US20200063281A1 - Method for preparing titanium plating solution and method for manufacturing titanium plated product - Google Patents

Method for preparing titanium plating solution and method for manufacturing titanium plated product Download PDF

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US20200063281A1
US20200063281A1 US16/462,618 US201716462618A US2020063281A1 US 20200063281 A1 US20200063281 A1 US 20200063281A1 US 201716462618 A US201716462618 A US 201716462618A US 2020063281 A1 US2020063281 A1 US 2020063281A1
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titanium
plating solution
potential
titanium plating
preparing
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Koma Numata
Masatoshi Majima
Tomoyuki Awazu
Mitsuyasu Ogawa
Toshiyuki Nohira
Kouji Yasuda
Yutaro NORIKAWA
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Sumitomo Electric Industries Ltd
Kyoto University NUC
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Sumitomo Electric Industries Ltd
Kyoto University NUC
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Assigned to KYOTO UNIVERSITY, SUMITOMO ELECTRIC INDUSTRIES, LTD. reassignment KYOTO UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AWAZU, TOMOYUKI, MAJIMA, MASATOSHI, NOHIRA, TOSHIYUKI, NORIKAWA, Yutaro, NUMATA, Koma, OGAWA, MITSUYASU, YASUDA, KOUJI
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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
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C25D21/12—Process control or regulation
    • 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

Definitions

  • the present disclosure relates to a method for preparing a titanium plating solution and a method for manufacturing a titanium plated product.
  • the present application claims the benefit of priority to Japanese Patent Application No. 2016-227050 filed on Nov. 22, 2016, the entire contents of which are incorporated herein by reference.
  • Titanium is a metal that is excellent in corrosion resistance, heat resistance and specific strength.
  • titanium is costly to manufacture and difficult to smelt and work, which hampers the wide use of titanium.
  • Dry deposition such as chemical vapor deposition (CVD) and physical vapor deposition (PVD)
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the dry deposition cannot be applied to a complex-shaped substrate.
  • electrodeposition of titanium in a molten salt may be adopted.
  • Japanese Patent Laying-open No. 2015-193899 (PTL 1) describes that an alloy film of Fe and Ti is formed on a Fe wire surface by using a molten salt bath of KF—KCl to which K 2 TiF 6 or TiO 2 is added.
  • a method for preparing a titanium plating solution according to an embodiment of the present disclosure includes measuring a titanium plating solution containing fluorine and titanium by cyclic voltammetry under the following conditions, and adding titanium to the titanium plating solution so that the potential difference between the spontaneous potential and the Ti3 + /Ti 4+ redox potential is 0.75 V or more, conditions: when the temperature of the titanium plating solution is 650° C. or more and 850° C.
  • the potential scanning is repeatedly performed on the working electrode for at least five times at a scanning speed of 1 mV/sec or more and 500 mV/sec or less between a lower potential limit which is the immersion potential of the working electrode and an upper potential limit which is a potential that is 2 V to 4 V higher than the lower potential limit.
  • FIG. 1 is a graph schematically illustrating a measurement result of a titanium plating solution by cyclic voltammetry
  • FIG. 2 is a schematic view illustrating an example of defining areas A to E on a titanium plated product in a method of measuring an average film thickness of a titanium plating film on the titanium plated product;
  • FIG. 3 is a conceptual diagram illustrating an example of a field of view (i) when the area A of the titanium plated product illustrated in FIG. 2 is observed with a scanning electron microscope.
  • FIG. 4 is a conceptual diagram illustrating an example of a field of view (ii) when the area A of the titanium plated product illustrated in FIG. 2 is observed with a scanning electron microscope;
  • FIG. 5 is a conceptual diagram illustrating an example of a field of view (iii) when the area A of the titanium plated product illustrated in FIG. 2 is observed with a scanning electron microscope.
  • FIG. 6 is a graph schematically illustrating a measurement result by cyclic voltammetry of a titanium plating solution No. 4 prepared in Example 4.
  • FIG. 7 is a graph schematically illustrating a measurement result by cyclic voltammetry of a titanium plating solution No. A prepared in Comparative Example 4.
  • an alloy film of Fe and Ti can be electrodeposited on the surface of a cathode used in the molten salt electrolysis by the method described in PTL 1, a metal Ti film cannot be electrodeposited by the method. Specifically, the alloy film of Fe and Ti is stable in the molten salt bath, whereas the metal Ti dissolves in the molten salt bath due to a comproportionation reaction.
  • the present disclosure it is possible to provide a method for preparing a titanium plating solution in which the concentration ratio between Ti 3+ and Ti 4+ in the titanium plating solution is monitored so that the concentration of Ti 3+ is maintained sufficiently high.
  • a method for preparing a titanium plating solution includes: measuring a titanium plating solution containing fluorine and titanium by cyclic voltammetry under the following conditions; and adding titanium to the titanium plating solution so that the potential difference between the spontaneous potential and the Ti3 + /Ti 4+ redox potential is 0.75 V or more, conditions: when the temperature of the titanium plating solution is 650° C. or more and 850° C.
  • the potential scanning is repeatedly performed on the working electrode for at least five times at a scanning speed of 1 mV/sec or more and 500 mV/sec or less between a lower potential limit which is the immersion potential of the working electrode and an upper potential limit which is a potential that is 2 V to 4 V higher than the lower potential limit.
  • the titanium plating solution is obtained by dissolving titanium in a molten salt of potassium fluoride and potassium chloride.
  • the titanium plating solution is obtained by dissolving K 2 TiF 6 in a molten salt of potassium fluoride and potassium chloride.
  • the content of the K 2 TiF 6 in the titanium plating solution is 0.1 mol % or more.
  • the molar mixing ratio between potassium fluoride and potassium chloride is 10:90 to 90:10.
  • the titanium added to the titanium plating solution is titanium sponge.
  • titanium sponge refers to a porous metal titanium having a porosity of 1% or more.
  • the porosity of the titanium sponge is calculated by the following formula:
  • a method for manufacturing a titanium plated product includes an electrolyzing step of carrying out a molten salt electrolysis by using a cathode and an anode provided in a titanium plating solution containing fluorine and titanium so as to electrodeposit titanium on the surface of the cathode, and the titanium plating solution is prepared by the method for preparing a titanium plating solution according to any one of the above (1) to (6).
  • the titanium plating solution used in the electrolyzing step is measured by cyclic voltammetry under the following conditions, and the potential difference between the spontaneous potential and the Ti3 + /Ti 4+ redox potential is controlled to be 0.75 V or more,
  • the potential scanning is repeatedly performed on the working electrode for at least five times at a scanning speed of 1 mV/sec or more and 500 mV/sec or less between a lower potential limit which is the immersion potential of the working electrode and an upper potential limit which is a potential that is 2 V to 4 V higher than the lower potential limit.
  • the method for manufacturing a titanium plated product may be used to continuously and stably produce a titanium plated product with a smooth titanium plating film formed on its surface.
  • a titanium plating solution containing fluorine and titanium is prepared. Then, the titanium plating solution is measured by cyclic voltammetry (hereinafter, abbreviated to “CV” where necessary), and titanium is added to the titanium plating solution so that the potential difference between the spontaneous potential and the Ti3 + /Ti 4+ redox potential is 0.75 V or more.
  • CV cyclic voltammetry
  • the CV measurement may be carried out in a non-oxidizing atmosphere which does not react with titanium to form a compound.
  • the CV measurement may be carried out in an inert gas atmosphere such as argon gas.
  • the CV measurement may be carried out under such a condition that the temperature is set to 650° C. or more and 850° C. or less so as to maintain the titanium plating solution in liquid state and the scanning speed of the potential scanning is set at 1 mV/sec or more and 500 mV/sec or less.
  • the temperature of the titanium plating solution is more preferably 650° C. or more and 850° C. or less, and further preferably 650° C. or more and 750° C. or less.
  • the scanning speed of the potential scanning is more preferably 50 mV/sec or more and 300 mV/sec or less, and further preferably 100 mV/sec or more and 200 mV/sec or less.
  • the working electrode may be, for example, graphite, glassy carbon or the like.
  • the reference electrode may be, for example, Pt, Ni or the like.
  • the counter electrode may be, for example, titanium, glassy carbon, graphite or the like.
  • the potential scanning is repeatedly performed on the working electrode for at least five times between a lower potential limit which is the immersion potential of the working electrode and an upper potential limit which is a potential that is 2 V to 4 V higher than the lower potential limit.
  • FIG. 1 illustrates the CV measurement result of a titanium plating solution.
  • the vertical axis represents the current (mA) and the horizontal axis represents the potential (V) of the reference electrode.
  • the spontaneous potential 1 refers to a potential difference between the working electrode and the reference electrode when no current is flowing therethrough.
  • the Ti 3+ /Ti 4+ redox potential 4 refers to a midpoint potential between the peak potential 2 resulting from the oxidation of Ti 3+ to Ti 4+ and the peak potential 3 resulting from the reduction of Ti 4+ to Ti 3+ .
  • the peak potential 2 resulting from the oxidation of Ti 3+ to Ti 4+ is an average value of the potentials obtained by repeating the potential scanning on the working electrode for at least five times.
  • the peak potential 3 resulting from the reduction of Ti 4+ to Ti 3+ is an average value of the potentials obtained by repeating the potential scanning on the working electrode for at least five times.
  • a titanium plating solution has a potential difference between the spontaneous potential 1 and the Ti 3+ /Ti 4+ redox potential 4 of 0.75 V or more
  • the concentration of Ti 3+ in the titanium plating solution is much greater than the concentration of Ti 4+ . Therefore, if the molten salt electrolysis is carried out by using a titanium plating solution having a potential difference between the spontaneous potential 1 and the Ti 3+ /Ti 4+ redox potential 4 of 0.75 V or more, a titanium plating film which is silvery white and highly smooth can be formed on the surface of the cathode.
  • the potential difference between the spontaneous potential 1 and the Ti 3+ /Ti 4+ redox potential 4 is more preferably 1.0 V or more, and further preferably 1.1 V or more.
  • the ratio between the concentration of Ti 3+ and the concentration of Ti 4+ in the titanium plating solution may be calculated by using the Nernst equation represented by the following formula (B):
  • E electrode potential
  • E 0 standard electrode potential
  • R gas constant
  • T absolute temperature
  • Z number of mobile electrons
  • F Faraday constant
  • a activity
  • the titanium plating solution before the CV measurement may be a molten salt containing fluorine and titanium.
  • the titanium plating solution may be a molten salt obtained by dissolving K 2 TiF 6 in KF—KCl, a molten salt obtained by dissolving K 2 TiF 6 in LiF—KCl, or a molten salt obtained by dissolving K 2 TiF 6 in NaF—KCl.
  • the titanium compound to be dissolved in the molten salt is not limited to K 2 TiF 6 , it may be TiCl 4 or the like.
  • the molten salt obtained by dissolving K 2 TiF 6 in KF—KCl is preferable.
  • the molten salt obtained by dissolving K 2 TiF 6 in KF—KCl is a titanium plating solution that may be used to form a smooth titanium plating film.
  • the molar mixing ratio between KF and KCl is preferably 10:90 to 90:10. If the content ratio of KF in KF—KCl is 10 mol % or more, a smooth titanium plating film may be electrodeposited on the surface of the cathode. If the content ratio of KF in KF—KCl is 90 mol % or less, the melting point may be made lower than that of the molten salt of KF alone. From these viewpoints, the molar mixing ratio between KF and KCl is more preferably 20:80 to 80:20, and further preferably 40:60 to 60:40.
  • titanium should be added to the titanium plating solution so that the potential difference between the spontaneous potential 1 and the Ti 3+ /Ti 4+ redox potential 4 is 0.75 V or more.
  • titanium sponge titanium powder which is processed as fine as possible or the like. Since titanium sponge has a higher porosity, the specific surface area is larger, which makes it easier to be dissolved in the molten salt bath. Thus, the porosity of titanium sponge to be used is more preferably 20% or more, and further preferably 40% or more. Using titanium sponge which has a higher porosity may facilitate the progress of the comproportionation reaction in the titanium plating solution.
  • the titanium plating solution obtained by the method for preparing a titanium plating solution according to an embodiment of the present disclosure is used to carry out the molten salt electrolysis, it is possible to manufacture a titanium plated product with a smooth titanium plating film having a small thickness distribution on its surface.
  • a method for manufacturing a titanium plated product according to an embodiment of the present disclosure includes an electrolyzing step of carrying out a molten salt electrolysis by using a cathode and an anode provided in the titanium plating solution which is obtained according to the method for preparing a titanium plating solution described in the above embodiment so as to electrodeposit titanium on the surface of the cathode.
  • a titanium plating film will be formed on the surface of the cathode.
  • a material suitable for forming the titanium plating film on the surface may be used as the cathode.
  • a metal, a conductive sintered body or the like may be given.
  • nickel, iron, SUS304, molybdenum, tungsten, copper, carbon or the like may be preferably used.
  • the base material used as the cathode is simply required to be conductive at least at its surface. If the base material is made of a material to be alloyed with titanium, a titanium alloy layer may be formed on the cathode side of the titanium plating film. On the other hand, if a high-purity titanium plating film is to be formed without a titanium alloy layer, a material that cannot be alloyed with Ti in the titanium plating solution may be used as the cathode.
  • the anode is not particularly limited, and it may be made of any conductive material such as glassy carbon or titanium, for example. From the viewpoint of stably and continuously producing the titanium plating film, the anode is preferably made of Ti.
  • the atmosphere in which the molten salt electrolysis is carried out may be vacuum or a non-oxidative atmosphere that does not form a compound with titanium.
  • the molten salt electrolysis may be carried out in a glove box filled or circulated with an inert gas such as argon gas.
  • the current density for carrying out the molten salt electrolysis is not particularly limited, and it may be, for example, 10 mA/cm 2 or more and 500 mA/cm 2 or less.
  • the current density is more preferably 50 mA/cm 2 or more and 250 mA/cm 2 or less, and further preferably 100 mA/cm 2 or more and 200 mA/cm 2 or less.
  • the temperature of the titanium plating solution is preferably 650° C. or more and 850° C. or less. If the temperature of the titanium plating solution is set to 650° C. or more, it is possible to maintain the titanium plating solution in liquid state so as to carry out the molten salt electrolysis stably. If the temperature of the titanium plating solution is set to 850° C. or less, it is possible to prevent the titanium plating solution from becoming unstable due to the evaporation of the components in the titanium plating solution. From these viewpoints, the temperature of the titanium plating solution is more preferably 650° C. or more and 750° C. or less, and further preferably 650° C. or more and 700° C. or less.
  • the time for carrying out the molten salt electrolysis is not particularly limited, and it may be carried out for a period of time in which the target titanium plating film is sufficiently formed on the surface of the cathode.
  • the titanium plating solution is measured regularly or irregularly by cyclic voltammetry and the potential difference between the spontaneous potential and the Ti 3+ /Ti 4+ redox potential is controlled to be 0.75 V or more.
  • the titanium ions may be oxidized from Ti 3+ to Ti 4+ , and thereby a smooth titanium plating film may not be formed. Further, when an electrode other than the titanium electrode is used as the anode, the concentration of the titanium ions in the titanium plating solution may change at anytime.
  • the titanium plating solution is subjected to CV measurement regularly or irregularly and controlled so that the potential difference between the spontaneous potential and the Ti 3+ /Ti 4+ redox potential is 0.75 V or more, which makes it possible to stably and continuously form a smooth titanium plating film on the surface of the cathode.
  • the conditions for the CV measurement are the same as those for the CV measurement in the method for preparing a titanium plating solution according to the embodiment of the present disclosure described above.
  • the potential difference between the spontaneous potential and the Ti 3+ /Ti 4+ redox potential of the titanium plating solution determined by the CV measurement becomes less than 0.75 V, for example, titanium sponge or the like may be added and dissolved in the titanium plating solution.
  • a smooth titanium plating film having a small film thickness distribution refers to such a film that either the maximum thickness or the minimum thickness of the titanium plating film measured at any of arbitrary five spots is preferably within ⁇ 50% of the average film thickness.
  • FIG. 2 is a conceptual diagram for illustrating a method for measuring the average film thickness.
  • the titanium plated product with a titanium plating film formed on its surface is arbitrarily and equally divided into areas, and five spots (area A to area E) are selected as measurement spots.
  • the cross section of the titanium plating film in each area is observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the magnifying power of the SEM is set in such a manner that the entire titanium plating film can be observed in the thickness direction and is enlarged in the thickness direction as much as possible in one field of view.
  • the maximum thickness and the minimum thickness of the titanium plating film in each area are measured at three points by changing the field of view, and the average value is defined as the average film thickness of the titanium plating film.
  • FIG. 2 illustrates a schematic view of a titanium plated product 21 with a titanium plating film formed on the surface of a substantially square-shaped base material, in which four corners are defined as areas A to D, and a central portion is defined as an area E.
  • FIG. 3 illustrates a conceptual view of a field of view (i) when the area A of the titanium plated product 21 illustrated in FIG. 2 is observed by SEM.
  • FIG. 4 illustrates a conceptual view of a field of view (ii) of the area A
  • FIG. 5 illustrates a conceptual view of a field of view (iii) of the area A.
  • the maximum thickness of the titanium plating film 23 (the maximum thickness A(i), the maximum thickness A(ii), and the maximum thickness A(iii)) and the minimum thickness of the titanium plating film 23 (the minimum thickness a(i), the minimum thickness a(ii), and the minimum thickness a(iii)) are measured.
  • the thickness of the titanium plating film 23 is defined as the length of the titanium plating film 23 extending in the vertical direction from the base material 22 .
  • the thickness of the titanium plating film 23 is defined as the total length of the titanium alloy layer and the titanium plating film extending in the vertical direction from the base material 22 .
  • the maximum thickness A(i) to A(iii) and the minimum thickness a(i) to a(iii) are determined in three fields of view.
  • the areas B, C, D and E the maximum thickness and the minimum thickness of the titanium plating film are measured in three fields of view in the same manner as the area A.
  • the average of the maximum thickness A(i) to A(iii), B(i) to B(iii), C(i) to C(iii), D(i) to D(iii) and E(i) to E(iii) and the minimum thickness a(i) to a(iii), b(i) to b(iii), c(i) to c(iii), d(i) to d(iii) and e(i) to e(iii) of the titanium plating film measured as described above are averaged, and the average value is defined as the average film thickness of the titanium plating film.
  • KCl, KF and K 2 TiF 6 were mixed so that the molar mixing ratio between KCl and KF was 55:45 and the concentration of K 2 TiF 6 was 0.1 mol %, and were heated to 650° C. to prepare a titanium plating solution.
  • the CV measurement was carried out at a potential scanning speed of 200 mV/sec under an atmosphere in which argon gas was circulated.
  • a graphite rod with a diameter of 3 mm was used as a working electrode
  • a Pt wire with a diameter of 1 mm was used as a reference electrode
  • a titanium rod with a diameter of 3 mm was used as a counter electrode.
  • the potential scanning was repeatedly performed on the working electrode for five times.
  • the potential difference between the spontaneous potential and the Ti 3+ /Ti 4+ redox potential of the titanium plating solution was 0.65 V.
  • titanium sponge 0.3 mg per 1 g of the titanium plating solution was added to the titanium plating solution, and sufficiently dissolved therein.
  • the used titanium sponge has a porosity of 50%.
  • the titanium plating solution was subjected to the CV measurement under the same conditions, and the potential difference between the spontaneous potential and the Ti 3+ /Ti 4+ redox potential was 0.75 V.
  • This titanium plating solution was used as the titanium plating solution No. 1.
  • a cathode and an anode were provided in the titanium plating solution No. 1, and the molten salt electrolysis was carried out for 40 minutes.
  • the molten salt electrolysis was carried out in a glove box under an argon flow atmosphere.
  • a Ni plate of 0.5 cm ⁇ 2.5 cm ⁇ 0.1 mm was used as the cathode, and a Ti rod was used as the anode.
  • a Pt wire was used as a pseudo-reference electrode.
  • the current density was set to 25 mA/cm 2 .
  • the potential of the pseudo-reference electrode was calibrated with the potential (K + /K potential) of metallic potassium electrochemically deposited on the Pt wire.
  • the titanium plated product was washed with water.
  • the salt that adhered to the surface of the titanium plated product was highly soluble in water and was easily removed.
  • the titanium plated product No. 1 with a titanium plating film formed on its surface was obtained.
  • Titanium plating solution No. 2 was prepared in the same manner as Example 1 except that the amount of titanium sponge added to the titanium plating solution after the CV measurement in Example 1 was modified to 0.5 mg of titanium sponge per 1 g of the titanium plating solution.
  • Titanium plating solution No. 3 was prepared in the same manner as Example 1 except that the amount of titanium sponge added to the titanium plating solution after the CV measurement in Example 1 was modified to 1 mg of titanium sponge per 1 g of the titanium plating solution.
  • Titanium plated product No. 3 was manufactured in the same manner as Example 1 except that the titanium plating solution No. 3 was used in place of the titanium plating solution No. 1 of Example 1.
  • Titanium plating solution No. 4 was prepared in the same manner as Example 1 except that the amount of titanium sponge added to the titanium plating solution after the CV measurement in Example 1 was modified to 1.2 mg of titanium sponge per 1 g of the titanium plating solution.
  • FIG. 6 illustrates the result of the CV measurement (the result of the fifth potential scanning) for the titanium plating solution No. 4.
  • the vertical axis represents the current (mA)
  • the horizontal axis represents the potential (V) of the reference electrode.
  • Titanium plated product No. 4 was manufactured in the same manner as Example 1 except that the titanium plating solution No. 4 was used in place of the titanium plating solution No. 1 of Example 1.
  • Titanium plating solution No. A was prepared in the same manner as Example 1 except that titanium sponge was not added to the titanium plating solution after the CV measurement in Example 1.
  • the titanium plating solution No. A was subjected to the CV measurement under the same conditions as Example 1, and the potential difference between the spontaneous potential and the Ti 3+ /Ti 4+ redox potential was 0.67 V.
  • FIG. 7 illustrates the result of the CV measurement (the result of the fifth potential scanning) for the titanium plating solution No. A.
  • the vertical axis represents the current (mA)
  • the horizontal axis represents the potential (V) of the reference electrode.
  • Titanium plated product No. A was manufactured in the same manner as Example 1 except that the titanium plating solution No. A was used in place of the titanium plating solution No. 1 of Example 1.
  • Titanium plating solution No. B was prepared in the same manner as Example 1 except that the amount of titanium sponge added to the titanium plating solution after the CV measurement in Example 1 was modified to 0.2 mg of titanium sponge per 1 g of the titanium plating solution.
  • Titanium plated product No. B was manufactured in the same manner as Example 1 except that the titanium plating solution No. B was used in place of the titanium plating solution No. 1 of Example 1.
  • the ratio between the concentration of Ti 3+ and the concentration of Ti 4+ (Ti 3+ concentration/Ti 4+ concentration) in each of the titanium plating solution No. 1 obtained in Example 1, the titanium plating solution No. 2 obtained in Example 2, the titanium plating solution No. 3 obtained in Example 3, the titanium plating solution No. 4 obtained in Example 4, the titanium plating solution No. A obtained in Comparative Example 1, and the titanium plating solution No. B obtained in Comparative Example 2 was calculated by using the Nernst equation. The results are listed in Table 1.
  • Titanium plating solution Difference (V) between Titanium plated product spontaneous Ti 3+ /Ti 4+ Surface Current potential and Concen- condition efficiency Ti 3+ /Ti 4 ⁇ tration of titanium of cathode No. redox potential ratio No. plating film (%) 1 0.75 10000 1 silvery white 20 2 0.85 40000 2 silvery white 30 3 1.00 290000 3 silvery white 90 4 1.10 1000000 4 silvery white 90 A 0.67 3500 A black plating impossible B 0.70 7000 B black plating impossible

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CN103060862B (zh) * 2012-12-26 2015-08-12 广东电网公司电力科学研究院 钛涂层及其制备方法
CN103320822A (zh) * 2013-06-27 2013-09-25 中国铝业股份有限公司 一种金属表面电镀钛的方法
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
JP6487258B2 (ja) * 2014-05-16 2019-03-20 アイ’エムセップ株式会社 金属製基材の表面に多孔質層を形成する方法

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