JPH0469224B2 - - Google Patents

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, fishing gear,
Some materials have already been put into practical use as reinforcing materials for the frames of golf shafts and tennis rackets. The shape of the amorphous alloy used as these reinforcing materials is thin ribbon-like fibers (hereinafter referred to as fibers).
is a wire rod (hereinafter referred to as wire) with a round cross section. The former method is mainly produced by a method called a single roll method, which is simple and highly productive, but the cross-sectional shape is irregular. The latter is produced by a method called a spin-in-spinning method. The rotating liquid spinning method was published in Japanese Patent Application Laid-Open No. 1983
- As described in Publication No. 52550, a cooling medium such as water is applied to the inside of a rotating drum by centrifugal force, and molten alloy is jetted into the liquid stream through a thin nozzle to rapidly solidify it. It is. 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, it shows elongation despite being an amorphous alloy, which is an important property in practice. However, since the cooling rate is approximately one order of magnitude lower than that of the single roll method (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, dullness, manufacturing conditions, dimensions of the resulting material, etc. That is a drawback. For example, in terms of alloy composition, Fe-Si-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, amorphous wires produced by spinning in a rotating liquid have 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. For corrosion-resistant amorphous alloys, see 58-41345.
and Japanese Patent Publication No. 59-40900. Fe-Cr-B-C alloys and Fe-Cr-(P,
C, B)-X alloy (here, the X component is Ni, Co,
Mo, Zr, Ti, Si, Al, Pt, Mn, Pd, V, Nb,
Ta, W, Ge, Be, Au, Cu, Zn, Cd, Sn, As,
One or more of Sb, Bi, and S) are known. However, the range of components described above is quite broad, and not all compositions disclosed are suitable for a particular application. Amorphous alloys used as reinforcing materials for tubular bodies include
In addition to corrosion resistance, since it is used in a rolled state, delayed fracture resistance under bending stress is required. 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 weaving, 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 amorphous fibers must have smooth edges. 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, in order to stably produce thin amorphous fibers with good shape over a long period of time, selection of alloy composition is extremely important. 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 parts 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.
%, B8~16%, C2~6%, the remainder is essentially Fe, and the cross-sectional dimensions are 0.2~1.5mm wide and 10~50μ thick.
This is a highly corrosion-resistant amorphous alloy fiber (hereinafter abbreviated as amorphous fiber) produced by a melt quenching method. The above alloy composition, the range of each component, and the dimensions of the material were determined in consideration of various properties required for reinforcing materials for tubular objects such as fishing rods, and ease of manufacture. That is, the tensile strength is at least 150Kgf/mm ²
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 over a long period of time, good product shape can be stably manufactured, and non-abiotic 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 took particular care in designing the composition. Here, the evaluation standard for corrosion resistance was that no rust occurred in seawater for a long period of time. Specifically, we adopted the salt spray test method described in JIS Z2371, and selected components that would not cause any rust for at least three weeks. 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 3 mm, and that there should be no fracture even after the sample was placed in a constant temperature bath and held in the atmosphere at 60°C for 5,000 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 fiber is within 10% with respect to the fiber length of 2000 m. Tensile strength and elastic elongation were measured using a conventional Instron type tensile test. As a result of the above test evaluation 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. The salt spray test results show that at least 8%
It was shown that Cr is necessary. Cr greater than 8%
further improves corrosion resistance but degrades manufacturability.
In particular, if it exceeds 12%, the flow of the molten metal will become unstable.
As a result, the fiber edges become rough and the uniformity of the board thickness decreases. In addition, the nozzle becomes easily clogged, making it difficult to make long objects with narrow fibers (≦0.5 mm). Addition of Ni is essential to improve manufacturability and shape deterioration due to increased Cr. Addition of Ni shows a significant effect when Cr exceeds 12%.
The required amount of Ni is correlated with the content of Cr, and Cr is 8
~12% Ni5~20%, Cr 12~16%
When Ni is 10-25% and Cr is 16-20%, Ni is 15-30
% addition is required. B and C are essential as amorphous forming elements. The present inventors have previously found that the composition with high amorphous formation ability in Fe-B-C alloys is around 12% B and 4% C. Some of the Fe
In the alloy of the present invention in which Cr and Ni are substituted, B
The appropriate contents of C and C were approximately the same as in the case of the Fe-B-C ternary system. Therefore, in the present invention, from the viewpoint of amorphous formation ability, the content is limited to B8 to 16% 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 in view of the mechanical properties and manufacturability 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 Si. As mentioned above, P is an element that promotes delayed fracture and should be kept as low as possible. Since P also deteriorates manufacturability, it is preferable that P<1%. C also promotes delayed destruction. For this reason, in the present invention, the upper limit of C is set to 6%. As long as the 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-Ni-B-C.
Basically the elemental system, but some of the constituent elements (≦5%)
may be replaced with Co, Mo, Nb, W, Ti, Zr, Hf, etc. In the present invention, the cross-sectional shape of the fiber is as important as the components. In the present invention, the dimensions of the fiber are defined as 0.2 to 1.5 mm in width and 10 to 50 μm in thickness. The above range is for ease of winding work when assembling tubular objects such as fishing rods,
It was determined by taking into account the workability of the process of compositing with other materials such as carbon fiber, glass fiber, and polymer fiber, the characteristics of the composite, and the wide degree of freedom in design. i.e. width less than 0.2mm or thickness 10μm
If it is less than that, the amorphous fibers often break during the winding or compositing process. On the other hand, the width is 1.5mm
If it exceeds this, there will be disadvantages such as the need for overlapping winding, which will not improve the strength despite the increase in weight, the flexibility of the tubular body will be impaired, and the workability will decrease even when it is made into a composite body. When the thickness exceeds 50 μm, the material tends to become vesicular, causing breakage during processing and deterioration of delayed fracture resistance. For the above reasons, the allowable range of fiber dimensions is 0.2
~1.5mm, and the thickness is 10~50μm. The amorphous fiber of the present invention is produced by a known melt quenching method (also called liquid quenching method). For example, using a single roll of metal such as Cu for the cooling body,
A method (single roll method) can be adopted in which molten alloy is jetted onto the outer peripheral surface through a nozzle and rapidly cooled. 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 nozzles used in manufacturing the amorphous fiber of the present invention are illustrated in FIGS. 1a to 1c. 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 is melted in a quartz crucible by high-frequency heating, and then ejected onto the outer peripheral surface of a Cu alloy roll (diameter 600 mm, width 70 mm) to produce amorphous fibers. did. The type of nozzle used was the same multi-hole nozzle as in Figure 1a, with 2 to 5 openings. Fiber dimensions for each charge,
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. For 180° bending, the fibers were woven and bent with the fingertips, and it was determined whether or not breakage occurred when the fibers were brought into close contact. Delayed fracture was determined by spirally winding a sample around a glass rod with a diameter of 3 mm, holding it in a thermostat at 60°C in the atmosphere, and determining whether or not fracture 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 10 after the start of casting.
The width of m and the width of approximately 2000 m were 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 composite processing 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.

【table】

[Table] Composite woven belts as shown in Figure 2, in which the amorphous fibers exemplified in Invention Materials No. 1 to 25 in the table are used singly or in combination with carbon fibers, glass fibers, etc., have corrosion resistance and mechanical properties. , the processability of the composite weave, the workability of winding it alone, the performance of the composite belt, etc. 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),
Due to its suitable cross-sectional dimensions, excellent mechanical properties, and excellent manufacturability, it can be used as a basic reinforcing material for fishing rods, tennis rackets, bicycle frames, golf shafts, etc., which generally have a tubular structure, and has a long life and is lightweight. It also contributes to improving the workability and productivity of the winding process.

[Brief explanation of the drawing]

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, where a shows a circular hole nozzle, b shows an elliptical nozzle, and c shows a rectangular 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. 1...Composite fabric, 2a, 2b, 2c...Amorphous fiber, 3a, 3b...Other material fibers arranged between amorphous metal fibers, 4a, 4b, 4c, 4d...For selvage threads, etc. Material fiber, 5... Other material fiber for weft.

Claims (1)

[Claims] 1. Alloy composition in atomic %, Cr8-20%, Ni5-30
%, B8~16%, C2~6%, the remainder is essentially Fe, and the cross-sectional dimensions are 0.2~1.5mm wide and 10~50μ thick.
A highly corrosion-resistant amorphous alloy fiber for reinforcing a tubular body produced by a melt quenching method. 2 When the alloy composition is 8 to 12% Cr in atomic%, Ni5
~20%, Cr12~16% Ni10~25%, Cr16~
When 20%, Ni15-30%, B8-16%, C2-6
%, the balance being substantially Fe, as claimed in claim 1.