JPS601371B2 - Manufacturing method of amorphous alloy - Google Patents

Description

[Detailed Description of the Invention] Recently, fiber-reinforced or laminated composite materials have been progressing.
There is a strong demand for metal fibers and foils to be of high quality and inexpensive.

Metals are generally excellent materials in terms of strength, ballability, etc., but forming them into fibers or foils requires many steps and requires a large amount of manufacturing cost.

For example, metal whisker crystals are ideal fiber materials with high strength, but they are expensive because they are produced through chemical reactions and phase changes such as precipitation from solutions, reduction, and vapor condensation.
It is also difficult to mass produce. Furthermore, fine metal wire, such as piano wire, is extremely expensive because it requires repeated drawing and intermediate drawing processes. The same applies to metal foil. Therefore, methods of directly producing metal fibers and metal foils from molten metal have been studied as an inexpensive means of producing these materials.

However, metal fibers and foils produced by conventional methods have been extremely inadequate in terms of strength and ductility. However, recently, an alloy of iron or nickel containing more than 10% of phosphorus, several percent of carbon, or even several percent of chromium has been sprayed from a molten state onto a metal conductor with good thermal conductivity and rapidly solidified. It has been discovered that a material with excellent strength and ductility can be obtained by crystallization. However, obtaining such an amorphous state depends to a large extent on the component system and cooling conditions, and hitherto published component systems were empirically limited to the above range. Therefore, the present inventors conducted extensive research on the component system and manufacturing conditions for obtaining an amorphous state, and as a result, found a lawful range of conditions.

That is, the present inventor first used a base as a basic component system of iron, cobalt, and nickel, which are group 8 transition elements of the periodic table, or a mixture thereof, and added one or more metalloid elements to this. However, more careful research revealed that nitrogen and aluminum, which are adjacent to metalloid elements on the periodic table, have similar effects to metalloid elements in creating an amorphous state. It has been revealed that it has The present inventors have determined that the amount of these elements added is determined so that the melting point of the entire alloy is the same as that of a binary alloy consisting of iron among the Group 8 elements constituting the alloy, and either nitrogen or an aluminum semimetal element added. It has been found that it is effective to keep the crystal temperature within +150°, preferably within +100°, from the highest temperature. Furthermore, regarding the cooling conditions, it has been found that it is necessary to rapidly cool the alloy from a molten state at a rate of 1 degree Celsius or more per second. The metal fibers or foils having an amorphous structure thus obtained have significantly superior strength and ductility compared to conventional crystalline solidified metal fibers or foils.

In this case, an amorphous structure refers to a state in which diffraction lines characteristic of metal crystals are not observed in ordinary X-ray diffraction.

In addition, metalloid elements refer to boron, carbon, poppy, element, and phosphorus. In the present invention, three elements of iron, cobalt, and nickel are targeted as group 8 transition elements, but it is easy to imagine that other group 8 elements may have similar effects. It goes without saying that there is no problem even if unavoidable impurities are included as ingredients. The theoretical basis on which the above-mentioned combination of components facilitates the creation of an amorphous metal alloy is currently unclear.

The present invention was obtained as a result of systematic experiments on the relationship between the tendency to form an amorphous structure, the type of added element, and the cooling rate. That is, the research conducted by the present inventors has revealed regularity on the periodic table regarding the types of added elements. One of the points of the present invention is to coarsely combine the Group 8 transition element, the element adjacent to the metalloid element, and the metalloid element. Conventionally, amorphous metals based on iron, nickel, or palladium have been announced, but as a result of a series of research on replacing the base iron with other elements, the inventor found that not only nickel but also cobalt can be substituted. Although an amorphous metal can be obtained, it has been found that substitution with manganese and copper, which are out of Group 8, makes it difficult to become amorphous. On the other hand, as elements to be combined with these base components, it has conventionally been known to simultaneously add more than ten percent of phosphorus and a few percent of carbon. However, the present inventors have conducted extensive research on these elements and have found that addition of nitrogen and aluminum, which are adjacent to them on the periodic table, in addition to metalloid elements, is also effective over a wide range of areas.
Furthermore, regarding the amounts of these additives, previous research has shown that the total amount of added elements other than iron or nickel is approximately 20%.
It was limited to atomic percent, and no regular guidelines for component design were available.

As a result of extensive experiments, the inventors of the present invention determined that the melting point of the alloy was one of the criteria, and that it was the group 8 element,
In particular, it is clear that it is determined by the relationship with the eutectic temperature of the binary alloy of iron and any of the added nitrogen, aluminum, or the above-mentioned metalloid elements such as boron, carbon, phosphorus, and elemental metal. I made it. That is, as mentioned before,
It is necessary to lower the melting point of the alloy to a certain degree, which is the lowest eutectic temperature of the 29th alloy of the Group 8 element, especially iron, and any of the added nitrogen, aluminum, or any of the metalloid elements mentioned above. 150 more than the expensive one
It has been found that it is effective to adjust the components to a value of 0.00 or less, preferably 10,000 or less. Of course, even if the alloy components are adjusted in this way, it is impossible to obtain an amorphous metal depending on the cooling rate, and it is necessary to solidify and cool the metal from a molten state sufficiently quickly.

The first area where rapid cooling is required is during solidification, but when the material is kept at a high temperature for a long time after solidification, it will crystallize due to atomic diffusion, so it is necessary to maintain a sufficient cooling rate even after solidification. Strictly speaking, it is conceivable that the required cooling rates are different during solidification and after solidification, but it is difficult to actually control them separately. The present inventors have found from experiments with various cooling rates and theoretical predictions that it is necessary to cool the material at a rate of at least 1 pi C/sec to about 3000 C, which is the point at which crystallization is stopped. The amorphous alloy obtained in this way has superior strength and ductility compared to ordinary crystalline rapidly solidified alloys, and is used in wire ropes, steel cords, fiber-reinforced composite materials, etc. There are materials, concrete reinforcement materials, filters, mesh, earthquake and soundproofing materials, etc.

The present invention is extremely significant in that it discovers a law that goes beyond the conventional limited experience when designing an amorphous alloy. Example 1 An alloy in which 11 at.% of phosphorus, 8 at.% of carbon, and 5 at.% of aluminum are added to iron has a melting point of 1090 degrees Celsius.

Among the eutectic temperatures of the binary systems of iron and phosphorus, iron and carbon, and iron and aluminum, the highest one is 1165°C for iron and aluminum, and the melting point of the above alloys is lower than the eutectic temperature (the highest (See Figure 2). An amorphous state was obtained when this alloy was rapidly cooled from the molten state at a rate of 1×1 °C/sec. The hardness of this alloy is Hv660, and it has better workability than a ternary amorphous alloy of iron, phosphorus, and carbon. Example 2 Iron with 10 at% boron, poppy, 8 at% element, and 0.1 nitrogen
The alloy with atomic % addition has a melting point of 1220oo.

Of the two elemental eutectic temperatures of iron and boron, iron and silicon, and iron and nitrogen, the one with the highest eutectic temperature is iron, with an elementary temperature of 120,000
The melting point of the above-mentioned alloy of the present invention is the above-mentioned iron and poppy;
It is only 20q○ higher than the elementary eutectic temperature. When this alloy was rapidly cooled from the molten state at a rate of 5 x 1 °C/sec, amorphous fibers were obtained. The hardness of this alloy was Hv1200, which was as hard as iron-boron and harder than the original ternary alloy. Example
3. An alloy in which 13 atomic percent of boron, 4 atomic percent of poppy, and 1 atomic percent of tin are added to iron has a melting point of 1160°.

Among the binary eutectic temperatures of iron and boron, iron and tin, the highest is iron and tin, 1200
00 and the melting point of the above alloy of the present invention is lower than this.
Amorphous fibers were obtained when this alloy was spun from the molten state at a rate of 5 x 1°C/sec. The hardness of this alloy is Hv12
00 was harder than the bare ternary alloy of iron-boron-poppy.
Example 4 Iron to boron 1 % rainbow fan, poppy, element 4 atomic %,
The alloy to which 6 atomic % of cobalt and 0.1 atomic % of nitrogen are added has a melting point of 1170°C.

Among the binary eutectic temperatures of iron and boron, iron and poppy, elemental, and iron and nitrogen, which are the main components, the highest is 1200 oo for iron and silicon, and the alloy of the present invention is higher than this. low.
When this alloy was rapidly cooled from the molten state at a rate of 5 x 1 °C/sec, amorphous fibers were obtained. The hardness of this alloy is Hvl
150, the iron-boron alloy was harder and had better corrosion resistance than the plain ternary alloy. Example 5 The alloy of Example 5 in which 6 atomic % of nickel was added in place of cobalt also had a melting point of 1170°C.

When this alloy was rapidly cooled from the molten state at a rate of 5 x 1°C/sec, amorphous fibers were obtained. The hardness of this alloy is Hvl
It was harder than the iron-boron-poppy ternary alloy and had excellent corrosion resistance.

[Brief explanation of the drawing]

Figure 1 shows iron-11 atomic% P- produced by the method of the present invention.
This is an x-ray diffraction photograph of an 8 atomic % C-5 atomic % AI amorphous alloy showing an amorphous state. FIG. 2 is a phase diagram of a binary iron-aluminum alloy. Melting point of iron-11 atom% P-8 atom% C-5 atom% mountain alloy 1
090℃ is the eutectic temperature of the binary system of iron and aluminum11
It shows that it is below 1315oo (shaded area) which is 150oo higher than 65o0. 3′ Diagram Z Diagram

Claims (1)

[Claims] 1 One or more of iron, cobalt, and nickel, one or two of nitrogen and aluminum, and two or more of boron, carbon, phosphorus, and silicon, and the melting point of the alloy is the same as the iron constituting the alloy. , cobalt, nickel, and one or more of the above-mentioned elements added, from the highest temperature plus 15
Contain so that the temperature is within 0℃, and from the molten state to 300℃
A method for producing an amorphous alloy, characterized by rapidly solidifying the amorphous alloy at a cooling rate of 10^5°C/sec or more over a temperature range of up to 10°C.