JPH0526588B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an amorphous metal thin wire with improved workability. It is known that when molten metal is ultra-quenched, an amorphous metal is obtained, which has properties superior to crystalline metals. That is, typical properties are known to be high mechanical strength and excellent corrosion resistance, and alloys with compositions mainly composed of transition metals have excellent electromagnetic properties. In order to take advantage of the excellent properties of these amorphous materials, studies have been made to put them into practical use in the form of films and ribbons. On the other hand, many amorphous metal wires and methods for manufacturing them are already known, and recently, methods for manufacturing wires with circular cross sections, which were considered difficult to manufacture, have been introduced. It is approaching practical application. However, conventionally known wires, including ribbons, cannot withstand high-level processing such as twisting, weaving, and knitting, and the current situation is that they have not yet reached the stage where they are fully practical. It is. When putting this metal wire into practical use, it is often necessary to go through processing steps such as winding, twisting, knitting, and weaving. Large deformation is possible,
In addition, it is essential that it has sufficient ability to bend in any direction. In the case of amorphous metal ribbons, which are currently known as amorphous metal thin wires, their deformation is anisotropic due to their flat shape, making it difficult to perform such high-order processing. What you get will also be of little practical use. In addition, many attempts have already been made to provide amorphous metal wires having a circular cross section, in addition to ribbon-shaped wires. For example, Japanese Patent Application Laid-Open No. 54-99035 states that an amorphous metal wire obtained by rapidly cooling a melt consisting of a suitable composition of transition metals and non-metals is a wire that structurally has molloy properties. As mentioned above, it cannot withstand high-level processing such as twisting, weaving, and knitting. In addition, Japanese Patent Application Laid-open No. 165016/1983 discloses that a liquid layer is formed in a rotating drum by centrifugal force, a molten metal stream is jetted into this liquid layer, and the liquid layer is cooled and solidified to form an amorphous metal thin wire having a circular cross section. A method has been proposed to obtain the . This method will be explained with reference to Figure 1.
4 is a cylindrical drum (hereinafter referred to as a rotating cylindrical drum) rotated by the drive unit 2, and 4 is a bearing that supports the rotating shaft 3. The structure of the rotating cylindrical drum 1 includes a disk portion 1A whose center portion is fixed to a rotating shaft 3, a liquid layer 5 formed by centrifugal force on the inner wall of the disk portion 1A having a cylindrical shape, and a manufactured metal. The cylindrical portion 1B holds the thin wire 6, and the outer end of the cylindrical portion 1B is formed into a donut shape to maintain the depth of the liquid layer 5.
It is composed of a crucible 9 for molten metal, a nozzle 7, and an outer edge part 1C having an opening that allows insertion of a liquid supply part (not shown) into the rotating drum and removal of the manufactured thin metal wire, The molten metal flow 8 ejected toward the liquid layer 5 formed on the cylindrical inner wall of the rotating cylindrical drum 1 is heated by the heating device 10 while supplying the metal raw material previously introduced into the crucible 9 under an inert gas atmosphere. By opening the valve 12 and introducing the inert gas from the inert gas inlet pipe 11, the metal stream 8 is immediately ejected from the nozzle 7 at the tip of the crucible 9 under the pressure of the inert gas for ejection. It enters the liquid layer 5 and is taken up by the inner wall of the rotating cylindrical drum 1 by centrifugal force.
It is rapidly cooled and becomes a thin metal wire 6,
The thin metal wires 6 are traversed by a traverse device (not shown) to form a uniform bundle on the inner wall of the rotating cylindrical drum 1. At this time, the liquid layer 5 is constantly updated by the circulation device, and the liquid temperature is kept constant. Although the above-mentioned apparatus and operating method produce amorphous metal thin wires, it is an excellent method for producing amorphous metal thin wires having a circular cross section. Wire diameter irregularities occur in thin metal wires, and as mentioned above, they may not be able to withstand high-order processing such as twisting, weaving, and knitting, and amorphous metal thin wires with excellent high-order processability have not yet been obtained. The current situation is that there is no such thing. Therefore, in view of the current situation, the present inventors conducted extensive research with the aim of providing an amorphous metal thin wire that has excellent high-order processability and satisfies practical performance. discovered that the amorphous metal thin wire having
We have arrived at the present invention. That is, the present invention is an amorphous metal thin wire with improved workability, which has bending characteristics satisfying the following formulas (1) and (2), and has a circular cross section. θmax−θmin≦40 ……(1) (However, θmax represents the maximum fracture bending angle (degrees) of the amorphous metal thin wire, and θmin represents the minimum fracture bending angle (degrees) of the amorphous metal thin wire.) 1 /L(1/sinθ/2-1)≦10.0...(2) (However, L is the average wire diameter (mm) of the amorphous metal thin wire,
θ represents the average fracture bending angle (degrees). ) In the present invention, the fracture bending angle refers to the diameter of 0.9±0.1 mm installed on the sample stage shown in Figure 2 at an interval of 3±0.3 mm.
Test specimen b of amorphous metal fine wire with a length of 20 mm was set on cylindrical supports C ₁ and C ₂ of mm, and the push-bending support C ₃ having the same curvature as the supports C ₁ and C ₂ was moved. After bending and deforming piece b and reading the angle A (degrees) at the moment when breakage occurs, it is the value (θ) obtained by subtracting A (degrees) from 180 degrees. For materials that are easy to bend, θ is large; for materials that are easy to break, θ is small;
180 degrees is defined as something that does not break during measurement. In particular, amorphous metal wires have structural anisotropy in their cross sections, and even the same wires have different fracture bending angles. For example, if the cross section is not a perfect circle but has an anisotropic shape such as a rectangle or a circular shape, and the cross section is irregular in the longitudinal direction of the thin wire (so-called a line with large unevenness), this line is When the wire is pressed and bent at several points in the direction to break it, when the wire diameter is large, the fracture bending angle θ is observed to be small, while when the wire diameter is small, θ is observed to be large. This is because in the direction of the wire with a large diameter, even if the wire is bent by a small angle, the actual strain applied to the material surface is large and exceeds the fracture strain of the material, resulting in fracture. This is because the fracture strain will not be exceeded unless it is bent.
As described above, in the case of a material with large wire irregularities or a wire having a cross section with large anisotropy that deviates greatly from a circular cross section, if a bending test is performed at multiple points at random, large variations in θ will occur. Furthermore, even if the cross section of the wire is a perfect circle, in the case of an amorphous metal wire, if crystals are partially mixed in the wire, it will become a moloy portion, which will still cause large variations in the bending angle θ. In other words, the maximum θ (=θmax) among the variations in the fracture bending angle of the amorphous metal thin wire
and the minimum θ (=θmin) occur. θmax and θmin in the present invention are obtained by sampling 5 m each from both ends of the obtained amorphous metal thin wire.
The maximum θ and minimum θ when measured at at least 20 locations. If the difference between θmax and θmin exceeds 40, the amorphous metal wire cannot be twisted or woven.
High-order workability such as knitting is lost. Next, equation (2) is derived from the necessity to represent the essential bending strength of the thin wire, since the average fracture bending angle (θ) of the thin amorphous metal wire is also related to the average wire diameter (L). When the value of 1/L (1/sin θ/2-1) exceeds 10.0, high-order processability such as twisting, weaving, or knitting of amorphous metal thin wires is obtained. will be lost. θ in equation (2) here means at least the above-mentioned
It refers to the average θ when measurements are taken at 20 locations, and L refers to the average value when measurements are made at those 20 locations. Among the amorphous metal thin wires of the present invention, θmax−
Preferably, the amorphous metal thin wire has θmin of 30 or less, 1/L (1/sin θ/2-1) of 8.0 or less, and cutting elongation of 1.7% or more. In order to obtain the amorphous metal thin wire of the present invention, for example,
It may be manufactured using the apparatus shown in FIG. This device is an improved version of the device described in the above-mentioned Japanese Patent Application Laid-open No. 56-165016, and 201 is a rotating cylindrical drum with a cylinder length of a wide range, for example, 200 mm. are partition plates 214 and 21
4' forms a liquid layer groove 215 and partitions the liquid layer. The depth (approximately 20 mm) and width (approximately 80 mm) of the liquid layer are determined by the height and width of the partition plates 214, 214'. That is, 201 is a rotating cylindrical drum,
This is the disc part of 201A, the cylindrical part of 201B, 2
It consists of the outer edge of 01C. Furthermore, partition plates indicated by 214 and 214' are provided inside the cylindrical portion. 216 is a blowing furnace system that blows out molten metal, and this is made up of a nozzle section 209 and 210.
It consists of a heating device. The cold electrolyte is 21
It is placed in a space partitioned by 4,214', 201
As the rotating cylindrical drum rotates, the liquid layer 215 is formed in a layered manner in the circumferential direction of the drum. The alloy is melted through the nozzle 209 by the heating device 210.
The liquid is dissolved in the water layer 215, is ejected from the hole at the lower end of the nozzle under appropriate gas pressure, is partitioned by a partition plate inside the rotating cylindrical drum, is introduced into the undisturbed water layer 215, and is cooled and solidified. After cooling and solidifying, the aqueous layer is suctioned and removed, the drum is stopped, and the amorphous metal thin wire 206 is collected from the drum wall while being traversed 213. The liquid layer formed by the partition plate provided on the inner peripheral surface of the rotating cylindrical drum is
The actual width is 5mm to 100mm and the depth is 10mm to 80mm.
Preferably, it is mm. In this way, by controlling the width and depth of the liquid layer, turbulence in the coolant fluid is significantly reduced, and the stability of the high-speed movement of the coolant liquid, which was previously difficult to achieve, is increased, resulting in improved cooling performance. , higher performance,
That is, the amorphous metal thin wire of the present invention was obtained. The amorphous metal applied to the present invention is "Science" No. 8, 1978, pp. 62-72, Bulletin of the Japan Institute of Metals.
Volume 15, No. 3, 1976, pp. 151-206, "Metals" 1971
December 1st issue, pages 73-78, as well as JP-A-49-91014
No., JP-A-50-101215, JP-A-49-135820,
JP-A-51-4017, JP-A-51-4018, JP-A-51
-4019, JP-A-51-65012, JP-A-51-73920
No., JP-A-51-73923, JP-A-51-78705, JP-A-51-79613, JP-A-52-5620, JP-A-52
-Described in many publications such as No. 114421. Among these, particularly preferred alloy compositions in terms of practical properties include metal-nonmetal combination alloys mainly composed of Fe or Co, which have excellent strength and elongation as well as excellent electromagnetic properties. is also excellent.
Additionally, those containing Ni and Cr also have corrosion resistance. Furthermore, those with high Cr content have increased hardness. In particular, Fe or Co, at least 50 atomic% or more,
Preferably, the alloy contains 60 atomic % or more, more preferably 65 atomic % or more, and other elements that may be contained in addition to Fe and Co include Ni, Al, V,
Examples include Sn, Cr, Ta, Zr, Mo, Mn, W, and Nb. On the other hand, nonmetallic elements include P, B,
Examples include C, Si, Ge, etc. Among them, P, B,
C and Si are preferred. Examples of materials exhibiting excellent processing properties include alloys mainly composed of Fe-Si-B and alloys mainly composed of Fe-P-C and Co-Si-B. Furthermore, in order to carry out the present invention more preferably, these Fe-Si-B, Fe-P-C,
Co-Si-B based amorphous metals that satisfy the following conditions are desired. That is, Si is 17 at % or less, B is 10 to 20 at %, the sum of Si and B is 17 to 30 at %, and the remaining 90 at % or more is
Alloys with a composition consisting of Fe, with P8 to 16 atomic% and C5 to 16 atomic% or less, and the sum of P and C
15 to 28 atomic%, and the remaining 90 atomic% or more is Fe.
An alloy having a composition consisting of 17 atomic % or less of Si, 11 to 20 atomic % of B, and a sum of Si and B of 19 to 32 atomic %.
It is an alloy having a composition in which the remaining 90 atomic % or more is Co. The amorphous metal thin wire of the present invention has a circular cross section with a roundness of 0.8 or more.
This roundness refers to the ratio Lmin/Lmax of the longest axis diameter Lmax and the shortest axis diameter Lmin of the same cross section. Since the amorphous metal thin wire of the present invention has the above-mentioned physical properties, it can be subjected to high-order processing such as twisting, weaving, and knitting. It can be applied to a wide range of fields such as radiation materials, electromagnetic shielding materials, mesh filters, and cords. The present invention will be specifically explained below using examples. Examples 1 to 11, Comparative Examples 1 to 4 Using the apparatus shown in Fig. 3, an alloy having a composition of Fe ₇₉ Si ₅ P ₁ B ₁₉ C ₁ (atomic %) was injected into a quartz nozzle having a hole diameter of 0.13 mmφ. A fine amorphous metal wire was produced and collected using a rotating liquid spinning method in which the material was blown out at a temperature of 1300°C and cooled in a 10°C water layer formed on the inner wall of a stainless steel drum with an inner diameter of 60cm. At this time, the height is parallel to the inner wall of the drum along the circumferential direction.
50 mm partition plates were provided with various widths shown in Table 1, and water layers were formed inside them at various heights shown in Table 1. The results are shown in Table 1. For comparison, an amorphous metal thin wire was manufactured in the same manner as above using the conventional apparatus (width 300 mm) shown in FIG. The results are also shown in Table 1. In addition, the length of the amorphous metal thin wire obtained above is
The length was 300 m, and 5 m of each end was cut out, and 20 2 cm samples were randomly taken out and the performance shown in Table 1 was measured.

【table】

[Table] Regarding the weavability in Table 1, when a 10-mesh square plain weave wire mesh is made using each thin wire in an area of 25 cm ² , the number of wire cuts found in that area is calculated. After inspection, if no cuts were observed, mark ◎, and if there were 1 to 5 cuts, mark ○.
Those with 6 to 10 locations are indicated by △, and those with 11 or more locations are indicated with ×. From Table 1, it can be seen that the amorphous metal thin wire of the present invention obtained by regulating the width of the slit satisfies both formulas (1) and (2) and had good weavability results. It is clear that the amorphous metal thin wires of Comparative Examples 1 to 3 obtained using devices that do not have the following conditions do not satisfy all of formulas (1) and (2), and have poor weavability results.

[Brief explanation of the drawing]

Figure 1 is a schematic sectional view of a conventional device, and Figure 2 is a
FIG. 3, an explanatory diagram for measuring the fracture bending angle in the present invention, is a partially schematic vertical sectional view showing an embodiment of the apparatus used in the present invention. 1,201...Rotating cylindrical drum, 5,215...
Liquid layer, 6,206... Amorphous metal thin wire, 9,20
9... Crucible, 10, 210... Heating device, 214,
214'...Partition plate.

Claims (1)

[Scope of Claims] An amorphous metal thin wire with improved workability, which has bending properties that satisfy linear equations (1) and (2), and has a circular cross section. θmax−θmin≦40 ……(1) (However, θmax represents the maximum fracture bending angle (degrees) of the amorphous metal thin wire, and θmin represents the minimum fracture bending angle (degrees) of the amorphous metal thin wire.) 1 /L(1/sinθ/2-1)≦10.0...(2) (However, L is the average wire diameter (mm) of the amorphous metal thin wire,
θ represents the average fracture bending angle (degrees). )