydrochloric acid, and nitric acid are used.
  • additives such as hydrofluoric acid and another surfactant may also be used as a pickling solution or an etchant.
  • Japanese Examined Patent Application, Second Publication No. S61-60148 discloses a method of recycling and recovering nitric acid and metallic copper powder through electrolysis from a waste solution containing copper and nitric acid, which is generated in the finishing process of pickling copper.
  • the waste solution containing copper and nitric acid which is generated in the process of pickling a product formed from a copper or copper-base alloy, is electrolyzed while maintaining the pH value of the cathode region in a range of 0.5 to 2.0, thereby recovering nitric acid in the anode region and copper powder in the cathode region.
  • Japanese Unexamined Patent Application, First Publication No. 2003-342763 discloses a method of efficiently removing tin, efficiently recovering copper in a treatment solution, and reusing sulfuric acid after treatment without generating fine solid materials, such as tin oxide and hydroxide, which cause problems when a waste solution after pickling the copper-base alloy is reused.
  • This method is a method of recycling the waste solution after pickling the copper-base alloy in which the waste solution is heated at 40° C. or higher to selectively separate tin by precipitation as a pretreatment for recycling.
  • a method of removing oxide film on a surface of a copper or copper-base alloy in which the above-described problems can be solved; and after the copper or copper-base alloy having oxide film formed on a surface thereof is dipped in a pickling bath to remove the oxide film, a pickling solution containing the oxide film is electrolyzed in an electrolytic bath so as to efficiently recover a high-purity copper or copper-base alloy, capable of being reused as a recycled material having superior handleability, and furthermore to return the electrolyzed pickling solution to the pickling bath for reuse.
  • oxide film can be efficiently removed by using a pickling solution including 50 g/L to 400 g/L of sulfuric acid, 1 g/L to 100 g/L of at least one oxidant selected from a group consisting of nitric acid, hydrogen peroxide, peroxodisulfate ions, and iron (III) ions, 0.01 g/L to 10 g/L of at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate, 0.005 g/L to 10 g/L of at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate, and 10 g/L to 300 g/L of copper sulfate; and a high-purity copper or copper-base alloy, capable of being reuse
  • a pickling solution can be efficiently reused by adding the oxidant, the additive, and the surfactant to the electrolyzed pickling solution in amounts equivalent to those consumed when the oxide film is removed and when the electrolysis is performed.
  • a method of removing oxide film formed on a surface of a copper or copper-base alloy including steps of: dipping the copper or copper-base alloy having oxide film formed on a surface thereof, to remove the oxide film, in a pickling bath which contains a pickling solution including 50 g/L to 400 g/L of sulfuric acid, 1 g/L to 100 g/L of at least one oxidant selected from a group consisting of nitric acid, hydrogen peroxide, peroxodisulfate ions, and iron (III) ions, 0.01 g/L to 10 g/L of at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate, 0.005 g/L to 10 g/L of at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenz
  • the amount of at least one oxidant selected from a group consisting of nitric acid, hydrogen peroxide, peroxodisulfate ions, and iron (III) ions is less than 1 g/L, an effect of removing oxide film deteriorates, and when the amount of the oxidant is greater than 100 g/L, the amount of gas generated during removal increases, which is disadvantageous.
  • the generated gas is mainly NO X and oxygen gas generated by the oxidant used.
  • At least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate deposits a high-purity copper or copper-base alloy, capable of being used as a recycled material having superior handleability, on a cathode during the electrolysis and prevents the reductive degradation of hydrogen peroxide on the cathode.
  • the additive works as a stabilizer for the oxidant in the pickling solution and thus also serves to suppress the consumption of the oxidant. When the addition amount thereof is less than 0.01 g/L or greater than 10 g/L, the effect cannot be obtained.
  • At least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate is chemically stable in the pickling solution, lowers the surface tension of the pickling solution for a long period of time to prevent dispersion of mist, and increases the osmotic strength of the pickling solution to enhance pickling capability.
  • the additive can prevent a large amount of sulfuric acid mist from being dispersed by oxygen gas which is generated from a cathode during the electrolysis. When the addition amount thereof is less than 0.005 g/L or greater than 10 g/L, the above-described effect cannot be obtained.
  • Advantageous effects of the present invention can be obtained with a combination of at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate and at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate.
  • at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate
  • at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate.
  • the amount of the copper sulfate is less than 10 g/L, the efficiency of the electrolysis in the next step decreases.
  • the amount of the copper sulfate is greater than 300 g/L, the amount approaches saturated solubility and thus unnecessary copper sulfate is deposited in the pickling solution.
  • the pickling solution can be efficiently reused as a new pickling solution.
  • oxide film on a surface of the copper or copper-base alloy can be removed not only in a batch treatment but in a continuous treatment.
  • the amounts of the oxidant, the additive, and the surfactant added (consumed) vary depending on the kind of the copper or copper-base alloy, but are about 0.5% to 10% of the initial amounts.
  • a surface tension of the pickling solution be less than or equal to 50 ⁇ 10 ⁇ 3 N/m.
  • the surface tension of the pickling solution is adjusted to be less than or equal to 50 ⁇ 10 ⁇ 3 N/m (50 dyn/cm) mainly by at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate.
  • the method further have steps of: in the electrolyzing step, adjusting a concentration of copper ions in the pickling solution containing the removed oxide film is 20 g/L to 60 g/L; controlling a current density in a range of 1 A/dm 2 to 25 A/dm 2 ; and rotating a cathode having a cylindrical body at a peripheral speed in a range of 0.08 m/s to 0.48 m/s.
  • the efficiency of the electrolysis can be increased to a large degree and the size of the electrolytic bath can be reduced by setting the concentration of copper ions in the pickling solution containing the removed oxide film to be 20 g/L to 60 g/L, the current density to be 1 A/dm 2 to 25 A/dm 2 , the cathode to be a rotating cylindrical body, and the peripheral speed of the rotating cylindrical body to be 0.08 m/s to 0.48 m/s.
  • the flow rate of a pickling solution supplied to the electrolytic bath and the current density in the electrolytic bath be adjusted such that the concentration of copper ions in the pickling solution containing the removed oxide film is 20 g/L to 60 g/L.
  • the removal method according to the present invention is performed in a continuous treatment, there are many cases where the amounts of the copper or copper-base alloy having oxide film formed on a surface thereof, which is to be dipped in the pickling bath, or the characteristics of the oxide film are uneven and different. As a result, the concentration of copper ions in the pickling solution containing the removed oxide film does not fall within the range of 20 g/L to 60 g/L and the electrolysis is not stably performed in the electrolytic bath, which may adversely affect the stable recovery of the copper or copper-base alloy.
  • the concentration of copper ions in the pickling solution is greater than 60 g/L
  • the recovery of the copper or copper-base alloy temporarily increases and the concentration of copper ions in the pickling solution is adjusted to be less than or equal to 60 g/L by increasing the amount of a pickling solution, which is supplied to the electrolytic bath, to increase the flow rate of the pickling solution to the electrolytic bath and increasing a current, which is applied to the electrolytic bath, to increase the current density in the electrolytic bath.
  • the concentration of copper ions in the pickling solution is less than 20 g/L
  • the recovery of the copper or copper-base alloy temporarily deteriorates and the concentration of copper ions in the pickling solution is adjusted to be greater than or equal to 20 g/L by reducing the amount of a pickling solution, which is supplied to the electrolytic bath, to reduce the flow rate of the pickling solution to the electrolytic bath and reducing a current, which is applied to the electrolytic bath, to reduce the current density in the electrolytic bath.
  • stable electrolysis can be continuously performed in the electrolytic bath.
  • the precipitation state of the copper or copper-base alloy recovered easily changes. Therefore, the flow rate is also changed at the same time to control the thickness of a diffusion layer in the pickling solution, thereby promoting stable electrolysis without changing the precipitation state of the copper or copper-base alloy recovered in the electrolytic bath.
  • the amount of the pickling solution supplied to the electrolytic bath be adjusted with a supply pump and that the current applied between electrodes of an electrolyzer be adjusted to adjust the current density in the electrolytic bath, thereby automatically promoting stable electrolysis in the electrolytic bath.
  • the optimum concentration of copper ions in the pickling solution be set to be 30 g/L to 40 g/L.
  • a copper or copper-base alloy according to the present invention is recovered using the above-described method of removing oxide film on a surface of a copper or copper-base alloy and is capable of being used as a recycled material.
  • the pickling solution contains the desired and optimum amounts of electrolytic solution components which are necessary when a metallic copper or metallic copper-base alloy is recovered through electrolysis. Therefore, the pickling solution containing the removed oxide film can be electrolyzed without using special means. As a result, the copper or copper-base alloy, capable of being used as a recycled material, can be efficiently recovered.
  • the copper or copper-base alloy which is recovered on a cathode through electrolysis, has not a powder form but a plate-like or columnar form having high purity and appropriate hardness. Therefore, handleability is superior, rinsing is easy, and impurities can be prevented from being mixed. Accordingly, an ingot obtained by melting and casting the recovered copper or copper-base alloy as the recycled material has a lower impurity content and barely causes problems, such as cracking, during hot rolling or hot extrusion thereafter.
  • a pickling solution containing the oxide film is electrolyzed in an electrolytic bath. Therefore, a high-purity copper or copper-base alloy, capable of being used as a recycled material having superior handleability, can be efficiently recovered and the electrolyzed pickling solution can be returned to the pickling bath for reuse.
  • FIG. 1 is a diagram schematically illustrating a device according to an embodiment of the present invention.
  • FIG. 2 is a diagram schematically illustrating a device according to another embodiment of the present invention.
  • FIG. 1 is a diagram schematically illustrating a device according to an embodiment of the present invention.
  • a pickling bath 3 is filled with a pickling solution 2 for oxide film on a surface of a copper or copper-base alloy, a copper or copper-base alloy 4 is dipped in the pickling bath 3 , and the oxide film on the surface is removed in the pickling solution 2 .
  • the thickness of the oxide film is 0.05 ⁇ m to 10 ⁇ m although it varies depending on heat treatment and the like in the previous step, an appropriate temperature of the pickling solution 2 for the oxide film is 30° C. to 60° C., and the dipping time is preferably 30 minutes to 120 minutes.
  • the copper or copper-base alloy 4 from which the oxide film is removed is transported from the pickling bath 3 for the next step.
  • the pickling solution 2 includes: 50 g/L to 400 g/L of sulfuric acid; 1 g/L to 100 g/L of at least one oxidant selected from a group consisting of nitric acid, hydrogen peroxide, peroxodisulfate ions, and iron (III) ions; 0.01 g/L to 10 g/L of at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate; 0.005 g/L to 10 g/L of at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate, and 10 g/L to 300 g/L of copper sulfate.
  • the amount of the sulfuric acid is less than 50 g/L, an effect of removing the oxide film is deteriorated, and when the amount of the sulfuric acid is greater than 400 g/L, the effect is saturated and the cost is wasted.
  • the amount of at least one oxidant selected from a group consisting of to nitric acid, hydrogen peroxide, peroxodisulfate ions, and iron (III) ions is less than 1 g/L, the effect of removing oxide film is deteriorated, and when the amount of the oxidant is greater than 100 g/L, the amount of gas generated during removal increases, which is disadvantageous.
  • the generated gas is mainly NO x and oxygen gas generated by the oxidant used.
  • At least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate deposits a high-purity copper or copper-base alloy 8 , capable of being used as a recycled material having superior handleability, on a cathode 7 during the electrolysis and prevents the reductive degradation of hydrogen peroxide on the cathode 7 .
  • the additive works as a stabilizer for the oxidant in the pickling solution 2 and thus also serves to suppress the consumption of the oxidant.
  • aromatic sulfonic acid examples include benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, ethyl benzene sulfonic acid, cumene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, sulfosalicylic acid, and sulfanilic acid.
  • alkylamine include methylamine, ethylamine, propylamine, butylamine, and pentylamine.
  • aromatic carboxylic acid examples include benzoic acid, salicylic acid, p-hydroxybenzoic acid, aminobenzoic acid, sulfobenzoic acid, and phthalic acid.
  • At least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate is chemically stable in the pickling solution 2 , lowers the surface tension of the pickling solution 2 for a long period of time to prevent dispersion of mist, and increases the osmotic strength of the pickling solution 2 to enhance pickling capability.
  • oxygen gas is generated from the cathode 7 during the electrolysis and a large amount of sulfuric acid mist is dispersed.
  • the surface tension of the pickling solution can be reduced and the dispersion of the sulfuric acid mist can be prevented by adding the additive.
  • surfactant examples include octylbenzene sulfonic acid, nonylbenzene sulfonic acid, decylbenzene sulfonic acid, undecylbenzene sulfonic acid, dodecylbenzene sulfonic acid, tridecylbenzene sulfonic acid, tetradecylbenzene sulfonic acid, and mixtures thereof.
  • Advantageous effects of the present invention can be obtained with a combination of at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate and at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate.
  • at least one additive selected from a group consisting of aromatic sulfonic acid, aromatic sulfonate, alkylamine, aromatic carboxylic acid, and aromatic carboxylate
  • at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate.
  • the amount of the copper sulfate is less than 10 g/L, the efficiency of the electrolysis in the next step decreases.
  • the amount of the copper sulfate is greater than 300 g/L, the amount approaches saturated solubility and thus unnecessary copper sulfate is deposited in the pickling solution.
  • surface tension of the pickling solution 2 be less than or equal to 50 dyn/cm (50 ⁇ 10 ⁇ 3 N/m).
  • the surface tension of the pickling solution 2 is adjusted to be less than or equal to 50 dyn/cm (50 ⁇ 10 ⁇ 3 N/m) mainly by at least one surfactant selected from a group consisting of alkylbenzene sulfonic acid and alkylbenzene sulfonate.
  • a pickling solution X containing the oxide film which is removed in the oxide film removal device 1 is transported to an electrolyzer 5 by a pump P 1 .
  • An anode 6 and the cathode 7 are set in the electrolyzer 5 and a current is applied therebetween.
  • the pickling solution X containing the removed oxide film is electrolyzed and the copper or copper-base alloy 8 , capable of being used as a recycled material, is efficiently recovered on the cathode 7 .
  • the cathode 7 tough pitch copper is generally used, but it is preferable that the optimum material for the recovered copper or copper-base alloy be used.
  • the form of the cathode is generally a thin plate shape, but is preferably a rotating cylindrical body.
  • a concentration of copper ions is set to be 20 g/L to 60 g/L
  • current density is set to be 1 A/dm 2 to 25 A/dm 2
  • peripheral speed of the rotating cylindrical cathode is set to be 0.08 m/s to 0.48 m/s.
  • the efficiency of the electrolysis increases to a large degree and the size of the electrolytic bath can be reduced. If the concentration of copper ions, the current density, and the peripheral speed of the rotating cathode do not fall within the above-described range, the efficiency of the electrolysis does not increase to a large degree.
  • an iridium oxide coated titanium plate be used as the anode 6 .
  • the current density is set to be 3 A/dm 2 to 10 A/dm 2 and the electrolysis is performed for about 6 hours to 10 hours although different conditions may be set depending on the state of the oxide film.
  • the copper or copper-base alloy 8 derived from the oxide film, is deposited on the cathode 7 in a plate shape having superior handleability.
  • the pickling solution 2 contains the desired and optimum amounts of electrolytic solution components which are necessary when a metallic copper or metallic copper-base alloy is recovered through electrolysis. Therefore, the pickling solution X containing the removed oxide film can be electrolyzed without using special means. As a result, the copper or copper-base alloy 8 , capable of being used as the recycled material, can be efficiently recovered.
  • the copper or copper-base alloy 8 which is recovered on a cathode through electrolysis according to the present invention, has not a powder form but a plate-like or columnar form having high purity and appropriate hardness. Therefore, handleability is superior, rinsing is easy, and impurities can be prevented from being mixed. Accordingly, an ingot obtained by melting and casting the recovered copper or copper-base alloy 8 as the recycled material has advantageous effects in that it has a lower impurity content and barely causes problems, such as cracking, during hot rolling or hot extrusion thereafter.
  • the amounts of the oxidant, the additive, and the surfactant consumed when the oxide film is removed during the electrolysis are determined by an analyzer, and the equivalent amounts of the oxidant, the additive, and the surfactant Z are added to an electrolyzed pickling solution Y in the electrolyzer 5 .
  • the electrolyzed pickling solution Y is transported to the oxide film removal device 1 by the pump P 2 and reused as a pickling solution.
  • the amounts of the oxidant, the additive, and the surfactant Z vary depending on the amount of the attached oxide film or the kind of the copper or copper-base alloy, but are about 0.5 to 10% of the amounts before being consumed.
  • the above-described processes are performed in a batch treatment but may be performed in a continuous treatment.
  • the optimum dipping time is selected according to the kind of the copper or copper-base alloy and the state of the oxide film thereof, the pickling solution 2 is circulated, and as a result, the oxide film on the surface thereof can be continuously removed.
  • the concentration of copper ions in the pickling solution 2 is greater than 60 g/L
  • the recovery of the copper or copper-base alloy 8 is temporarily increased and the concentration of copper ions in the pickling solution X is adjusted to be less than or equal to 60 g/L by increasing the amount of the pickling solution X, which is supplied to the electrolytic bath 5 , to increase the flow rate of the pickling solution X to the electrolytic bath and increasing a current, which is applied to the electrolytic bath 5 , to increase the current density in the electrolytic bath 5 .
  • the concentration of copper ions in the pickling solution X is less than 20 g/L, the recovery of the copper or copper-base alloy 8 is temporarily deteriorated and the concentration of copper ions in the pickling solution X is adjusted to be greater than or equal to 20 g/L by reducing the amount of the pickling solution X, which is supplied to the electrolytic bath 5 , to reduce the flow rate of the pickling solution X to the electrolytic bath 5 and reducing a current, which is applied to the electrolytic bath 5 , to reduce the current density in the electrolytic bath 5 .
  • stable electrolysis can be continuously performed in the electrolytic bath 5 .
  • the precipitation state of the recovered copper or copper-base alloy 8 easily changes. Therefore, the flow rate is also changed at the same time to control the thickness of a diffusion layer in the pickling solution X, thereby promoting stable electrolysis without changing the precipitation state of the recovered copper or copper-base alloy 8 in the electrolytic bath 5 .
  • the amount of the is pickling solution X supplied to the electrolytic bath 5 be adjusted (the flow rate of the pickling solution X in the electrolytic bath 5 be adjusted) with the pump P 1 and that the current applied between the electrodes 6 and 7 through a rectifier 9 , which are connected to a power supply (not illustrated) of the electrolyzes, be adjusted to adjust the current density in the electrolytic bath 5 , thereby automatically promoting stable electrolysis in the electrolytic bath 5 .
  • the optimum prescribed value of the concentration of copper ions in the pickling solution X be set to be 30 g/L to 40 g/L.
  • a plate of tough pitch copper (manufactured by Mitsubishi Materials Corporation; Cu: 99.92%, O: 300 ppm, P: 0 ppm) having a length of 500 mm, a width of 100 mm, and a thickness of 30 mm was subjected to hot rolling (600° C., roll reduction: 50%), followed by rapid cooling. As a result, a tough pitch copper plate having a thickness of 15 mm was prepared. On a surface of this tough pitch copper plate, oxide film having a thickness of about 0.7 ⁇ m was formed.
  • This tough pitch copper plate was dipped in a pickling bath containing 1 m 3 of pickling solution having a composition and a surface tension shown in Table 1 at 40° C. for 30 minutes to be pickled and remove the oxide film. Then, a surface of the tough pitch copper plate after the oxide film was removed was visually inspected.
  • A represents nitric acid
  • B hydrogen peroxide
  • C represents peroxodisulfate ion
  • D represents iron (III) ion
  • E represents benzene sulfonic acid
  • F represents sodium benzene sulfonic acid
  • G represents polyoxyethyleneamine
  • H represents dodecylbenzene sulfonic acid
  • I represents sodium dodecylbenzene sulfonic acid
  • J represents benzoic acid
  • K represents sodium benzoic acid.
  • the total amount of the pickling solution containing the removed oxide film which had the composition shown in Table 1 was poured into an electrolytic bath.
  • electrolysis was performed for 8 hours under conditions of a temperature of 40° C., a current density of 5 A/dm 2 , a distance between the electrodes of 50 mm, and a flow rate of 0.5 m/min.
  • copper derived from the oxide film, was deposited on the cathode in a plate shape.
  • This plate-like copper was collected from the electrolytic bath to measure the average surface roughness Ra, the purity of copper, and the hardness of the surface.
  • this plate-like copper was pickled with sulfuric acid aqueous solution, followed by melting and casting to obtain an ingot.
  • This ingot was heated at 600° C. to be molded into a bar through extrusion, and the content of sulfur (content of S) and whether there were cracks or not were visually inspected.
  • the surface roughness Ra of the surface of the copper plate was measured using an SPM (manufactured by SIT NanoTechnology Inc.).
  • the purity of the copper plate was measured by measuring impurities included in copper and subtracting the content of the impurities from 100%.
  • Impurities other than C were measured using Glow Discharge Mass Spectrometry (GD-MS) and C was measured by measuring the infrared absorption of CO 2 gas, which was generated after combustion of a degreased copper sample in a high-frequency induction furnace in an oxygen atmosphere, to be converted to an amount of C.
  • the content of S was measured by measuring the content of S in the ingot with infrared absorption spectrometry.
  • the total amount of the pickling solution containing the removed oxide film which had the composition of Example 4 was poured into an electrolytic bath.
  • electrolysis was performed under conditions of a distance between the electrodes of 50 mm, a flow rate of 0.5 m/min, and a temperature of 40° C.; and a concentration of copper ions, a current density and a peripheral speed of the rotating cathode shown in Table 3.
  • a time was measured which was taken to deposit the same amount of copper on the cathode as that of a case where a tough pitch copper plate was used in the pickling solution having the above-described composition of Example 4 (where electrolysis was performed for 8 hours under conditions of a temperature of 40° C., a current density of 5 A/dm 2 , a distance between the electrodes of 50 mm, and a flow rate of 0.5 m/min).
  • this cylindrical copper was collected from the electrolytic bath to measure the average surface roughness Ra, the purity of copper, and the hardness of the surface. Then, the cylindrical copper was pickled with sulfuric acid aqueous solution, was heated at 600° C. and was molded into a bar through extrusion. In the bar, the content of sulfur (content of S) and whether there were cracks or not were visually inspected.
  • the surface roughness Ra of the surface of the copper bar was measured using a SPM (manufactured by SII NanoTechnology Inc.).
  • the purity of the copper bar was measured by measuring impurities included in copper and subtracting the content of the impurities from 100%.
  • Impurities other than C were measured using Glow Discharge Mass Spectrometry (GD-MS) and C was measured by measuring the infrared absorption of CO 2 gas, which was generated after combustion of a degreased copper sample in a high-frequency induction furnace in an oxygen atmosphere, to be converted to an amount of C.
  • the content of S was measured with infrared absorption spectrometry.
  • the electrolyzed pickling solution was analyzed to add an oxidant, an additive, and a surfactant (total amount: 0.002 g) to the pickling solution in amounts equivalent to the consumed amounts.
  • the total amount of the pickling solution was poured again into the pickling bath to be used as a pickling solution in the next process.
  • Oxide films of other tough pitch copper were removed in the same manner as those of Examples 1 to 8 and 41 to 45. These processes were further repeated twice.
  • the respective results of the fourth test of removing the oxide film are shown in Table 4. Accordingly, it could be seen that the results of the fourth test were the same as those of the first test.
  • the pickling solution of Example 1 was circulated and oxide films of plural tough pitch copper plates were continuously and sequentially removed for 150 hours.
  • the thickness of these tough pitch copper plates was 5 mm, and oxide films having is thicknesses of about 0.4 ⁇ m to 0.9 ⁇ m were formed on surfaces thereof.
  • the maximum concentration of copper ions was 80 g/L and the minimum concentration thereof was 15 g/L in the pickling solution of the pickling bath.
  • a pickling solution containing the oxide film is electrolyzed in an electrolytic bath so as to recover a high-purity copper or copper-base alloy having superior handleability and to return the electrolyzed pickling solution to the pickling bath for reuse.
US13/714,746 2011-12-15 2012-12-14 Method of removing oxide film on surface of copper or copper-base alloy and copper or copper-base alloy recovered using the method Abandoned US20130156631A1 (en)

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WO2021168537A1 (en) * 2020-02-28 2021-09-02 Sixring Inc. Modified sulfuric acid and uses thereof
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