JPH0611909B2 - Corrosion resistant coated composite material and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a corrosion resistant coated composite material and a method for producing the same.

[Prior Art and Problems] Valve metals represented by Ta metal are generally known to have excellent corrosion resistance. Further, a valve metal-iron group metal amorphous alloy based on Ni-Ta is relatively corrosive even in an environment with severe corrosiveness such as boiling concentrated hydrochloric acid or boiling concentrated nitric acid in which corrosion is advanced in a general corrosion resistant metal material. It has been disclosed in JP-A-61-210143 that it has good corrosion resistance.

However, since the above-mentioned amorphous alloy is usually produced by the liquid quenching method, it is possible to use thin ribbons, thin wires,
Since it is restricted by the shape of powder or the like, it is not always satisfactory as a corrosion resistant material that can be used in various shapes.

On the other hand, forming an amorphous film on a metal substrate by a film forming method has been studied. For example, there are various ion plating methods, various sputter vapor deposition methods, ion beam mixing methods, and the like. However, in the case of forming these films, it is difficult to eliminate defects such as pinholes and minute cracks generated in the film, and the corrosive liquid reaches the underlying metal base material through these defects to form a film. There has been a problem that an undermining phenomenon or the like in which the corrosion of the interface of the base material progresses progresses.

From the above problems, there is a demand for more efficient film formation, ensuring high-quality film quality, and forming an interface between a base material and a film having excellent corrosion resistance.

The present invention has been made to solve the above-mentioned conventional problems, and is a nitrogen-containing T that has excellent corrosion resistance in a harsh environment.
a Corrosion resistant coating composite material in which two or more kinds selected from an amorphous layer and an amorphous alloy layer having a different composition (iron group metal-valve metal) are laminated and the laminated film is adhered and efficiently to a substrate. It is an object of the present invention to provide a method capable of forming a corrosion resistant coating composite material by forming a film.

[Means for Solving the Problems] The corrosion-resistant coating composite material according to the present invention is selected from a nitrogen-containing Ta amorphous layer and a different composition (iron group metal-valve metal) amorphous alloy layer on the surface of a metal substrate.
One or more kinds are laminated and coated.

The metal base material may be any metal as long as it is a corrosion resistant metal, and for example, a Ni-base alloy, a Ti-base alloy, SUS or the like can be used.

Examples of the iron group metal include Fe, Ni, Co and the like.

Examples of the valve metal include Ta, Ti, Zr,
Nb and the like can be mentioned, and it is particularly preferable to use Ta alone or Ta and Ti, Zr, and Nb in combination.

The above different (iron group metal-valve metal) amorphous alloy layer contains nitrogen (iron group metal-valve metal)
Examples thereof include an amorphous alloy layer and an amorphous alloy layer containing no nitrogen (iron group metal-valve metal).

The corrosion-resistant coated composite material according to the present invention is manufactured by the following method.

． The nitrogen-containing Ta amorphous layer and the composition are different depending on the step of depositing Ta on the surface of the metal base material in a nitrogen atmosphere and the step of depositing one or more iron group metals and one or more valve metals in a nitrogen atmosphere. Metal-valve metal)
Two or more kinds selected from amorphous alloy layers are laminated and coated to produce a corrosion-resistant coated composite material.

． Ion beam mixing step of irradiating nitrogen ions at the same time as Ta is deposited on the surface of a metal substrate, and irradiating nitrogen ions or inert gas ions at the same time as depositing at least one iron group metal and at least one valve metal The Ta-amorphous layer containing nitrogen and the amorphous alloy layer having a different composition (iron group metal-valve metal) are laminated and coated to produce a corrosion-resistant coated composite material.

Another corrosion-resistant coated composite material according to the present invention has a nitrogen-containing Ta amorphous layer on the surface of a metal substrate having a metal phase of at least one of an iron group metal and a valve metal formed on the surface layer and a different composition (iron group metal- (Valve metal) A layered coating of two or more selected from amorphous alloy layers.

Another corrosion resistant coated composite material according to the present invention is manufactured by the following method.

． At least one of an iron group metal and a valve metal is ion-implanted into the surface layer of the metal base material to form a metal phase, and then Ta is vapor-deposited on the surface of the base material in a nitrogen atmosphere. Corrosion-resistant coating composite by layer-coating two or more kinds selected from a nitrogen-containing Ta amorphous layer and an amorphous alloy film having a different composition (iron group metal-valve metal) by a step of depositing one or more kinds of valve metals in a nitrogen atmosphere Manufacture materials.

． An ion beam mixing step of ion-implanting at least one of an iron group metal and a valve metal into the surface layer of a metal base material to form a metal phase, and then performing Ta ion deposition on the surface of the base material and simultaneously irradiating nitrogen ions A nitrogen-containing Ta amorphous layer and a different composition (iron group metal-valve metal) are formed by an ion beam mixing process in which the above iron group metal and one or more kinds of valve metals are vapor-deposited and at the same time irradiation of nitrogen ions or inert gas ions is performed. ) Two or more kinds selected from amorphous alloy layers are laminated and coated to produce a corrosion resistant coated composite material.

In the above methods (1) to (3), as the vapor deposition means of the iron group metal and the valve metal, for example, an electron beam vapor deposition method, an ion beam sputter vapor deposition method using a target of the iron group metal or the valve metal can be adopted. In the case of the sputter deposition method, an Ar ion beam is usually used. However, although the sputtering rate is low due to the formation of the nitrogen-containing (iron group metal-valve metal) amorphous alloy film,
Using a nitrogen ion beam is also a good idea under some conditions.

In the above methods and, the (iron group metal-valve metal) amorphous alloy phase contains nitrogen.
In these methods, one or more iron group metals and
If the composition ratio of more than one kind of valve metal is suitable for amorphization, a predetermined amorphous (iron group metal-valve metal) alloy layer can be formed even if vapor deposition is performed in a vacuum atmosphere instead of a nitrogen atmosphere. Is possible.

In the above methods (1) and (2), when nitrogen ions are irradiated during deposition of one or more iron group metals and one or more valve metals, a nitrogen-containing (iron group metal-valve metal) amorphous alloy layer is formed, and inert gas ions are formed. Is irradiated, a nitrogen-free (ferrous metal-valve metal) amorphous alloy layer is formed.

[Operation] According to the present invention, a plurality of amorphous materials are formed by coating the surface of a metal substrate with at least two kinds selected from a nitrogen-containing Ta amorphous layer and an amorphous alloy layer having a different composition (iron group metal-valve metal). Due to the denseness and high corrosion resistance of the alloy layer, it is possible to obtain a composite material having excellent corrosion resistance in a harsh environment.

Further, by stacking a plurality of amorphous layers having high corrosion resistance, it is possible to prevent the progress of corrosion at the interface between the laminated film and the metal substrate due to defects such as pinholes and minute cracks in each amorphous layer. That is, the present inventors pay attention to the fact that pinholes and minute defects are generated in the amorphous layer depending on the component composition, and by stacking the amorphous layers having different component compositions, the amorphous layer having the same component composition is formed. In the unlikely event that a pinhole etc. occurs,
It is possible to prevent the growth of pinholes, etc. at the stacking interface and prevent the formation of pinholes, etc. that penetrate the entire stacked film and reach its surface. As a result, even if the corrosive liquid enters the pinhole, In order to prevent the corrosive liquid from reaching the metal base material as an underlayer, the inventors have found a corrosion resistant coating composite material that can prevent the progress of corrosion at the interface between the laminated film and the base material.

Further, the nitrogen-containing Ta amorphous layer and the composition differ depending on the step of depositing Ta on the surface of the metal substrate in a nitrogen atmosphere and the step of depositing one or more iron group metals and one or more valve metals in a nitrogen atmosphere. (Ferrous metal-Valve metal) By laminating and coating two or more kinds selected from amorphous alloy layers, it is possible to efficiently form a laminated film of an amorphous layer excellent in denseness and high corrosion resistance on a base material, which in turn leads to harshness. A composite material having excellent corrosion resistance under the environment can be manufactured.

Further, an ion beam mixing step of irradiating nitrogen ions at the same time as Ta is vapor-deposited on the surface of the metal substrate, and at least one iron group metal and one or more valve metals are vapor-deposited, and at the same time, nitrogen ions or inert gas ions By accelerating the ion beam accelerating voltage, current, by stacking and coating two or more kinds selected from a nitrogen-containing Ta amorphous layer and an amorphous alloy layer having a different composition (iron group metal-valve metal) by an irradiation ion beam mixing step. The sputter rate of the film formed can be controlled by changing the irradiation angle, etc., and the degree of mixing can be easily controlled.Therefore, each amorphous layer is densified to improve the corrosion resistance, the optimum interface structure is formed, and the substrate is formed. It is possible to improve the adhesion to the material.

On the other hand, Ni, which is a corrosion-resistant metal, is used as the base material of the composite material.
A base alloy, a Ti base alloy, a SUS material, etc. are used. When the base material made of these materials does not contain a composition component that compositionally forms a film, or when the content is small, a metal phase of at least one of an iron group metal and a valve metal is formed on the surface layer of the base material. As a result, the base material and a nitrogen-containing Ta amorphous layer or a film formed on the base material (iron group metal-valve metal)
The continuity of components with the amorphous alloy layer can be obtained, the adhesion of the laminated film to the base material can be improved, and the corrosion resistance at the interface between them can be improved.

The metal phase is formed on the surface layer of the base material by an ion implantation method of at least one of an iron group metal and a valve metal. In such an ion implantation method, the concentration, distribution, etc. of the metal phase can be arbitrarily controlled, and a gradient structure of the metal phase in the depth direction can be formed. The metal layer phase formed on the surface layer of the base material is preferably an amorphous phase, but even if it is crystalline, the effect is large and nitrogen may be contained. Therefore, by forming the above-mentioned laminated film after ion implantation of at least one of the iron group metal and the valve metal, the interfacial structure is modified by the metal phase formed in the surface layer, so that the corrosion resistance at the interface between the laminated film and the substrate is improved. Can be further improved. In particular, the adhesion is excellent due to the combination of the ion implantation of at least one of the iron group metal and the valve metal and the formation of the laminated film by the ion mixing method,
A composite material having better corrosion resistance can be obtained.

When forming the nitrogen-containing tantalum amorphous film,
Depending on the formation conditions, it may be observed by electron diffraction observation with a TEM or the like that an extremely fine crystalline phase is mixed during film formation. However, it is a well-known fact that the rapidly solidified microcrystalline stainless steel is a fine grain, so even if the grain boundary density, which is a crystal defect, is high, composition fluctuation such as segregation does not occur at the grain boundary part, and the amorphous Shows high corrosion resistance equivalent to that of phase.
Also in the present invention, it has been confirmed that the presence of the extremely fine crystalline phase does not hinder the high corrosion resistance of the film.

[Examples] Examples of the present invention will be described in detail below.

Example 1 First, pure iron (SPH) having a size of 30 × 30 × 2 mm was used as a base material.
C) A plate was prepared, one surface of which was mirror-polished, ultrasonically cleaned, dried, and then placed on a holder in a vacuum chamber equipped with ion irradiation and vapor deposition functions. Then, after evacuating the chamber to 5 × 10 ^-6 torr, Ar ions from the ion source were irradiated on the mirror surface of the pure iron plate for 5 minutes at an acceleration voltage of 5 kV for pretreatment for surface cleaning. gave.

Then, the pure iron plate on the holder is heated to 300 ° C., Ta is vapor-deposited on the surface of the pure iron plate at a rate of 3Å / sec by a single hearth electron beam evaporation method, and at the same time, nitrogen ions are extracted from the ion source to accelerate voltage. 33kV, ion current 16
The pure iron plate was irradiated with ions under the condition of mA to perform ion beam mixing, so that the pure iron plate had a nitrogen-containing T of 0.2 μm.
An amorphous layer was formed. Subsequently, Ta is subjected to single-hearth method electron beam evaporation and at the same time sputter evaporation is performed using a Ni target. At the same time, nitrogen is extracted from another ion source, acceleration voltage is 33 kV, and beam current is 16
Ion irradiation was performed under the condition of mA to form a 0.2 μm thick Ni-40 at% Ta amorphous layer on the amorphous layer. The sputtering conditions at this time were as follows: Ar ions were irradiated at an acceleration voltage of 3 kV and an ion current of 1.5 A, and the film formation rate was 2.7 A.
/ Sec. Such two kinds of film formation were alternately performed 5 times to form a laminated film having a total thickness of 2.0 μm on a pure iron plate to manufacture a composite material.

Comparative Example 1 After pretreating a pure iron plate in the same manner as in Example 1, the pure iron plate on the holder was heated to 300 ° C., and Ta was vapor-deposited at a rate of 3 Å / sec by a single hearth electron beam evaporation method. , Sputter deposition using Ni target (irradiation with Ar ions at accelerating voltage 3 kV, ion current 1.5 A) 2.7 A /
Ni vapor deposition is performed at a speed of sec, and at the same time, nitrogen ions are extracted from another ion source, acceleration voltage 33 kV, beam current 16 m.
Ion irradiation was performed under the condition of A and the thickness of Ni-40at was 2.0μm.
A% Ta amorphous film was formed on the pure iron plate to manufacture a composite material.

A ferroxil test (pinhole test JIS H8663 porosity test) was performed on the composite materials of Example 1 and Comparative Example 1. The result shows that the amorphous film of the composite material of Comparative Example 1 had a pinhole area ratio of 0.10, whereas the laminated film of the composite material of the present Example 1 in the amorphous state was pinhole-free, and the effect of lamination was obtained. Was confirmed.

Examples 2 to 10 A base material of a corrosion-resistant alloy (SUS304L, Hastelloy) having a size of 30 × 30 × 2 mm, which was subjected to the same pretreatment as in Example 1, was used as follows.
Nine kinds of composite materials were manufactured by forming various laminated films under the conditions shown in the table.

Comparative Examples 2 and 3 Pretreated in the same manner as in Example 1 and having dimensions of 30 × 30 × 2 mm
Two kinds of composite materials were manufactured by forming a nitrogen-containing amorphous alloy film on the SUS304L plate under the conditions shown in Table 1 below.

Thus, the composite materials of Examples 2 to 10 and Comparative Examples 2 and 3
Corrosion test was carried out by immersing the composite material of (1) in a 6N-HCl solution at 80 ° C. The results are also shown in Table 1 above.

[Effects of the Invention] As described in detail above, according to the present invention, a nitrogen-containing Ta amorphous layer and a different composition (iron group metal-
(Valve metal) By stacking two or more selected from amorphous alloy layers, it is possible to form a laminated film in an amorphous state with high corrosion resistance and no penetration pinholes in the film, which is excellent even in a severe corrosive environment. It is possible to provide a highly versatile corrosion-resistant coating composite material that has excellent corrosion resistance and is not restricted in shape, and a method for easily producing such a corrosion-resistant coating composite material.

Claims (6)

[Claims] 1. A corrosion-resistant coated composite material comprising a surface of a metal base material and two or more selected from a nitrogen-containing Ta amorphous layer and a nitrogen-containing (iron group metal-valve metal) amorphous alloy layer having a different composition. 2. A nitrogen-containing T is deposited by a step of depositing Ta on a surface of a metal substrate in a nitrogen atmosphere and a step of depositing at least one iron group metal and at least one valve metal in a nitrogen atmosphere.
2. The method for producing a corrosion-resistant coated composite material according to claim 1, wherein two or more kinds selected from an amorphous layer and an amorphous alloy layer having a different composition (iron group metal-valve metal) are laminated and coated. 3. An ion beam mixing process in which Ta is vapor-deposited on a surface of a metal substrate and at the same time nitrogen ion irradiation is performed, and at least one iron group metal and one or more valve metals are vapor-deposited, and at the same time nitrogen ions or an inert gas is deposited. 2. An ion beam mixing process of irradiating with gas ions, to laminate-coat two or more kinds selected from a nitrogen-containing Ta amorphous layer and an amorphous alloy layer having a different composition (iron group metal-valve metal). A method for producing the corrosion-resistant coated composite material as described. 4. A nitrogen-containing Ta amorphous layer or an amorphous alloy layer having a different composition (iron group metal-valve metal) on the surface of a metal substrate on which at least one metal phase of an iron group metal and a valve metal is formed on the surface layer. A corrosion-resistant coated composite material obtained by laminating and coating two or more of the above. 5. A step of depositing Ta in a nitrogen atmosphere after forming a metal phase by ion-implanting at least one of an iron group metal and a valve metal into the surface layer of a metal substrate, and at least one kind. Of at least two selected from a nitrogen-containing Ta amorphous layer and an amorphous alloy layer having a different composition (iron group metal-valve metal) by a step of depositing an iron group metal and one or more valve metals in a nitrogen atmosphere. The method for producing a corrosion-resistant coated composite material according to claim 4, wherein the composite material is corrosion-resistant. 6. An ion beam in which at least one of an iron group metal and a valve metal is ion-implanted into a surface layer of a metal base material to form a metal phase, and then Ta is vapor-deposited on the surface of the base material and at the same time, nitrogen ion irradiation is performed. The mixing step and the ion beam mixing step of depositing at least one iron-group metal and at least one valve metal and at the same time irradiating nitrogen ions or inert gas ions differ in the nitrogen-containing Ta amorphous layer and composition (iron. Metal-valve metal)
The method for producing a corrosion-resistant coated composite material according to claim 4, wherein two or more kinds selected from amorphous alloy layers are laminated and coated.