JP3313832B2 - High corrosion resistance and high strength amorphous copper alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a high-strength amorphous copper alloy having excellent corrosion resistance.

[0002]

2. Description of the Related Art Amorphous copper alloy has a tensile strength of about 500 MPa or more, excellent strength, and high hardness. Conventionally, as an amorphous copper alloy, one having a composition in which Ag and P or Ni and P are added as an amorphizing element is known.

[0003]

However, it has been found that a conventional amorphous copper alloy is liable to produce patina on the surface, similarly to a copper-based crystal alloy. Therefore, when an amorphous copper alloy is used in an environment where corrosion is likely to occur as a mechanical structure component requiring high strength, such as a spring material and a gasket material, the deterioration of the surface accompanying the corrosion causes problems such as deterioration of the strength and fatigue. .

Further, since any amorphous alloying element other than Ag significantly increases the electric resistance of copper, the surface becomes insulative due to the formation of patina, so that it is possible to apply the amorphous copper alloy to the use of conductive materials. Is almost gone.

[0005] Further, since the hardness of the conventional amorphous copper alloy is about Hv200, flaws and wear easily occur during use, and the appearance and performance are unstable.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the conventional difficulties in performance and to provide an amorphous copper alloy having particularly high strength and excellent corrosion resistance.

[0007]

DISCLOSURE OF THE INVENTION The copper alloy according to the present invention comprises:
General formula: Cu100-ab Aga Mb (where M is at least one element selected from Ce and misch metal,
a and b have a composition represented by a value on a line connecting points a to j in FIG. 1 or within a range surrounded by this line), and have an amorphous structure. Here, the above points a to j are expressed as follows in a coordinate system of a horizontal axis (Ag): a vertical axis (Ce and / or misch metal). a: 25 at%; 2.5 at% b: 55 at%; 2.5 at% c: 55 at%; 3.5 at% d: 65 at%; 3.5 at% e: 65 at%; 7.5 at% f: 55 at%; 7.5 at% g: 55 at%; 10.5 at% h: 35 at%; 10.5 at% i: 35 at%; 9.5 at% j : 25 atomic%; 9.5 atomic% Hereinafter, the composition and properties of the alloy of the present invention will be described.

[0008] Ag makes Cu amorphous by combining it with Ce and / or misch metal. Further, when compared with conventional P, Ce and / or misch metal do not cause deterioration of corrosion resistance and electric conductivity, and have a property of increasing hardness even with the same strength. If the content of these elements is out of the range shown in FIG. 1, part or all of the structure is crystallized, and a desired structure cannot be obtained. In particular, when the amount of these alloying elements is small, the strength and corrosion resistance are poor, and when the amount of the alloying elements is large, ductility and corrosion resistance are poor.

The raw material having the above-mentioned composition is prepared by a single roll method or a submerged spinning method for producing a normal amorphous alloy.
By cooling at a cooling rate of 2 / sec or more, an alloy having an amorphous structure can be obtained.

The typical characteristics of the alloy having the above composition are as follows: (a) a tensile strength of about 600 MPa or more in a rapidly solidified state;
(B) The foil strip is capable of 180 ° close-contact bending and has excellent toughness; (c) has little corrosion of greenish blue in a high-temperature and / or humid atmosphere, and has excellent corrosion resistance;
90 × 10 −6 Ω · cm; (e) Hardness is Hv = 250-3
The range is 30. Thus, this material has high strength, excellent corrosion resistance and moderate electrical conductivity. Hereinafter, the present invention will be described in more detail with reference to examples.

[0011]

EXAMPLE After weighing each metal raw material so as to have the composition shown in Table 1, it was subjected to high-frequency melting in a graphite crucible in an argon atmosphere and cast into a round bar having a diameter of 10 mm. The master alloy was set in the melting section 2 of the single roll quenching device shown in FIG.
High frequency melted. After that, it was set at the lower part of the melting part 2,
The molten metal is sprayed onto the copper roll 1 rotating at a peripheral speed of 20 m / sec to be rapidly solidified, and the thickness is 20 to 30 μm, the width is 2 mm,
A metal ribbon 3 having a length of 10 m was manufactured.

A test was performed on the amorphous ribbon prepared by the above-described method by the following method. (1) Structure: It was confirmed by X-ray diffraction whether it was an amorphous single phase, completely crystalline, or a crystal precipitated in an amorphous phase. (2) Tensile strength: An amorphous ribbon cut to a length of 500 mm was tested with a rheological tensile tester. (3) Corrosion resistance: An amorphous ribbon cut to a length of 500 mm in distilled water at room temperature was allowed to stand for 250 hours, and thereafter the surface of the ribbon was visually observed. Was regarded as good. (4) Electric resistance: measured by a four-terminal method. Table 1 shows the test results.

[0013]

[Table 1] Composition Tension strength Hardness Electric resistance Corrosion resistance (MPa) (Hv) (Ωcm) Invention 1 Cu57Ag40Ce3 amorphous 705 290 80 × 10-6 Good 2 Cu52Ag45Ce3 ↑ 675 276 30 ３3 Cu47Ag50Ce3 ↑ 630 285 20 ４4 Cu61Ag35Ce4 ↑ 660 299 90 ５5 Cu51Ag45Ce4 630 630 630 630 630 630 630 630 630 630 630 630 Cu50Ag45Ce5 ↑ 695 304 31 ８ 8 Cu45Ag50Ce5 ↑ 680 263 25 ↑ 9 Cu40Ag55Ce5 ↑ 680 287 21 ↑ 10 Cu54Ag40Ce6 ↑ 610 317 51 ↑ 11 Cu49Ag45Ce6 ↑ 780 305 A6 ↑ 780 305 40 ↑ 12 Cu44A ↑ 12 Cu44Ag ↑ 710 295 54 １５ 15 Cu42Ag50Ce8 ↑ 705 290 68 １６ 16 Cu51Ag40Ce9 ↑ 715 285 90 ↑ 17 Cu43Ag50Ce7 ↑ 720 290 43 ↑ Comparative Example 1 120 Poor 4 Cu73Ni10P17 ↑ 670 220 141 Poor 5 Cu70Ag20Ce10 Crystal + fragile − − Poor Amorphous 6 Cu20Ag77Ce3 ↑ ↑ − − Poor

[0014]

As described above, since the amorphous copper alloy of the present invention has better strength and corrosion resistance than the conventional amorphous copper alloy, it can be suitably used for various applications including springs, and is extremely useful in industry. is there. In particular, since the copper alloy of the present invention is excellent in corrosion resistance and has little deterioration in performance and appearance during use, the use environment may be high temperature and high humidity, and the range of application is expanded. Further, since the hardness is high, the fatigue resistance is excellent and the spring force is hardly reduced, so that the spring material is extremely excellent.

[Brief description of the drawings]

FIG. 1 is a diagram showing the composition of an amorphous copper alloy of the present invention.

FIG. 2 is a schematic diagram of a rapid solidification device.

[Explanation of symbols]

 1 Copper roll 2 Melting section

Continued on the front page (72) Inventor Hitoshi Yamaguchi 1-9-9, Yaesu, Chuo-ku, Tokyo Imperial Piston Ring Co., Ltd. (72) Inventor Akihisa Inoue 806 (72) Inventor Ken Masumoto 3-8-22 Uesugi, Aoba-ku, Sendai-shi, Miyagi (56) References JP-A-63-169348 (JP, A) JP-A-58-193334 (JP, A) Hei 5-339662 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C22C 9/00-9/10 C22C 45/00-45/10

Claims (1)

(57) [Claims] 1. Cu100-ab Aga Mb (where M is at least one element selected from Ce and misch metal, and a and b are values on a line connecting points a to j in FIG. 1 or surrounded by this line) A high-corrosion-resistant, high-strength amorphous copper alloy having a composition represented by the following range) and having an amorphous structure.