JPH07233466A - Corrosion resistant metallic article and its production - Google Patents

Abstract

PURPOSE:To obtain a corrosion resistant metallic article having further improved corrosion resistance by dispersing Ti, Zr, Hf, V, Nb or Ta from the surface of a metallic article to a specified depth while reducing the concn. CONSTITUTION:One or more kinds of metals selected from among Ti, Zr, Hf, V, Nb and Ta or, as necessary, further Cr are dispersed from the surface of a metallic article to >=0.5mum depth while reducing the concn. This surface treatment is carried out by impressing about 700-2,000V bias voltage to the metallic article and irradiating the article with ions of the metals by a cathode arc discharge type ion plating method using a cathode of the metals. The metals can be dispersed from the surface of the metallic article to about 0.5-3mum depth so that the concn. is gradually reduced from about 100%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal article having surface corrosion resistance and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in order to improve the corrosion resistance of metal articles, the surface thereof is plated with a metal having a high corrosion resistance such as Ni or Cr. However, the above Ni, Cr
Since the metal plating film such as is a thin film of several μm near the surface of the metal article, the boundary surface between the metal article and the plating layer is a discontinuous surface having different physical properties such as thermal expansion coefficient and thermal conductivity. Therefore, there is a problem that it is easily broken by abrasion, impact, heating, etc., and corrosion progresses from the broken part.

The Applicant has found that 0.5 μm from the surface of a metal article
A corrosion-resistant metal article in which Cr is dispersed while reducing the concentration to the above depth, and a corrosion-resistant metal article characterized by irradiating the surface of the metal article with Cr ions by an ion plating method and a method for producing the same have been proposed. (Application for Japanese Patent Application No. 4-150071).

[0004]

The present applicant has conducted further tests to arrive at a new corrosion resistant metal article and a method for producing the same. Therefore, it is an object of the present invention to provide a novel corrosion-resistant metal article which solves the above-mentioned problems of the conventional plating treatment and has further improved corrosion resistance, and a method for producing the same.

[0005]

In order to achieve the above object, the corrosion-resistant metal article of the present invention is provided with Ti, Zr, Hf, V, N from the surface of the metal article to a depth of 0.5 μm or more.
The present invention is characterized in that at least one metal selected from the group consisting of b and Ta is dispersed with decreasing concentration, and the production method of the present invention for producing these is characterized in that the surface of the metal article is ion-plated. Ti, Z by the Ting method
It is characterized in that the metal article is irradiated with ions of the metal by using a cathode of at least one metal selected from the group consisting of r, Hf, V, Nb and Ta.

Further, the corrosion-resistant metal article of the present invention comprises Ti, Zr, H up to a depth of 0.5 μm or more from the surface of the metal article.
The present invention is characterized in that at least one metal selected from the group consisting of f, V, Nb and Ta and Cr are dispersed while decreasing the concentration, and the production method of the present invention for producing these is A cathode of at least one metal selected from the group consisting of Cr and Ti, Zr, Hf, V, Nb or Ta and a cathode of Cr are used on the surface of a metal article by an ion plating method, and ions of these metals are applied to the surface of the metal article. The feature is that it irradiates to.

Furthermore, the corrosion-resistant metal article of the present invention is characterized by the fact that Ti, Cr,
It is characterized in that at least one metal selected from the group consisting of Zr, Hf, V, Nb or Ta and Al are dispersed while reducing the concentration, and the production of the present invention for producing these The method is to deposit Ti, Cr, Zr, Hf, V, on the surface of a metal article by an ion plating method.
It is characterized in that the cathode of an alloy of at least one metal selected from the group consisting of Nb or Ta and Al is used to irradiate the metal article with ions of these metals.

[0008]

The corrosion-resistant metal article of the present invention is 0.5 μm from the surface.
The metal elements constituting the cathode described in claims 2, 4, and 6 are dispersed to the depth of m while decreasing the concentration. The depth of the region where these are dispersed from this surface may be at most 10 μm, and is usually 0.5 to 3 μm.
If it is shallower than m, sufficient corrosion resistance cannot be obtained. The concentration gradient of these metals does not have to be constant, but the concentration must decrease continuously from the surface to the inside and there must be no discontinuous concentration gap.

A region having a depth of 0.5 μm or more from the surface of the metal article is claimed in claims 2, 4, and 6.
It is a mixed layer of each metal element constituting the cathode described in 1. and the material of the metal article, the concentration of which is high on the surface,
It is almost 100% and continuously decreases toward the inside. Therefore, there is no discontinuous interface between the surface-treated layer and the metal article base material, which is seen in plating or coating treatment, and the surface layer does not peel off due to abrasion, impact, heating or the like. Further, the properties such as abrasion resistance and hardness of the metal article base material can be maintained.

The material of the metal article used in the present invention is a pure metal or an alloy material, and is particularly effective for a steel material. As the steel material used, for example, S1
Case hardening steel such as 5C, structural steel such as S45C, SUP1
0 etc. spring steel, SUJ2 etc. bearing steel, SACM1 etc. nitrided steel, SKD6 etc. hot working tool steel, SKD
Examples include cold working tool steels such as No. 11, high speed steels such as SKH51, heat resistant steels such as SUS310S, and corrosion resistant acid resistant steels such as SUS410.

In the production of the metal article of the present invention, any known ion plating method can be used. The ion plating method is a method of evaporating a metal, ionizing the evaporated metal, and further accelerating the ionized metal molecule by an electric field in a reactive gas atmosphere to drive the metal surface onto the surface of the article.

To vaporize the metal, there are methods such as resistance heating and electron gun heating. Ionization of the evaporated metal may be performed by any of known methods such as cathode arc discharge, glow discharge, high frequency discharge, a method using an ionization electrode, and a hollow cathode method. Among these, the cathodic arc discharge type ion plating method simultaneously evaporates and ionizes the metal, and has a higher metal ionization efficiency than other methods. In other methods, since the metal elements constituting the cathode are not completely ionized, vapors of these metals cover the surface of the metal article to form a layer, which makes it difficult to disperse them deep inside the article. Although there is a problem, this does not occur in the cathodic arc discharge type ion plating method, that is, they are easily dispersed deep inside the article, and the entire surface of the metal article is covered with the ionized metal so that the metal article is covered. 0.5μ from the surface of
Under appropriate conditions such that the metal is dispersed to a depth of m or more, the concentrations of these metals are almost 100% and the corrosion resistance is improved, which is optimal for the practice of the present invention.

In the cathode arc discharge type ion plating method, the metal element constituting the metal cathode is vaporized and ionized under a vacuum of 10 ⁻³ Torr or less. The voltage (bias voltage) applied to the metal article to accelerate the ionized metal is preferably 500 to 2000V, and
The optimum value is 00 to 1500V. This is because if the voltage applied to the metal article is less than 500 V, the kinetic energy of the ionized metal is not sufficient and the implantation effect on the surface of the metal article becomes small, and if it exceeds 2000 V, the kinetic energy of the ionized metal increases. This is because the probability of spattering the surface of the metal article and damaging it increases.

A pure metal or an alloy composed of two or more kinds is used as the cathode. A plurality of these metal sources may be used at the same time, in which case a plurality of cathodes having different compositions may be used at the same time. Especially Al
Is preferable as a cathode component because it has an effect of improving oxidation resistance, but since the cathode itself heats up, if arc discharge is performed by using Al alone as the cathode, only melt dispersion occurs and discharge is not stable, Since it is difficult to use alone, it is preferable to use it as an alloy with other elements.

[0015]

【Example】

Example 1 Size 17 × 17 × 2 mm, Vickers hardness Hv = 85
The metal article of the present invention was manufactured by using a plate material of SKH51 steel of No. 0 as a base material and using a cathode arc type ion plating apparatus equipped with a Ti cathode. After setting the sheet at a predetermined position of the apparatus the reaction vessel, the reaction vessel 10 ^-5
The plate was evacuated to Torr and a bias voltage of 1000 V was applied to the plate material to cause arc discharge from the Ti cathode. At this time, the arc discharge current was 60A. This arc discharge was continued for 5 minutes while monitoring the surface temperature of the plate material with an infrared radiation thermometer to vaporize and ionize the metal Ti. During arc discharge, a rise in the plate surface temperature was recognized up to 450 ° C.

When the plate material was taken out after being cooled in a reaction vessel under vacuum, the appearance had metallic luster and the Vickers hardness was Hv = 750. This plate material is subjected to Ti in the depth direction from the plate surface by SIMS (secondary ion mass spectrometer).
Was measured. After starting SIMS sputtering 4
Ti of a certain value or more was continuously detected for 0 minutes, and it was confirmed that Ti was present while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.5 μm or more. The depth in which Ti was dispersed was determined from the correspondence between the SIMS sputtering time and the depth of the sputter trace of the sample at that time measured with a stylus type surface roughness meter.

Next, the plate material irradiated with Ti ions was masked with tape except the surface irradiated with Ti ions, and 10%, 2
The corrosion resistance was evaluated by immersing in a hydrochloric acid solution at 0 ° C. for 50 hours. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 2 Z was prepared in the same manner as in Example 1 except that the cathode was changed to Zr.
A plate material irradiated with r ions was produced. When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 720. The Zr distribution of the plate material was measured in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer). Zr of a certain value or more was continuously detected for 40 minutes after the start of SIMS sputtering, and it was confirmed that the Zr was present while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.6 μm or more. Next, the plate material irradiated with Zr ions was masked with a tape except the surface irradiated with Zr ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 3 H was produced in the same manner as in Example 1 except that the cathode was changed to Hf.
A plate material irradiated with f ions was produced. When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 780. The Hf distribution of this plate material was measured in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer). After the start of SIMS sputtering, Hf of a certain value or more was continuously detected for 40 minutes, and it was confirmed that the Hf existed while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.6 μm or more. Next, the plate material irradiated with Hf ions was masked with a tape except the surface irradiated with Hf ions, and immersed in a hydrochloric acid solution at 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 4 A plate material irradiated with V ions was produced in the same manner as in Example 1 except that the cathode was changed to V. When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 770. The distribution of V was measured in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer). V of a certain value or more was continuously detected for 40 minutes after the start of SIMS sputtering, and it was confirmed that the V was present while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.6 μm or more. Next, the plate material irradiated with V ions was masked with a tape except for the V ion irradiation surface, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 5 N was produced in the same manner as in Example 1 except that the cathode was changed to Nb.
A plate material irradiated with b ions was produced. When the plate material was taken out after cooling in a reaction vessel under vacuum, the appearance had metallic luster and the Vickers hardness was Hv = 710. The Nb distribution of the plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). It was confirmed that Nb of a certain value or more was continuously detected for 40 minutes after the start of SIMS sputtering, and that it was present while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.5 μm or more. Next, the plate material irradiated with Nb ions was masked with a tape except for the surface irradiated with Nb ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 6 T was produced in the same manner as in Example 1 except that the cathode was changed to Ta.
A plate material irradiated with a ions was produced. When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 750. The distribution of Ta was measured in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer). Ta of a certain value or more was continuously detected for 40 minutes after the start of SIMS sputtering, and it was confirmed that Ta was present while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.6 μm or more. Next, the plate material irradiated with Ta ions was masked with tape except for the Ta ion irradiation surface, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Comparative Example 1 A plate material irradiated with Ti ions was prepared in the same manner as in Example 1 except that the bias voltage was 200 V, and the distribution of Ti in the depth direction from the surface of the plate material was measured by SIMS. A layer of metallic Ti was formed from the surface to a depth of 0.2 μm, and Ti implanted by Ti ion irradiation was detected only to a depth of 0.4 μm from the surface of the plate material.
When the corrosion resistance was investigated by the same method as in Example 1, the substrate after immersion lost the metallic luster and was discolored.

Comparative Example 2 A plate material irradiated with Ti ions was manufactured in the same manner as in Example 1 except that the bias voltage was set to 2200 V, and the surface of the plate material was damaged and damaged.

Example 7 Size 17 × 17 × 2 mm, Vickers hardness Hv = 85
A metal article of the present invention was manufactured by using a cathodic arc type ion plating apparatus equipped with a No. 0 SKH51 steel plate as a base material and having a Cr cathode and a Ti cathode. After setting the plate at a predetermined position in the reaction container of the device,
Evacuate the inside of the reaction vessel to 10 ^-5 Torr,
Applying a bias voltage of 000V, Cr cathode and T
An arc discharge was generated from the i cathode. At this time Ti
The arc discharge currents of the cathode and the Cr cathode were both 60A. This arc discharge was continued for 5 minutes while monitoring the surface temperature of the plate material with an infrared radiation thermometer
And Ti were vaporized and ionized. Maximum 4 during arc discharge
An increase in the plate surface temperature was recognized up to 50 ° C.

When the plate material was taken out after being cooled under a vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 750. This plate material was subjected to Cr in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer).
And Ti distribution was measured. Cr and Ti above a certain value are continuously detected for 40 minutes after the start of SIMS sputtering, and Cr and Ti in a concentration clearly higher than the Cr concentration contained in the base metal SKH51 steel are 0.5 μ from the plate surface.
It was confirmed that the carbon dioxide was present while monotonically decreasing the concentration to a depth of m or more.

Next, the plate material irradiated with Cr and Ti ions was masked with a tape except the surface irradiated with Cr and Ti ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 8 A plate material irradiated with Cr and Zr ions was prepared in the same manner as in Example 7 except that the cathode was changed to Cr and Zr.
When the plate material was taken out after being cooled under a vacuum in the reaction vessel, the appearance had a metallic luster and the Vickers hardness was Hv = 7.
It was 80. The distribution of Cr and Zr of this plate material was measured in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer). 40 after the start of SIMS sputtering
Cr and Zr of a certain value or more are continuously detected for a minute, and the concentration of Cr and Zr clearly higher than the Cr concentration contained in the base metal SKH51 steel monotonically increases from the plate surface to a depth of 0.5 μm or more. It was confirmed that it exists while decreasing. Next, the plate material irradiated with Cr and Zr ions was masked with a tape except the surface irradiated with Cr and Zr ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 9 A plate material irradiated with Cr and Hf ions was prepared in the same manner as in Example 7 except that the cathode was changed to Cr and Hf.
When the plate material was taken out after being cooled under a vacuum in the reaction vessel, the appearance had a metallic luster and the Vickers hardness was Hv = 7.
It was 30. The distribution of Cr and Hf of this plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). 40 after the start of SIMS sputtering
Cr and Hf of a certain value or more are continuously detected for a minute, and the concentration of Cr and Hf clearly higher than the concentration of Cr contained in the base metal SKH51 steel monotonically increases from the plate surface to a depth of 0.6 μm or more. It was confirmed that it exists while decreasing. Next, the plate material irradiated with Cr and Hf ions was masked with a tape except the surface irradiated with Cr and Hf ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 10 A plate material irradiated with Cr and V ions was prepared in the same manner as in Example 7 except that the cathode was changed to Cr and V. When the plate material was taken out after cooling in a reaction vessel under vacuum, the appearance had metallic luster and the Vickers hardness was Hv = 790. The distribution of Cr and V was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). Cr and V above a certain level are continuously detected for 40 minutes after the start of SIMS sputtering, and the base metal SKH
51 Cr with a clearly higher concentration than that contained in steel
It was confirmed that V and V existed while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.5 μm or more.
Next, the plate material irradiated with Cr and V ions was masked with tape except the surface irradiated with Cr and V ions, and 10%, 2
The corrosion resistance was evaluated by immersing in a hydrochloric acid solution at 0 ° C. for 50 hours. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 11 A plate material irradiated with Cr and Nb ions was prepared in the same manner as in Example 7 except that the cathode was changed to Cr and Nb.
When the plate material was taken out after being cooled under a vacuum in the reaction vessel, the appearance had a metallic luster and the Vickers hardness was Hv = 7.
It was 30. The distribution of Cr and Nb of this plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). 40 after the start of SIMS sputtering
Cr and Nb above a certain level are continuously detected for a minute, and the concentration of Cr and Nb clearly higher than the Cr concentration contained in the base metal SKH51 steel monotonically increases from the plate surface to a depth of 0.6 μm or more. It was confirmed that it exists while decreasing. Next, the plate material irradiated with Cr and Nb ions was masked with a tape except for the Cr and Nb ion irradiation surface, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 12 A plate material irradiated with Cr and Ta ions was prepared in the same manner as in Example 7 except that the cathode was changed to Cr and Ta.
When the plate material was taken out after being cooled under a vacuum in the reaction vessel, the appearance had a metallic luster and the Vickers hardness was Hv = 7.
It was 70. The distribution of Cr and Ta was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). 40 after the start of SIMS sputtering
Cr and Ta above a certain value were continuously detected for a minute, and the concentration of Cr and Ta clearly higher than the Cr concentration contained in the base metal SKH51 steel monotonically increased to a depth of 0.5 μm or more from the plate surface. It was confirmed that it exists while decreasing. Next, the plate material irradiated with Cr and Ta ions was masked with a tape except the surface irradiated with Cr and Ta ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Comparative Example 3 A plate material irradiated with Cr and Ti ions was prepared in the same manner as in Example 7 except that the bias voltage was 200 V.
When the distribution of Cr and Ti was measured from the surface of the plate material in the depth direction by MS, a layer of metallic Cr and Ti was formed from the surface of the plate material to a depth of 0.2 μm, and Cr and Ti were implanted by Cr and Ti ion irradiation Was detected only up to a depth of 0.4 μm from the surface of the plate material. When the corrosion resistance was investigated by the same method as in Example 1, the substrate after immersion lost the metallic luster and was discolored.

Comparative Example 4 A plate material irradiated with Cr and Ti ions was prepared in the same manner as in Example 7 except that the bias voltage was set to 2200 V. The surface of the plate material was damaged and damaged.

Example 13 Size 17 × 17 × 2 mm, Vickers hardness Hv = 85
The metal article of the present invention was manufactured by using a cathodic arc type ion plating apparatus having a No. 0 SKH51 steel plate as a base material and equipped with a TiAl alloy cathode (Al content is 50 atomic%). After the plate material is set at a predetermined position in the reaction vessel of the apparatus, the inside of the reaction vessel is evacuated to 10 ^-5 Torr, a bias voltage of 1000 V is applied to the plate material, and T
Arc discharge was generated from the iAl alloy cathode. At this time, the arc discharge current of the TiAl alloy cathode was 60A. While monitoring the surface temperature of the plate material with an infrared radiation thermometer, this arc discharge was continued for 5 minutes to obtain metallic Al and Ti.
Was evaporated and ionized. During arc discharge, a rise in the plate surface temperature was recognized up to 450 ° C.

When the plate material was taken out after being cooled under a vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 770. This plate material was Al-treated in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer).
And Ti distribution was measured. Al and Ti above a certain value were continuously detected for 40 minutes after the start of SIMS sputtering, and it was confirmed that Al and Ti existed while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.5 μm or more. It was

Next, the plate material irradiated with Al and Ti ions was masked with a tape except the surface irradiated with Al and Ti ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate the corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 14 A plate material irradiated with Cr and Al ions was prepared in the same manner as in Example 13 except that the cathode was changed to a CrAl alloy (Al content is 50 atomic%). When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 760. The distribution of Al and Cr of this plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). SIM
Al and Cr of a certain value or more were continuously detected for 40 minutes after the start of S sputtering, and Cr and Al of a concentration clearly higher than the V concentration contained in the base metal SKH51 steel were 0.5 μm or more from the plate surface. It was confirmed that the monolayer was present with a monotonically decreasing concentration up to the depth. Next, the plate material irradiated with Al and Cr ions was masked with a tape except the surface irradiated with Al and Cr ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 15 A plate material irradiated with Al and Zr ions was prepared in the same manner as in Example 13 except that the cathode was changed to ZrAl alloy (Al content was 55 atomic%). When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 730. The distribution of Al and Zr of this plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). SIM
Al and Zr above a certain value were continuously detected for 40 minutes after the start of S sputtering, and it was confirmed that Al and Zr existed monotonically decreasing the concentration from the surface of the plate material to a depth of 0.6 μm or more. It was Next, the plate material irradiated with Al and Zr ions was masked with a tape except the surface irradiated with Al and Zr ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 16 A plate material irradiated with Al and Hf ions was produced in the same manner as in Example 13 except that the cathode was changed to the HfAl alloy (Al content was 55 atomic%). When the plate material was taken out after cooling in a reaction vessel under vacuum, the appearance had metallic luster and the Vickers hardness was Hv = 790. The distribution of Al and Hf of this plate material was measured in the depth direction from the surface of the plate material by SIMS (secondary ion mass spectrometer). SIM
Al and Hf above a certain value were continuously detected for 40 minutes after the start of S sputtering, and it was confirmed that Al and Hf existed while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.6 μm or more. It was Next, the plate material irradiated with Al and Hf ions was masked with a tape except the surface irradiated with Al and Hf ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 17 A plate material irradiated with Al and V ions was prepared in the same manner as in Example 13 except that the cathode was changed to AlV alloy (Al content is 50 atomic%). When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 730. SI this plate material
The distribution of Al and V was measured in the depth direction from the surface of the plate material by MS (secondary ion mass spectrometer). Al and V of a certain value or more were continuously detected for 40 minutes after the start of SIMS sputtering, and V and Al having a concentration clearly higher than the V concentration contained in the base metal SKH51 steel was 0.5 from the plate surface.
It was confirmed that the particles were present while monotonically decreasing the concentration to a depth of μm or more. Next, the plate material irradiated with Al and V ions was masked with a tape except the surface irradiated with Al and V ions, and immersed in a hydrochloric acid solution at 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 18 A plate material irradiated with Al and Nb ions was prepared in the same manner as in Example 13 except that the cathode was changed to NbAl alloy (Al content is 50 atomic%). When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 750. The distribution of Al and Nb of this plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). SIM
Al and Nb above a certain value were continuously detected for 40 minutes after the start of S sputtering, and it was confirmed that Al and Nb existed while monotonously decreasing the concentration from the surface of the plate material to a depth of 0.5 μm or more. It was Next, the plate material irradiated with Al and Nb ions was masked with a tape except the surface irradiated with Al and Nb ions, and immersed in a hydrochloric acid solution at 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Example 19 A plate material irradiated with Al and Ta ions was prepared in the same manner as in Example 13 except that the cathode was changed to a TaAl alloy (Al content was 55 atomic%). When the plate material was taken out after being cooled under vacuum in the reaction vessel, the appearance had metallic luster and the Vickers hardness was Hv = 780. The distribution of Al and Ta of this plate material was measured in the depth direction from the surface of the plate material by SIMS (Secondary Ion Mass Spectrometer). SIM
It was confirmed that Al and Ta above a certain value were continuously detected for 40 minutes after the start of S sputtering, and Al and Ta existed while monotonically decreasing the concentration from the surface of the plate material to a depth of 0.5 μm or more. It was Next, the plate material irradiated with Al and Ta ions was masked with a tape except for the surface irradiated with Al and Ta ions, and immersed in a hydrochloric acid solution of 10% and 20 ° C. for 50 hours to evaluate corrosion resistance. No change was observed in the appearance of the substrate after immersion, and the metallic luster was maintained.

Comparative Example 5 A plate material irradiated with Al and Ti ions was prepared in the same manner as in Example 13 except that the bias voltage was set to 200V.
When the distribution of Al and Ti was measured from the surface of the plate material in the depth direction by IMS, a layer of metal Al and Ti was formed from the surface of the plate material to a depth of 0.2 μm, and Al and Ti were implanted by Al and Ti ion irradiation. Was detected only up to a depth of 0.4 μm from the surface of the plate material. When the corrosion resistance was investigated by the same method as in Example 1, the substrate after immersion lost the metallic luster and was discolored.

Comparative Example 6 A plate material irradiated with Al and Ti ions was prepared in the same manner as in Example 13 except that the bias voltage was set to 2200 V. The surface of the plate material was damaged and damaged.

[0046]

According to the present invention, a novel corrosion resistant metal article having significantly improved corrosion resistance and a method for producing the same are obtained.

Claims (6)

[Claims] 1. A corrosion-resistant metal in which at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb and Ta is dispersed in a decreasing concentration from the surface of a metal article to a depth of 0.5 μm or more. Goods. 2. A metal article is irradiated with ions of the metal by using a cathode of at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb and Ta on the surface of the metal article by an ion plating method. The method for producing a corrosion-resistant metal article according to claim 1, wherein 3. At least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb or Ta and Cr are dispersed while decreasing the concentration from the surface of the metal article to a depth of 0.5 μm or more. Corrosion resistant metal articles. 4. An ion plating method is used to deposit at least one metal cathode selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta on the surface of a metal article, and a Cr cathode is used to generate ions of these metals. The method for producing a corrosion-resistant metal article according to claim 3, wherein the metal article is irradiated. 5. Ti, Cr, Zr, Hf, V, Nb or Ta from the surface of the metal article to a depth of 0.5 μm or more.
A corrosion-resistant metal article in which at least one metal selected from the group consisting of and Al are dispersed with decreasing concentration. 6. Ti, Cr, Zr, Hf, V, Nb or T on the surface of a metal article by an ion plating method.
at least one metal selected from the group consisting of a and Al
6. The method for producing a corrosion-resistant metal article according to claim 5, wherein the metal article is irradiated with ions of these metals by using a cathode of an alloy of.