JPH05263265A - Production of titanium plate and titanium alloy plate having excellent coatability - Google Patents

Abstract

(57) [Summary] [Object] The present invention provides a titanium coil having excellent coating adhesion. [Structure] Titanium coil with iron, tin, which has excellent paint adhesion
A titanium coil excellent in coating adhesion is provided by applying zinc, ceramics or the like in close contact with a physical coating device using impact force so that the dispersion index becomes 1000 or more. [Effect] Prevention of corrosion of titanium and other metals by contact with different metals, prevention of hydrogen absorption of titanium, reduction of required anticorrosion current of titanium, increase of surface color variations from the viewpoint of decorativeness, civil engineering and building structures, chemistry, energy The use of titanium can be expanded in a wide range of fields such as plants and automobiles, and its industrial effect is extremely large.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a titanium plate and a titanium alloy plate having excellent coatability. In the present invention, the plate is used to include a band, and hereinafter, these are collectively referred to as a titanium coil.

[0002]

2. Description of the Related Art Titanium and titanium alloys have very high corrosion resistance, so that there is no need for anti-corrosion coating. Therefore, with respect to the decorative property, various contrivances have been made and an anodic oxidation method and a plating method have been disclosed. For example, Japanese Patent Laid-Open No. 62-1029
No. 7 discloses a barrier type in which titanium or a titanium alloy is subjected to direct current electrolytic treatment in an electrolytic solution containing an electrodeposition resin and an acid capable of forming a barrier type anodic oxide film with the titanium or titanium alloy as an anode. A method for simultaneously forming an anodized film and an electrodeposition coating film is disclosed. Further, Japanese Patent Laid-Open No. 62-10299 discloses a method for forming a colored film of titanium or a titanium alloy.

Further, as a plating method, Japanese Patent Laid-Open No. 61-8
In Japanese Patent No. 7893, titanium or titanium alloy is finished to a required surface roughness by a mechanical method, and then aluminum is deposited to 20 to 30 μm by dry plating, and then aluminum is pretreated by a conventional method to perform copper and gold plating. A surface treatment method is disclosed. In addition, JP-A-6
No. 1-110793 discloses a nickel-plated titanium or titanium alloy material, fluorine ions and nickel,
Manufacture of electrolytic nickel plating on titanium or titanium alloy wires in an aqueous solution of an inorganic acid or an inorganic mixed acid containing heavy metal ions such as copper, zinc and iron, which are relatively easy to plate, and then electroplating with nickel. A method is disclosed.

Further, Japanese Patent Laid-Open No. 63-310993 discloses a method of treating a titanium-based material with a treatment liquid containing a fluoride, performing ruthenium strike plating, and then further plating a noble metal thereon. ing. Further, in JP-A-64-36788, titanium hydride is prepared by immersing a titanium material in a fluoride solution containing ammonium hydrogen fluoride of 0.2 to 0.4% and a water-soluble reducing agent for 1 to 4 minutes. A method is disclosed in which (TiH ₂ ) is formed, nickel plating is performed, and then heat treatment at 200 ° C. or higher is performed, and then a precious metal is plated. Further, in JP-A-3-47991, in a solution having a composition of about 4 to 6% by volume of 70% hydrofluoric acid and 94 to 96% by volume of hydrochloric acid of 36 to 38% concentration,
It is disclosed that the method has a step of etching the surface of the composition, and that the surface of the composition is subjected to cathodic plating of a nickel layer.

However, the above example does not disclose a method for coating a titanium coil. In addition, these electrochemical surface treatment methods applied to a titanium plate or a titanium alloy to improve the plating property in strong acid require special equipment and many steps, and the control of the solution must be strict. Since it is difficult to continuously process the titanium coil, the titanium plate or titanium alloy plate manufactured by such a process becomes very expensive and not practical. The conventional anodic oxidation method and plating method improve the decorativeness of the surface by means of chemical reaction such as electrolysis, and solve the original problem that it is difficult to paint like titanium or titanium alloy. Has not been done.

[0006]

SUMMARY OF THE INVENTION According to the present invention, at least one of iron, tin, zinc, and ceramics having excellent coating adhesion is applied to the titanium coil which has been difficult to coat.
The seeds are coated in close contact, and at this time, by providing these materials with a predetermined dispersion index (Index), a titanium coil manufacturing method with improved coating adhesion is provided. It is an object of the present invention to make it possible to manufacture a titanium coil that is inexpensive and has excellent paintability by continuously performing a large amount of continuous treatment in a short time using.

[0007]

The gist of the present invention is that a titanium coil is coated with at least one material selected from the group consisting of iron, tin, zinc and ceramics having excellent coating adhesion, and the following formula (1) And a titanium coil having excellent coatability, which is characterized by being dispersion-adhered so that the value of the dispersion index (Index) defined in (1) is 1000 or more, and the coil is coated.

Dispersion index (Index) = {(number less than 20 μm) + (number greater than 20 μm and less than 50 μm) ×
4+ (number exceeding 50 μm and less than 100 μm) × 25 +
(Number exceeding 100 μm) × 100} / (measured area 1
mm × 1 mm) ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥ (1) Since the titanium coil can be coated according to the present invention, it prevents the corrosion of dissimilar metal contact when titanium serves as the cathode, or prevents the occurrence of electrical protection. It is expected that the absorption of hydrogen by titanium can be prevented, the required anticorrosion current of titanium at the time of electric protection can be reduced, and the variation of the surface color can be increased in terms of decorativeness.

[0009]

According to the present invention, a material such as iron, tin, zinc, ceramics or the like having excellent coating adhesion is dispersed on the surface of the titanium coil by the dispersion index (I
Adhesive coating so that the (ndex) is 1000 or more.
Originally, titanium and titanium alloys have very excellent corrosion resistance because an inactive film is formed on the surface, but coating becomes difficult. To alleviate this difficulty, iron, tin, zinc, ceramics, etc., which form an active surface coating, were applied to the titanium surface by a physical contact coating apparatus using impact force to improve the coating adhesion.

The reason for selecting iron, tin, zinc and ceramics is that iron and tin greatly improve the affinity with the coating film due to the active surface, and zinc and ceramics have the performance of coated titanium. It is for improving. In other words, zinc is to prevent the zinc coated as a sacrificial anode from leaching the dispersed coated iron even if a local defect such as a pinhole occurs when it is used in an actual environment after coating. In addition, ceramics have a very large electrical resistance, which significantly reduces the conductivity on the coated surface and the electrochemical reaction. It is possible to greatly improve the inflow loss current prevention and hydrogen absorption prevention performance.

The dispersion index (Index) is a concept that is close to the area ratio of the coating on the surface of the titanium coil, but it is easy to measure, and the relationship between the dispersion state depending on the particle size of the coating and the coating adhesion. Investigation was conducted to derive the dispersion index (Index) formula (1) according to the particle size of the coating. Dispersion index (Ind
For the reason for coating ex) of 1000 or more,
When the dispersion index (Index) of the titanium coil is less than 1000, almost the same coating adhesion as when the titanium coil is coated without a coating is obtained, and thus the dispersion index (In
Dex) was set to 1000 or more.

[0012]

[Examples] Titanium and titanium alloy coils having a thickness of 1 mm were subjected to shot blasting with iron having particle diameters of 20 μm, 40 μm and 60 μm, respectively, and the iron dispersion index (Index) =
It was set to 200 to 10,000. 100mm x from this coil
A plate having a size of 100 mm was cut out, a zinc rich primer coating (thickness: 20 μm) was applied to the plate, and the coating adhesion was examined by a cross-cut test (JIS K5400).
Furthermore, after conducting a corrosion acceleration test simulating the splashed part environment of the marine structure on the coated plate, the adhesion of the coating after being exposed to the corrosive environment was investigated by a cross-cut test. As a corrosion acceleration test condition, spray 308K (35 ° C) artificial seawater for 4 hours,
333K (60 ° C) Dry for 2 hours, 323K (50
C.) humidity of 95% and exposed for 2 hours, these three states were continuously repeated for 30 days.

Tables 1 to 6 show the results.
When titanium or titanium alloy was not coated with iron or coated with a dispersion index of less than 1000, the titanium / titanium alloy of the present invention did not peel off and showed high coating adhesion.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

[0020]

As described above, according to the present invention, the titanium coil can be coated. Therefore, when titanium is used as a cathode, corrosion of dissimilar metal contact is prevented, or hydrogen absorption of titanium during electric protection is prevented. It can be expected to reduce the required anticorrosion current of titanium during protection, and the variation of the surface color will increase from the viewpoint of decorativeness, and the use of titanium will be expanded in a wide range of fields such as civil engineering and building structures, chemistry, energy plants, and automobiles. It is possible and its industrial effect is extremely large.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Honma 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corp. Technology Development Division

Claims (2)

[Claims] 1. A dispersion index (Index) defined by the following formula (1) on the surface of a titanium plate or a titanium alloy plate of at least one material selected from iron (including impurities), tin, zinc and ceramics. The method for producing a titanium plate and a titanium alloy plate having excellent coatability, which is characterized by performing dispersion adhesion coating so that the value of is 1000 or more. Dispersion index (Index) = {(number of particles less than 20 μm) +
(The number exceeding 20 μm and less than 50 μm) × 4 + (50 μm
m + m less than 100 μm) × 25 + (100 μm
> 100} / (measurement area 1mm x 1mm)
‥‥‥‥‥‥‥‥‥‥ (1) 2. A method for producing a titanium plate and a titanium alloy plate which are coated and have excellent coatability.