JPS63317645A - High corrosion resistant amorphous fiber for reinforcing of tubular body - Google Patents

Abstract

PURPOSE:To obtain the titled fiber having high corrosion resistance to brine and having excellent mechanical characteristics which contains specific amounts of Cr, Ni, B, C and the balance consisting substantially of Fe and is formed by regulating each width and thickness of the section thereof. CONSTITUTION:Said amorphous alloy fiber contg., by atom., 8-20% Cr, 5-30% Ni, 8-16% B, 2-6% C and the balance consisting substantially of Fe, having the following sectional size and produced by liquid-quenching is provided: as said sectional size, 0.2-1.5mm width and 10-50mum thickness are regulated. The above-mentioned amorphous alloy fiber is furthermore produced by known melt-quenching. The method in which a single roll made of metal such as Cu, etc., is used to a cooling body and the molten metal of the alloy is projected via a nozzle to the outer circumferential surface thereof to quench to cooling body is, e.g., adapted. Since said amorphous alloy fiber has the above-mentioned characteristics, the long service-life and light weight are promoted at the time of using it as the reinforcing material of a base body having generally a tubular structure such as a fishing rod, tennis racket, the frame of an automobile, and said fiber furthermore contributes to the improvement of workability and productivity at the coiling stage.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an amorphous alloy fiber used as a reinforcing material for tubular bodies such as fishing rods, golf shafts, tennis racket frames, and lightweight bicycle frames.

(Prior Art) Amorphous alloys are characterized by significantly higher tensile strength than conventional metal materials, and various applications as strength materials have been investigated. Among them, some have already been put into practical use as reinforcing materials for fishing gear, golf shafts, and tennis racket frames.

The shape of the amorphous alloy used as these reinforcing materials is either a thin ribbon-like fiber (hereinafter referred to as fiber) or a wire rod with a round cross section (hereinafter referred to as wire).

The former method is mainly produced by a method called the single roll method, which is simple and highly productive, but the cross-sectional shape is rectangular. The latter is produced by a method called a spin-in-spinning method.

As described in Japanese Patent Application Laid-Open No. 57-52550, the rotating liquid spinning method involves applying a cooling medium such as water to the inside of a rotating drum by centrifugal force, and then passing the molten alloy into the liquid stream through a thin nozzle. The liquid is ejected through the pipe and rapidly solidified. Materials made by spinning in a rotating liquid have a round cross-section due to the surface tension of the molten metal. The cast wire can be drawn and, as a result, exhibits practically important properties such as elongation despite being an amorphous alloy.

However, since the cooling rate is approximately one order of magnitude lower than that of the single roll method (a method in which rapid cooling is performed on the outer circumferential surface of a cooling roll), there are significant restrictions on the applicable alloy composition, purity, manufacturing conditions, dimensions of the resulting material, etc. is a drawback. For example, in terms of alloy composition, Fe-5i-B alloys are relatively easy to produce, but it is said that stable production becomes difficult if large amounts of Cr, Mo, P, etc. are added to improve corrosion resistance. For this reason, the amorphous wire produced by spinning in a rotating liquid has insufficient corrosion resistance. Corrosion resistance, especially salt water resistance, is an essential property for materials used in fishing gear.

In addition, for other applications, the amorphous alloy may be used in an exposed or nearly exposed state due to the design. In such cases, the occurrence of rust poses problems both in terms of aesthetics and strength.

Corrosion-resistant amorphous alloys are disclosed in Japanese Patent Publication No. 5B-41345 and Japanese Patent Publication No. 40900-1987.

Fe-Cr-B-C alloys and Fe-Cr-(P,
C.

B)-X alloy (here, the X component is Ni, Co, Mo
, Zr+Ti, Sit Af, Pi, Mn,
Pd+V, Nb, Ta, W, Ge.

Be, Au, Cu, Zn, C+L Sn, A
s, Sb+ Bi+ S) are known. However, the range of components described above is quite broad, and not all compositions disclosed are amenable to a particular application.

In addition to corrosion resistance, amorphous alloys used as reinforcing materials for tubular bodies are required to have delayed fracture resistance under bending stress because they are used in a rolled state. Furthermore, since it is often used in composites with other materials such as carbon fibers, glass fibers, and other polymeric materials, the workability of composites (composite fibers, etc.) is important. Amorphous alloys are hard, so if the edges are jagged like a saw, they can damage and break the other material during the compounding process. To improve the yield of the composite process, the edges of the amorphous fibers must be smooth. The properties of the edge are related to the stability of the flow of the molten metal during casting and the reactivity with air.

Therefore, selection of alloy composition is extremely important in order to stably produce long-term, thin amorphous fibers with good shape.

The compositions of highly corrosion-resistant amorphous alloys disclosed so far have not been developed with consideration to product shape and manufacturability.

(Problems to be Solved by the Invention) Conventional amorphous alloy fibers or wires used as reinforcing materials for tubular bodies such as fishing rods have poor corrosion resistance, mechanical properties, product shape, and manufacturability. However, it did not satisfy all of the characteristics required for practical use. In contrast, the present invention proposes the chemical composition and shape dimensions of an amorphous alloy that has high corrosion resistance against salt water, excellent mechanical properties, and can stably produce products with good shapes.

(Means for Solving the Problems) The material for reinforcing tubular bodies such as fishing rods of the present invention has an alloy composition (expressed in atomic %) of 8 to 20% Cr, 5 to 30% Ni, 8
8 to 16%, C2 to 6%, the remainder is substantially Fe, and the cross-sectional dimensions are 0.2 to 1.5 tm wide and 10 to 50 tm thick.
The melt 2 is a highly corrosion-resistant amorphous alloy fiber (hereinafter abbreviated as amorphous fiber) produced by cold treatment.

The above alloy composition, the range of each component, and the dimensions of the material were determined in consideration of the strength characteristics required for reinforcing materials for tubular objects such as fishing rods, and ease of manufacture.

That is, the tensile strength is at least 150 kgf/mj
The elastic elongation is at least 2%, the corrosion resistance against seawater etc. is very good, delayed fracture due to bending strain does not occur for a long time, good product shape can be stably manufactured, and amorphous formation. The ingredients were selected to ensure high performance and satisfy all of the above requirements.

Among these, corrosion resistance, delayed fracture, and stable manufacturability with a good shape are highly dependent on the alloy composition, so we designed the composition especially for the warehouse.

Here, the evaluation standard for corrosion resistance was that no rust occurred in seawater for a long period of time. Specifically, JIS
The salt spray test method described in Z2371 was adopted, and components that did not generate any rust for at least 3 weeks were selected.

In the test for delayed fracture due to bending strain, the selection criterion was that the sample should be spirally wound around a glass rod with a diameter of 31ItI11, and that there should be no fracture even after the sample was placed in a constant temperature bath and kept in the atmosphere at 60°C for 5000 hours.

Furthermore, manufacturability is expressed as a ratio of the degree of reduction in fiber width due to nozzle clogging in atmospheric casting to fiber length. Specifically, from the viewpoint of use, it is required that the reduction rate of the width of the fibers with respect to the length of 2000 m is within 10%.

Tensile strength and elastic elongation were measured using a conventional Instron type tensile test.

As a result of the above tests and evaluations of various properties, the composition of the amorphous alloy for reinforcing a tubular body of the present invention was determined. The reasons for limiting the component range of each element are as follows.

It is well known that Cr is an essential element for imparting corrosion resistance. Salt spray test results showed that at least 8% Cr is required to exceed the standards of the present invention. Cr exceeding 8% further improves corrosion resistance but deteriorates manufacturability. In particular, if it exceeds 12%, the flow of the molten metal will become unstable. As a result, the edges of the fibers become rough and the uniformity of the board thickness decreases. In addition, the nozzle becomes easily clogged, and it becomes difficult to make long products with narrow fibers (50.5 mm).

Addition of Ni is essential for improving manufacturability and shape deterioration due to increase in Cr. Ni addition is Cr 12
%, it shows a remarkable effect. The required amount of Ni is C
There is a correlation with the r content; when Cr is 8-12%, Ni is 5-20%, and when Cr is 12-16%, Ni1O~
25%, when Cr is 16-20%, Ni is 15-3
0% addition is required.

B and C are essential as amorphous forming elements.

In the past, the present inventors have found that in Fe-B-C alloys, the composition with high amorphous formation ability is around 8 to 12% and 0 to 4%. Even in the alloy of the present invention in which a part of Fe is replaced by Cr and Ni, the appropriate contents of B and C were approximately the same as in the case of the Pe-B-0 ternary system.

Therefore, in the present invention, from the viewpoint of amorphous formation ability, 88-1
6% and C2 to 6%. P, which has been considered essential from the viewpoint of corrosion resistance, is not used in the present invention. This is because it has been found that it is preferable not to add P from the viewpoint of mechanical properties and manufacturability as described below.

Delayed fracture resistance is an indispensable property for applications where the material is wrapped around a tubular body to achieve a reinforcing effect. Elements related to delayed fracture are mainly semimetals such as B, C, P, and St. As mentioned above, P is an element that promotes delayed fracture and should be kept as low as possible. P also degrades manufacturability, so P < 1%.
It is better to

C also promotes delayed destruction. For this reason, in the present invention, the upper limit of C is set to 6%.

As long as other mechanical properties, tensile strength, elastic elongation, etc. are within the above component ranges, all of them satisfy the properties necessary as a reinforcing material for a tubular body.

The alloy composition of the present invention is Fe-Cr-Nt-B-C.
Basically, a part of the constituent elements (≦5%) is Co
+Mo+Nb+W, Ti+Zr, Hf, etc. may be substituted.

In the present invention, the cross-sectional shape of the fiber is as important as the components. In the present invention, the fiber size is IPIo, 2 to
The thickness was defined as 1.5III and 10 to 50 μm.

The above ranges include ease of winding when assembling tubular objects such as fishing rods, workability of composite processes with other materials such as carbon fiber, glass fiber, and polymer fiber, properties as a composite, and wide degree of freedom in design. It was determined by taking into account the following.

i.e. width less than 0.2 mm or thickness 10μ
If it is less than m, the amorphous fibers often break during the winding or compositing process. On the other hand, if the width exceeds 1.5 mm, there will be a need for overlapping wrapping, and the strength will not improve despite the increased weight, the flexibility of the tubular body will be impaired, and workability will decrease when forming a composite body. There are disadvantages such as: When the thickness exceeds 50 μm, the material tends to become brittle, causing breakage during processing and deterioration of delayed fracture resistance.

For the above reasons, the allowable range of fiber dimensions is 0.2 to 1.
5 rHs and a thickness of 10 to 50 μm.

The amorphous fiber of the present invention is produced by a known melt quenching method (also called liquid quenching method). For example, a method (single roll method) can be adopted in which a single roll made of metal such as Cu is used as the cooling body, and molten alloy is jetted onto the outer peripheral surface of the roll through a nozzle to rapidly cool the roll.

In addition, there is also a method (twin roll method) in which the molten metal is spouted between two rolls rotating in opposite directions and rolled while being rapidly cooled. Alternatively, a method of rapidly cooling the molten metal by spouting it onto the inner peripheral surface of a rotating metal drum (centrifugal quenching method) can also be used. In the present invention, any of the above methods may be adopted. However, from the viewpoint of mass production and manufacturing cost, the single roll method is the best.

Next, the nozzle used in the production of the amorphous fiber of the present invention is illustrated in FIGS. 1(a) to 1(C). In both cases, multiple continuous fibers can be produced simultaneously using a multi-hole nozzle. However, the method for producing amorphous fibers is not necessarily limited to the above method.

It is also possible to manufacture a wide ribbon in advance and then slit it to a predetermined width.

(Example) Next, an example will be given and explained.

Example 0.5 to 1.5 kg of a master alloy having the composition shown in Table 1 was melted in a quartz crucible by high-frequency heating, and was sprayed onto the outer peripheral surface of a Cu alloy roll (diameter 600 mm, width 70 mm) to form an amorphous material. produced quality fibers. The type of nozzle used is shown in Figure 1 (
It is the same circular hole nozzle as in a), and has 2 to 5 openings. The dimensions of the fibers for each charge and the results of various characteristic evaluations are shown in Table 1.

In Table 1, an Instron type testing machine was used for the tensile test. Corrosion resistance was measured using the method described in JIS Z2371, and the time until rust appeared was recorded.

180° bending is when you bend the fibers with your fingertips and bring them together.
It was determined whether rupture occurred. For delayed destruction, the sample was wound spirally around a glass rod with a diameter of 3 mm and heated in a constant temperature bath for 60 minutes.
It was held in the atmosphere at .degree. C., and it was determined whether or not destruction occurred after 5000 hours.

The shape was evaluated by touching the edges with a fingertip to determine the roughness (jaggedness) of the edges. The change in width is about 10m after the start of casting and about 2
The width of 000 m was measured with a micrometer and the rate of change (generally the rate of decrease) was displayed. Further, tensile strength and elastic elongation were measured using an Instron type testing machine. Workability refers to the workability of spiral winding as a single material or in combination with other materials.

From the evaluation results shown in Table 1, it is clear that the amorphous fibers having the alloy composition and dimensions of the present invention are more suitable as reinforcing materials for tubular bodies than the comparative examples.

The composite edge sintered band shown in Figure 2, which is made by using the amorphous fibers exemplified as the invention materials No. 091 to 25 in Table 1 alone or in combination with carbon fibers, glass fibers, etc., has excellent corrosion resistance, mechanical properties, and composite edges. The processability of rolling, the workability of winding as a single unit, and the performance of composite strips were extremely excellent. Thus, it is recognized that the amorphous fiber of the present invention is extremely excellent as a reinforcing material for tubular bodies.

(Effects of the Invention) As explained above, the amorphous alloy fiber of the present invention has extremely high corrosion resistance (especially against salt water), has suitable cross-sectional dimensions, and has excellent mechanical properties and manufacturability. When used as a reinforcing material for substrates that generally have a tubular structure, such as rackets, bicycle frames, and golf shafts,
It has a long life, is lightweight, and contributes to improving workability and productivity in the winding process.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the shapes of various nozzles that can be used to produce the amorphous alloy fiber of the present invention, in which (a) is a circular hole nozzle, (b) is an elliptical nozzle, and (C) is a rectangular nozzle. Shows the nozzle. FIG. 2 is a diagram showing an example of a composite of the amorphous alloy fiber of the present invention and another material such as carbon fiber. l...Composite fibers, 2a, 2b, 2c...amorphous fibers, 3a, 3b...other material fibers arranged between amorphous metal fibers, 4a, 4b, 4c, 4d... - Material fiber for the selvage thread, 5... Material fiber for the weft thread. Figure 1

Claims (2)

[Claims] (1) Alloy composition is atomic%, Cr8~20%, Ni5~
30%, B8-16%, C2-6%, the remainder is substantially F
E, cross-sectional dimensions are 0.2 to 1.5 mm wide and 1 mm thick.
A highly corrosion-resistant amorphous alloy fiber for reinforcing a tubular body produced by a melt quenching method and having a diameter of 0 to 50 μm. (2) When the alloy composition is 8 to 12% Cr in atomic %, Ni
5-20%, 12-16% Cr, 10-25% Ni
, when Cr is 16-20%, Ni is 15-30%, and B8
2. The highly corrosion resistant amorphous alloy fiber for reinforcing a tubular body according to claim 1, wherein the fiber is comprised essentially of ~16% C, 2~6% C, and the remainder Fe.