WO2018216319A1 - チタンめっき部材の製造方法 - Google Patents

チタンめっき部材の製造方法 Download PDF

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WO2018216319A1
WO2018216319A1 PCT/JP2018/009738 JP2018009738W WO2018216319A1 WO 2018216319 A1 WO2018216319 A1 WO 2018216319A1 JP 2018009738 W JP2018009738 W JP 2018009738W WO 2018216319 A1 WO2018216319 A1 WO 2018216319A1
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Prior art keywords
titanium
molten salt
plating film
titanium plating
cleaning
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PCT/JP2018/009738
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English (en)
French (fr)
Japanese (ja)
Inventor
昂真 沼田
真嶋　正利
知之 粟津
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住友電気工業株式会社
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Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to CN201880022080.7A priority Critical patent/CN110475910A/zh
Priority to US16/500,557 priority patent/US20200102664A1/en
Priority to KR1020197029051A priority patent/KR20200010182A/ko
Priority to JP2019519484A priority patent/JPWO2018216319A1/ja
Priority to EP18806582.5A priority patent/EP3633078A4/de
Publication of WO2018216319A1 publication Critical patent/WO2018216319A1/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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/28—Cleaning or pickling metallic material with solutions or molten salts with molten salts
    • C23G1/32—Heavy metals
    • 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/08—Rinsing

Definitions

  • the present disclosure relates to a method for manufacturing a titanium plated member.
  • the present disclosure claims priority based on Japanese Patent Application No. 2017-1000075, which is a Japanese patent application filed on May 22, 2017. All the descriptions described in the Japanese patent application are incorporated herein by reference.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2015-193899
  • Patent Document 1 an alloy film of Fe and Ti is formed on the surface of an Fe wire by using a plating bath in which K 2 TiF 6 and TiO 2 are added to KF-KCl. It is described.
  • Non-Patent Document 1 describes a method of forming a titanium film on the surface of Ni and Fe substrates using a plating bath in which K 2 TiF 6 is added to LiF—NaF—KF.
  • a method for manufacturing a titanium-plated member includes a step of preparing a base material having a conductive surface, and the base material includes at least one Group 1 metal ion of lithium ions and sodium ions.
  • the titanium plating film is cleaned by contacting with a molten salt for cleaning containing at least one compound selected from the group consisting of: In the step of forming a plating film, in the step of removing the first deposit adhered to the surface of the titanium plating film, and in the step of washing the titanium plating film with water and washing with the molten salt for washing, the titanium plating Removing a second deposit adhering to the surface of the film.
  • FIG. 1 is a schematic cross-sectional view showing an example of a part of a titanium plating 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 the molten salt titanium plating solution composition.
  • FIG. 4 is a graph showing the corrosion current density of each electrode in physiological saline.
  • FIG. 5 is a graph showing the correlation between the current density and potential of each electrode in simulated seawater.
  • FIG. 6 is a graph showing the correlation between the current density and potential of each electrode in a simulated electrolyte solution of a polymer electrolyte fuel cell (PEFC).
  • FIG. 7 is another graph showing the correlation between the current density and potential of each electrode in a simulated electrolyte solution of a polymer electrolyte fuel cell (PEFC).
  • PEFC polymer electrolyte fuel cell
  • a method for producing a titanium-plated member includes a step of preparing a base material having a conductive surface, and the base material is at least one group 1 of lithium ions and sodium ions.
  • a step of immersing in a molten salt titanium plating solution composition containing metal ions, fluoride ions, and titanium ions, and the substrate immersed in the molten salt titanium plating solution composition as a cathode A step of forming a titanium plating film on the surface by energizing and covering the surface of the substrate with titanium; and the titanium plating film is made of an alkali metal chloride, an alkaline earth metal chloride, and Cleaning the titanium plating film by contacting with a molten salt for cleaning containing at least one compound selected from the group consisting of potassium fluoride, In the step of forming a tan plating film, in the step of removing the first deposit adhered to the surface of the titanium plating film, and in the step of washing the titanium plating
  • Titanium has a strong binding force with oxygen, so it easily reacts with water to form oxides and hydroxides and is not suitable for plating from aqueous solutions. Therefore, in order to form a titanium plating film on a substrate, a plating bath of a molten salt titanium plating solution composition made of a molten salt containing titanium ions is used.
  • a molten salt titanium plating solution composition containing a predetermined amount of a metal fluoride that is a source of fluoride ions is selected. Potassium fluoride is used as a metal fluoride that is a source of fluoride ions.
  • representative metal fluorides that are sources of fluoride ions include alkali metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF).
  • Lithium fluoride (LiF) and sodium fluoride (NaF) are ionized into lithium ions (LI + ) or sodium ions (Na + ) and fluoride ions (F ⁇ ) in the molten salt.
  • LI + , Na + , and F ⁇ work effectively in the molten salt for plating, there is a problem that LiF and NaF re-formed after plating are poorly water-soluble and cannot be removed sufficiently by washing with water. is there.
  • the substrate to be plated is a structure having a complicated shape such as a porous shape, it is difficult to sufficiently remove the poorly water-soluble metal fluoride from the plating film only by washing with water. Therefore, reduction of the residual amount of the hardly water-soluble fluoride on the surface of the titanium plating film is required.
  • the titanium plated film is at least selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides, and potassium fluoride.
  • the first deposit contains one or both of poorly water-soluble LiF and NaF. Since the compound contained in the cleaning molten salt has a higher compatibility with LiF and NaF than water, the compound is washed with the cleaning molten salt to remove the first deposits, thereby obtaining titanium. The amount of LiF and NaF remaining on the surface of the plating film can be reduced.
  • the manufacturing method of the titanium plating member of the present disclosure further includes a step of removing the second deposit adhered to the surface of the titanium plating film in the step of washing the titanium plating film with water and washing with the molten salt for washing.
  • the alkali metal chloride, alkaline earth metal chloride, and potassium fluoride contained in the molten salt for washing have higher solubility in water than LiF and NaF. Therefore, after passing through the step of washing with the washing molten salt, the surface of the titanium plating film is further washed with water to remove the second deposit, thereby reducing the amount of residue on the surface of the titanium plating film. Can do.
  • the contact of the titanium plating film with the molten salt for washing is performed by immersing the substrate on which the titanium plated film is formed in the molten salt for washing. May be performed.
  • a method of contacting the titanium plating film with the molten salt for cleaning a method of immersing the substrate on which the titanium plating film is formed in the molten salt for cleaning sufficiently melts the entire surface of the titanium plating film for cleaning. Salt can be contacted. As a result, the residual amount of poorly water-soluble substances such as LiF and NaF on the surface of the titanium plating film can be more suitably reduced.
  • the molten salt titanium plating solution composition may further contain chloride ions.
  • chloride ions By containing chloride ions together with fluoride ions, the melting point of the molten salt titanium plating solution composition can be lowered by lowering the melting point. As a result, it is possible to perform titanium plating at a lower temperature.
  • the amount of fluoride ions may be 30 mol% or more and 50 mol% or less with respect to 100 mol% in total of the chloride ions and the fluoride ions. Within such a range, the melting point of the molten salt titanium plating solution composition can be further lowered. As a result, it is possible to perform titanium plating at an even lower temperature.
  • the content of the titanium ion with respect to 100 mol% of all cations contained in the molten salt titanium plating solution composition is preferably 0.1 mol% or more and 12 mol% or less.
  • the titanium plated member is preferably an insoluble electrode. This makes it possible to provide an insoluble electrode having a titanium plating film with a reduced amount of surface residue.
  • the titanium-plated member is preferably a current collector. This makes it possible to provide a current collector having a titanium plating film with a reduced amount of surface residue.
  • the titanium plated member is preferably a biomaterial. This makes it possible to provide a biomaterial having a titanium plating film with a reduced amount of surface residue. Such a biomaterial can also be excellent in corrosion resistance.
  • a to B means the upper and lower limits of the range (that is, not less than A and not more than B), and there is no unit description in A, and the unit is described only in B.
  • the unit of and the unit of B are the same.
  • FIG. 1 is a schematic cross-sectional view showing an example of a part of a titanium plating 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 the molten salt titanium plating solution composition.
  • a titanium plating member 1 includes a base material 10 and a titanium plating film 20 (hereinafter, also simply referred to as “plating film 20”) formed on the surface of the base material 10.
  • the plating film 20 is a film made of titanium.
  • the titanium plated member 1 is manufactured through steps S10 to S50 shown in FIG.
  • the manufacturing method of the titanium plating member 1 which concerns on this Embodiment is a process (S10) which prepares the base material 10 which has an electroconductive surface, and the base material 10 is 1st at least 1st among lithium ion and sodium ion.
  • plating solution composition containing a group metal ion, a fluoride ion, and a titanium ion, and a molten salt titanium plating
  • the titanium plating film 20 is at least selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides, and potassium fluoride.
  • the first deposit adhered to the surface of the titanium plating film 20 is removed in the step of forming the titanium plating film 20. It is a process.
  • the step (S50) of washing the surface of the titanium plating film 20 with water the second deposit adhered to the surface of the titanium plating film 20 in the step of washing the titanium plating film 20 with water and washing with the molten salt for washing is removed. It is a process.
  • processes other than S10, S20, S30, S40, and S50 may be included. Hereinafter, each of these steps will be described.
  • a base material 10 having a conductive surface is prepared (S10).
  • the material which comprises the base material 10 is not specifically limited as long as it is a material which has an electroconductive surface.
  • Examples of the base material 10 include a base material made of iron or nickel, or a base material made of an alloy thereof, or a multilayer base material having a layer of iron, nickel, or an alloy thereof on the surface.
  • the shape of the substrate 10 is not particularly limited.
  • a substrate 10 having various shapes such as a plate shape, a column shape, a pipe shape, and a mesh shape can be employed.
  • the substrate 10 is immersed in the plating solution composition 50 (S20).
  • the plating solution composition 50 includes at least one Group 1 metal ion of lithium ions (Li + ) and sodium ions (Na + ), fluoride ions (F ⁇ ), and titanium. Ions (Ti n + (n is an integer of 2 or more and 4 or less; the same applies hereinafter)).
  • the plating solution composition 50 can contain a plurality of types having different valences as titanium ions.
  • the plating solution composition 50 preferably further contains chloride ions (Cl ⁇ ).
  • the plating solution composition 50 is, for example, 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). It can be prepared as a molten salt by dissolving a titanium compound as a source of Ti n + .
  • titanium compounds that supply Ti n + include hexafluorotitanic acid (H 2 TiF 6 ), potassium potassium fluoride (K 2 TiF 6 ), ammonium titanium fluoride ((NH 4 ) 2 TiF 6 ), and titanium fluoride. Soda (Na 2 TiF 6 ), potassium potassium oxalate dihydrate (K 2 TiO (C 2 O 4 ) 2 .2H 2 O), titanium chloride (III) (TiCl 3 ), titanium chloride (IV) (TiCl 4 ).
  • the plating solution composition 50 may contain cations other than Li + and Na + .
  • the plating solution composition 50 may contain potassium ions (K + ).
  • K + potassium ions
  • the content of K + with respect to 100 mol% of all ionic components contained in the plating solution composition 50 is 5 mol% or less, or other that does not generate K + . It is preferably used in combination with a titanium compound (for example, titanium (IV) chloride).
  • the plating solution composition that is a molten salt
  • LiF, NaF, LiCl, and NaCl are ionized and exist in the states of Li + , Na + , F ⁇ , and Cl ⁇ .
  • the titanium compound is ionized and exists in the state of Ti n + .
  • the presence of Li + , Na + , F ⁇ , Cl ⁇ and Tin + in the plating solution composition 50 of the present embodiment means that, for example, the plating solution composition 50 is dissolved in a mixed solution of nitric acid and hydrofluoric acid.
  • the solution can be confirmed by analyzing the solution by ICP emission spectrometry (Inductively Coupled Plasma Spectrometry).
  • ICP emission spectroscopic analyzer for example, iCAP6200 manufactured by Thermo Fisher Scientific Co., Ltd. can be used.
  • the amount of F ⁇ with respect to the total of 100 mol% of Cl ⁇ and F ⁇ is preferably 30 mol% or more and 50 mol% or less.
  • Cl - and F - F to the total 100 mol% of the - is a large melting point depression effect when in a predetermined range ratio.
  • the amount of F ⁇ relative to the total of 100 mol% of Cl ⁇ and F ⁇ is in the range of 30 mol% or more and 50 mol% or less, the decrease in melting point is large, and plating can be easily performed even at lower temperatures.
  • the amount of F ⁇ relative to the total of 100 mol% of Cl ⁇ and F ⁇ is in the range of 30 mol% or more and 45 mol% or less, the amount of decrease in the melting point is more preferable.
  • Anion fraction of - F in the plating solution composition 50 of the present embodiment is preferably 0.1 to 0.9, 0. More preferably, it is 25 or more and 0.75 or less.
  • the anion fraction of F ⁇ is 0.1 or more, particularly 0.25 or more, the titanium plating member 1 having the plating film 20 with high surface smoothness can be obtained more reliably.
  • the anion fraction of F ⁇ is 0.9 or less, particularly when it is 0.75 or less, removal of the residual material after the formation of the plating film 20 tends to be easy. Therefore, the anion fraction of F ⁇ is preferably within the above range.
  • the content of Ti n + in the plating solution composition is not particularly limited, and is appropriately set according to the plating conditions. However, if the content of Ti n + is too large, unnecessary precipitates are formed, resulting in a large reduction in current efficiency. On the other hand, if the content of Ti n + is too small, the titanium plating film is not sufficiently formed. Therefore, the content of Ti n + is preferably 20 mol% or less, more preferably 12 mol% or less with respect to 100 mol% of all cations in the plating solution composition.
  • the content of Ti n + is preferably 0.1 mol% or more, more preferably 0.5 mol% or more with respect to 100 mol% of all cations in the plating solution composition. That is, it is preferable that the content of the titanium ion with respect to 100 mol% of all cations contained in the molten salt titanium plating solution composition is 0.1 mol% or more and 12 mol% or less.
  • the substrate 10 immersed in the plating solution composition 50 is energized so as to become a cathode, and the surface of the substrate 10 is coated with titanium, thereby forming the titanium plating film 20 on the surface (S30). .
  • a voltage is applied between the anode 30 immersed in the plating solution composition 50 and the substrate 10 as a cathode in a state where the substrate 10 is immersed in the plating solution composition 50. It is carried out by applying and energizing to electrolyze the plating solution composition 50. Thereby, titanium ions are reduced to titanium on the surface of the base material 10 which is a cathode, and the surface of the base material 10 is covered with titanium, whereby the plating film 20 is formed on the surface of the base material 10.
  • the electrolysis of the plating solution composition 50 is performed so that the absolute value of the current density on the substrate 10 of the current flowing between the anode 30 and the substrate 10 is 1 mA / cm 2 or more and 500 mA / cm 2 or less.
  • the absolute value of the current density is preferably 1 mA / cm 2 or more and 300 mA / cm 2 or less.
  • the plating film 20 having higher surface smoothness can be formed.
  • the surface of the plating film 20 is washed with a washing molten salt (S40).
  • a washing molten salt containing at least one compound selected from the group consisting of an alkali metal chloride, an alkaline earth metal chloride, and potassium fluoride.
  • the first deposit contains one or both of poorly water-soluble LiF and NaF. Since the compound contained in the cleaning molten salt has higher compatibility with LiF and NaF than water, LiF and NaF remaining on the surface of the plating film 20 are obtained by performing a cleaning step with the cleaning molten salt. The amount of can be reduced.
  • alkali metal chloride examples include lithium chloride (LiCl), sodium chloride (NaCl), and potassium chloride (KCl).
  • alkaline earth metal chloride examples include magnesium chloride (MgCl 2 ) and calcium chloride (CaCl 2 ).
  • the molten salt may contain these alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride alone or in combination of two or more.
  • the molten salt may contain salts other than these alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride.
  • Alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride (KF) have higher compatibility with LiF and NaF than water. Therefore, the amount of LiF and NaF on the surface of the plating film 20 can be reduced by bringing the plating film 20 into contact with the cleaning molten salt.
  • the method for bringing the plating film 20 into contact with the molten salt for cleaning is not particularly limited.
  • the substrate 10 on which the plating film 20 is formed is immersed in the molten salt for cleaning, or the molten salt is allowed to flow over the surface of the plating film 20.
  • a method of cleaning the surface of the plating film 20 by spraying or the like can be used.
  • the method of bringing the plating film 20 into contact with the cleaning molten salt is preferably performed by immersing the substrate 10 on which the plating film 20 is formed in the cleaning molten salt.
  • the substrate 10 on which the plating film 20 is formed is immersed in the cleaning molten salt, whereby the cleaning molten salt can be sufficiently brought into contact with the entire surface of the plating film 20.
  • poorly water-soluble substances such as LiF and NaF on the surface of the plating film 20 can be more effectively cleaned.
  • the surface of the plating film 20 is washed with water (S50).
  • the titanium plating film 20 is washed with water, and the second adhering matter adhering to the surface of the plating film 20 in the step of washing with the molten salt for washing (S40) is removed.
  • the residual amount of poorly water-soluble LiF and NaF on the surface of the plating film 20 is reduced by performing the step (S40) of cleaning the surface of the plating film 20 with the cleaning molten salt.
  • the second deposit attached to the surface of the plating film 20 is mainly composed of components contained in the washing molten salt, that is, chlorides of alkali metal and alkaline earth metal. And KF.
  • Alkali metal chlorides, alkaline earth metal chlorides and KF are not only compatible with LiF and NaF, but also highly soluble in water. Therefore, the second deposit can be removed more easily than LiF and NaF by washing with water.
  • the two-step cleaning process S40 and S50
  • the residual material remaining on the surface of the plating film 20 can be reduced. As a result, a high-quality titanium plated member 1 with a small amount of residual impurities can be manufactured.
  • a water-soluble solvent such as alcohol or other detergent such as a surfactant may be used in combination with water.
  • a water-soluble solvent such as alcohol or other detergent such as a surfactant may be used in combination with water.
  • the titanium plated member 1 thus manufactured is a member having a protective film having high hardness, high surface smoothness, and excellent corrosion resistance and wear resistance. Furthermore, it is a high-quality titanium plating member 1 with a small amount of residual impurities on the plating film 20. Therefore, it can be used in various fields.
  • the ratio ((Ra / R) ⁇ 100 (%)) of the average surface roughness Ra to the average thickness R of the plating film 20 in the titanium plated member 1 manufactured by the above manufacturing method is preferably 10% or less. More preferably, it is 5% or less. If it is such a range, the titanium plating member 1 which has the plating film 20 with sufficiently high surface smoothness can be provided.
  • the surface average roughness Ra of the plating film 20 can be measured using a cross-sectional observation by SEM (Scanning Electron Microscope) or a surface roughness meter. Furthermore, the average thickness R of the plating film 20 can be determined by cross-sectional observation with an SEM.
  • the surface average roughness Ra of the plating film 20 means the arithmetic average roughness Ra defined in JIS B 0601 (2001).
  • the average thickness R of the plating film 20 means, for example, the arithmetic average of the thickness of the plating film 20 at any 10 points in the SEM image.
  • the manufacturing method of the titanium plating member 1 according to the present embodiment it is possible to reduce the residual amount of the hardly water-soluble fluoride on the surface of the titanium plating film.
  • the molten salt titanium plating solution composition 50 containing chloride ions (Cl ⁇ ) has been described.
  • the molten salt titanium plating solution composition 50 can also be prepared without including Cl ⁇ .
  • the molten salt titanium plating solution composition 50 can be prepared so as to include other anions instead. In this case, it is desirable to select the other anions so as not to form a residue such as a salt that is stable at the plating temperature and difficult to remove after plating.
  • the titanium plating member is preferably an insoluble electrode. This makes it possible to provide an insoluble electrode having a titanium plating film with a reduced amount of surface residue.
  • Such an insoluble electrode is preferably used for hydrogen production.
  • the insoluble electrode is for hydrogen production, it can be provided as an insoluble electrode for hydrogen production with low resistance. This makes it possible to produce high purity hydrogen.
  • the titanium plated member is preferably a current collector. This makes it possible to provide a current collector having a titanium plating film with a reduced amount of surface residue.
  • Such a current collector is preferably for a fuel cell.
  • the current collector is for a fuel cell, it can be provided as a fuel cell current collector having good electrical conductivity.
  • the current collector is for a fuel cell, it is more preferably for a polymer electrolyte fuel cell.
  • the titanium plated member is preferably a biomaterial. This makes it possible to provide a biomaterial having a titanium plating film with a reduced amount of surface residue. Such a biomaterial can also be excellent in corrosion resistance.
  • the use of the biomaterial is preferably selected from the group consisting of spinal fixation devices, fracture fixing materials, artificial joints, artificial valves, intravascular stents, denture bases, artificial tooth roots and orthodontic wires.
  • Example 1 Preparation of molten salt titanium plating solution composition and preparation of titanium plated member
  • 2 mol of K 2 TiF 6 powder or 13 mol of TiCl 4 was dissolved as a titanium source in 100 mol of the main component of the molten salt titanium plating solution composition shown in Table 1 below.
  • sample no. 1-No. No. 4 molten salt titanium plating solution composition was prepared.
  • sample no. 1-No. In any of the molten salt titanium plating solution compositions of No. 4, the content of potassium ions is 5 mol% or less with respect to 100 mol% of all ion components contained in the composition. Furthermore, sample no.
  • the molten salt titanium plating solution composition No. 1 is a sample in which the amount of fluoride ions exceeds 50 mol% (51 mol%) with respect to 100 mol% in total of chloride ions and fluoride ions. Sample No.
  • the molten salt titanium plating solution composition No. 2 is a sample not containing chloride ions. Sample No. 3 and no. The molten salt titanium plating solution composition No.
  • the molten salt titanium plating solution composition of No. 4 has a titanium ion content of 0.1 mol% or more and 12 mol% or less (1.9 mol% or 11.5 mol%) with respect to 100 mol% of all cations contained in the composition. It is.
  • sample no. No. 1 molten salt titanium plating solution composition produced by using a titanium plating member precursor specimen No. 1 corresponds to a titanium plating member precursor.
  • Sample No. The titanium plating member precursor produced using the molten salt titanium plating solution composition of No. 2 corresponds to the titanium plating member precursor.
  • Sample No. No. 3 molten salt titanium plating solution composition prepared by using a titanium plating member precursor, 3 corresponds to the titanium plating member precursor.
  • Sample No. No. 4 molten salt titanium plating solution composition produced by using a titanium plating member precursor specimen No. 4 corresponds to a titanium plated member precursor.
  • the above-described cleaning molten salt A to cleaning molten salt D and pure water are used.
  • Specimen No. 1 titanium plating member precursor was washed to remove the first deposit and the second deposit on the surface.
  • the test specimen No. Five titanium plated member precursors 1 were prepared and immersed for 10 minutes in a container containing the molten salt A for cleaning to the molten salt D for cleaning and pure water shown in Table 2 (S40). Thereafter, the test specimen No. 1 titanium plating member precursor was pulled up from each container and ultrasonically cleaned with pure water for 10 minutes (S50). Thereby, the test body No. 1 titanium plating member was produced.
  • the molten salt D for cleaning and pure water serve as a comparative cleaning agent.
  • a cleaning molten salt (cleaning molten salt A to cleaning) containing at least one compound selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride. It can be seen that the metal fluoride and molten salt residue components did not remain on the surface of the titanium plated member washed with molten salt C).
  • Example 2 >> Specimen No. produced in Example 1 Five titanium plating member precursors 2 were prepared. This specimen No. The steps of S40 to S50 (see FIG. 2) in the method for producing a titanium plated member are performed under the same conditions as in Example 1 for the titanium plated member precursor of FIG. The first deposit and the second deposit were removed. As a result, the test specimen No. 2 titanium plated members were produced. Furthermore, specimen No. The presence or absence of residual components of the metal fluoride and the molten salt A for washing to the molten salt D for washing was analyzed for the titanium plated member 2 under the same conditions as in Example 1. The results are shown in the EDX column of Table 3. “Salt component” in Table 3 also means the residual components of metal fluoride and cleaning molten salt A to cleaning molten salt D.
  • a molten salt for cleaning (cleaning molten salt A to cleaning) containing at least one compound selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride It can be seen that the metal fluoride and molten salt residue components did not remain on the surface of the titanium plated member washed with molten salt C).
  • Example 3 Specimen No. produced in Example 1 Five titanium plating member precursors 3 were prepared. This specimen No. The steps of S40 to S50 (see FIG. 2) in the method of manufacturing a titanium plated member are performed on the titanium plated member precursor of No. 3 under the same conditions as in Example 1, thereby obtaining the surface of the titanium plated member precursor. The first deposit and the second deposit were removed. As a result, the test specimen No. 3 titanium plated members were produced. Furthermore, specimen No. The presence or absence of residual components of the metal fluoride and the molten salt A for cleaning to the molten salt D for cleaning was analyzed for the titanium plated member 3 under the same conditions as in Example 1. The results are shown in the EDX column of Table 4. “Salt component” in Table 4 also means the residual components of metal fluoride and cleaning molten salt A to cleaning molten salt D.
  • molten salt for cleaning cleaning molten salt A to cleaning material
  • at least one compound selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride It can be seen that the metal fluoride and molten salt residue components did not remain on the surface of the titanium plated member washed with molten salt C).
  • Example 4 Specimen No. produced in Example 1 Five titanium plating member precursors 4 were prepared. This specimen No. The surface of the titanium plated member precursor is obtained by performing steps S40 to S50 (see FIG. 2) in the titanium plated member manufacturing method under the same conditions as in Example 1 for the titanium plated member precursor of FIG. The first deposit and the second deposit were removed. As a result, the test specimen No. 4 titanium plated members were prepared. Furthermore, specimen No. Each of the titanium plated members of 4 was analyzed for the presence or absence of residual components of metal fluoride and cleaning molten salt A to cleaning molten salt D under the same conditions as in Example 1. The results are shown in the EDX column of Table 5. “Salt component” in Table 5 also means the residual components of metal fluoride and cleaning molten salt A to cleaning molten salt D.
  • a cleaning molten salt (cleaning molten salt A to cleaning) containing at least one compound selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides and potassium fluoride. It can be seen that the metal fluoride and molten salt residue components did not remain on the surface of the titanium plated member washed with molten salt C).
  • the titanium plating film is at least selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides, and potassium fluoride.
  • the metal fluoride remaining on the surface of the titanium plating film and the residual components of the molten salt for cleaning are obtained by cleaning the titanium plating film by bringing it into contact with a cleaning molten salt containing one compound and washing the titanium plating film with water.
  • the amount of (eg LiF and NaF) can be reduced.
  • Example 5 Corrosion resistance to physiological saline
  • the corrosion resistance with respect to the physiological saline was evaluated in the following procedures.
  • a nickel porous substrate (3 cm ⁇ 5 cm ⁇ 1 mmt, porosity is 96%, average pore diameter is 300 ⁇ m, hereinafter “nickel porous body” Ti plating was performed on the surface of) to produce a Ti-plated product.
  • Ni porous body (trade name: “Celmet (registered trademark)”, manufactured by Sumitomo Electric Industries, Ltd.) and a Ti metal plate (manufactured by Niraco Co., Ltd.) were prepared as test samples of comparative examples.
  • Electrolyte solution 0.9 mass% sodium chloride aqueous solution (saline)
  • Working electrode Test specimen of Example or Comparative specimen (Ti plated product, Ni or Ti)
  • Reference electrode Ag / AgCl electrode
  • Counter electrode Ni metal plate Scanning speed: 10 mV / sec Liquid temperature: 25 degreeC.
  • the results of FIG. 4 show that the Ti-plated product as an example has a low corrosion current density compared to the Ni porous material as a comparative example, and is stable in a physiological saline environment. It was done. From this result, it was found that the Ti plated product as an example is suitable as a biomaterial. Further, the Ti plated product as an example had a low corrosion current density compared to the Ti metal plate as a comparative example. From this result, it was shown that the stability with respect to the environment of physiological saline is further improved by adopting the structure of the metal porous body instead of the metal plate.
  • Example 6 Corrosion resistance to salt water simulating seawater.
  • the corrosion resistance with respect to the salt solution which simulated seawater was evaluated in the following procedures.
  • a Ti-plated product produced by the same method as the Ti-plated product used in Example 5 was prepared as a test body of the example.
  • a Ti metal plate manufactured by Niraco Co., Ltd. was prepared as a test sample of a comparative example.
  • the Ti plated product as an example has a lower current density than the Ti commercial product as a comparative example, and exhibits high corrosion resistance against seawater. Thereby, it turned out that the Ti plating goods which are an Example are promising as an insoluble electrode (anode) for salt electrolysis.
  • Example 7 Evaluation of suitability for polymer electrolyte fuel cells. The suitability of the following Ti-plated products for polymer electrolyte fuel cells was evaluated by the following procedure.
  • a Ti-plated product produced by the same method as the Ti-plated product used in Example 5 was prepared as a test body of the example.
  • a test body of a comparative example a Ni porous body (trade name: “Celmet (registered trademark)”, manufactured by Sumitomo Electric Industries, Ltd.) and a Ti metal plate (manufactured by Nilaco Corporation) were prepared.
  • the Ti plated product as an example has a lower current density than that of a comparative Ni sample, and a current collector used in a polymer electrolyte fuel cell It proved promising as a material.
  • titanium plating member 10 base material, 20 plating film, 30 anode, 40 container, 50 plating solution composition.

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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
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US16/500,557 US20200102664A1 (en) 2017-05-22 2018-03-13 Method for manufacturing titanium-plated member
KR1020197029051A KR20200010182A (ko) 2017-05-22 2018-03-13 티탄 도금 부재의 제조 방법
JP2019519484A JPWO2018216319A1 (ja) 2017-05-22 2018-03-13 チタンめっき部材の製造方法
EP18806582.5A EP3633078A4 (de) 2017-05-22 2018-03-13 Verfahren zur herstellung eines titanbeschichteten elements

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KR102625422B1 (ko) * 2022-03-11 2024-01-23 주식회사 제로원파트너스 에너지 효율이 향상된 ptc 난방 필름 및 이의 제조 방법

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EP3633078A1 (de) 2020-04-08
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