US20200080216A1 - Molten-salt titanium plating solution composition and method for manufacturing titanium-plated member - Google Patents

Molten-salt titanium plating solution composition and method for manufacturing titanium-plated member Download PDF

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US20200080216A1
US20200080216A1 US16/603,920 US201816603920A US2020080216A1 US 20200080216 A1 US20200080216 A1 US 20200080216A1 US 201816603920 A US201816603920 A US 201816603920A US 2020080216 A1 US2020080216 A1 US 2020080216A1
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plating solution
solution composition
molten
titanium
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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.
  • 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.
  • 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.
  • FIG. 4 is a graph showing the corrosion current density of each electrode in a physiological saline solution.
  • FIG. 5 is a graph showing a correlation between the potential and the current density of each electrode in a simulated seawater.
  • FIG. 6 is a graph showing a correlation between the potential and the current density of each electrode in a simulated electrolyte for a polymer electrolyte fuel cell (PEFC).
  • PEFC polymer electrolyte fuel cell
  • FIG. 7 is another graph showing a correlation between the potential and the current density of each electrode in a simulated electrolyte for a polymer electrolyte fuel cell (PEFC).
  • PEFC polymer electrolyte fuel cell
  • 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 molten-salt titanium plating solution composition (hereinafter also referred to as “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 plating solution composition.
  • titanium Because of a strong bonding strength of titanium with oxygen, titanium is likely to react with water to form oxide and hydroxide, and is therefore not suitable for plating from an aqueous solution.
  • a plating bath of a molten-salt titanium plating solution composition made up of a molten salt containing titanium ions is therefore used.
  • a composition containing a predetermined amount of a metal fluoride serving as a source of fluoride ions is selected. Potassium fluoride is used as a metal fluoride serving as a source of fluoride ions.
  • metal fog of potassium is generated during formation of the plating film. Because there is a sufficient separation between the redox potential of potassium and the redox potential of titanium, usually potassium is not electrodeposited in a condition where titanium is electrodeposited. Metal fog of potassium, however, has a redox potential closer to the redox potential of titanium. Therefore, in a condition where titanium is electrodeposited, metal fog of potassium is likely to be generated simultaneously.
  • potassium metal suspends in the plating bath.
  • current flows through the potassium metal between a cathode and an anode, resulting in deterioration of current efficiency. It is therefore necessary to suppress generation of metal fog from the plating bath.
  • the molten-salt titanium plating solution composition of the present disclosure can form a titanium plating film having high surface smoothness while suppressing generation of metal fog.
  • the molten-salt titanium plating solution composition of the present disclosure contains fluoride ions and can therefore form a titanium plating film having high surface smoothness.
  • the molten-salt titanium plating solution composition of the present disclosure contains, as cations, ions of at least one Group I metal selected from the group of lithium and sodium having a lower reduction potential (harder to reduce) than potassium, and the content of potassium ions in the plating solution composition is less than or equal to 5 mol %. In the condition where titanium plating is performed, metal fog is less likely to be generated from lithium ions and sodium ions. The content of potassium in the molten-salt titanium plating solution composition is sufficiently low. Therefore, generation of metal fog during plating can be suppressed.
  • a 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 this ratio enables a titanium-plated member having a titanium plating film excellent in surface smoothness to be manufactured.
  • the molten-salt titanium plating solution composition may further contain chloride ions.
  • the molten-salt titanium plating solution composition containing fluoride ions as well as chloride ions can be reduced in melting point by depression of melting point. As a result, a titanium plating film can be formed at a lower temperature.
  • the molten-salt titanium plating solution composition may contain more than or equal to 30 mol % and less than or equal to 50 mol % of the fluoride ions, with respect to 100 mol % of a total of the chloride ions and the fluoride ions.
  • the content falling in this range enables further reduction of the melting point of the molten-salt titanium plating solution composition. As a result, a titanium plating film can be formed at a still lower temperature.
  • the molten-salt titanium plating solution composition preferably contains more than or equal to 0.1 mol % and less than or equal to 12 mol % of the titanium ions with respect to 100 mol % of all cations contained in the molten-salt titanium plating solution composition. Accordingly, a titanium plating film having high surface smoothness can be formed with a high yield.
  • the molten-salt titanium plating solution composition is used for manufacturing an insoluble electrode.
  • an insoluble electrode having a titanium plating film excellent in surface smoothness 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 excellent in surface smoothness can be manufactured.
  • the molten-salt titanium plating solution composition is used for manufacturing a biomaterial.
  • a biomaterial having a titanium plating film excellent in surface smoothness can be manufactured.
  • Such a biomaterial can also be excellent in corrosion resistance.
  • a method for manufacturing a titanium-plated member includes: preparing a substrate having an electrically conductive surface; immersing the substrate in the above-described 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.
  • a titanium-plated member having a titanium plating film with high surface smoothness can be manufactured while generation of metal fog is 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 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′ + 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′ + 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
  • the plating solution composition that is a molten salt
  • LiF, NaF, LiCl, and NaCl are ionized to be present in the form of Li + , Na + , 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 + ; Cr; and Ti n+ in this way.
  • Li + , Na + , Cl ⁇ , and Ti′ + are present in the plating solution composition of the present embodiment
  • 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 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 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 with respect to 100 mol % of the total of 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′ + does not allow a titanium plating film to be formed sufficiently.
  • the content of Ti 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.
  • 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. Referring to FIGS. 2 and 3 , titanium-plated member 1 is manufactured through steps S 10 to S 40 shown in FIG. 2 .
  • a method for manufacturing titanium-plated member 1 includes: the step of preparing substrate 10 having an electrically conductive surface (S 10 ); the step of immersing substrate 10 in plating solution composition 50 (S 20 ); 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 (S 30 ). Further, the method for manufacturing titanium-plated member 1 preferably includes the step of cleaning a surface of plating film 20 (S 40 ). The method for manufacturing titanium-plated member 1 of the present embodiment may include any step besides the steps S 10 , S 20 , S 30 , and S 40 . In the following, each of these steps is described.
  • substrate 10 having an electrically conductive surface is prepared (S 10 ).
  • 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 ⁇ ). 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 %.
  • 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 with respect to 100 mol % of the total of 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 .
  • the step of forming plating film 20 is performed in the following way.
  • electric current is applied by applying a voltage between an anode 30 and substrate 10 serving as a cathode that are immersed in plating solution composition 50 to cause electrolysis of plating solution composition 50 .
  • titanium ions are reduced to titanium and the surface of substrate 10 is coated with titanium.
  • 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 CF, 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 S 10 to S 40 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%.
  • small amount was generated means that white smoke was confirmed during cleaning with water, and “generated” means that white smoke and sparks were confirmed.
  • 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 S 10 to S 40 of the method for manufacturing a titanium-plated member as described above (see FIG. 2 ).
  • a respective substrate made of nickel, 0.1 mm in thickness, 5 mm ⁇ 25 mm in size
  • titanium-plated members of Experiment Nos. 5 to 16 were manufactured.
  • the plating performance was evaluated by the same evaluation method as Example 1.
  • Experiment Nos. 5 to 16 are as follows. Specifically, a titanium-plated member produced using the molten-salt titanium plating solution composition of Experiment No. 5 corresponds to the titanium-plated member of Experiment No. 5. The same applies as well to the subsequent Experiments, i.e., a titanium-plated member produced using a molten-salt titanium plating solution composition of Experiment No. “X” corresponds to a titanium-plated member of Experiment No. “X” (X is an arbitrary numeral).
  • 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 S 10 to S 40 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
  • a Ni porous material product name: “Celmet®” manufactured by Sumitomo Electric Industries, Ltd.
  • a Ti metal sheet manufactured by Nilaco Corporation
  • electrolyte 0.9 mass % sodium chloride aqueous solution (physiological saline solution)
  • working electrode specimen of Example or specimen of Comparative Example (Ti-plated product, Ni, or Ti)
  • 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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  • Electroplating Methods And Accessories (AREA)
US16/603,920 2017-05-22 2018-03-13 Molten-salt titanium plating solution composition and method for manufacturing titanium-plated member Abandoned US20200080216A1 (en)

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JP7207411B2 (ja) * 2018-07-18 2023-01-18 住友電気工業株式会社 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
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Family Cites Families (18)

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Publication number Priority date Publication date Assignee Title
US3479159A (en) * 1966-11-10 1969-11-18 Gen Electric Process for titaniding base metals
US3979267A (en) * 1972-01-24 1976-09-07 Townsend Douglas W Electrolytic method
JPS5417304B2 (de) * 1974-04-18 1979-06-28
JPS51138511A (en) * 1975-05-27 1976-11-30 Sony Corp Method for regulating the hardness of metallic tita nium
US4483752A (en) * 1982-09-28 1984-11-20 Eltech Systems Corporation Valve metal electrodeposition onto graphite
JPH06173065A (ja) * 1992-12-09 1994-06-21 Japan Energy Corp Ｔｉの精製方法
JP3779368B2 (ja) * 1996-02-09 2006-05-24 松田医科工業株式会社 生体用複合インプラント材
JP2000256898A (ja) * 1999-03-03 2000-09-19 Permelec Electrode Ltd ウェーハの銅めっき方法
WO2006038476A1 (ja) * 2004-10-01 2006-04-13 Sumitomo Electric Industries, Ltd. 溶融塩浴、この溶融塩浴を用いて得られた析出物、金属製品の製造方法および金属製品
KR101204588B1 (ko) * 2004-11-24 2012-11-27 스미토모덴키고교가부시키가이샤 용융염욕, 석출물 및 금속석출물의 제조방법
JP4919225B2 (ja) * 2007-02-02 2012-04-18 住友電気工業株式会社 電気二重層キャパシタ用電極
JP2013147731A (ja) * 2011-12-22 2013-08-01 Sumitomo Electric Ind Ltd 溶融塩電解による金属の製造方法
CN103882477B (zh) * 2012-12-21 2016-12-28 攀钢集团攀枝花钢铁研究院有限公司 一种用于制备金属钛的电解质和熔盐及金属钛的制备方法
JP6405199B2 (ja) 2013-11-19 2018-10-17 住友電気工業株式会社 電析用電解質および金属膜の製造方法
CN105112963B (zh) * 2015-10-10 2017-10-24 东北大学 一种利用熔盐电沉积法制备金属铝及其合金的方法
JP6518577B2 (ja) 2015-11-30 2019-05-22 株式会社吉野工業所 内容物を計量して塗布する塗布容器
CN110023544A (zh) * 2016-11-22 2019-07-16 住友电气工业株式会社 钛电镀液的制备方法和镀钛制品的制造方法
WO2019171744A1 (ja) * 2018-03-08 2019-09-12 住友電気工業株式会社 チタンめっき部材の製造方法及びチタンめっき部材

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