JPS6320570B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an amorphous material, and an object thereof is to provide a method for producing a new type of amorphous material that has not been seen before.

Conventionally, various methods have been proposed for making amorphous material by rapid cooling. For example, with the vapor deposition method or the sputtering method, the thickness is limited to several μm, and it is difficult to provide a film with a large thickness. Furthermore, the gun method and piston-anvil method yield only small, irregularly shaped flakes. The roll method is much more suitable for mass production than these methods, but only tape-shaped products can be obtained, and it is extremely difficult to control as tens of meters of tape-shaped amorphous material can be produced in an instant. In addition, it is not possible to manufacture multi-layered products or composites. With the most recent laser methods, only the very surface layer of a bulk body can be amorphized. As seen in these methods, the conventional methods have restrictions on shape, size, etc., and therefore have various restrictions on application.

Therefore, the present invention eliminates these conventional drawbacks, provides a method that is extremely easy to control, and provides a method for manufacturing an amorphous composite thick film that has not been possible in the past.

Hereinafter, one embodiment of the present invention will be described based on the drawings. In FIG. 1, 1 is a spray nozzle having a thermal spraying port 2, 3 is a supply port for microparticles that communicates with the thermal spraying port 2 formed in the nozzle 1, and 4 is formed at the rear of the thermal spraying port 2 of the nozzle 1. high pressure gas inlet, 5
is a base body disposed in front of the thermal spraying port 2, which moves at high speed in a direction perpendicular to the gas blowing direction A.

In this configuration, microparticles are supplied through the supply port 3 into a high-temperature flame such as an oxygen-propane flame, an arc flame, or a plasma flame generated at the thermal spraying port 2 to melt them, and at the same time, the particles are supplied through the introduction port 4 to melt them. A high-pressure gas is introduced in the direction of arrow A, and this gas causes the dissolved microparticles to fly and collide with the substrate 5, which is moving at high speed in a direction perpendicular to the direction of arrow A, and rapidly solidify them. This forms a film 6.

In the above embodiment, the fine particles were supplied into the spray nozzle 2 of the injection nozzle 1 through the supply port 3.
The rod-shaped body 7 may be inserted into the thermal spraying port 2 as shown by the solid line in FIG. 2, or the rod-shaped body 7 may be supplied in front of the thermal spraying port 2 as shown by the phantom line in FIG. .

If the base 5 used here has good heat dissipation,
It may be in any shape such as a flat plate, a belt, or a cylinder, and if it is a cylinder, it is better if it is rotated.
Due to such high-speed movement and because the amount of heat accumulated at one point is small, the solidification heat generated per unit area is small, and therefore the temperature rise of the base body 5 is small. Further, even if the next high-temperature melt overlaps and solidifies at the point where solidification has finished due to heat loss due to heat radiation, the temperature is unlikely to rise due to this. Usually, the temperature of the substrate 5 remains at 100 to 200°C. Further, it is a useful method to cool the substrate 5 by spraying a cooling medium such as a cooling gas on the front and back surfaces thereof, and it is easy to maintain the temperature of the substrate 5 at 100° C. or less. In this method, the moment the molten spherical or teardrop-shaped microparticles collide with the substrate 5, they are flattened as shown in FIG.
It is rapidly cooled and solidified as soon as it comes into close contact with the surface. For example, in plasma spraying, microparticles are estimated to fly at a speed close to the speed of sound. Therefore, the cooling rate is estimated to easily reach 10 ⁶ °C/sec. This cooling rate is sufficient not only for Au-Si alloys that easily become amorphous, but also for a series of amorphous alloys called Metaglass. Moreover, the temperature of the substrate 5 can be kept lower than the temperature at which the film 6, that is, the amorphous body recrystallizes.

When using the above-mentioned method, a long belt-like object is used as the base 5, and the spray nozzle 2 is moved in the longitudinal direction at high speed in the transverse direction of the base 5, or a large number of spray nozzles 2 are used. Arrange them in different rows,
By uniformly applying the coating 6 to the entire substrate 5, it is possible to form, for example, a tape-shaped amorphous body. At this time, by moving the belt not only in its longitudinal direction but also in its width direction, a multilayered amorphous film 6 is formed. A similar effect can be obtained by rotating the belt. Note that if the substrate 5 is not subjected to pretreatment such as sandblasting, the coating 6 can be easily peeled off from the substrate 5, so that continuous operation is also possible. Peeling was particularly easy for mirror-finished surfaces. In order to uniformly apply the coating 6 to the substrate 5, as can be seen from the cross-sectional shape of a single sprayed coating 6 shown in FIG.
It is necessary to overlap each point (width of the point), and this L
The value varies depending on the conditions, but is approximately 5 to 20 mm. When moving the thermal spraying port 2, the base 5
It is desirable that the pitch be the same 5 to 20 mm. It is sufficient that the relative moving speed of the substrate 5 with respect to the thermal spraying port 2 is approximately 30 cm/sec or more in one direction and 0.5 cm/sec or more in the other direction. The thickness of the film 6 formed in one operation is limited by the cooling of the substrate 5, etc., and approximately 5 to 50 μm is appropriate and within a range that is easy to handle. Furthermore, the distance between the thermal spray nozzle 2 and the base 5 is usually 50 to 300 mm.
was appropriate. Although it is possible to exceed this range, it is not appropriate because the operation becomes difficult.

Since the film 6 created by the method described above is the surface of a new substrate 5, it is easy to stack the next film 6 on top of it to form a multilayer structure one after another.
At this time, if the same material is multilayered, a thick bulk amorphous material can be obtained, and if different materials are layered together, an amorphous composite material can be obtained. At this time, a composite body in which one layer is made of an amorphous alloy magnetic material and the other layer is made of an insulating material is particularly useful because it prevents eddy currents and exhibits high magnetic permeability at high frequencies. Of course, the amorphous material itself must be a soft magnetic material, but since it is a thin layer interposed with an insulating material, it is less susceptible to erosion due to eddy currents and can provide an ideal magnetic core material. be. Moreover, it has the characteristic that the adhesive force between the multiple layers created by this method is extremely strong. Note that the insulator does not have to be an amorphous material, and there is no problem even if it is a thermally sprayed oxide film of alumina, silica, or the like. Such multilayer bodies are also suitable for magnetic heads.

The inventors have investigated that the amorphous material has a small amount of wear and is similar to ferrite material, which has excellent wear resistance.Moreover, since the laminated layer is a thin layer with a thickness of 5 to 50 μm, it has good high frequency characteristics. is better than normal permalloy (normal permalloy has a thickness
It is difficult to reduce the thickness to 100 μm or less. As a result, high frequency characteristics deteriorate due to the skin effect), and the saturation magnetic flux density is higher than that of ferrite and close to that of permalloy, making it an excellent magnetic head.

As is clear from the above description and the examples below, according to the present invention, a bulk amorphous material with a thickness more than 6 times that conventionally limited to a thickness of about 50 μm can be produced. Compared to the roller method currently being developed for mass production, which can produce long, thin tapes of several tens of meters in an instant, with almost no control, it is possible to control thickness, length, and production speed. Not only does it have great features such as sufficient control, but it can also produce not only thin films like conventional ones, but also thick films with a thickness of 0.3 mm or more and bulk amorphous materials with a thickness larger than that. It is clear that the field of application will be greatly expanded compared to the past.

Furthermore, as the thickness increases, the distance between the high-temperature flame and the substrate 5 becomes shorter, and the characteristics of the amorphous material may differ due to overheating of the substrate 5 or different quenching conditions. This problem can be solved by moving the base 5 back from the thermal spraying port 2 as the thickness of the coating 6 increases so that the distance between the flame and the base 5 becomes constant.

Next, specific examples will be described.

Example 1 In Fig. 1, (Fe 0.8 Ni
A molten metal of 0.1 Co 0.1) 0.75 B 0.15 Si 0.1 was atomized to obtain an alloy powder with an average particle size of 55 μm. Plasma output 35V, 700A, using Ar as gas,
Plasma spraying was performed at approximately 5Kg/hr. The flight speed of the molten particles at this time was estimated to be greater than the speed of sound. The base body 5 is 110 mm away from the spray nozzle 2, 3 mm
It is a thick Al plate, and the surface was forcibly cooled with two cooling gas streams. The base 5 is moved vertically at a speed of 50 cm/sec and horizontally at a speed of 1 cm/sec, and the sprayed surface is moved at a speed of 250 cm/sec.
×150mm. The thickness of the obtained film 6 was 1.7 mm.
As a result of X-ray diffraction, it was found to be an amorphous substance with no obvious diffraction peaks.

Example 2 The same conditions as Example 1 were set, but the thermal spray port 2
is moved parallel to the base 5 and perpendicular to the moving direction of the base 5 at a rate of 30 cm/sec, and the width is 30 cm and the length is 30 cm.
Thermal spraying was carried out on a substrate 5 made of an iron plate moving at a speed of 1.2 cm/sec. The coating 6 sprayed once is easily separated from the base 5, has a width of 30 cm, a length of 30 m, and an average thickness.
A 40 μm amorphous tape was obtained.

Furthermore, when thermal spraying was performed twice under the same conditions without separating the coating 6 from the base 5, the average thickness was approximately
A thick tape of 115 μm was obtained. This tape could be easily separated from the substrate 5. The three thermally sprayed layers remained in close contact with each other even in repeated bending tests, and did not separate even when the tape was broken. As a result of X-ray diffraction, all of them were found to be amorphous.

Example 3 Three thermal spray ports 2 were installed, spaced apart by 70 mm in the horizontal direction, and shifted by 14 mm in the vertical direction. The base body 5 has a width of 35
It is a thin stainless steel plate with a length of 20 m. Base 5 to 50
When moved at cm/sec, the width was 24μm on average.
I was able to peel off a tape-shaped amorphous material that was 35mm long and 20m long.

Example 4 On the coating 6 obtained in Example 1, immediately following
An alloy powder of Ni0.8 Cr0.2 was sprayed. The thickness of the second film was 0.2 mm, giving a total thickness of 1.9 mm. When the multilayer film was peeled off from the substrate 5 (it could be easily peeled off because the surface of the substrate was not sandblasted), there was no peeling between the layers when a bending test was performed, and no peeling was observed when cutting with a hacksaw. . As a result of X-ray diffraction, the first film was found to be amorphous.

Example 5 In Example 3, immediately after finishing thermal spraying,
Al ₂ O ₃ −2.5% TiO ₂ fine powder was sprayed to a thickness of 5 μm, and an amorphous layer was then sprayed on top of it.
Total thickness of 20 layers (10 layers each of amorphous layer and insulating layer)
An amorphous insulator composite of 0.6 mm in width, 35 mm in length and 20 m in length was obtained. When it was bent at a right angle, it broke, but the delamination was not noticeable. The adhesive strength between layers is
Cylindrical carbon test estimated it to be about 300Kg/cm ² or more.

Example 6 A molten metal of (Co0.95 Fe0.05)0.75 B0.15 Si0.1 was atomized to obtain an alloy powder with an average particle size of 60 μm.
After thermal spraying to a thickness of about 30 μm in the same manner as in Example 3, SiO ₂ fine powder was immediately layered and thermal sprayed to a thickness of about 3 μm, which was repeated to obtain a total thickness of about 300 μm, 5 layers each, 10 layers in total. At this time, in order to particularly improve the cooling effect, liquid nitrogen was injected onto the back surface of the substrate 5 to cool it. Magnetic alloys such as permalloy and sendust
Although it is not easy to make a 30 μm thin plate, when we compared magnetic heads made by laminating such thin plates into the same shape, there was no significant difference in electromagnetic properties between the three. However, in a corrosion resistance test using 1% NaCl, almost no corrosion was observed in the amorphous head according to the present invention, whereas Permalloy and Sendust were significantly corroded. The wear resistance is 13 μm, which is close to 10 μm for MnZn ferrite, compared to 75 μm and 35 μm (wear amount per 100 hours) for Permalloy and Sendust. That is, the magnetic head of the present invention had excellent electromagnetic properties as a metal head, and also exhibited excellent corrosion resistance and abrasion resistance comparable to ferrite.

Example 7 Instead of atomizing, the molten metal was drawn up into a thin pipe and formed into a linear shape with a diameter of about 3 mm. When this was quantitatively inserted into a plasma flame and thermal sprayed in the same manner as in Example 1 (see FIG. 2), the same results as in Example 1 were obtained. In other words, it was found that there was no significant change whether powder was supplied or rod-shaped bodies were supplied. Furthermore, although only plasma flames have been described in the above embodiments, it goes without saying that high-temperature flames such as arc flames and oxygen-propane flames can also be applied to form molten microparticles.

As described above, according to the method for manufacturing an amorphous body of the present invention, it is possible to provide a method for manufacturing an amorphous body that is extremely easy to control, and it is also possible to provide a method for manufacturing an amorphous body that is extremely easy to control. It is possible to provide a method for easily forming crystalline bodies and multilayer composite layers, and thereby to provide excellent materials such as transformer magnetic cores and magnetic heads. It is an excellent product that significantly expands the applications of the body.

[Brief explanation of the drawing]

FIG. 1 is a schematic vertical cross-sectional view showing one embodiment of the present invention, FIG. 2 is a schematic vertical cross-sectional view of the main part showing another embodiment of the present invention, and FIG. FIG. 4 is a cross-sectional view of the quenched state, and FIG. 4 is a cross-sectional view of the state where thermal spraying is performed in a straight line. 2... thermal spraying port, 3... fine particle supply port, 5...
...Substrate, 6... Film (amorphous body), 7... Rod-shaped body.

Claims (1)

[Scope of Claims] 1. A raw material powder is melted in a high-temperature flame and then blown away by an inert high-pressure gas flow, or a rod-shaped raw material is melted and atomized by an inert high-pressure gas flow to create molten microscopic particles. Let particles fly,
A method for producing an amorphous material, which comprises colliding once or multiple times with a substrate moving at high speed in a direction perpendicular to the flight direction, and rapidly cooling the substrate to form an amorphous material on the substrate. 2. A method for producing an amorphous material according to claim 1, characterized in that microparticles made of the same raw material are made to collide with a substrate multiple times. 3. Claim 1, characterized in that microparticles made of two or more types of raw materials are collided with a substrate and rapidly cooled to form an amorphous body consisting of two or more types of heterogeneous layers on the substrate. 2. Method for producing an amorphous material as described in Section 1. 4. Claim 1, characterized in that the elongated substrate is moved at high speed in one direction, and the high-temperature flame is moved in a direction perpendicular to the moving direction of the substrate, so that the entire surface of the substrate is covered with the high-temperature flame. A method for producing the described amorphous body. 5. The amorphous material according to claim 1, wherein a plurality of high-temperature flames are arranged at appropriate intervals, and a long substrate is moved at high speed in one direction to cover the entire surface of the substrate with each of the high-temperature flames. How to make a solid body. 6. The method for producing an amorphous material according to claim 1, characterized in that a cooling medium is injected onto the substrate to suppress a rise in temperature of the substrate. 7. Claims 1 to 5, characterized in that the surface of the substrate to which the amorphous material adheres is mirror-finished.
A method for producing an amorphous body according to any one of paragraphs. 8. The method for producing an amorphous material according to any one of claims 1 to 5, wherein the surface of the substrate to which the amorphous material adheres is roughened. 9. A patent characterized in that as the thickness of the amorphous material on the substrate increases, the gap between the high temperature flame and the amorphous surface is maintained constant by relatively separating the high temperature flame and the substrate. A method for producing an amorphous body according to any one of claims 1 to 5.