US20170159204A1 - Basket-type anode - Google Patents

Basket-type anode Download PDF

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Publication number
US20170159204A1
US20170159204A1 US15/316,599 US201515316599A US2017159204A1 US 20170159204 A1 US20170159204 A1 US 20170159204A1 US 201515316599 A US201515316599 A US 201515316599A US 2017159204 A1 US2017159204 A1 US 2017159204A1
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United States
Prior art keywords
plating
basket
less
type anode
reticulated member
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Abandoned
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US15/316,599
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Inventor
Hideya Kaminaka
Kyota SHIRASAWA
Hiroyuki Yamaguchi
Yuta DAIROKUNO
Hidenori Namba
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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Assigned to NIPPON STEEL & SUMITOMO METAL CORPORATION reassignment NIPPON STEEL & SUMITOMO METAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAMAGUCHI, HIROYUKI, DAIROKUNO, Yuta, NAMBA, HIDENORI, SHIRASAWA, Kyota, KAMINAKA, HIDEYA
Publication of US20170159204A1 publication Critical patent/US20170159204A1/en
Assigned to NIPPON STEEL CORPORATION reassignment NIPPON STEEL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: NIPPON STEEL & SUMITOMO METAL CORPORATION
Abandoned legal-status Critical Current

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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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/005—Anodic protection
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention relates to a basket-type anode used for the electrolytic plating of a steel strip.
  • a box-shaped basket-type anode In electrolytic plating in which plating is continuously performed on the surface of a steel strip, a box-shaped basket-type anode is widely used.
  • the front surface that faces the steel strip in the plating bath is formed of a reticulated member (laths), and plating pellets are stored.
  • the plating pellets in the basket-type anode are electrolyzed and ionized, and the metal ions are guided to the surface of the steel strip; thus, plating is formed.
  • the main body and the reticulated member of the basket-type anode are required to have corrosion resistance, and are therefore made of pure Ti (pure titanium).
  • plating pellets When the damage to the reticulated member is significant, it is highly likely that plating pellets will leak out of the basket-type anode. If plating pellets leak out, the amount of plating pellets stored in the basket-type anode decreases rapidly, and the amount of metal ions in the plating bath varies. Furthermore, plating pellets that have leaked out in the plating bath may get between rollers that convey the steel strip.
  • JP-UM H4-37907B (Patent Literature 1) and JP 2011-89148A (Patent Literature 2) describe technologies, in which the reticulated member is insulated from the anode main body to suppress undesired corrosion of the reticulated member and thereby the damage to the reticulated member is suppressed.
  • Patent Literature 1 describes a basket-type anode, in which the structure of attachment of the reticulated member to the anode main body is improved.
  • the reticulated member is attached to the anode main body via an insulating material.
  • Patent Literature 2 describes a basket-type anode, in which the structure of the reticulated member itself is improved.
  • an Al 2 O 3 (alumina) insulating coating is formed on the surface of the reticulated member, and the insulating coating is processed by sealing with a coating of PTFE (polytetrafluoroethylene).
  • Patent Literature 1 JP-UM H4-37907B
  • Patent Literature 2 JP 2011-89148A
  • a basket-type anode is a basket-type anode for storing plating pellets in a plating bath and to be used for electrolytic plating of a steel strip, the basket-type anode including a reticulated member made of Ti to be placed facing the steel strip, wherein the reticulated member contains one or more platinum group elements.
  • the amount of the one or more platinum group elements contained is preferably, in mass %, 0.01% to 0.15%.
  • the reticulated member can further contain one or more of Ni and rare earth elements.
  • the amount of the Ni contained is preferably, in mass %, 0.2% to 1.0%, and the amount of the one or more rare earth elements contained is preferably, in mass %, 0.0005% to 0.020%.
  • Fe 0.3% or less, O: 0.35% or less, C: 0.18% or less, H: 0.015% or less, N: 0.03% or less, Al: 0.3% or less, Cr: 0.2% or less, Zr: 0.2% or less, Nb: 0.2% or less, Si: 0.02% or less, Sn: 0.2% or less, Mn: 0.01% or less, Co: 0.35% or less, and Cu: 0.1% or less, amounting to 0.6% or less in total, may be contained.
  • mass % Fe: 0.3% or less, O: 0.35% or less, C: 0.18% or less, H: 0.015% or less, N: 0.03% or less, Al: 0.3% or less, Cr: 0.2% or less, Zr: 0.2% or less, Nb: 0.2% or less, Si: 0.02% or less, Sn: 0.2% or less, Mn: 0.01% or less, Co: 0.35% or less, and Cu: 0.1% or less, amounting to 0.6% or less in total, may be contained.
  • the anode mentioned above can be used for electrolytic plating, in which the plating pellets are Ni particles. Further, the anode mentioned above can be used for electrolytic plating, in which the plating bath is a Watts bath.
  • FIG. 1 is a front view of a basket-type anode.
  • FIG. 2 is a vertical cross-sectional view along the vertical direction of the basket-type anode.
  • FIG. 3 is a schematic diagram of a test apparatus used for a basic test of the investigation of corrosion resistance.
  • the present inventors investigated the cause of a corrosion of a reticulated member made of pure titanium and of damage to the reticulated member in the operation of electrolytic plating, in which a large current is supplied to the main body of a basket-type anode, and remedial measures against it.
  • the investigation was performed using electrolytic Ni plating, which is a typical example of the electrolytic plating, as an example.
  • electrolytic Ni plating the plating pellets are Ni particles, and a Watts bath is used as the plating bath.
  • FIG. 1 is a front view of a basket-type anode.
  • FIG. 2 is a vertical cross-sectional view along the vertical direction of the basket-type anode.
  • the hollow arrow indicates the flow of the current supplied to the main body of the basket-type anode.
  • a basket-type anode 1 is immersed in a plating bath 11 and stores plating pellets 10 in the plating bath 11 , and is used to perform electrolytic plating on a steel strip 12 .
  • the basket-type anode 1 is in a box shape, in which the upper surface is opened, and comprises an anode main body 2 and a reticulated member 3 that forms the front surface.
  • the reticulated member 3 is placed facing the steel strip 12 in the plating bath 11 .
  • the internal space of the basket-type anode 1 is charged with the plating pellets 10 .
  • the anode main body 2 comprises a rear surface plate 2 a , a pair of side surface plates 2 b and 2 c on the left and right, and a bottom surface plate 2 d .
  • a bus bar 2 e for supplying a current to the anode main body 2 is provided on the upper side of the rear surface plate 2 a .
  • the reticulated member 3 is installed on the front surface side of the anode main body 2 of such a configuration. Specifically, a plurality of support columns 4 protrude forward from the rear surface plate 2 a .
  • the reticulated member 3 is attached to the front ends of the support columns 4 , and a pressing plate 5 is attached to the reticulated member 3 at the position of each support column 4 .
  • the pressing plate 5 is fastened to each support column 4 by a bolt 6 . Thereby, the reticulated member 3 is held on the front surface side of the anode main body 2 in a state of being sandwiched between each support column 4 and each pressing plate 5 .
  • the reticulated member 3 is configured exactly in such a manner that two wire nets 3 a and 3 b are stacked.
  • the front surface side of a bag 7 made of cloth is sandwiched between the wire nets 3 a and 3 b .
  • the bag 7 allows the metal ions of the plating pellets 10 electrolyzed during electrolytic plating to permeate, and at the same time prevents the plating pellets 10 with the size reduced by electrolysis from leaking out through the meshes of the reticulated member 3 .
  • the technology described in Patent Literature 2 mentioned above may be applied to the wire nets 3 a and 3 b herein. That is, in the wire nets 3 a and 3 b , an insulating coating of Al 2 O 3 may be formed on the surface, and the insulating coating may be processed by sealing with a coating of PTFE.
  • a reticulated member 3 divided in a plurality of stages in the vertical direction is attached to the anode main body 2 .
  • the basket-type anode 1 shown in FIG. 1 a configuration in which the reticulated member 3 is divided in four stages is shown.
  • a current is supplied to the main body 2 of the basket-type anode 1 through the bus bar 2 e of the rear surface plate 2 a .
  • the plating pellets 10 in the basket-type anode 1 are electrolyzed and ionized, and the metal ions are guided to the surface of the steel strip 12 ; thus, plating is formed.
  • the reticulated member has been made of pure Ti, including the case of employing the technology described in Patent Literature 2 mentioned above.
  • the occurrence manner of damage (hole making) to the reticulated member was investigated in the operation of electrolytic Ni plating in which the conventional basket-type anode was used and a large current was supplied to the anode main body. As a result, the following findings have been obtained.
  • the damage to the reticulated member is likely to occur in the upper portion of the reticulated member. This is presumed to be due to the fact that, as shown below, the pH of the plating bath is reduced particularly in the upper portion of the reticulated member.
  • the Watts bath contains boric acid for pH buffering. Even in this case, when O 2 gas is generated in the plating bath in the upper portion of the reticulated member based on Formula (1) above, a great reduction in the pH of the plating bath occurs likewise.
  • the reticulated member made of pure Ti is not corroded, nor is damaged.
  • the pH of the plating bath has reached the region where the de-passivation of Ti is caused, the reticulated member made of pure Ti is corroded, and is damaged as a result of this.
  • the cause of the occurrence of damage due to corrosion in the upper portion of the reticulated member is that the pH of the plating bath has reached the region where the de-passivation of Ti is caused.
  • the upper limit of the pH at which the de-passivation of Ti occurs is approximately 1.
  • the present inventors conducted extensive studies on the countermeasures that can prevent the corrosion of the reticulated member even when the pH of the plating bath is greatly reduced. As a result, it has been revealed that it is effective to improve the chemical components of the reticulated member itself, with Ti as the base, and produce a reticulated member made of Ti containing one or more platinum group elements.
  • the platinum group element(s) When one or more platinum group elements are contained in Ti material, either of following states is occurred: the platinum group element(s) is dissolved as a solid solution in Ti or a Ti-platinum group compound(s) is(are) generated.
  • a Ti-platinum group compound(s) In such a reticulated member made of Ti containing one or more platinum group elements, when the pH reduction of the plating bath is significant, the passive coating of the surface dissolves and Ti dissolves out, and in association with this also the platinum group element(s) dissolves out.
  • the platinum group element(s) that has dissolved out together with Ti has a very noble oxidation-reduction potential, and is therefore immediately electrodeposited on the surface of the reticulated member.
  • the platinum group element(s) electrodeposited on the surface of the reticulated member is a metal having a low hydrogen overvoltage, and reduces the hydrogen overvoltage. Therefore, in the reticulated member, the corrosion potential of Ti is ennobled, and the surface is re-passivated. By the re-passivation, the dissolution of Ti can be stopped.
  • the following basic test was performed.
  • a simulated situation was employed in which a current flows directly from the main body of the basket-type anode to the plating bath in electrolytic plating using a Watts bath as the plating bath.
  • a cathode was likened to a steel strip to be plated
  • an anode was likened to the main body of the basket-type anode
  • a test piece was likened to the reticulated member of the basket-type anode, and the corrosion resistance of the test piece was investigated.
  • a sheet material of pure Ti (type 2 of the JIS standards) with a thickness of 1 mm was prepared.
  • a sheet material of pure Ti (type 2 of the JIS standards) with a thickness of 1 mm was obtained, and the surface of the sheet material made of pure Ti was subjected to alumina thermal spraying processing.
  • a plasma jet produced by a plasma thermal spray gun was used to heat and accelerate alumina of the thermal spraying material (gray alumina, Al 2 O 3 -2.5% TiO 2 , produced by Sanko Shokai Co., Ltd.), and thereby the alumina was made into a molten state or a state close to it and was sprayed on the surface of the sheet material made of pure Ti; thus, an insulating coating was formed. Since air pores were present in the insulating coating, the insulating coating was further processed by sealing with a PTFE coating.
  • an industrial pure Ti sponge (type 1 of the JIS standards), a Pd (palladium) powder with a purity of 99.9% (produced by Kishida Chemical Co., Ltd.), a Ru (ruthenium) powder with a purity of 99.9% (produced by Kishida Chemical Co., Ltd.), Y (yttrium) turnings with a purity of 99.9% (produced by Kishida Chemical Co., Ltd.), massive rare earth elements, and massive electrolytic Co (cobalt) with a purity of 99.8% were obtained.
  • Mm misch metal, mixed rare earth metals
  • La lanthanum
  • Nd neodymium
  • the chemical components of Mm were, in mass %, La: 28.6%, Ce (cerium): 48.8%, Pr (praseodymium): 6.4%, and Nd: 16.2%.
  • rectangular ingots with different chemical components were prepared, with the mixing ratio of the source materials mentioned above variously altered.
  • the size of each rectangular ingot was set to a thickness of 15 mm, a width of 75 mm, and a length of 95 mm.
  • five 80-g ingots were prepared first, then those ingots were re-melted together to prepare a rectangular ingot with a thickness of 15 mm, after that the rectangular ingot was re-melted for homogenization, and a rectangular ingot of the size mentioned above was prepared.
  • All the prepared rectangular ingots contained a minute amount of one or more platinum group elements, and in some cases further contained one or more rare earth elements; hence, heat treatment for homogenization was performed in order to lessen the segregation of each element.
  • the conditions of the homogenization heat treatment were as follows.
  • the rectangular ingot that has undergone the homogenization heat treatment was rolled under the following conditions and was finally made into a sheet material with a thickness of 1 mm.
  • the sheet material obtained by the rolling was subjected to annealing for strain relief.
  • the conditions of the annealing were as follows.
  • the hot-rolled sheet thus obtained was subjected to machining to prepare a test piece.
  • the size of all the test pieces of test materials of the inventive examples and comparative materials 1 and 2 mentioned above was set to a thickness of 1 mm, a width of 15 mm, and a length of 15 mm.
  • the surface of each test piece of test materials of the inventive examples and comparative material 1 mentioned above was mirror-polished using a #600 buff.
  • test materials 1 to 17 of the inventive examples and comparative materials 1 and 2 mentioned above were as shown in Table 1 below.
  • test pieces of test materials 1 to 17 of the inventive examples are a Ti alloy containing one or more platinum group elements.
  • test materials 5, 6, 9, 11, 15, and 16 are materials further containing Ni
  • test materials 7 to 9, 14, and 17 are materials further containing one or more rare earth elements.
  • Test material 13 is a material containing two kinds of platinum group elements.
  • Test material 12 is a material, in which the amount of the platinum group element contained, is below the preferred lower limit of the present invention.
  • Test material 14 is a material, in which the amount of the rare earth element contained, exceeds the preferred upper limit of the present invention.
  • Test materials 15, 16, and 17 are examples containing Cr, Al, and Zr, respectively, as an impurity element.
  • FIG. 3 is a schematic diagram of a test apparatus used for the basic test of corrosion resistance investigation.
  • the test apparatus used for the basic test comprises a plating vessel 20 storing a plating solution (a plating bath).
  • the plating vessel 20 is immersed in a constant temperature vessel 21 , and the temperature of the plating solution in the plating vessel 20 can be kept constant.
  • a cathode 22 likened to the steel strip to be plated was immersed, and an anode 23 likened to the main body of the basket-type anode was immersed.
  • the cathode 22 a soft steel sheet with a thickness of 1 mm and a width of 20 mm was used.
  • the immersion length of the cathode 22 in the plating bath was set to 20 mm.
  • the anode 23 a sheet material of pure Ti (type 2 of the JIS standards) with a thickness of 1 mm and a width of 20 mm was used.
  • the pure Ti sheet that is the anode 23 is a sheet cut out of the same material as that used in Comparative Material 1 mentioned above, and the immersion length thereof in the plating bath was set to 20 mm like in the cathode 22 .
  • test piece 24 likened to the reticulated member of the basket-type anode that is, the test piece of test materials 1 to 11 of the inventive examples and comparative materials 1 and 2 mentioned above was immersed in the plating solution in the plating vessel 20 .
  • each test piece 24 was hung between the anode 23 and the cathode 22 with a platinum wire 25 so as not to be directly electrically connected to either of the anode 23 and the cathode 22 .
  • a Watts bath was used as the plating bath (plating solution).
  • the Watts bath one in which the nominal composition is NiSO 4 (nickel sulfate): 300 to 380 g/L, NiCl 2 (nickel chloride): 60 to 80 g/L, and boric acid: 35 to 55 g/L was used.
  • the amount of the solution of the Watts bath was set to 60 cc.
  • the pH of the plating solution was evaluated. Specifically, after the current passage of 24 hours, the pH of the plating solution was measured with a pH measuring device (pH Meter D-70 Series/ES-71/OM-71, manufactured by Horiba, Ltd.).
  • the rate of corrosion was evaluated. Specifically, on the assumption that the entire surface of each test piece corrodes uniformly, the corrosion thickness (mm) per 24 hours was calculated from Formula (2) below on the basis of the corrosion weight loss (weight loss) of each test piece due to the current passage of 24 hours and the specific gravity of the test piece (4.51 g/cm 3 ). At this time, as the surface area of each test piece, a value calculated from the thickness, width, and length of the test piece before the test was used.
  • Rate of corrosion corrosion thickness per 24 hours ⁇ 365 days (3)
  • test piece of comparative material 1 because of being pure Ti not containing a platinum group element, a significant weight loss and a significant wall thickness loss were found, and the rate of corrosion reached 2.0 mm/year.
  • test pieces of test materials 1 to 17 of the inventive examples since they are a Ti alloy containing one or more platinum group elements, the rate of corrosion was less than 0.1 mm/year, and a significant corrosion resistance was exhibited.
  • test materials 1 to 5, 8, 13, 15, and 16 in which the amount of the one or more platinum group elements contained is 0.04 mass % or more the rate of corrosion was less than 0.01 mm/year, and in spite of the pH of the plating solution being well below 1.0, an almost perfect corrosion resistance was exhibited.
  • the rate of corrosion was approximately 0.02 mm/year. Further, in the test pieces of test materials 10 and 11 of the inventive examples in which the amount of the platinum group element contained is less than 0.02 mass %, the rate of corrosion was approximately 0.05 mm/year. In the test piece of test material 12 in which the amount of the platinum group element contained is below 0.01 mass %, the rate of corrosion was 0.1 mm/year.
  • the corrosion resistance of the test pieces of these test materials 6, 7, 9, 10, 11, 12, 14, and 17 was distinctly improved as compared to comparative materials 1 and 2 although not as good as the perfect corrosion resistance of test materials 1 to 5, 8, 13, 15, and 16.
  • test material 12 was 0.1 mm/year, and slightly exceeded the standard that is assessed as corrosion-resistant ( ⁇ 0.1 mm/year).
  • Test material 14 is a material in which the amount of the rare earth element contained slightly exceeds the preferred upper limit. In this case, the rate of corrosion was 0.1 mm/year, and slightly exceeded the standard that is assessed as corrosion-resistant ( ⁇ 0.1 mm/year).
  • Test materials 15, 16, and 17 are materials containing an impurity, but are unaffected in corrosion resistance and exhibited an excellent corrosion resistance in the test.
  • the basket-type anode of the present invention has been completed based on the above findings. In the following, an embodiment of the basket-type anode of the present invention is described.
  • platinum group elements Six kinds of elements of Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (iridium), and Pt (platinum) fall under the platinum group elements.
  • the platinum group element(s) may comprise one or more of the six kinds of elements.
  • the platinum group elements are rare and very expensive, it is preferable to select Ru or Pd among the six kinds of elements from the economic point of view. This is because recycling technology is established for Ru and Pd and in particular Ru can be obtained stably at relatively low cost.
  • the amount of the one or more platinum group elements contained is not particularly limited. However, containing a large amount of one or more platinum group elements is not preferable from the economic point of view. Hence, the upper limit of the amount of the one or more platinum group elements contained is preferably set to 0.15 mass %. A more preferred upper limit of the amount of the one or more platinum group elements contained is 0.08 mass %.
  • the lower limit of the amount of the one or more platinum group elements contained is preferably set to 0.01 mass % in order to improve the lifetime of the reticulated member sufficiently.
  • a more preferred lower limit of the amount of the one or more platinum group elements contained is 0.02 mass %, and a still more preferred lower limit is 0.04 mass %.
  • Ni or one or more rare earth elements are contained compositely in addition to the one or more platinum group elements, by the synergy by the containing of Ni or the one or more rare earth elements, it becomes possible to reduce the amount of the one or more platinum group elements contained.
  • the containing of Ni or one or more rare earth elements has an advantage from the economic point of view.
  • the lower limit of the amount of the one or more rare earth elements contained is preferably set to 0.0005 mass %.
  • a more preferred lower limit of the amount of the one or more rare earth elements contained is 0.001 mass %.
  • the upper limit of the amount of the one or more rare earth elements contained might be, in terms of the mechanism, the upper limit of the solid solution range of the rare earth element(s), this has a concern that segregation etc. will occur during dissolution.
  • the upper limit of the amount of the one or more rare earth elements contained in the case where the one or more rare earth elements are incorporated is preferably set to 0.020 mass % from the viewpoint of obtaining a solid solution state reliably.
  • the rare earth element(s) is a general term of Y and Sc in addition to the 15 elements of the lanthanoids from La of atomic number 57 to Lu of atomic number 71, a total of 17 elements, and may comprise one or more selected from these elements.
  • the amount of the one or more rare earth elements contained refers to the total amount of these elements contained.
  • the reticulated member (the wire net) of the basket-type anode of the embodiment is a titanium material that contains one or more platinum group elements and in some cases further contains one or more of Ni and the rare earth elements.
  • the impurity elements contained in addition to these elements Fe, O, C, H, N, etc. that enter from the source material, the solution electrode, or the environment are given, and further Al, Cr, Zr, Nb, Si, Sn, Mn, Co, Cu, etc. that get mixed in when scrap or the like is used as the source material are given. There is no problem with these impurity elements getting mixed in as long as they are within the range in which the effect by the embodiment is not inhibited.
  • the amounts of the impurities are, in mass %, Fe: 0.3% or less, O: 0.35% or less, C: 0.18% or less, H: 0.015% or less, N: 0.03% or less, Al: 0.3% or less, Cr: 0.2% or less, Zr: 0.2% or less, Nb: 0.2% or less, Si: 0.02% or less, Sn: 0.2% or less, Mn: 0.01% or less, Co: 0.35% or less, and Cu: 0.1% or less, and the total amount of these is 0.6% or less.
  • the present invention is not limited to the embodiment described above, and various alterations are possible without departing from the spirit of the present invention.
  • the basket-type anode of the embodiment can be suitably used for electrolytic Ni plating in which the plating pellets are Ni particles and a Watts bath is used as the plating bath, there are no limitations on the types of the plating pellets and the plating bath to the extent that they are used for electrolytic plating.
  • the plating pellets that is, the type of plating for which the basket-type anode of the embodiment can be used, gold, silver, copper, tin, zinc, etc. are given as well as Ni.
  • a spherical shape, a crown-like shape, etc. are given.
  • a type of the plating bath for which the basket-type anode of the embodiment can be used a nickel sulfamate sergeant bath, a nickel sulfamate high-speed bath, a strike bath (a Wood's bath), a black nickel plating bath, etc. are given as well as a Watts bath.
  • reticulated members In the test, five kinds of reticulated members (exactly, wire nets) were prepared.
  • three kinds of test materials 21, 22, and 23 with different chemical components were used as shown in Table 3 below.
  • two kinds of comparative materials 1 and 2 in which the chemical components of the material are the same but the surface form is different were used.
  • all the reticulated members of test materials 21, 22, and 23, which are examples of the present invention were formed of a Ti alloy containing a platinum group element.
  • the reticulated member of test material 21 was made to further contain Ni
  • the reticulated member of test material 23 was made to further contain Mm (misch metal, mixed rare earth metals), which is rare earth elements.
  • all the reticulated members of comparative materials 21 and 22, which are comparative examples were formed of pure Ti (type 2 of the JIS standards).
  • the reticulated member of comparative material 22 was configured to be a member in which the surface of the net was subjected to alumina thermal spraying processing, similarly to comparative material 2 in the basic test mentioned above.
  • the composition of the Watts bath was nickel sulfate: approximately 340 g/L, nickel chloride: approximately 70 g/L, and boric acid: approximately 45 g/L.
  • the temperature of the Watts bath was approximately 55° C.
  • the pH of the Watts bath was 3.5 to 4.6.
  • a current was continuously passed through the anode main body by applying an electrolysis voltage of approximately 30 V, at a current density in the steady state of 34.5 A/dm 2 .
  • Each basket-type anode was charged with crown-like Ni particles, and was replenished periodically. At this time, with the consumption of Ni particles, often a state where only the plating solution was present immediately below the surface of the solution of the Watts bath appeared.
  • the thickness of the net of each reticulated member was measured before and after the continuous operation, and the degree of corrosion was evaluated from the thickness loss.
  • the measurement of the thickness of the net of each reticulated member was performed on three points A, B, and C specified in advance.
  • Measurement point A was set to a point in a position 50 mm inside from the left end of the reticulated member of the uppermost stage and 200 mm below from the upper end thereof.
  • Measurement point B was set to a point in a position at the lateral center of the reticulated member of the uppermost stage and 200 mm below from the upper end thereof.
  • Measurement point C was set to a point in a position 50 mm inside from the right end of the reticulated member of the uppermost stage and 200 mm below from the upper end thereof. These measurement points A, B, and C correspond to positions immediately below the surface of the solution of the Watts bath, which have been positions where damage to the reticulated member is likely to occur.
  • the basket-type anode of the present invention can be effectively used for any electrolytic plating.

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  • Chemical Kinetics & Catalysis (AREA)
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US15/316,599 2014-06-25 2015-06-18 Basket-type anode Abandoned US20170159204A1 (en)

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US5584975A (en) * 1995-06-15 1996-12-17 Eltech Systems Corporation Tubular electrode with removable conductive core
IT1291604B1 (it) * 1997-04-18 1999-01-11 De Nora Spa Anodo per l'evoluzione di ossigeno in elettroliti contenenti fluoruri o loro derivati
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US20030066756A1 (en) * 2001-10-04 2003-04-10 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
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