JPH07103439B2 - Amorphous metal wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention adds Co while maintaining the excellent fatigue properties and corrosion resistance of an amorphous alloy of Fe-Cr-Si-B. The present invention relates to an amorphous metal thin wire having a circular cross section with improved toughness.

(Prior Art) Amorphous metal materials have been studied for various practical applications due to their excellent electromagnetic and mechanical properties. Among them, Fe-based amorphous metal fine wires having a circular cross section are described in JP-A-56-165016, and those having excellent fatigue properties are disclosed in JP-A-58-213857 and further. Those having excellent fatigue characteristics and toughness are described in JP-A-60-106949. And, in particular, JP-A-60-1069
The one described in Japanese Patent Publication No. 49 has improved cold workability and has been improved to the point that it can be processed into a stranded wire.

On the other hand, Fe-based amorphous alloys having excellent corrosion resistance are described in JP-A-59-193248 and JP-A-59-13056, but amorphous alloys having excellent corrosion resistance and toughness are described. There are no proposals for thin metal wires.

(Problems to be solved by the invention) The thin metal wire is drawn into a wire having an appropriate diameter,
Alternatively, it is very often used by twisting, weaving, or knitting in a state of a strand before being drawn or a state of being drawn. In order to perform these processing,
Not only the fatigue property or the corrosion resistance is excellent, but also the toughness is required. If the toughness is not excellent, the fine metal wire will be cut during the above processing. When a conventional thin metal wire is drawn using, for example, a diamond die, it may be cut several to several tens of times per 2000 m of the original wire. Therefore, the length of the thin metal wire is shortened, which reduces the commercial value and also reduces the above work efficiency. Also, when stressed processing such as twisting, weaving, or knitting is performed, this also results in 2000 m of original wire.
It may cut several times to several tens of times.

(Means for Solving Problems) Therefore, in view of these present circumstances, the present inventors have considered Fe-Cr-S.
As a result of earnest research for the purpose of providing an amorphous alloy material having excellent toughness while maintaining the fatigue characteristics or the corrosion resistance of the amorphous alloy of i-B, a specific Fe- By adding a specific amount of Co to the alloy composition of Cr-Si-B, the above-mentioned object is achieved, and the fact that an amorphous metal fine wire having a circular cross section can be obtained and the obtained fine wire is cut in the middle of processing The present invention has been achieved by finding the fact that the above phenomenon hardly occurs.

That is, the present invention provides a composition formula _{Fe a Co b Cr c Si x} B y (53 atomic% ≦ a + b ≦ 80 atomic%, 3 at% ≦ c ≦ 20 atomic%, and 0.025c + 0.25 ≦ b / ( a + b) ≦ 0.012c + 0.73
5 atomic% ≤ x ≤ 15 atomic%, 5 atomic% ≤ y ≤ 15 atomic%, and 17 atomic% ≤ x + y ≤ 27 atomic%. The main point is an amorphous metal fine wire having a circular cross section, which is composed of a composition shown in) and has excellent toughness.

The amorphous metal thin wire of the present invention is a material having excellent fatigue characteristics or corrosion resistance and improved toughness, and its alloy composition needs to be limited as follows in order to satisfy the above characteristics. is there.

That is, in order to improve toughness, the sum of Fe and Co is 53
Atomic% or more and 80 atomic% or less, Cr content of 3 atomic% or more and 20 atomic% or less, and Fe, Co, Cr content of 0.025c + 0.25 ≦ b / (a +
b) ≦ 0.012c + 0.73 (a: Fe added atomic%, b: Co added atomic%, c: Cr added atomic%) must be satisfied, and the sum of Fe and Co must be 57 Atomic% or more, 76 atomic% or less, Cr
The amount is 5 atomic% or more and 18 atomic% or less, and the Fe, Co, Cr contents are
It is more preferable to satisfy the relational expression 0.025c + 0.27 ≦ b / (a + b) ≦ 0.012c + 0.68.

Fatigue properties improve with increasing Cr addition amount, reach almost equilibrium at about 10 atomic% or more, and corrosion resistance improves with Cr adding amount, but with addition amount less than 10 atomic%, for example, 1N Concentrations of hydrochloric acid, sulfuric acid, nitric acid or seawater are still insufficient.
Corrosion resistance equal to or higher than that of US304 is exhibited, but if more than 20 atomic% is added, even if the optimal amount of Co is added, the amorphous forming ability is significantly reduced, and an amorphous metal fine wire with excellent toughness is obtained. I can't.

That is, Cr is added to improve fatigue properties or corrosion resistance, but in order to maintain excellent toughness, C is added.
The addition ratio of Fe and Co corresponding to the addition amount of r is important.When the addition amount of Cr is small, the addition amount of Co to Fe is small.
It is necessary to increase the amount of Co added as the amount of Cr added increases. In particular, in order to improve toughness while maintaining excellent fatigue properties, Cr is 3 atom% or more and 12 atom% or less, preferably 5 atom% or more and 10 atom% or less. Is 20 atom% or more and 40 atom% or less, preferably 25 atom% or more and 35 atom% or less, C
o is 30 atom% or more and 60 atom% or less, 35 atom% or more,
It is preferably 55 atomic% or less.

Further, Si and B must be 5 at% or more and 15 at% or less, preferably 7 at% or more and 15 at% or less. Further, the total sum of Si and B must be 17 at% or more and 27 at% or less, preferably 19 at% or more and 25 at% or less.

In the present invention, for the purpose of improving the corrosion resistance by the composition of the Fe-Co-Cr-Si-B system, Ni is 30 atomic% or less, preferably 0.1 atomic% or more, 30 atomic% or less, Ti, Al and At least one of Cu is 10 atomic% or less, preferably 0.1 atomic% or more and 10 atomic% or less, and at least 1 of Ta, Nb, Mo and W is used for the purpose of improving heat resistance, corrosion resistance and mechanical properties. Seed content is 10 atomic% or less, preferably 0.1 atomic% or more, 10 atomic% or less. For the purpose of improving heat resistance and mechanical properties, V, M
At least one of n and Zr can be added in an amount of 10 atomic% or less, preferably 0.1 atomic% or more and 10 atomic% or less. Further, for the purpose of improving the amorphous forming ability, strength and fatigue characteristics, C can be added in an amount of 2 atomic% or less, preferably 0.1 atomic% or more and 2 atomic% or less. In particular, in order to improve the corrosion resistance among these additive elements, Ni is added to 1 to 2
It is preferable to add 0 atom% and 0.5 to 5 atom% of Mo.

In order to manufacture the thin wire of the present invention, the above alloy composition is used,
It may be solidified by quenching by a spinning method in a rotating liquid which is particularly preferable as a manufacturing method. As a spinning liquid spinning method, Japanese Patent Laid-Open No. 56-
As described in Japanese Patent No. 165016, water is put into a rotating drum, a water film is formed on the inner wall of the drum by centrifugal force, and the alloy melted in the water film is discharged from a spinning nozzle having a diameter of about 80 to 200 μm. There is a method of jetting to obtain a fine wire having a circular cross section. In particular, in order to obtain a uniform continuous thin wire, it is desirable that the peripheral velocity of the rotating drum be equal to or higher than the velocity of the molten metal flow ejected from the spinning nozzle. The speed is preferably 5 to 30% faster than the speed of the molten metal flow ejected from the spinning nozzle. Further, the angle between the molten metal flow ejected from the spinning nozzle and the water film formed on the inner wall of the drum is preferably 20 ° or more.

Further, as another preferable method for producing the thin wire of the present invention, as described in JP-A-58-173059,
About 80 to 20 molten alloy consisting of the above alloy composition is added to the cooling liquid layer formed on the running grooved conveyor belt.
There is also a method of ejecting from a spinning nozzle having a diameter of 0 μm to obtain a fine wire having a circular cross section.

The thin wire of the present invention has a wire diameter of about 50 to 250 μm, and
It is a fine wire having a roundness of 60% or more, preferably 80% or more, particularly preferably 90% or more, and preferably a uniform shape with a wire diameter unevenness of 4% or less.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples.

The tensile rupture strength, fatigue property, corrosion resistance, toughness and shape in the examples were evaluated as follows.

(1) Fatigue limit (λe) As shown in FIG. 1, using a model bending fatigue tester (one-way repeated bending tester) having a horizontal slider 4 and a rotating disk 5, a constant load W (unit cross-sectional area) Constant load per load: 4 kg / mm ² ) 1, under a fixed number of cycles of 100 times / min,
By adjusting the surface strain (λ) of the sample 3 by changing the diameter of the pulley 2, as shown in FIG. 2, the SN curve (sample surface strain (λ)
Is the vertical axis and the number of repetitions N is the horizontal axis. ) Was obtained, and the sample surface strain at which the S-N curve became horizontal was defined as the fatigue limit (λe) of this sample.

The sample surface strain (λ) was calculated from the following equation.

(However, t represents the diameter of the sample and r represents the radius of the pulley.) (2) Corrosion resistance Measured by the weight loss method.

That is, the sample was immersed in 1N hydrochloric acid, sulfuric acid, and nitric acid at 20 ° C. for 8 hours, and the weight residual amount (%) of the sample was determined by the following formula.

(However, ω ₀ represents the sample weight before the treatment and ω represents the sample weight after the treatment.) (3) Tensile breaking strength of the sample Using an Instron type tensile tester, sample length 12 cm, strain rate 4.17 × 10 ^It was determined from the SS curve measured at ^-4 / s.

(4) Toughness (cutting / 2000m) Pulley 2 shown in Fig. 3 with thin metal wire (measurement sample 3)
(Change the pulley diameter according to the diameter of the thin wire so that the surface strain applied to the thin wire will be 2.2%.) Wrap it once and apply back stress (40 kg / mm ² ) to the thin wire. When the sample 3 was continuously run from the feeding roller 6 and wound by the winding roller 7, the number of breaks per 2000 m of the original wire was measured and evaluated. The surface strain applied to the thin wire was calculated by the same formula as in the fatigue test.

The evaluation here is a reference when performing stressed processing such as twisting, weaving, or knitting.

(5) Toughness (cut / 2000m) 0.150mmφ of amorphous metal wire with a diameter of 0.130mmφ
Up to 0.10 mmφ, a plurality of diamond dies were arranged with a 0.005 mm pitch, and an ultrafine wire drawing machine of the type in which thin metal wires were passed in series was drawn to 0.10 mmφ at a speed of 100 m / min. At this time, the number of cuts per 2000 m of the original wire was obtained and evaluated.

The evaluation here is a guide when performing wire drawing.

(6) Shape Roundness is the longest shaft diameter R _max and the shortest shaft diameter R _min of the same cross section.
And the ratio. The thickness variation in the length direction was determined by measuring the diameter at 10 random points in a 10 m sample length, dividing the difference between the maximum and minimum diameters by the average diameter, and multiplying it by 100.

Examples 1 to 14 and Comparative Examples 1 to 13 Alloys having various compositions shown in Table 1 were melted in an argon atmosphere, and then an argon gas jet pressure of 4.5 kg / cm ² was applied to the ruby spinning nozzle having a hole diameter of 0.135 mmφ. Uniformly with a circular cross section with an average diameter of 1.13 mmφ, sprayed into a cooling liquid with an internal diameter of 600 mmφ rotating at 320 rpm and spun into a cooling liquid with a temperature of 4 ° C and a depth of 3.0 cm to solidify rapidly. A thin amorphous metal wire was obtained.

At this time, the distance between the tip of the spinning nozzle and the surface of the rotating cooling liquid was kept at 1 mm, and the angle between the molten metal flow ejected from the spinning nozzle and the surface of the rotating cooling liquid was 70 °.

The jetting speed of the molten metal flow from the spinning nozzle was measured from the weight of metal collected by jetting into the atmosphere for a certain period of time, and the jetting argon gas pressure was adjusted to about 570 m / min.

Tensile rupture strength, fatigue properties and toughness of the obtained amorphous metal wires were measured in the atmosphere at a temperature of 20 ° C and a relative humidity of 65%.

The results are summarized in Table-1.

In addition, the corrosion resistance of the obtained typical amorphous metal thin wire was
It was measured by a weight loss method in which it was immersed in a 1N hydrochloric acid, sulfuric acid or nitric acid solution at 8 ° C for 8 hours.

The results are summarized in Table-2.

For comparison, generally used corrosion-resistant wire
The results obtained by the same method for SUS304 (130 μmφ) are also shown.

From Table-1 and Table-2, in Comparative Example 1, the amount of Cr added was 0, so the fatigue performance and corrosion resistance were low, and the toughness was not sufficient. In Comparative Examples 2 and 3, Co Is clearly not enough.

In Comparative Example 4, the amount of Co added was large relative to the amount of Cr added, and therefore the amount of Fe added was small, so that 0.025c + 0.25 ≦ b /
(A + b) ≦ 0.012c + 0.73 is not satisfied (a =
6, b = 65, c = 7, b / (a + b) = 0.92,0.012c + 0.73
= 0.81, which does not satisfy the above formula. ), The toughness is not sufficient. On the other hand, in Comparative Examples 5 and 7, on the contrary, the amount of Fe added was too large for the amount of Cr added, and therefore the Co content was small, so 0.025c + 0.25 ≦ b / (a + b) ≦ 0.012c + 0.73
Is not satisfied (in Comparative Example 5, a = 60, b =
From 11, c = 7, 0.025c + 0.25 = 0.43, b / (a + b) = 0.15
Therefore, the above equation is not satisfied. In Comparative Example 7, since a = 30, b = 34, c = 14, 0.025c + 0.25 = 0.60, b / (a
+ B) = 0.53, which does not satisfy the above formula. ), The toughness is not sufficient. In Comparative Example 6, since the amount of Cr added is small, the fatigue characteristics and toughness are not sufficient, and in Comparative Example 8, the amount of Cr added is too large, and the toughness is not sufficient.

Further, in Comparative Example 9, the amount of Si added was too small, in Comparative Example 10, the amount of Si added was too large, in Comparative Example 11, the sum of Si and B was too large, and in Comparative Example 12, the amount of B added was too large. Since it was too small, no continuous (approximately 2000 m) thin metal wire was obtained. In Comparative Example 13, the toughness is not sufficient because the amount of B added is large.

On the other hand, it is clear that Examples 1 to 14 have excellent toughness. As is clear from Tables 1 and 2, the fatigue limit and corrosion resistance tend to improve with the amount of Cr added. However, the fatigue limit is almost equilibrium when the Cr content is about 9 atomic% (fatigue limit 1.20 in Example 3), and even if more Cr is added (fatigue limit 1.30 in Example 8), the fatigue limit is not so much improved. I can't expect.

On the other hand, the corrosion resistance is not sufficient with the addition amount of about 7 atomic% of Cr (Example 2), and 9 atomic% of Cr is added together with 2 atomic% of Mo (Example 12) or more than 12.5 atomic% of Cr (Example 6) is added. It shows excellent corrosion resistance on SUS304, and it has a Cr content of 12.5 atomic%.
In Example 13 in which Mo2 atom% was added in combination, an amorphous metal thin wire having extremely excellent corrosion resistance was obtained.

That is, it was found that Cr is added in an amount of 10 atomic% or more in order to satisfy both fatigue properties and corrosion resistance.

Next, using the planetary type twisting machine, the amorphous metal thin wire obtained in Example 4 was twisted into 7 strands at a speed of 50 cm / min for 1000 m.
When manufactured, the cutting during processing was 0. The twist number at this time was 195 turns / m.

For comparison, the amorphous metal thin wires obtained in Comparative Examples 1 and 3 were twisted in the same manner as described above, but the cutting was frequently caused, which failed.

(Effects of the Invention) The amorphous metal fine wire of the present invention has excellent fatigue characteristics or corrosion resistance, and has improved toughness, so that cutting hardly occurs during processing, and any processing such as wire drawing is performed. Can be efficiently performed on an industrial scale.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a model bending fatigue testing machine for measuring fatigue characteristics, and FIG. 2 is S measured using the apparatus of FIG.
-N curve and FIG. 3 are schematic views of a model testing machine for measuring toughness. 1: unit area (mm ²⁾ per constant load (4 kg / mm ²⁾ load for applying a 2: pulley for adjusting the surface strain of the sample 3: Measurement Sample 4: horizontal movement slider 5: rotating disk 6 : Feed roller 7: Take-up roller

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihisa Yamada 23 Uji Kozakura, Uji City, Kyoto Prefecture Central Research Institute of Unitika Co., Ltd. (72) Inventor Miyuri Sasaki 23 Koji Sakura Uji, Uji City, Kyoto Unitika Co., Ltd. Central Research In-house examiner Hitoshi Maeda

Claims (1)

[Claims] 1. A by the composition formula _{Fe a Co b Cr c Si x} B y (53 atomic% ≦ a + b ≦ 80 atomic%, 3 at% ≦ c ≦ 20 atomic%, and 0.025c + 0.25 ≦ b / (a + b ) ≤ 0.012c + 0.73
5 atomic% ≤ x ≤ 15 atomic%, 5 atomic% ≤ y ≤ 15 atomic%, and 17 atomic% ≤ x + y ≤ 27 atomic%. ) Amorphous metal wires with a circular cross section, which have excellent toughness and have the composition shown in).