JPS5943882A - Corrosion and wear resistant amorphous alloy and its manufacture - Google Patents

Abstract

PURPOSE:To improve the corrosion and wear resistances of an amorphous alloy, by forming an oxide film on the surface of the alloy by oxidation treatment in a specified high temp. and high pressure atmosphere. CONSTITUTION:An alloy having a specified composition contg. Fe, Co and other metals or nonmetals is very rapidly cooled to manufacture an amorphous alloy. The amorphous alloy is subjected to oxidation treatment in an atmosphere at 150-500 deg.C high temp. under 40-200atm. high pressure to form crystalline oxide of 0.01-5mum grain size on the surface of the amorphous alloy as an oxide film of 0.05-5mum thickness. The corrosion and wear resistances of the amorphous alloy are remarkably improved by the oxide film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an amorphous alloy and a method for producing the same, and more particularly to an amorphous alloy with improved corrosion resistance and wear resistance and a method for producing the same.

[Technical background of the invention and its problems]

Recently, amorphous alloys produced using the liquid quenching method have excellent magnetic properties and mechanical properties! ↓, tftft It is attracting attention as a new metal material with sexual properties. In particular, its use as a magnetic material is expected to be significant.

Since magnetic materials are exposed to various atmospheres, their corrosion resistance, such as corrosion resistance under high temperature, high humidity conditions, or basic atmospheres, is of important significance.

It is known that amorphous alloys exhibit excellent corrosion resistance when they contain cr-pt composites, but other amorphous alloys are generally active and do not have good corrosion resistance. Containing P lowers the crystallization temperature, tends to cause segregation under high-temperature conditions, and has poor thermal stability, so it is not preferable. Therefore, for good thermal stability, CrP
It is not possible to use products that contain a combination of .

A decrease in corrosion resistance is inevitable. It is also known that although amorphous alloys are very hard, they generally have poor wear resistance. For example, the amount of wear caused by magnetic tape is much greater than that of ferrite, which has a hardness of approximately V2.

Conventionally, when an amorphous alloy is used as a magnetic material, the amorphous alloy is used to form an insulating layer.
A method is known in which an oxide film is formed on the surface by immersing the material in an oxidizing bath at the following temperature or by using an anodic oxidation method (Japanese Patent Publication No. 15iI 1984-46539). However, the oxide film formed by this method does not contain crystalline +4 oxide. Furthermore, according to the research of the present inventors, in the method of forming an oxide film using such a method, the oxide film is thin and in an amorphous state, and the bond between the oxide film 11Q and the amorphous alloy is reduced. The disadvantage was that sufficient IAij corrosion resistance and abrasion resistance could not be obtained due to the low strength.

[Purpose of the invention]

The present invention eliminates the drawbacks of the conventional amorphous alloy and its manufacturing method described above, and aims to provide an amorphous alloy having excellent corrosion resistance and surface wear resistance, and a manufacturing method thereof. .

[Length of invention]

As a result of extensive research in view of the above points, the present inventors have discovered that the purpose of the present invention is to carry out the oxidation treatment of an amorphous alloy at We have discovered what can be achieved and have completed the present invention.

Specifically, the amorphous alloy Fi of the present invention is characterized in that it is an amorphous alloy having an oxide film containing a crystalline oxide on its surface.

The amorphous alloy of the present invention can be manufactured as follows.

As the amorphous alloy, one having the following composition is used.

That is, when expressed in atomic units, the following formula: (Col-x-yFexMy)zGtoo-Z
or ((:a 1-x-y FexMy ) uT
xoo-u (where MitTi, V, Cr, Mn, N
i, Cu+Zr+Nb, Mo, Ru, Rh, Pd, A
G represents at least one element selected from the group consisting of g+H, f, Ta+W+Retpt, Au, Y, and rare earth elements; G is B;

Represents at least one element selected from the group consisting of c + si + p and Qe; T is 'I'' i + Z r
+IIftV, Nb, TalWIMOIY and at least one element selected from the group consisting of rare earth elements; X r yT Z and U each satisfy 0≦X≦1
．． 0≦y≦0.2.65≦2≦90 and 85≦U≦95
represents a number that satisfies the relationship. ) is used.

One of the requirements for an amorphous alloy to have excellent corrosion resistance and wear resistance is to have an oxide film containing a crystalline oxide on the surface of the amorphous alloy. In order to manufacture the alloy, it is necessary to perform an oxidation treatment at high temperature and under high pressure.

It is desirable that the temperature at this time be as high as possible to form crystalline oxides in a short time, but if the temperature is too high, the problem of crystallization of the amorphous alloy will occur, so crystallization will not occur. It is desirable that the temperature is below the temperature, specifically 150 to 50
It is preferably 0 C, and more preferably 250 to 400 C. As a means of increasing the pressure, either gas or liquid may be used, but the pressure obtained is 40 to 2
00 atm, preferably 60 to 1o.

More preferably, it is atmospheric pressure. The processing time varies depending on the processing temperature and processing pressure, but is generally 0.5 to 10
It is preferably 0 hours, particularly 5 to 24 hours.

A common and easy method is to process in high-temperature steam, such as in an autoclave.

The oxide film formed and the crystalline oxide contained therein vary depending on the main component of the amorphous alloy, but for example, in an amorphous alloy whose main component is Fe, For example, Fe3O4Iγ-Fe2O3 etc., and for amorphous alloys whose main component is CO, Coo or Co
30. are often formed, but these vary depending on the manufacturing conditions.

In addition, in the case of an amorphous alloy containing both Co and Fe, a monoclonal product of Co-1i'e yarn such as CoFe2O4 is formed.

No matter where any of the above-mentioned crystalline oxides are formed, it is found that the eating and abrasion properties are significantly improved. This was confirmed from the results of the i-eating test and the rubbing test 1.

The obtained amorphous 1'' alloy has an oxide film thickness of
Those with a diameter of 0.05 to 5 μm are considered feminine and 0.1
More preferably, the thickness is 1 μm. This thickness is 0.0
When it is less than 5 ttnt, the growth of crystalline oxide is small.

If the thickness exceeds 5 μm, the proportion of the amorphous alloy layer decreases, which is not preferred in practice, without improving corrosion resistance and wear resistance.

The size of the crystalline oxide contained in the oxide film is 0
．． It is preferably 0.1 to 5 μm, and 0.1 to 2 μm.
More preferably, it is m. This size is 0.01μ
If it is less than m, corrosion resistance and wear resistance will not be improved much, and if it exceeds 5 μm, a part of the internal amorphous alloy phase below the oxide film layer will crystallize, making it impossible to obtain sufficient mechanical strength. .

〔Effect of the invention〕

The amorphous alloy obtained according to the invention has excellent corrosion and wear resistance.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Using a single roll method, a (Fe0
．． A 95CrO,05)85S 13B12 amorphous alloy was prepared. A length of about 1 m was cut out from this, and it was placed in an autoclave at 400 C and 105 atm for 12 hours. The surface of the sample taken out was black. When the surface condition was observed using a scanning electron microscope (SEM), as shown in Figure 1, approximately 1
Fine crystalline oxides of μm size were precipitated. When this crystalline oxide was identified using X-rays, it was found to be Fe3O4.

A wrapping tape was run at a speed of 4.75 cm/sec to measure wear on the amorphous alloy whose surface had been oxidized and the amorphous alloy with the same composition that had not been oxidized. , compared the two.

The amount of wear after 100 hours was 2 μm for the autoclaved sample and 20 μm for the non-autoclaved sample, indicating that the surface 1 abrasion properties of the former were significantly improved.

Example 2 Using a single roll method, a (Coo
9oFeo, o6cro, o4)yysiIoB13
An amorphous alloy was produced. A length of 5m was cut from this and was placed in an autoclave at 300C and 80atm for 2 hours.
I dressed up for 4 hours. The surface of the sample taken out was black. When the surface condition was observed using SEM, it was found that approximately 0
．． A fine crystalline oxide of 5 μm was precipitated. When this crystalline oxide was identified using X-rays, it was found that CO3O4 was the main component, and other crystalline oxides that were not identical were also present.

CO-
A VTR tape coated with γFe 203 was run at a speed of 7 ml/sec, wear 111 was measured, and the two were compared.

The amount of wear after 100 hours was 3 μm for the autoclaved sample and 45 μm for the non-autoclaved sample, indicating that the former had significantly improved wear resistance.

Example 3 Using a single roll method, a (C00
,91FeO,Off Mo,03)75S'
10 B15 amorphous alloy (M: MO, Nb + Ta
) was created. Cut out 5 m long pieces from this and use a sciauto crepe to make 300 t:', 2 at 80 atm.
I dressed up for 4 hours. The surfaces of all the samples taken were black. When the surface condition was observed using SEM, it was found that crystalline oxides of about 0.5 μm were finely precipitated.

FIG. 2 schematically shows each of the autoclaved samples described above. t i, I,: fa
Polarization resistance IIj in water using c+ - total measurement 5Q +/
＠ No autocrane treatment・Rinnor and Sen'
< L 1t-0 autoclave treatment, l/
'L ``Dannol tj) min 4M JiL anti tJ, M
: Alo, Nb.

'fn no valley' 7buA i7? IL, -r knee 4:trA:h, 25. C4, ZOQ.

20Ω and 23. - Rehabilitation auto crane place!
l sandals min 4i <lit; anti-kl-M:
Mo, Nb, Ta no Iichi, J" it &n
r=J L'T: 41 m (+ (+ (lΩ
't#JJ-(llb P, L, E tetraphagous /
E. A similar experiment was conducted with 0. I N -lieノ and (1
, I N -NaCJ, but A-
Corrosion resistance after crepe treatment is unresolved.
'J! The corrosion resistance is about 100 times higher than that of 4'J.

・As shown in the practical example, U114♂ between Kien and h
The alloy has remarkable corrosion resistance and 1illll wear resistance,
However, it is a highly practical amorphous alloy.

[Brief explanation of drawings]

1A1 [A21 is a photograph taken by magnifying 4000 times of the surface of the amorphous alloy related to unexploded IJ14. Figure 2 is a schematic diagram of the positional electrolyte +n 16°, where rj,, + has a four-feeding habit. A...Bote/Schostat. B...Electrometer, C...11glft! 1 generator, D... recorder. E... Auxiliary electrode, F... Sample, l... Electrolytic cell, 2... Corrosion static, 3... Verification 11 as the pole. ): 1°511・,jl 21st・4

Claims (1)

[Scope of Claims] 1. A corrosion-resistant, surface-wearing, amorphous alloy characterized by having an oxide film containing a crystalline oxide on its surface. 2. The corrosion-resistant and wear-resistant amorphous alloy according to claim 1, wherein the crystalline oxide has a size of 0.01 to 5 μm. 3. The corrosion-resistant and abrasion-resistant amorphous alloy according to claim 1 or 2, wherein the oxide film has a thickness of 0.05 to 5 ttm. 4. In a method for producing an amorphous alloy in which an oxidation treatment is performed on an amorphous alloy to form an oxide film on the surface of the amorphous alloy, the oxidation treatment of the amorphous alloy is carried out at high temperature and under high pressure. A manufacturing method for amorphous alloys with characteristic corrosion and wear resistance. 5 Oxidation treatment conditions are 150-500C, 40-200C
The manufacturing method according to claim 4, wherein the pressure is atmospheric pressure.