WO2015198958A1 - バスケット型アノード - Google Patents

バスケット型アノード Download PDF

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Publication number
WO2015198958A1
WO2015198958A1 PCT/JP2015/067588 JP2015067588W WO2015198958A1 WO 2015198958 A1 WO2015198958 A1 WO 2015198958A1 JP 2015067588 W JP2015067588 W JP 2015067588W WO 2015198958 A1 WO2015198958 A1 WO 2015198958A1
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WIPO (PCT)
Prior art keywords
type anode
less
basket
plating
mesh member
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PCT/JP2015/067588
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English (en)
French (fr)
Japanese (ja)
Inventor
上仲　秀哉
教太 白澤
山口　博幸
裕太 大六野
秀徳 難波
Original Assignee
新日鐵住金株式会社
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Application filed by 新日鐵住金株式会社 filed Critical 新日鐵住金株式会社
Priority to EP15811491.8A priority Critical patent/EP3128046A4/de
Priority to KR1020167035004A priority patent/KR101862971B1/ko
Priority to JP2016529508A priority patent/JP6319439B2/ja
Priority to US15/316,599 priority patent/US20170159204A1/en
Priority to CN201580032599.XA priority patent/CN106460224A/zh
Publication of WO2015198958A1 publication Critical patent/WO2015198958A1/ja

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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
    • 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
    • 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
    • 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 electrolytic plating of a steel strip.
  • a box-shaped basket type anode In the electrolytic plating in which the surface of the steel strip is continuously plated, a box-shaped basket type anode is widely used.
  • the front surface facing the steel strip in the plating bath is constituted by a mesh member (lass) and accommodates the plating raw material grains.
  • the plating raw material grains in the basket type anode are electrolyzed and ionized, and the metal ions are guided to the surface of the steel strip to form plating.
  • the main body and the net-like member of the basket type anode are made of pure Ti (pure titanium) because corrosion resistance is required.
  • the mesh member If the mesh member is severely damaged, the possibility of leakage of plating raw material grains from the basket type anode increases. If the plating raw material grains leak out, the amount of the plating raw material grains in the basket type anode rapidly decreases, and the amount of metal ions in the plating bath varies. Moreover, the plating raw material grains leaking into the plating bath may be caught in a roller that conveys the steel strip. Such a situation causes a deterioration in the quality of the plated steel sheet.
  • Patent Document 1 Japanese Utility Model Publication No. 4-37907 (Patent Document 1) and Japanese Unexamined Patent Application Publication No. 2011-89148 (Patent Document 2), the mesh member is inadvertently corroded by insulating the mesh member from the anode body.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2011-89148
  • Patent Document 1 describes a basket type anode having an improved structure for attaching a mesh member to an anode body.
  • the mesh member is attached to the anode main body portion via an insulating material.
  • Patent Document 2 describes a basket type anode in which the structure of the mesh member itself is improved.
  • an Al 2 O 3 (alumina) insulating film is formed on the surface of a mesh member, and this insulating film is sealed with a PTFE (polytetrafluoroethylene) film.
  • the object of the present invention is to provide a basket type anode having the following characteristics: To improve the life of the mesh member.
  • a basket-type anode is a basket-type anode that contains plating raw material grains in a plating bath and is used for electrolytic plating of a steel strip,
  • the said basket type anode is equipped with the mesh member made from Ti arrange
  • the platinum group element content is preferably 0.01% to 0.15% by mass%.
  • the mesh member may further contain one or more of Ni and rare earth elements.
  • the Ni content is preferably 0.2% to 1.0% by mass
  • the rare earth element content is preferably 0.0005% to 0.020% by mass.
  • impure elements by mass%, Fe: 0.3% or less, O: 0.35% or less, C: 0.18% or less, H: 0.015% or less, N: 0 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 may be contained in total of 0.6% or less.
  • the anode can be used for electrolytic plating in which the plating raw material grains are Ni grains. Further, the anode can be used for electrolytic plating in which the plating bath is a watt bath.
  • the basket type anode of the present invention has the following remarkable effects: The life of the mesh member can be improved.
  • FIG. 1 is a front view of a basket type anode.
  • FIG. 2 is a longitudinal sectional view along the vertical direction of the basket type anode.
  • FIG. 3 is a schematic diagram of a test apparatus used in the basic test for the corrosion resistance investigation.
  • the inventors of the present invention have studied the cause of the net member made of pure titanium corroding and causing the breakage of the mesh member in the operation of electroplating for supplying a large current to the main part of the basket type anode, and the improvement measures.
  • the examination was performed by taking electrolytic Ni plating, which is a typical example of electrolytic plating, as an example.
  • electrolytic Ni plating the plating raw material grains are Ni grains, and a watt bath is adopted as the plating bath.
  • FIG. 1 is a front view of a basket type anode.
  • FIG. 2 is a longitudinal sectional view along the vertical direction of the basket type anode.
  • white arrows indicate the flow of current supplied to the main body of the basket type anode.
  • the basket type anode 1 is immersed in a plating bath 11, accommodates the plating raw material grains 10 in the plating bath 11, and is used for electrolytic plating on the steel strip 12.
  • the basket-type anode 1 has a box shape with an open upper surface, and includes an anode main body 2 and a mesh member 3 constituting the front surface.
  • the net member 3 is disposed in the plating bath 11 so as to face the steel strip 12.
  • Plating raw material grains 10 are filled in the internal space of the basket type anode 1.
  • the anode body 2 includes a back plate 2a, a pair of side plates 2b and 2c on the left and right sides, and a bottom plate 2d.
  • a bus bar 2e for supplying current to the anode main body 2 is provided on the upper portion of the back plate 2a.
  • the mesh member 3 is attached to the front surface side of the anode main body 2 having such a configuration. Specifically, a plurality of support columns 4 protrude forward from the back plate 2a.
  • the mesh member 3 is addressed to the front end of each column 4, and the pressing plate 5 is addressed to the mesh member 3 at the position of each column 4.
  • the holding plate 5 is fastened to each column 4 by bolts 6. As a result, the mesh member 3 is held on the front side of the anode main body 2 in a state of being sandwiched between each support column 4 and the pressing plate 5.
  • the net-like member 3 is configured by overlapping two metal nets 3a and 3b.
  • the front side of the cloth bag 7 is sandwiched between the metal meshes 3a and 3b.
  • the bag 7 allows the metal ions of the plating raw material grains 10 electrolyzed during electrolytic plating to pass through, while preventing the plating raw material grains 10 that have been reduced by electrolysis from leaking out from the mesh of the mesh member 3.
  • the technique described in Patent Document 2 may be applied to the wire nets 3a and 3b here. That is, the metal nets 3a and 3b may have an Al 2 O 3 insulating film formed on the surface thereof, and the insulating film may be sealed with a PTFE film.
  • the mesh member 3 is usually attached to the anode body 2 by being divided into a plurality of stages in the vertical direction.
  • a mode in which the mesh member 3 is divided into four stages is shown.
  • a current is supplied to the main body 2 of the basket type anode 1 through the bus bar 2e of the back plate 2a.
  • the plating raw material grains 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 to form plating.
  • the breakage of the mesh member is likely to occur at the top of the mesh member. This is considered to be due to a decrease in the pH of the plating bath, particularly at the upper part of the mesh member, as shown below.
  • the Watt bath when a Watt bath is employed in electrolytic Ni plating, the Watt bath contains boric acid for pH buffering. Even in this case, when the O 2 gas according to the above formula (1) is generated in the plating bath on the upper part of the mesh member, the pH of the plating bath is largely lowered.
  • the cause of the damage due to corrosion at the upper part of the mesh member is that the pH of the plating bath has reached the region where Ti depassivation occurs.
  • the upper limit of pH at which Ti depassivation occurs is about 1.
  • the present inventors have made extensive studies on countermeasures that can prevent corrosion of the mesh member even when the pH of the plating bath is greatly reduced. As a result, the present inventors have found that it is effective to improve the chemical components of the net member itself based on Ti to obtain a Ti net member containing a platinum group element.
  • the platinum group element electrodeposited on the surface of the mesh member is a metal having a low hydrogen overvoltage, and reduces the hydrogen overvoltage. For this reason, the mesh member has a noble Ti corrosion potential and the surface is repassivated. This repassivation can terminate the dissolution of Ti.
  • Comparative material 1 Pure Ti A plate material of pure Ti (2 types of JIS standards) having a thickness of 1 mm was prepared.
  • Comparative material 2 Technology described in Patent Document 2 A plate material made of pure Ti (two types of JIS standards) having a thickness of 1 mm was obtained, and the surface of the plate material made of pure Ti was subjected to alumina spraying. Specifically, the Ar plasma spraying method is applied, and the spray material alumina (produced by Sanko Shokai Co., Ltd .: gray alumina Al 2 O 3 -2.5% TiO 2 ) is heated using a plasma jet generated by a plasma spray gun. -By accelerating, alumina was melted or close to it and sprayed onto the surface of a pure Ti plate material to form an insulating film. Since this insulating film has pores, the insulating film was further sealed with a PTFE film.
  • alumina spraying Specifically, the Ar plasma spraying method is applied, and the spray material alumina (produced by Sanko Shokai Co., Ltd .: gray alumina Al 2 O 3 -2.5% TiO 2 ) is heated using a plasma
  • Test material of the present invention Improvement of chemical composition based on Ti (titanium alloy)
  • A Raw materials As raw materials, industrial pure Ti sponge (a kind of JIS standard), 99.9% pure Pd (palladium) powder (manufactured by Kishida Chemical Co., Ltd.), 99.9% pure Ru (ruthenium) powder (Kishida Chemical Co., Ltd.), 99.9% -purified Y (yttrium) in shape (Kishida Chemical Co., Ltd.), massive rare earth elements, and massive electrolytic Co (cobalt) having a purity of 99.8% did.
  • the massive rare earth elements were Mm (Misch metal: mixed rare earth), La (lanthanum), and Nd (neodymium), and those other than Mm having a purity of 99% were used.
  • the chemical components of Mm were, by mass%, La: 28.6%, Ce (cerium): 48.8%, Pr (praseodymium): 6.4%, and Nd: 16.2%.
  • Each of the produced square ingots contained a trace amount of a platinum group element and, in some cases, further contained a rare earth element. Therefore, in order to reduce segregation of each element, homogenization heat treatment was performed.
  • the conditions for this homogenization heat treatment were as follows. Atmosphere: Vacuum ( ⁇ 10 ⁇ 3 torr (0.133 Pa)) ⁇ Heating temperature: 1100 ° C ⁇ Heating time: 24 hours
  • ⁇ ⁇ -phase region hot rolling Heating temperature is 1000 ° C., rolling 15 mm to 9 mm ⁇ ⁇ + ⁇ -phase region hot rolling: heating temperature is 875 ° C., rolling 9 mm to 1 mm
  • the plate material obtained by rolling was annealed to remove distortion.
  • the annealing conditions were as follows. Atmosphere: Vacuum ( ⁇ 10 ⁇ 3 torr (0.133 Pa)) ⁇ Heating temperature: 680 ° C ⁇ Heating time: 7 hours
  • the hot-rolled sheet thus obtained was machined to produce a test piece.
  • the size of each test piece of the test material of the present invention and the comparative materials 1 and 2 was 1 mm in thickness, 15 mm in width, and 15 mm in length.
  • the surface of each of the test piece of the inventive example and the comparative material 1 was mirror-polished using a # 600 buff.
  • test materials 1 to 17 of the present invention were as shown in Table 1 below.
  • the test pieces of the comparative materials 1 and 2 are pure Ti.
  • the comparative material 2 employs the technique described in Patent Document 2, and an insulating film is formed on the surface, and this insulating film is sealed with a PTFE film.
  • the test pieces of the test materials 1 to 17 of the present invention are all Ti alloys containing a platinum group element.
  • the test materials 5, 6, 9, 11, 15, and 16 further contain Ni, and the test materials 7 to 9, 14, and 17 further contain rare earth elements.
  • the test material 13 contains two types of platinum group elements.
  • the test material 12 has a platinum group element content below the desirable lower limit of the present invention.
  • the test material 14 has a rare earth element content exceeding the desirable upper limit of the present invention.
  • Test materials 15, 16, and 17 are examples containing Cr, Al, and Zr as impurity elements.
  • FIG. 3 is a schematic diagram of a test apparatus used for the basic test of the corrosion resistance survey.
  • the test apparatus used for the basic test includes a plating bath 20 containing a plating solution (plating bath).
  • the plating bath 20 is immersed in the constant temperature bath 21, and the temperature of the plating solution in the plating bath 20 can be kept constant.
  • the cathode (cathode) 22 assumed to be the steel strip to be plated was immersed in the plating solution in the plating bath 20, and the anode 23 assumed to be the main body of the basket type anode was immersed.
  • a mild steel plate having 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 20 mm.
  • a plate material of pure Ti (two kinds of JIS standards) having a thickness of 1 mm and a width of 20 mm was used.
  • the pure Ti plate as the anode 23 was cut out from the same material as that used for the comparative material 1, and the immersion length in the plating bath was set to 20 mm as with the cathode 22.
  • test pieces 24 that are regarded as basket-type anode mesh members, that is, the test pieces 1 to 11 of the present invention example and the test pieces of the comparative materials 1 and 2 are immersed.
  • each test piece 24 was suspended between the anode 23 and the cathode 22 by a platinum wire 25 so that neither the anode 23 nor the cathode 22 was directly electrically connected.
  • a Watt bath was adopted as the plating bath (plating solution).
  • the Watt bath was used with nominal compositions of NiSO 4 (nickel sulfate): 300-380 g / L, NiCl 2 (nickel chloride): 60-80 g / L, and boric acid: 35-55 g / L.
  • the amount of the watt bath was 60 cc.
  • the corrosion rate was evaluated about each test piece. Specifically, assuming that the entire surface of each test piece is evenly corroded, based on the corrosion weight loss (weight loss) of each test piece and the specific gravity (4.51 g / cm 3 ) of the test piece by energization for 24 hours, From the equation (2), the corrosion thickness (mm) per 24 hours was calculated. In that case, the surface area of each test piece used the value computed from the thickness, the width
  • variety, and length of the test piece before a test. Corrosion thickness per 24 hours corrosion loss / (specific gravity ⁇ surface area) (2)
  • test piece of comparative material 1 since it was pure Ti containing no platinum group element, significant weight loss and thinning were observed, and the corrosion rate reached 2.0 mm / year.
  • test pieces 1 to 17 of the inventive examples were all Ti alloys containing a platinum group element, the corrosion rate was less than 0.1 mm / year, and remarkable corrosion resistance was recognized.
  • the corrosion rate was less than 0.01 mm / year, and the pH of the plating solution was 1.0. Almost complete corrosion resistance was observed despite being significantly below this value.
  • the corrosion rate is 0.02 mm / year. It was about. Moreover, the corrosion rate was about 0.05 mm / year in the test piece of the test materials 10 and 11 of this invention example whose content of a platinum group element is less than 0.02 mass%. In the test piece of the test material 12 in which the platinum group element content was less than 0.01% by mass, the corrosion rate was 0.1 mm / year.
  • the corrosion resistance of the test pieces of these test materials 6, 7, 9, 10, 11, 12, 14, 17 is not as high as the complete corrosion resistance of the test materials 1 to 5, 8, 13, 15, 16 but the comparative material 1 Compared with 2, it was clearly improved.
  • the corrosion rate of the test material 12 was 0.1 mm / year, which was slightly higher than the standard ( ⁇ 0.1 mm / year) judged to be corrosion resistance.
  • the rare earth element content slightly exceeds the preferable upper limit.
  • the corrosion rate was 0.1 mm / year, which was slightly higher than the standard ( ⁇ 0.1 mm / year) judged to be corrosion resistance.
  • the test materials 15, 16, and 17 contain impurities, there was no effect on the corrosion resistance, and excellent corrosion resistance was exhibited in this test.
  • the basket type anode of the present invention has been completed based on the above knowledge.
  • embodiments of the basket type anode of the present invention will be described.
  • the mesh member contains a platinum group element.
  • This network member may further contain one or more of Ni and rare earth elements. If the mesh member contains a platinum group element, corrosion of the mesh member can be prevented, and the life of the mesh member can be improved.
  • the platinum group element includes six kinds of elements of Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (iridium), and Pt (platinum). As long as it is selected from these six elements, there is no limitation on the type of platinum group element. That is, the platinum group element can contain one or more of six elements. However, since platinum group elements are rare and very expensive, it is preferable to select Ru or Pd among the six elements from the viewpoint of economy. This is because Ru and Pd have established recycling technologies and, among others, Ru can be stably obtained at a relatively low cost.
  • the content of platinum group elements is not particularly limited. However, a large amount of platinum group element is not preferable from the viewpoint of economy. Therefore, the upper limit of the platinum group element content is preferably 0.15% by mass. A more preferable upper limit of the platinum group element content is 0.08% by mass.
  • the lower limit of the platinum group element content is preferably 0.01% by mass in order to sufficiently improve the life of the mesh member.
  • the lower limit of the platinum group element content is more preferably 0.02% by mass, and still more preferably 0.04% by mass.
  • Ni or a rare earth element is contained in combination with the platinum group element, the content of the platinum group element can be reduced by a synergistic effect due to the inclusion of Ni or the rare earth element. For this reason, the inclusion of Ni or rare earth elements is advantageous from the viewpoint of economy.
  • Ni like the platinum group elements, has the effect of lowering the hydrogen overvoltage and making the corrosion potential of Ti noble.
  • the lower limit of the Ni content is preferably 0.2% by mass.
  • a more preferable lower limit of the Ni content is 0.4% by mass.
  • the upper limit of Ni content in the case of containing Ni is 1.0 mass%.
  • Rare earth elements have the effect of accelerating the electrodeposition of platinum group elements on the surface of Ti materials containing platinum group elements when exposed to a corrosive environment within the range of content dissolved in Ti. .
  • the lower limit of the rare earth element content is preferably 0.0005 mass%.
  • a more preferable lower limit of the rare earth element content is 0.001% by mass.
  • the rare earth element when the rare earth element is contained excessively, the rare earth element alone may be precipitated, and the deposited rare earth element may be a factor of corrosion.
  • the upper limit of the rare earth element content is considered to be the upper limit of the solid solution range of the rare earth element from the viewpoint of the mechanism, but there is a concern that segregation or the like occurs during dissolution. For this reason, the upper limit of the rare earth element content when the rare earth element is contained is preferably 0.020% by mass from the viewpoint of reliably obtaining a solid solution state.
  • the rare earth element is a generic name of 17 elements obtained by adding Y and Sc to 15 elements of lanthanoid from La of atomic number 57 to Lu of 71 of the same, and contains one or more selected from these elements be able to.
  • the rare earth element content means the total content of these elements.
  • the basket-type anode mesh member (metal mesh) of the present embodiment is a titanium material and contains a platinum group element, and further contains at least one of Ni and rare earth elements.
  • Impurity elements contained in addition to these elements include Fe, O, C, H, and N that enter from raw materials, melting electrodes, and the environment, and Al and Cr mixed when scrap is used as a raw material. , Zr, Nb, Si, Sn, Mn, Co, Cu and the like. There is no problem even if these impure elements are mixed as long as the effects of the present embodiment are not impaired.
  • 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 0.01% or less
  • Co 0.35% or less
  • Cu 0.1% or less
  • the basket type anode of this embodiment can be suitably used for electrolytic Ni plating in which the plating raw material grains are Ni grains and a Watt bath is adopted as the plating bath.
  • the plating raw material grains to which the basket-type anode of this embodiment can be applied that is, the type of plating, include Ni, gold, silver, copper, tin, zinc, and the like.
  • the shape of the plating raw material grains include a spherical shape and a crown shape.
  • the types of plating baths to which the basket type anode of this embodiment can be applied include a nickel sulfamate normal bath, a nickel sulfamate high speed bath, a strike bath (wood bath), and a black nickel plating bath. Etc.
  • the mesh members of the test materials 21, 22 and 23 according to the present invention were Ti alloys containing platinum group elements.
  • the mesh member of the test material 21 further contains Ni
  • the mesh member of the test material 23 further contains Mm (Misch metal: mixed rare earth) which is a rare earth element.
  • the net members of the comparative materials 21 and 22 which are comparative examples are both pure Ti (two types of JIS standards).
  • the mesh member of the comparative material 22 was subjected to an alumina spraying treatment on the surface of the mesh in the same manner as the comparative material 2 in the basic test described above.
  • the composition of the watt bath was nickel sulfate: about 340 g / L, nickel chloride: about 70 g / L, boric acid: about 45 g / L.
  • the temperature of the Watt bath was about 55 ° C., and the pH of the Watt bath was 3.5 to 4.6.
  • the anode body was continuously supplied with an electrolytic voltage of about 30 V at a steady-state current density of 34.5 A / dm 2 .
  • Each basket type anode was filled with crown type Ni grains and replenished periodically. At that time, just under the liquid level of the watt bath, with the consumption of Ni grains, often only the plating solution was present.
  • the thickness of the mesh of each mesh member was measured before and after continuous operation, and the degree of corrosion was evaluated from the reduction in thickness.
  • the thickness of each mesh member was measured at three predetermined points A, B, and C.
  • the measurement point A was a point 50 mm inside from the left end of the uppermost mesh member and 200 mm below the upper end.
  • the measurement point B was a point at the center of the left and right of the uppermost mesh member and 200 mm below the upper end.
  • the measurement point C was a point 50 mm inside from the right end of the uppermost mesh member and 200 mm below the upper end.
  • the mesh member of the comparative material 21 In the mesh member of the comparative material 21, a part of the mesh was corroded and melted, and even if it remained, the mesh thickness was 1/2 or less. Further, in the mesh member of the comparative material 22, a reduction in the mesh thickness due to corrosion was observed at the portion where the formation of the insulating film was incomplete. On the other hand, in the mesh members of the test materials 21 to 23, which are examples of the present invention, no decrease in the mesh thickness due to corrosion was observed.
  • the basket-type anode of the present invention can be effectively used for any electrolytic plating.

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  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Prevention Of Electric Corrosion (AREA)
PCT/JP2015/067588 2014-06-25 2015-06-18 バスケット型アノード WO2015198958A1 (ja)

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EP15811491.8A EP3128046A4 (de) 2014-06-25 2015-06-18 Korbartige anode
KR1020167035004A KR101862971B1 (ko) 2014-06-25 2015-06-18 바스켓형 애노드
JP2016529508A JP6319439B2 (ja) 2014-06-25 2015-06-18 バスケット型アノード
US15/316,599 US20170159204A1 (en) 2014-06-25 2015-06-18 Basket-type anode
CN201580032599.XA CN106460224A (zh) 2014-06-25 2015-06-18 篮筐型正极

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5744183U (de) * 1980-08-25 1982-03-11
JPH01247592A (ja) * 1988-03-29 1989-10-03 Nisshin Steel Co Ltd アルミニウムの連続電気メッキ方法
JP2010265519A (ja) * 2009-05-15 2010-11-25 Nippon Steel Engineering Co Ltd 錫イオンの供給装置
JP2011089148A (ja) * 2009-10-20 2011-05-06 Nippon Steel Corp バスケット型アノード

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4778572A (en) * 1987-09-08 1988-10-18 Eco-Tec Limited Process for electroplating metals
JPH0437907A (ja) 1990-06-01 1992-02-07 Nachi Fujikoshi Corp スムージング加減速方式
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
US7247229B2 (en) * 1999-06-28 2007-07-24 Eltech Systems Corporation Coatings for the inhibition of undesirable oxidation in an electrochemical cell
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
EP1961842A1 (de) * 2007-02-22 2008-08-27 Atotech Deutschland Gmbh Vorrichtung und Verfahren zum elektrolytischen Galvanisieren eines Metalls
CN103717766B (zh) * 2011-07-26 2016-11-23 新日铁住金株式会社 钛合金

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5744183U (de) * 1980-08-25 1982-03-11
JPH01247592A (ja) * 1988-03-29 1989-10-03 Nisshin Steel Co Ltd アルミニウムの連続電気メッキ方法
JP2010265519A (ja) * 2009-05-15 2010-11-25 Nippon Steel Engineering Co Ltd 錫イオンの供給装置
JP2011089148A (ja) * 2009-10-20 2011-05-06 Nippon Steel Corp バスケット型アノード

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KARL-H. TOSTMANN: "Korrosion von Titan im galvanotechnischen Einsatz", GALVANOTECHNIK, vol. 71, no. 12, 15 December 1980 (1980-12-15), pages 1310 - 1313, XP008184877 *
See also references of EP3128046A4 *

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CN106460224A (zh) 2017-02-22
EP3128046A1 (de) 2017-02-08
JP6319439B2 (ja) 2018-05-09
US20170159204A1 (en) 2017-06-08
KR101862971B1 (ko) 2018-05-30
KR20170005477A (ko) 2017-01-13
EP3128046A4 (de) 2017-11-15

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