JPS6234817B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides that a second
The present invention relates to a method for producing a second phase particle dispersed super rapidly solidified alloy, which is a novel composite material in which phase particles are dispersed to complement the functional properties of the super rapidly solidified alloy and the second phase particles.

In recent years, the functions and performances required of metal materials have become more stringent and diverse. Composites of materials are being considered as one way to meet this demand.

Particle-dispersed composite materials based on a combination of second phase particles and metal alloy phases are currently being actively studied as composite materials. For example, Cu-C, Fe-BN as sliding materials, WC as cemented carbide
-Co, WC-TiC-Co, etc. Since these materials are all made using powder metallurgy, the materials themselves tend to be porous, and there are significant restrictions on the shape of the materials. Powder metallurgy methods provide a three-dimensional homogeneous dispersion of second phase particles, but have the disadvantage that pores tend to exist in the composite. In addition, in melting methods in which there are almost no such pores, on the contrary, the second phase particles are not uniformly dispersed in the molten metal, but often float to the surface and separate, resulting in a material separated into two layers. Various methods have been studied to solve this drawback of being susceptible to mechanical stress, but none have been sufficient. Therefore, composite materials obtained by conventional manufacturing methods have the disadvantage of being brittle against mechanical stress.

On the other hand, in recent years, the liquid quenching method has been actively researched as a method for producing ribbons of amorphous alloys or some crystalline alloys. The ultra-quenched alloy obtained by this method exhibits excellent mechanical strength and magnetic properties, and its practical application in various fields is being considered. However, in order to realize practical application in a wider range of fields in the future, the functions and properties required of materials will become even more diverse, as described above. As an effective method to satisfy these requirements, it is considered that second phase particles are dispersed in the ultra-quenched alloy ribbon to achieve composite functions and properties.

The present invention was made in view of these points,
The purpose is to provide a method for manufacturing a second phase particle dispersed ultra-quenched alloy that has a wide variety of excellent functions and properties.

To achieve this objective, the present invention provides amorphous,
A method for producing a second phase particle-dispersed super rapidly solidified alloy comprising at least one kind of second phase particles uniformly dispersed three-dimensionally in a super rapidly solidified alloy matrix consisting of a crystalline or a mixed phase thereof, After heating and melting the alloy base material constituting the rapidly solidified alloy matrix, and before the alloy base material is pseudo-solidified, the second phase particles are sprayed and dispersed onto the alloy base material together with an injection medium made of an inert gas. The ingot is then cooled to form an ingot containing second phase particles, and this ingot is remelted to such an extent that the second phase particles do not dissolve, and then ultra-quenched and pseudo-solidified to form the second phase particles in the ultra-quenched alloy matrix. It is characterized by being uniformly dispersed in three dimensions.

1 and 2 are principle explanatory diagrams for explaining the manufacturing method of the second phase particle dispersed ultra-quenched alloy according to the present invention. FIG. 1 is a diagram for explaining the process of making an ingot, Figure 2 is a diagram for explaining the process of melting the ingot to make a ribbon of ultra-quenched alloy.

In FIG. 1, an alloy base material 1 constituting an ultra-quenched alloy matrix is melted in a high frequency melting furnace 2, and then poured into an ingot mold 3. On the other hand, the second phase particles 4 are forcibly injected into the molten alloy base material 1 while being injected into the mold 3 by a plasma spray powder feeder 5, and are cooled and pseudo-solidified to form the second phase particles. An ingot in which 4 is uniformly dispersed and held is obtained. For spraying and dispersing the second phase particles 4, a spraying medium made of an inert gas such as argon gas, which is filled in a cylinder 6, is used.

In order to avoid deterioration of the alloy base material 1 during injection dispersion, an inert gas such as argon is preferably used as the injection medium. As a powder feeder for supplying the second phase particles 4, the second phase particles 4 must be able to be supplied uniformly at all times, injection conditions such as injection pressure can be adjusted relatively easily, and the nozzle must have excellent heat resistance. For these reasons, a powder feeder for plasma spraying is suitable.

Ultra-quenching methods include single-roll, twin-roll, and centrifugal methods for producing ribbon-shaped alloys, as well as water-spinning, spinning-spinning, and spinning-spinning methods for producing wire-shaped alloys. Examples include glass-coated spinning methods. These ultra-quenching methods can produce metastable materials that are not in the equilibrium phase diagram, such as amorphous phases, non-equilibrium crystalline layers, or equilibrium crystalline phases, by controlling quenching conditions such as selection of alloy composition or quenching rate. is obtained.

FIG. 2 shows the manufacturing process of super-quenched alloy by the twin roll method. The ingot 8 having the second phase particles uniformly dispersed therein is placed in a heat-resistant tube 7 made of quartz glass having a small hole at the lower end, and the inside of the tube is sufficiently replaced with an inert gas 9 such as argon gas.
A high frequency melting furnace 10 is installed around the outer periphery of the heat-resistant tube 7, and the ingot 8 is remelted by the melting furnace 10 to such an extent that the second phase particles are not melted. After that, the two rolls 12, 12 are rotated at high speed by operating the piston 11 to rotate the lower end nozzle part of the heat-resistant tube 7.
The gas pressure inside the heat-resistant tube 7 is rapidly increased. As the pressure increases, the remelted ingot 8 is gradually supplied from the nozzle portion as a uniform continuous jet to the joint portion of the rolls 12, 12. Since the rolls 12, 12 are rotating at high speed and are always in pressure contact, when ejected, they are instantaneously super-quenched and pseudo-solidified to obtain a continuous ribbon 13.

FIG. 3 is an enlarged cross-sectional view of this ribbon 13, in which second phase particles 4 are uniformly dispersed three-dimensionally in a super-quenched alloy matrix 14 made of an amorphous, crystalline, or mixed phase thereof. . The thickness and width of the ribbon 13 are determined by the circumferential speed and pressure of the roll 12,
It can be adjusted by varying the temperature and ejection speed of the melt.

The twin roll method explained using FIG. 2 has the advantage that the thickness of the obtained ribbon 13 is uniform, the surface roughness is small, and relatively thick ribbons can be easily obtained. On the other hand, in the single-roll method, a molten alloy base material is jetted onto the circumferential surface of one roll rotating at high speed, and is ultra-quenched and solidified to obtain a second-phase particle-dispersed ultra-quenched alloy. It has the advantage of being easy to obtain.

In the above example, the heat-resistant tube 7 having a nozzle (small hole) was used, but the lower part of the heat-resistant tube may have a flat shape and be provided with a slit-shaped ejection opening.

In the present invention, alloy base materials include, for example, cobalt-based alloys such as cobalt-iron alloys containing cobalt as a main component, iron-based alloys such as iron-silicon-boron alloys and iron-molybdenum alloys containing iron as a main component, and nickel alloys. Nickel-based alloys such as nickel-silicon-boron alloys whose main components are nickel-silicon-boron alloys, or various alloys such as copper-zirconium alloys and zirconium-niobium alloys are used.

In the present invention, the second phase particles include carbon or carbide such as C, WC, TiC, NbC, etc.
Nitrides such as NbN and TaN, MgO, ZrO ₂ , Y ₂ O ₃ ,
Oxides such as WO ₃ , ThO ₂ , Al ₂ O, Fe ₂ O ₃ , ZnO, and SiO ₂ , borides such as BN, silicates such as SiC, and metals such as Ti, Fe, Mo, and W are used.

The present inventors have discovered that when producing an ingot of the alloy base material constituting the ultra-quenched alloy matrix, or when remelting the ingot for liquid quenching, the second phase particles are kept in a molten state without using the injection dispersion method. It has been found that a material in which the second phase particles are added to the alloy matrix and then ultra-quenched to three-dimensionally disperse the second phase particles in the alloy matrix has various excellent properties.

However, in this method, there are limitations on the type of second phase particles used and the amount that can be dispersed. In particular, when the second phase particles are metal oxides, they have poor wettability with molten metals such as iron, cobalt, and nickel, and are dispersed in very small amounts, and tend to be dispersed only in the surface layer, resulting in three-dimensional not dispersed into Therefore, improvements in mechanical properties such as wear resistance and other properties,
There are limits to improvement.

In this regard, when making an ingot of the alloy base material as in the present invention, the injection dispersion method is used to forcibly add and disperse the second phase particles into the molten alloy base material, thereby increasing the wettability of the alloy base material. Even second phase particles with poor properties are uniformly dispersed three-dimensionally, which greatly contributes to improving the properties and functions of the material.

Next, examples of the present invention will be described.

Example 1 (Co _70.5 Fe _{4.5 Si 15 B 10 ) 99.5 (WC) 0.5 (Co 70.5 Fe 4.5 Si 15 B 10 ) 99 ( WC ) 1 ( Co 70.5} Fe _{4.5 Si 15} B ₁₀ ) ₉₇ (WC) ₃ (Co _{70. 5} Fe _{4. 5} Si ₁₅ B ₁₀ ) ₉₅ (WC) ₅ (Co _{70. 5} Fe _{4. 5} Si ₁₅ B ₁₀ ) ₉₀ (WC ) A second-phase particle-dispersed super-quenched alloy named ₁₀ was prepared by the twin-roll method. The composition of the ultra-rapidly solidified alloy is shown in parentheses on the left in the above compositional formula, the numbers at the bottom right of each element indicate atomic %, and the second phase particle constituents are shown in parentheses on the right in the compositional formula. The numbers at the bottom right of both parentheses represent the respective volume %. Other embodiments also use this same display method.

Next, the specific creation procedure will be explained. First, in order to obtain the composition of the desired ultra-quenched alloy, the constituent metals are
Co, Fe, Si, B Co420.9g, Fe25.5g, Si42.7
g and B11.0 g, respectively, and melt them together in a vacuum high-frequency melting furnace 2 (see Fig. 1) to produce a molten alloy base material 1. This alloy base material 1 is poured into a mold 3 after being melted.

On the other hand, WC fine powder (second phase particles 4 with an average particle size of 1 μm) is filled in advance in a powder feeder 5 for plasma spraying, and high-pressure argon gas from a cylinder 6 is used to mold the alloy base material 1 into a mold. It is injected towards the injection flow.The injection amount of WC fine powder is
The powder feeder 5 adjusts the volume % shown in the above-mentioned compositional formula. In addition, mold 3
The temperature of the alloy base material 1 injected into the alloy is adjusted to maintain its molten state and at a temperature at which the second phase particles, WC fine powder, do not melt, that is, approximately 1200°C. Alloy base material 1 in molten state
The WC fine powder that is forcibly injected toward the mold injection flow is dispersed in the alloy base material 1 in a finely divided state without forming lumps, and the distance between the particles is short. The WC fine powder dispersed in a fine state has a slow floating speed in the alloy base material 1, and therefore does not segregate when the alloy base material 1 solidifies in the mold 3. , the dispersion state is stable. As a result, an ingot 8 made of a Co--Fe--Si--B alloy in which WC fine powder is uniformly dispersed is obtained.

Next, this ingot 8 is placed in a heat-resistant tube 7 made of quartz glass as shown in FIG. 2, the inside of the tube is sufficiently replaced with argon gas 9, and then the ingot 8 is melted in a high frequency melting furnace 10. At this time also WC
It is maintained at a temperature of 1200°C, which is such that the fine powder does not dissolve. Next, actuate the piston 11 to
The lower end nozzle portion is brought as close as possible to the joint between the two rollers 12, 12 rotating at high speed, and the argon gas pressure within the heat-resistant tube 7 is rapidly increased, gradually forming a uniform continuous jet from the nozzle portion. roll 12,1
2 joints. The rolls 12, 12 are rotating at high speed and are constantly in pressure contact, and when ejected, they are instantly solidified by ultra-rapid cooling to a width of 4 mm and a thickness of 4 mm.
A ribbon 13 of 30 μm and 5 m in length was obtained.

When the surface and the cross section in the thickness direction of this ribbon were observed using a scanning electron microscope, it was found that WC fine powder was present in the ultra-quenched alloy matrix with short particle spacing.
The WC fine powders do not aggregate and become bulky, but are uniformly dispersed as individual fine particles, and there are no pores at all. This confirmed that the WC fine powder was uniformly dispersed three-dimensionally in the alloy matrix. Furthermore, it was confirmed by X-ray diffraction that this ultra-quenched alloy matrix alloy was amorphous.

Obtained according to this Example 1.

_{( Co 70 . 5 Fe 4 .} A magnetic head is assembled using each of the materials of the composition as a core material. Each of these magnetic heads was subjected to a running test using a commercially available magnetic tape at a test temperature of 20 DEG C. and a humidity of 50%, and the results are shown in FIG.
The straight line A in the figure is the characteristic line for the material according to the embodiment of the present invention, and the straight line B is the characteristic line for the material for which the injection dispersion method is not applied. It can be seen that it has excellent abrasion resistance.

Example 2 Second phase particle-dispersed superstructure of (Ni ₇₈ Si ₁₀ B ₁₂ ) ₉₇ (WC) ₃ (Ni ₇₈ Si ₁₀ B ₁₂ ) ₉₂ (WC) ₈ (Ni ₇₈ Si ₁₀ B ₁₂ ) ₈₂ (WC) ₁₈ Rapidly solidified alloys were prepared using a single roll method.

Next, the specific creation procedure will be explained. First, the constituent metals to obtain the composition of the desired ultra-quenched alloy
Ni, Si, and B are weighed to give 459 g of Ni, 28 g of Si, and 13 g of B, respectively, and are melted in a vacuum high-frequency melting furnace 2 to produce an alloy base material 1, which is then poured into a mold 3.

WC fine powder (second phase particles 4) with an average particle size of 1 μm is injected from the plasma spray powder feeder 5 together with high-pressure argon gas into the injection flow of the alloy base material 1, and is then cooled to form the WC fine powder. Uniformly dispersed Ni
-Create ingot 8 of Si-B alloy. If the temperature of the alloy base material 1 having the above composition is adjusted to about 1150°C when the WC fine powder is sprayed and dispersed, the added WC fine powder will not dissolve in the alloy base material 1. Uniformly dispersed as fine particles. The amount of WC fine powder added to alloy base material 1 is:
The powder feeder 5 adjusts the powder according to the composition formula.

The ingot is placed in a heat-resistant tube made of quartz glass placed directly above one roll, and the inside of the tube is sufficiently purged with argon gas. Next, the heat-resistant tube is heated and maintained at about 1150° C. in a vacuum high-frequency melting furnace provided on the outer periphery of the tube, and only the alloy base material 1 is remelted. Then, the argon gas pressure inside the heat-resistant tube is rapidly increased, and the molten alloy base material 1 containing fine WC powder is ejected from the slit-shaped opening provided at the bottom of the heat-resistant tube onto the roll rotating at 2000 rpm. be done. When ejected, it was instantaneously ultra-quenched and solidified to obtain a ribbon with a width of 4 mm, a thickness of 30 μm, and a length of 5 m.

When the surface of this ribbon and the cross section in the thickness direction were observed using a scanning electron microscope, it was found that, as in the first example, the WC fine powder was contained in the ultra-quenched alloy matrix at short particle intervals. They do not aggregate and become coarse, but are uniformly dispersed individually as fine particles, and there are no pores at all. This confirmed that the WC fine powder was uniformly dispersed three-dimensionally in the alloy matrix. Furthermore, it was confirmed by X-ray diffraction that this ultra-quenched alloy matrix was amorphous. This new composite material, a second-phase particle-dispersed ultra-quenched alloy, has the following excellent mechanical properties. That is, as the WC volume fraction increased, the yield stress and Young's modulus increased. The mechanical properties of these two are as follows (1)
A simple compound rule as shown in Eq. (2) was followed.

E=E _n (1-V _f )+E _p V _f ...(1) σ=σym {1+V _f (E _p /E _n -1)}...(2) E in formulas (1) and (2) , E _n and E _p are composite materials, respectively.
Young's modulus of the super-quenched alloy matrix and the second phase particles, σy and σym are the yield stress of the composite material and the super-quenched alloy matrix, respectively, and _Vf is the volume fraction of the second phase particles.

Figure 5 shows that as the WC volume fraction (V _f ) increases, (1)
FIG. 2 is a characteristic diagram showing that the Young's modulus (E) of a composite material increases according to the formula. This characteristic diagram shows the change in Young's modulus (E) and E/Em of the composite material with respect to the change in WC volume fraction (Vf) when E _p (Young's modulus of second phase particles) is 68.000Kg/mm ² . There is. In addition, when observing the fractured surface of the alloy of this example in a tensile test, it was found that WC was found on the two fracture surfaces at corresponding positions.
The fractured parts of the particles were observed, indicating that cracks do not occur and propagate at the interface between the amorphous super-quenched alloy matrix and the WC particles.
It was confirmed that the WC particles became the final load bearing area after the matrix was fractured. This indicates that the strength of the interface between the amorphous super-quenched alloy matrix and the WC particles is extremely large.

More preferably, the alloy of this example has both strength and high toughness.
That is, in the alloy of this example, complete contact bending was possible up to a WC volume fraction of about 20%.

Example 3 (Co _70.5 Fe _4.5 Si _{15 B 10} ) _99.9 (WO ₃ ) _0.1 (Co _{70.5 Fe 4.5 Si 15 B 10} ) _{99.7 ( WO 3 ) 0} . ₃ (Co _{70.5 Fe 4.5 Si 15 B 10} ) _99.5 (WO ₃ ) _0.5 (Co _70.5 Fe _{4.5 Si 15 B 10 ) 99} (WO ₃ ) ₁ ( _{Co 70.5} A _{second phase} particle _- dispersed ultra _- quenched alloy _of Fe _{4 .}

Example 4 (Co _70.5 Fe _{4. 5 Si 15 B 10} ) _99.9 (ZrO ₂ ) _0.1 (Co _{70. 5} Fe _{4. 5} Si ₁₅ B ₁₀ ) _{99. 7} (ZrO ₂ ) _{0 . 3} (Co ₇₀ . ₅ Fe ₄ . ₅ Si ₁₅ B ₁₀ ) ₉₉ . ₅ (ZrO ₂ ) ₀ . ₅ (Co ₇₀ . ₅ Fe ₄ . ₅ Si ₁₅ B ₁₀ ) ₉₉ (ZrO ₂ ) ₁ (Co ₇₀ . ₅ A _{second -} phase particle _- dispersed ultra _- quenched alloy _{of Fe 4} .

Example 5 (Co _{70.5 Fe 4.5 Si 15 B 10} ) _99.9 (Y ₂ O ₃ ) _0.1 (Co _{70. 5} Fe _{4. 5 Si 15} B ₁₀ ) _{99. 7} (Y ₂ O _{3 ) 0.3} (Co _{70.5 Fe 4.5 Si 15} B ₁₀ ) _99.5 (Y ₂ O ₃ ) _0.5 (Co _{70. 5} Fe _{4. 5 Si 15} B ₁₀ ) _{99 (} Y ₂ O ₃ ) A second-phase particle-dispersed ultra-quenched alloy of ₁ (Co _70.5 Fe _{4.5 Si 15 B 10} ) ₉₇ (Y ₂ O ₃ ) ₃ was prepared by a single roll method in almost the same manner as in the _second embodiment. I created it.

Example 6 A second phase particle-dispersed ultra-quenched alloy of (Ni ₇₈ Si ₁₀ B ₁₂ ) ₉₀ (ThO ₂ ) ₁₀ (Ni ₇₈ Si ₁₀ B ₁₂ ) ₈₀ (ThO ₂ ) ₂₀ was prepared in exactly the same manner as in Example 2. Created with. The average particle size of the ThO ₂ particles was 2 μm. The produced second phase particle dispersed super-quenched alloy had a width of 4 mm, a thickness of 30 μm, and a length of 5 m. Scanning electron microscopy revealed that ThO ₂ particles were uniformly dispersed three-dimensionally in the super-quenched alloy matrix, with no pores, and that the super-quenched alloy matrix was
It was confirmed by line diffraction that it was an amorphous phase. In this example alloy, as in the previous example, the characteristics of the amorphous ultra-quenched alloy matrix and the second phase particles are organically combined, that is, the mechanical properties of each are complementary, resulting in high strength and high toughness. A composite material with both of these properties was obtained. In addition, it was confirmed that the yield stress and Young's modulus of the alloy of this example follow a simple compound law as shown in Example 2.

Example 7 A second phase particle-dispersed ultra-quenched alloy of (Fe ₇₅ Si ₁₀ B ₁₅ ) ₉₅ (TiC) ₅ (Fe ₇₅ Si ₁₀ B ₁₅ ) ₉₀ (TiC) ₁₀ was formed into a wire shape by a well-known spinning method. Created in. The ingot was prepared in the same manner as in the first embodiment, and water was used as the refrigerant during ultra-rapid solidification.
The rotational speed of the rotating drum was 1000 rpm, and the argon gas jetting speed was about 0.6 to 0.9 times the rotational speed of the rotating drum. The average particle size of the TiC particles was 1 μm. Scanning electron microscopy revealed that TiC particles were three-dimensionally uniformly dispersed in the super-quenched alloy matrix, with no pores, and X-ray diffraction confirmed that the super-quenched alloy matrix was an amorphous phase. The shape of the alloy in this example is a wire with a diameter of 150 μm.
It was 4m long. The alloy of this example also had good mechanical properties similar to those of the previous example, and in particular had a high yield strength of 500 kg/mm ² , which far exceeded that of the currently highest strength piano wire. Further, the yield stress and Young's modulus followed the simple compound rule shown in Example 2.

Example 8 A second phase particle dispersed super-quenched alloy of (Ni ₇₈ Si ₁₀ B ₁₂ ) ₉₀ (BN) ₁₀ (Ni ₇₈ Si ₁₀ B ₁₂ ) ₈₀ (BN) ₂₀ was created in exactly the same manner as in Example 2. did. The average particle size of the BN particles was 1 μm. The produced second phase particle-dispersed ultra-quenched alloy had a rib shape with a width of about 4 mm, a thickness of about 30 μm, and a length of 3 m. Through scanning electron microscopy,
It was confirmed that the BN particles were three-dimensionally uniformly dispersed in the super-quenched alloy matrix, with no pores, and that the super-quenched alloy matrix was an amorphous phase by X-ray diffraction. In this example alloy, as in Example 2, the respective properties of the amorphous ultra-quenched alloy matrix and the second phase particles are organically combined, that is, the mechanical properties of each are complemented, resulting in high strength and high toughness. A composite material with both properties was obtained. In addition, it was confirmed that the yield stress and Young's modulus of the alloy of this example follow a simple compound law as shown in Example 2.

Example 9 A second phase particle dispersed super-quenched alloy of (Cu ₆₀ Zr ₄₀ ) ₉₀ (SiC) ₁₀ (Cu ₆₀ Zr ₄₀ ) ₇₀ (SiC) ₃₀ was prepared in exactly the same manner as in Example 2. Note that the average particle size of the SiC particles was 3 μm. The created second phase particle dispersed ultra-quenched alloy has a width of 4 mm, a thickness of 30 μm, and a length of 3 m.
It was ribbon-like. In this example, scanning electron microscopy revealed that the SiC particles were uniformly and three-dimensionally dispersed in the super-quenched alloy matrix, with no pores, and X-ray diffraction revealed that the super-quenched alloy matrix was in an amorphous phase. I confirmed that there is. Unlike the cases of Examples 1 to 4, the super-quenched alloy matrix of this example alloy is a so-called metal-metal amorphous alloy that does not contain a metalloid, and the second phase of this type of matrix and particles is a particle dispersion. It can be seen that type super-quenched alloys can also be created. In this example alloy, Example 2
Similarly, the yield stress and tensile strength were improved compared to the conventional Cu ₆₀ Zr ₄₀ amorphous alloy.

Example 10 A second phase particle-dispersed ultra-quenched alloy of (Fe ₈₂ B ₁₈ ) ₉₉ (Fe) ₁ (Fe ₈₂ B ₁₈ ) ₉₈ (Fe) ₂ was prepared in exactly the same manner as in Example 2. The average particle size of the Fe particles was 5 μm. In this example as well, it was confirmed by scanning electron microscopy that the Fe particles were uniformly and three-dimensionally dispersed. Further, the super-quenched alloy matrix is an invar alloy. As an Fe-B-based amorphous alloy, it has a high saturation magnetic flux density and is expected to be used as a material for transformers. The magnetic properties required for transformer materials include high saturation magnetic flux density, low iron loss, high magnetic permeability, low magnetostriction, and little magnetic deterioration. The current advantages of amorphous transformer materials over silicon steel sheets are that they possess both of the above properties. Other points remain as future issues.

In this example, by combining Fe particles at a volume content of 1%, a saturation magnetic flux density 3% higher than that of the matrix amorphous alloy was obtained.

Example 11 A second phase particle dispersed ultra-quenched alloy (Zr ₄₅ Nb ₄₀ Si ₁₅ ) ₈₀ (NbN) ₂₀ was prepared in exactly the same manner as in Example 2. The average particle size of the NbN powder was 3 μm.

Observation of the composition image of this example alloy using a scanning electron microscope revealed that NbN particles were uniformly dispersed three-dimensionally in the ultra-quenched alloy matrix, with no pores, and the ultra-quenched alloy matrix was found to be amorphous by X-ray diffraction. It was confirmed that it was the phase.

Example 12 (Co ₇₀ . ₅ Fe ₄ . ₅ Si ₁₅ B ₁₀ ) ₉₉ (C) ₁ (Co ₇₀ . 5 Fe ₄ . _{5 Si 15} B ₁₀ ) ₉₅ (C) ₅ (Co ₇₀ . ₅ Fe ₄ . ₅ A second phase particle-dispersed ultra-quenched alloy of Si ₁₅ B ₁₀ ) ₉₀ (C) ₁₀ was prepared in exactly the same manner as in Example 2. The average particle size of C particles is 1
It was μm. The produced second phase particle-dispersed ultra-quenched alloy had a ribbon shape with a width of 4 mm, a thickness of 30 μm, and a length of 4 m. Scanning microscope observation of this ribbon revealed that the C particles were uniformly dispersed three-dimensionally in the super-quenched alloy matrix, and it was dense with no pores, and X-ray diffraction revealed that the super-quenched alloy matrix was amorphous. confirmed.

Next, an example of a second phase particle dispersed super rapidly solidified alloy consisting of a crystalline super rapidly solidified alloy and second phase particles will be given.

Example 13 In the same manner as in Example 2, a second phase particle-dispersed ultra-quenched alloy was prepared in which NbC particles were dispersed in Fe ₈₉ . ₄ Mo ₉ C ₁ . ₆ , which is a non-equilibrium austenite phase. That is, (Fe ₃₉ . ₄ Mo ₉ C ₁ . ₆ ) ₉₈ (NbC) ₂ (Fe ₃₉ . ₄ Mo ₉ C ₁ . ₆ ) ₉₅ (NbC) ₅ (Fe ₃₉ . ₄ Mo ₉ C ₁ . ₆ ) ₉₀ (NbC ) ₁₀ is an alloy. Observation of the composition image of the obtained alloy using a scanning microscope revealed that the NbC particles were uniformly dispersed three-dimensionally in the ultra-quenched alloy matrix, with no pores, and the ultra-quenched alloy matrix had a structure of ultra-fine crystal grains. It was confirmed that it was a non-equilibrium γ-austenite single phase. Since the non-equilibrium γ-austenite phase that makes up this ultra-quenched alloy matrix is a crystalline alloy, it has higher thermal stability than an amorphous alloy, and has high strength and toughness as a crystalline alloy. Inferior to amorphous alloys, its strength is 100~
It is ^about 150Kg/mm2, which is about half that of amorphous alloys. In this example alloy, when the NbC volume fraction is 5% or 10%, the strength is as high as 200 to 300 Kg/mm ² and is comparable to iron-based amorphous alloys. Furthermore, since it has γ-austenite as a matrix, it has higher thermal stability than amorphous metals.

As a method of dispersing the second phase particles in the super-quenched alloy matrix, it is also possible to add the second phase particles to the molten alloy base material constituting the super-quenched alloy matrix. In this method the second
In order to uniformly disperse the phase particles in the alloy, the second phase particles are injected near the injection port of the alloy base material, but this has the disadvantage that the structure of the nozzle part becomes particularly complicated. There is.

The present invention has the above-mentioned structure, and since the second phase particles are added in advance at the stage of creating an ingot of the alloy base material constituting the ultra-quenched alloy, the second phase particles are added in advance.
It is easy to add phase particles, and the manufacturing equipment for super-rapidly solidified alloys does not become complicated.

Further, since the second phase particles are forcibly injected into the alloy base material after melting, the particles are individually dispersed in a fine state in the alloy base material without agglomerating and becoming coarse. Therefore, since the floating speed in the alloy base material is slow, there is no segregation, the dispersion state is extremely uniform, and the particle spacing is short. For this reason, it is possible to provide a second phase particle dispersed ultra-rapidly solidified alloy having excellent properties such as mechanical strength.

[Brief explanation of the drawing]

1 and 2 are principle diagrams for explaining the manufacturing method of the second phase particle-dispersed super-quenched alloy according to the embodiment of the present invention, and FIG. 3 is the produced second-phase particle-dispersed super-quenched alloy. An enlarged cross-sectional view of the alloy ribbon, Figure 4 is a characteristic diagram showing wear resistance, and Figure 5 is the change in Young's modulus of the composite material with respect to the WC addition rate of the second phase particle dispersed ultra-quenched alloy according to the example of the present invention. FIG. DESCRIPTION OF SYMBOLS 1... Alloy base material, 4... Second phase particles, 8... Ingot, 13... Ribbon, 14... Ultra-quenched alloy matrix.

Claims (1)

[Scope of Claims] 1. Second phase particles comprising at least one kind of second phase particles uniformly dispersed three-dimensionally in an ultra-quenched alloy matrix consisting of an amorphous, crystalline, or mixed phase thereof. In the method for producing a dispersed super-quenched alloy,
After heating and melting the alloy base material constituting the super-quenched alloy matrix, and before the alloy base material is pseudo-solidified, the second phase particles are injected onto the alloy base material together with an injection medium made of an inert gas. The ingot is dispersed and then cooled to create an ingot containing the second phase particles, which is remelted to such an extent that the second phase particles do not dissolve, and then ultra-quenched and pseudo-solidified to form the second phase in the ultra-quenched alloy matrix. 3 particles
The second method is characterized in that it is dimensionally uniformly dispersed.
A method for producing a phase particle dispersed ultra-quenched alloy. 2. The method for producing a second phase particle dispersed super rapidly solidified alloy according to claim 1, wherein the super rapidly solidified alloy matrix is a cobalt-based amorphous alloy containing cobalt as a main component. 3. The method for producing a second phase particle dispersed super rapidly solidified alloy according to claim 1, wherein the super rapidly solidified alloy matrix is an iron-based amorphous alloy containing iron as a main component. 4. The method for producing a second phase particle dispersed super rapidly solidified alloy according to claim 1, wherein the super rapidly solidified alloy matrix is a nickel-based amorphous alloy containing nickel as a main component. 5. The second aspect of claim 1, wherein the second phase particles are carbon or carbide.
A method for producing a phase particle dispersed ultra-quenched alloy. 6. The second aspect of claim 5, wherein the second phase particles are tungsten carbide.
A method for producing a phase particle dispersed ultra-quenched alloy. 7. The method for producing a second phase particle dispersed ultra-rapidly solidified alloy according to claim 1, wherein the second phase particles are nitrides. 8. The method for producing a second phase particle dispersed ultra-quenched alloy according to claim 1, wherein the second phase particles are oxides. 9. The method for producing a second phase particle dispersed ultra-rapidly solidified alloy according to claim 1, wherein the second phase particles are a boride. 10. The method for producing a second phase particle dispersed ultra-rapidly solidified alloy according to claim 1, wherein the second phase particles are silicate. 11. The method for producing a second phase particle dispersed super-quenched alloy according to claim 1, wherein the second phase particles are metal. 12. The method for producing a second phase particle-dispersed ultra-quenched alloy according to claim 1, wherein the inert gas is argon. 13. Claim 1, characterized in that the re-melted ingot is jetted onto the joint surface of two rolls rotating at high speed and solidified by ultra-rapid cooling.
A method for producing a second phase particle-dispersed ultra-quenched alloy as described in 2. 14. The second phase particle-dispersed superstructure according to claim 1, wherein the re-melted ingot is jetted onto the circumferential surface of one roll rotating at high speed and solidified by ultra-rapid cooling. Method for producing rapidly solidified alloys.