EP3633076A1 - Schmelzsalz-titan-plattierungslösungszusammensetzung und verfahren zur herstellung eines titanbeschichteten elements - Google Patents

Schmelzsalz-titan-plattierungslösungszusammensetzung und verfahren zur herstellung eines titanbeschichteten elements Download PDF

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EP3633076A1
EP3633076A1 EP18806263.2A EP18806263A EP3633076A1 EP 3633076 A1 EP3633076 A1 EP 3633076A1 EP 18806263 A EP18806263 A EP 18806263A EP 3633076 A1 EP3633076 A1 EP 3633076A1
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Prior art keywords
plating solution
solution composition
molten
titanium
mol
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English (en)
French (fr)
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EP3633076A4 (de
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Koma NUMATA
Masatoshi Majima
Tomoyuki Awazu
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • 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

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  • the present disclosure relates to a molten-salt titanium plating solution composition and a method for manufacturing a titanium-plated member.
  • the present disclosure claims priority to Japanese Patent Application No. 2017-100757 filed on May 22, 2017 , the disclosure of which is hereby incorporated by reference in its entirety.
  • Patent Laying-Open No. 2015-193899 discloses that a plating bath containing KF-KCl to which K 2 TiF 6 and TiO 2 are added is used to form an alloy film of Fe and Ti on the surface of an Fe wire.
  • NPL 1 discloses that a plating bath containing LiF-NaF-KF to which K 2 TiF 6 is added is used to form a titanium film on the surface of a substrate of Ni and Fe.
  • NPL 1 A. ROBIN et.al., "ELECTOLYTIC COATING OF TITANIUM ONTO IRON AND NICKEL ELECTRODES IN THE MOLTEN LiF+NaF+KF EUTECTIC", Journal of Electroanal. Chem., 230 (1987), pp. 125-141
  • a molten-salt titanium plating solution composition contains: ions of at least one Group I metal selected from the group of lithium and sodium, fluoride ions, and titanium ions.
  • the molten-salt titanium plating solution composition contains less than or equal to 5 mol% of potassium ions with respect to 100 mol% of all ion components contained in the molten-salt titanium plating solution composition.
  • a method for manufacturing a titanium-plated member includes: preparing a substrate having an electrically conductive surface; immersing the substrate in the molten-salt titanium plating solution composition; and forming a titanium plating film on the surface of the substrate by applying electric current to cause the substrate immersed in the molten-salt titanium plating solution composition to serve as a cathode and cause the surface of the substrate to be coated with titanium.
  • fluoride ions F -
  • fluoride ions F -
  • fluoride ions F -
  • fluoride ion source potassium fluoride (KF) is widely used.
  • KF is a good fluoride ion source, and a molten-salt titanium plating solution composition containing potassium ions (K + ) generated from KF exhibits good plating performance in titanium plating.
  • the molten-salt titanium plating solution composition enables generation of metal fog during plating to be suppressed.
  • a to B herein specifies an upper limit and a lower limit of a range (i.e., more than or equal to A and less than or equal to B).
  • A is not accompanied by a unit but only B is accompanied by a unit
  • the unit for B is identical to the unit for A.
  • a molten-salt titanium plating solution composition in the present embodiment contains ions of at least one Group I metal selected from the group of lithium (Li + ) and sodium (Na + ), fluoride ions (F - ), and titanium ions (Ti n+ (n is an integer of 2 or more and 4 or less, the same applies as well to the following)).
  • the plating solution composition contains less than or equal to 5 mol% of potassium ions (K + ) with respect to 100 mol% of all ion components contained in the plating solution composition.
  • the plating solution composition further contains chloride ions (Cl - ).
  • the plating solution composition can be prepared as a molten salt by dissolving a titanium compound serving as a source of Ti n+ in a mixture of at least one of lithium fluoride (LiF) and sodium fluoride (NaF) and at least one of lithium chloride (LiCl) and sodium chloride (NaCl), for example.
  • the plating solution composition may contain, as Ti n+ in a titanium compound, multiple types of titanium that are different in valence.
  • Examples of the titanium compound serving as a source of Ti n+ may include hexafluorotitanic acid (H 2 TiF 6 ), potassium hexafluorotitanate (K 2 TiF 6 ), ammonium hexafluorotitanate ((NH 4 ) 2 TiF 6 ), sodium hexafluorotitanate (Na 2 TiF 6 ), potassium titanium oxalate dihydrate (K 2 TiO(C 2 O 4 ) 2 • 2H 2 O), titanium chloride (III)(TiCl 3 ), titanium chloride (IV)(TiCl 4 ), and the like.
  • H 2 TiF 6 hexafluorotitanic acid
  • K 2 TiF 6 potassium hexafluorotitanate
  • ammonium hexafluorotitanate (NH 4 ) 2 TiF 6 )
  • sodium hexafluorotitanate Na 2 TiF 6
  • potassium titanium oxalate dihydrate K 2 Ti
  • Potassium hexafluorotitanate (K 2 TiF 6 ) and potassium titanium oxalate dihydrate (K 2 TiO(C 2 O 4 ) 2 • 2H 2 O) contain potassium ions, and therefore, these titanium compounds are used at respective contents so that the K + content with respect to 100 mol% of all ion components contained in the plating solution composition is less than or equal to 5 mol%, or these titanium compounds are used together with another titanium compound (such as titanium chloride (IV) or the like, for example) that generates no K + .
  • another titanium compound such as titanium chloride (IV) or the like, for example
  • LiF, NaF, LiCl, and NaCl are ionized to be present in the form of Li + , Na + , F - , and Cl - .
  • the titanium compound is also ionized to be present in the form of Ti n+ . It is preferable to prepare, as a molten salt, a plating solution composition containing: ions of at least one Group I metal selected from the group of Li + and Na + ; F - ; Cl - ; and Ti n+ in this way.
  • Li + , Na + , F - , Cl - , and Ti n+ are present in the plating solution composition of the present embodiment can be confirmed, for example, by dissolving the plating solution composition in a solution of a mixture of nitric acid and hydrofluoric acid, and analyzing the solution by ICP (Inductively Coupled Plasma Spectrometry) or IC analysis (Ion Chromatography).
  • ICP Inductively Coupled Plasma Spectrometry
  • IC analysis Ion Chromatography
  • ICP apparatus iCAP6200 or the like manufactured by Thermo Fisher Scientific Inc. may be used, for example.
  • the ratio of the fluoride ions to all anions contained in the molten-salt titanium plating solution composition may be more than or equal to 30 mol% and less than or equal to 100 mol%.
  • the molten-salt titanium plating solution composition containing fluoride ions at such a ratio enables manufacture of a titanium-plated member having a titanium plating film excellent in surface smoothness.
  • the ratio of fluoride ions to all anions is preferably more than or equal to 40 mol% and less than or equal to 90 mol%, and more preferably more than or equal to 45 mol% and less than or equal to 75 mol%.
  • the content of F - with respect to 100 mol% of a total of Cl - and F - is more than or equal to 30 mol% and less than or equal to 50 mol%.
  • the melting point of the plating solution composition is once reduced by depression of melting point, and thereafter increased again.
  • the melting point depression effect is large when the ratio of the F - content relative to 100 mol% of the total content of Cl - and F - falls in a predetermined range.
  • reduction of the melting point is large when the content of F - with respect to 100 mol% of the total of Cl - and F - is more than or equal to 30 mol% and less than or equal to 50 mol%, which facilitates plating at a lower temperature. More preferably, the content of F - with respect to 100 mol% of the total of Cl - and F - is more than or equal to 30 mol% and less than or equal to 45 mol%, because reduction of the melting point is larger.
  • the content of Ti n+ in the plating solution composition is not particularly limited, but set appropriately depending on plating conditions. However, an excessively high content of Ti n+ may cause unnecessary precipitates to be formed, which increases reduction of current efficiency. In contrast, an excessively low content of Ti n+ does not allow a titanium plating film to be formed sufficiently.
  • the content of Ti n+ is therefore preferably less than or equal to 20 mol% and more preferably less than or equal to 12 mol%, with respect to 100 mol% of all cations in the plating solution composition.
  • the content of Ti n+ is preferably more than or equal to 0.1 mol%, and more preferably more than or equal to 0.5 mol%, with respect to 100 mol% of all cations in the plating solution composition. In other words, the content of titanium ions with respect to 100 mol% of all cations contained in the molten-salt titanium plating solution composition is preferably more than or equal to 0.1 mol% and less than or equal to 12 mol%.
  • Fig. 1 is a schematic cross-sectional view showing an example of a part of a titanium-plated member.
  • Fig. 2 is a flowchart showing a procedure for manufacturing a titanium-plated member.
  • Fig. 3 is a schematic cross-sectional view showing an example of a state in which a substrate is immersed in a molten-salt titanium plating solution composition.
  • a titanium-plated member 1 is made up of a substrate 10 and a titanium plating film 20 (hereinafter also referred to simply as "plating film 20") formed on a surface of substrate 10.
  • Plating film 20 is a film made of titanium.
  • titanium-plated member 1 is manufactured through steps S10 to S40 shown in Fig. 2 .
  • a method for manufacturing titanium-plated member 1 includes: the step of preparing substrate 10 having an electrically conductive surface (S10); the step of immersing substrate 10 in plating solution composition 50 (S20); and the step of forming titanium plating film 20 on the surface of substrate 10 by applying electric current to cause substrate 10 immersed in plating solution composition 50 to serve as a cathode and cause the surface of substrate 10 to be coated with titanium (S30). Further, the method for manufacturing titanium-plated member 1 preferably includes the step of cleaning a surface of plating film 20 (S40). The method for manufacturing titanium-plated member 1 of the present embodiment may include any step besides the steps S10, S20, S30, and S40. In the following, each of these steps is described.
  • substrate 10 having an electrically conductive surface is prepared (S10).
  • the material forming substrate 10 is not particularly limited as long as the material has an electrically conductive surface.
  • Examples of substrate 10 include, for example, a substrate made of iron or nickel, a substrate made of an alloy of them, or a multilayer substrate having a surface made of a layer of iron or nickel or an alloy thereof.
  • substrate 10 is not particularly limited.
  • substrate 10 in the shape of any of various shapes such as plate, column, pipe, mesh, or the like may be employed as substrate 10.
  • plating solution composition 50 As plating solution composition 50, a plating solution composition prepared in the above-described way is used.
  • plating solution composition 50 contains ions of at least one Group I metal selected from the group of lithium (Li + ) and sodium (Na + ), fluoride ions (F - ), titanium ions (Ti n+ ), and chloride ions (Cl - ). Further, plating solution composition 50 is prepared so that the content of potassium ions (K + ) with respect to 100 mol% of all ion components contained in plating solution composition 50 is less than or equal to 5 mol%.
  • Group I metal selected from the group of lithium (Li + ) and sodium (Na + ), fluoride ions (F - ), titanium ions (Ti n+ ), and chloride ions (Cl - ).
  • plating solution composition 50 is prepared so that the content of potassium ions (K + ) with respect to 100 mol% of all ion components contained in plating solution composition 50 is less than or equal to 5 mol%.
  • plating solution composition 50 is prepared so that the ratio of the fluoride ions to all anions contained in the molten-salt titanium plating solution composition is more than or equal to 30 mol% and less than or equal to 100 mol%. Further, preferably plating solution composition 50 is prepared so that plating solution composition 50 contains more than or equal to 30 mol% and less than or equal to 50 mol% of F - , with respect to 100 mol% of the total of Cl - and F - . Preferably plating solution composition 50 is prepared so that plating solution composition 50 contains more than or equal to 0.1 mol% and less than or equal to 12 mol% of Ti n+ with respect to 100 mol% of all cations contained in plating solution composition 50.
  • plating film 20 is formed on the surface of substrate 10.
  • Electrolysis of plating solution composition 50 is preferably performed so that the absolute value of the current density, on substrate 10, of current flowing between anode 30 and substrate 10 is more than or equal to 1 mA/cm 2 and less than or equal to 500 mA/cm 2 , and more preferably performed so that the absolute value of the current density is more than or equal to 1 mA/cm 2 and less than or equal to 300 mA/cm 2 .
  • plating film 20 can be formed on the surface of substrate 10 in a shorter time.
  • plating film 20 having higher surface smoothness can be formed.
  • a cleaning agent can be used to clean the surface of plating film 20 to thereby remove the components remaining on the surface of plating film 20.
  • water may be used.
  • substrate 10 on which plating film 20 is formed may be cleaned with water.
  • a cleaning agent other than water may be used such as a cleaning agent containing water-soluble salt having a high compatibility with components contained in plating solution composition 50, instead of or in combination with water. In this way, titanium-plated member 1 having a surface of substrate 10 coated with plating film 20 is manufactured.
  • Titanium-plated member 1 manufactured in this way can be used in a variety of fields, as a member having a protective film with a high hardness and a high surface smoothness as well as excellent corrosion resistance and excellent wear resistance.
  • the ratio of average surface roughness Ra to average thickness R of plating film 20 ((Ra/R) ⁇ 100 (%)) of titanium-plated member 1 manufactured by the above-described method is preferably less than or equal to 10%, and more preferably less than or equal to 5%. With the ratio falling in this range, titanium-plated member 1 having plating film 20 with a sufficiently high surface smoothness can be provided.
  • Average surface roughness Ra of plating film 20 can be measured through observation of a cross section with an SEM (Scanning Electron Microscope) or by means of a surface roughness meter. Average thickness R of plating film 20 can be determined through observation of a cross section with an SEM. Average surface roughness Ra of plating film 20 refers to an arithmetic mean roughness Ra specified under JIS B 0601 (2001). Average thickness R of plating film 20 may be an arithmetic mean thickness of plating film 20 determined from thicknesses at any 10 points on an SEM image, for example.
  • SEM Scnning Electron Microscope
  • the molten-salt titanium plating solution composition is used for manufacturing an insoluble electrode.
  • a molten-salt titanium plating solution composition for manufacturing an insoluble electrode an insoluble electrode having a titanium plating film excellent in surface smoothness can be manufactured.
  • the insoluble electrode is used for manufacturing hydrogen.
  • the electrode can be provided as a hydrogen-manufacturing insoluble electrode with a low resistance. Accordingly, hydrogen with a high purity can be manufactured.
  • the molten-salt titanium plating solution composition is used for manufacturing a current collector.
  • a current collector having a titanium plating film with excellent surface smoothness can be manufactured.
  • the current collector is used for a fuel cell.
  • a current collector for a fuel cell can be provided as a fuel-cell current collector having a good electrical conductivity.
  • the current collector is more preferably used for a polymer electrolyte fuel cell.
  • the molten-salt titanium plating solution composition is used for manufacturing a biomaterial.
  • a biomaterial-manufacturing molten-salt titanium plating solution composition a biomaterial having a titanium plating film with an excellent surface smoothness can be manufactured. This biomaterial is also excellent in corrosion resistance.
  • the use of the biomaterial is preferably selected from the group consisting of spinal fixation device, fracture fixation device, artificial joint, artificial heart valve, intravascular stent, denture base, artificial dental root, and orthodontic wire.
  • molten-salt titanium plating solution composition 50 according to the present embodiment enables generation of metal fog during plating to be suppressed. Further, in accordance with the method for manufacturing titanium-plated member 1, titanium-plated member 1 having plating film 20 with high surface smoothness can be manufactured.
  • molten-salt titanium plating solution composition 50 containing chloride ions (Cl - ) is described. Molten-salt titanium plating solution composition 50, however, may be prepared without containing Cl - . As a molten-salt titanium plating solution composition 50 containing no Cl - , molten-salt titanium plating solution composition 50 can be prepared to contain other anions instead of Cl - . In this case, the aforementioned other anions are preferably selected that are stable at the plating temperature and will not form a residue such as salt that is difficult to remove after plating.
  • plating solution composition 50 is prepared to contain more than or equal to 30 mol% and less than or equal to 50 mol% of F - with respect to 100 mol% of the total of Cl - and F - , and contain more than or equal to 0.1 mol% and less than or equal to 12 mol% of Ti n+ with respect to 100 mol% of all cations contained in plating solution composition 50.
  • the limitations on respective contents are not requisite ones. The contents can be set appropriately in consideration of the required plating temperature and plating performance.
  • Experiment No. 1 is an example where a plating solution composition of an Example within the range of the molten-salt titanium plating solution composition of the present disclosure was used.
  • Experiment Nos. 2 to 4 are each an example where a plating solution composition of a comparative example out of the range of the molten-salt titanium plating solution composition of the present disclosure was used.
  • Molten-salt titanium plating solution compositions of Experiment Nos. 1 to 4 were each prepared by dissolving, in the main agent for the plating solution composition shown in Table 1, one or both of K 2 TiF 6 powder and TiCl 4 gas as a titanium source at a ratio of 2 mol of the total of one or both of K 2 TiF 6 powder and TiCl 4 gas with respect to 100 mol of the main agent. Further, through the steps S10 to S40 of the method for manufacturing a titanium-plated member as described above (see Fig. 2 ), each of the molten-salt titanium plating solution compositions of Experiment Nos.
  • the ratio of an abnormal plating portion resulting from discoloration of the plated surface and/or lack of plating on the surface to be plated was evaluated based on the area ratio (%) of the abnormal plating portion.
  • the level of the plating performance is classified into those termed "good,” “average,” “somewhat poor” and “poor” respectively. “Good” means that the abnormal portion is less than 5%, “average” means that the abnormal portion is more than or equal to 5% and less than 20 %, “somewhat poor” means that the abnormal portion is more than or equal to 20% and less than 50%, and “poor” means that the abnormal portion is more than or equal to 50%.
  • the plating performance was good and generation of metal fog was not confirmed.
  • generation of metal fog of potassium could be suppressed by performing titanium plating using a molten-salt titanium plating solution composition in which the content of K + with respect to 100 mol% of all ion components contained in the molten-salt titanium plating solution composition was less than or equal to 5 mol%.
  • the plating performance was also good in the case of a molten-salt titanium plating solution composition containing K + at a smaller content and containing Li + as main cations instead.
  • Molten-salt titanium plating solution compositions of Experiment Nos. 5 to 16 were each prepared by dissolving, in the main agent for the plating solution composition shown in Tables 2 to 4, one or both of K 2 TiF 6 powder and TiCl 4 gas as a titanium source at the ratio shown in Tables 2 to 4 with respect to 100 mol of the main agent.
  • the molten-salt titanium plating solution composition of Experiment No. 5 contains more than 5 mol% of K + with respect to 100 mol% of all ion components contained in the molten-salt titanium plating solution composition, and is therefore a Comparative Example.
  • Respective molten-salt titanium plating solution compositions of Experiment Nos. 6 to 16 each contain less than or equal to 5 mol% of K + with respect to 100 mol% of all ion components contained in the molten-salt titanium plating solution composition, and are therefore Examples.
  • Respective molten-salt titanium plating solution compositions of Experiment Nos. 7 and 15 are Examples containing no chloride ions.
  • Respective molten-salt titanium plating solution compositions of Experiment No. 8, Nos. 10 to 12, and No. 16 are Examples in which the content of fluoride ions with respect to 100 mol% of the total of chloride ions and fluoride ions is more than or equal to 30 mol% and less than or equal to 50 mol%.
  • the molten-salt titanium plating solution composition of Experiment No. 12 contains more than 12 mol% of titanium ions with respect to 100 mol% of all cations contained in the molten-salt titanium plating solution composition.
  • the molten-salt titanium plating solution composition of Experiment No. 16 contains less than 0.1 mol% of titanium ions with respect to 100 mol% of all cations contained in the molten-salt titanium plating solution composition.
  • each of the molten-salt titanium plating solution compositions of Experiment Nos. 5 to 16 was used to plate a surface of a respective substrate (made of nickel, 0.1 mm in thickness, 5 mm ⁇ 25 mm in size) with titanium through the steps S10 to S40 of the method for manufacturing a titanium-plated member as described above (see Fig. 2 ).
  • titanium-plated members of Experiment Nos. 5 to 16 were manufactured.
  • the plating performance was evaluated by the same evaluation method as Example 1.
  • whether or not metal fog was generated in the process of titanium plating was also confirmed by the same evaluation method as Example 1. The results are shown in Tables 2 to 4.
  • LiF-KCl-KF LiF-KCl-KF LiF LiF-LiCl makeup of plating solution composition (molar ratio) LiF 45 45 100 30 LiCl 55 55 0 70 NaF 0 0 0 0 KF 8 6 0 0 KCl 0 0 0 K 2 TiF 6 2 2 2 2 TiCl 4 0 0 0 0 ratio of K + (mol%) to 100 mol% of all ion components 5.1 4.3 1.8 1.8 F - /(Cl - +F - ) (mol%) 54 53 100 38 ratio of Ti n+ (mol%) to 100 mol% of all cations 1.8 1.8 1.9 1.9 plating temperature (°C) 650 650 900 650 plating performance good good good good good generation of metal fog small amount was generated not generated not generated not generated not generated [Table 3] Experiment No.
  • molten-salt titanium plating solution composition 50 and the method for manufacturing titanium-plated member 1 according to the present embodiment enable generation of metal fog during plating to be suppressed.
  • the molten-salt titanium plating solution composition of Experiment No. 8 was used and, through the steps S10 to S40 of the method for manufacturing a titanium-plated member described above (see Fig. 2 ), the surface of a nickel porous substrate (3 cm ⁇ 5 cm ⁇ 1 mmt, porosity: 96%, average pore size: 300 ⁇ m, hereinafter referred to as "nickel porous material") was plated with titanium.
  • nickel porous material 3 cm ⁇ 5 cm ⁇ 1 mmt, porosity: 96%, average pore size: 300 ⁇ m, hereinafter referred to as "nickel porous material"
  • a Ni porous material product name: "Celmet®” manufactured by Sumitomo Electric Industries, Ltd.
  • a Ti metal sheet manufactured by Nilaco Corporation
  • the Ti-plated product of the Example is lower in corrosion current density than the Ni porous material of the Comparative Example, and is thus stable in an environment of physiological saline solution. It is seen from this result that the Ti-plated product of the Example is suitable as a biomaterial. Further, the Ti-plated product of the Example is lower in corrosion current density than the Ti metal sheet of the Comparative Example. It is seen from this result that the structure of a metal porous material instead of a metal sheet is used to further improve the stability in an environment of physiological saline solution.
  • the corrosion resistance of the following Ti-plated product to saline solution simulating seawater was evaluated through the following procedure.
  • Example 3 As a specimen of the Example, a Ti-plated product manufactured by the same method as the Ti-plated product used for Example 3 was prepared. As a specimen of the Comparative Example, a Ti metal sheet (manufactured by Nilaco Corporation) was prepared.
  • the Ti-plated product of the Example is lower in current density than the Ti commercial product of the Comparative Example, and thus exhibits high corrosion resistance to seawater. It is seen from the above that the Ti-plated product of the Example is promising as an insoluble electrode (anode) for electrolysis of salt.
  • Example 3 As a specimen of the Example, a Ti-plated product manufactured by the same method as the Ti-plated product used in Example 3 was prepared. As specimens of the Comparative Example, an Ni porous material (product name: "Celmet®” manufactured by Sumitomo Electric Industries, Ltd.) and a Ti metal sheet (manufactured by Nilaco Corporation) were prepared.
  • Ni porous material product name: "Celmet®” manufactured by Sumitomo Electric Industries, Ltd.
  • Ti metal sheet manufactured by Nilaco Corporation
  • Fig. 7 shows these plots by expanding the scale of the vertical axis (current density) so that the plot depicting the correlation for "Ti-plated product” can be distinguished from the plot depicting the correlation for "comparative Ti.”

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EP18806263.2A 2017-05-22 2018-03-13 Schmelzsalz-titan-plattierungslösungszusammensetzung und verfahren zur herstellung eines titanbeschichteten elements Withdrawn EP3633076A4 (de)

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PCT/JP2018/009739 WO2018216320A1 (ja) 2017-05-22 2018-03-13 溶融塩チタンめっき液組成物およびチタンめっき部材の製造方法

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WO2020017148A1 (ja) * 2018-07-18 2020-01-23 住友電気工業株式会社 チタンめっき用電解質、チタンめっき用電解質の評価方法及びチタンめっき用電解質を用いたチタンめっき部材の製造方法
JP7489309B2 (ja) 2020-12-24 2024-05-23 東邦チタニウム株式会社 チタンめっき材の製造方法
US20260117409A1 (en) * 2024-01-17 2026-04-30 Battelle Memorial Institute Composition for plating metal coatings and methods of making and using the same

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EP3633076A4 (de) 2021-03-03
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