JPH0422856B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel iron-lead amorphous compound material and a method for producing the same. In recent years, with the development of electronics and related technologies, research has been actively conducted on oxide ceramics mainly containing iron oxide (Fe ₃ O ₄ ) and their single crystals. Research is being conducted as a conversion element material in fields such as , atmospheric gas-electricity, photoacoustic polarization, and X-ray spectroscopy, and as a catalyst material. As a stable compound of Fe ₃ O ₄ and PbO, only a few types of crystals have been described in a few documents, and although research on the single crystallization of these compounds is being actively conducted, No studies have been conducted on amorphous compounds. The present invention is based on (Fe ₃ O ₄ ) _1-xy・(PbO) _x・(M) _y (where M is Co,
Provided are an iron-lead amorphous compound material containing at least one of the oxides of Ni, Mn, and Zn, and having a composition of 0.30≦x≦0.70 and 0<y≦0.50, and a method for producing the same. The iron-lead amorphous compound of the present invention is a magnetic material,
It is useful as a photo-responsive element, a temperature-responsive element, a magnetic memory material, an ion-conductive material, a magnetic tape, a catalyst, a light-transparent conductive material, a dielectric material, a photo-electrical switching element, a thermo-electrical switching element, etc. The iron-lead material containing the third component represented by (M) _y in the above compositional formula has significantly improved magnetic properties, especially compared to a material consisting only of iron-lead. The usefulness in each application is further enhanced. The iron-lead amorphous oxide of the present invention is produced as follows. The raw material used in the present invention is a mixture of iron oxide, lead oxide, and at least one of cobalt oxide, nickel oxide, manganese oxide, and zinc oxide. As the latter third component source, carbonates or the like which can be decomposed by heating to produce oxides may be used. The composition ratio of these mixtures is (Fe ₃ O ₄ ) _1-xy・(PbO) _x・(M) _y (where M is Co,
It represents at least one kind of oxide of Ni, Mn, and Zn, and has a quantitative ratio of 0.30≦x≦0.70 and 0<y≦0.50. A raw material mixture having the above composition ratio is heated and melted in an inert atmosphere or in a vacuum, and then ultra-quenched in an inert atmosphere or in a vacuum. The heating and melting may be carried out at a temperature higher than the temperature at which these raw material mixtures are sufficiently dissolved, preferably at a temperature of 50 to 50°C higher than the melting temperature.
Temperature range as high as 200℃, especially preferably 80~150℃
Heat at a moderately high temperature. The atmosphere during heating is an inert atmosphere or a vacuum, and is preferably N ₂ or Ar atmosphere. Next, the melt of the raw material mixture is ultra-quenched. Ultra-quenching is an essential requirement for the method of the present invention, and only through this can a new amorphous compound be obtained. Very acute cases are usually 10 ⁴ to 10 ⁶
The cooling rate is approximately ℃/second. This ultra-rapid cooling can be carried out by a wide variety of methods as long as it can be cooled at the above-mentioned cooling rate.The melt of the raw material mixture is injected onto the surface of a roll rotating at high speed and solidified in the atomic arrangement of the liquid state. A typical example is the method of forcing people to do something. An example of a quenching apparatus for a molten raw material mixture used in carrying out the method of the present invention will be described below with reference to the drawings. FIG. 1 shows a front view of the rapid cooling device main body 3 installed on the pedestal 1. As shown in FIG. The quenching device includes a dielectric heating coil 5, a raw material heating tube 7, a support 9 for the tube 7, a nozzle 11 for spouting the molten raw material, a quenching roll 13, a cooling nozzle 15 for the nozzle 11, an eddy current prevention air nozzle 17, Fine adjustment mechanism 1 of nozzle 11
9, an air cylinder 21, a receiving box 23 for the cooled material, a cooling material outlet 25, etc. are the main components. A fan for cooling the roll is installed inside the cooling roll 13, and N ₂ is applied to the end of the roll surface.
By installing an inert gas inlet such as Ar,
The molten raw material can be rapidly cooled stably.
FIG. 2 shows details of the support 9. In FIG. 2, the support body 9 includes a cooling water inlet passage 29 with a valve 27, a cooling water discharge passage 31, and a needle valve 33.
A blow air introduction path 35 equipped with a blow air introduction path 35, a mechanism 37 for finely adjusting the distance between the surface of the roll 13 and the nozzle 11, and a rectifying perforated plate 39 for uniformly extruding the raw material melt are provided. When carrying out the method of the present invention using the quenching device 3 shown in FIGS. 1 and 2, first, a raw material mixing portion having a predetermined composition is housed in a tube 7 having a nozzle 11 for blowing out the melt. This tube 7 is made of a material that is sufficiently durable under high temperature non-oxidizing atmosphere conditions.
For example, those made of platinum-rhodium, iridium, silicon nitride, boron nitride, etc. are preferred.
Note that the material of the portion not in direct contact with the raw material melt may be high melting point ceramics, glass, or metal. The shape of the nozzle opening is determined appropriately depending on the target product; for example, in the case of thin wire materials, it is circular;
For wide products, use a slit-shaped one. The shape of the nozzle opening may be oval or other shape. The raw material mixture stored in the tube 7 is then heated to a temperature equal to or higher than its melting point to form a melt, and then a constant gas pressure is applied from the mouth of the nozzle 11 onto the surface of the roll 13 rotating at high speed. It is blown out with active gas and rapidly cooled on the roll surface. The blowing angle of the raw material melt between the nozzle opening and the roll surface may be perpendicular to the roll surface if the width of the target compound is approximately 3 mm or less, and perpendicular to the roll surface if the width is approximately 3 mm or more. 0°～
It is 45°. Although these blowout angle adjustment mechanisms can be incorporated into the device itself as a mechanism that can set a predetermined angle, it is preferable to process the nozzle itself. The heating method for the raw material mixture is not particularly limited, but it is usually carried out in a furnace equipped with a heating element, a dielectric heating furnace, or a condensing heating furnace. The temperature of the raw material melt is preferably 50 to 200°C, preferably 80 to 150°C higher than its melting point. At this time, if it is too close to the melting point,
While the melt is being blown onto the roll surface, there is a risk that it will cool and solidify in the vicinity of the nozzle, and conversely, if the temperature becomes too high, it tends to be difficult to rapidly cool the melt on the roll surface. The pressurizing gas used to blow out the melt onto the roll surface is preferably an inert gas, such as argon, nitrogen, helium, etc., in order to maintain the melt raw material in a predetermined oxidation state. The gas pressure depends on the size of the nozzle opening, but is usually about 0.1 to 2.0 Kg/ ^cm2 , preferably about 0.5 to 1.0 Kg/ ^cm2 . In addition, the distance between the nozzle opening and the roll surface when blowing out the raw material melt is preferably about 0.01 to 1.0 mm, more preferably 0.05 mm.
~0.5mm. If smaller than 0.01mm,
If the puddle amount becomes very small and a uniform material cannot be obtained, on the other hand, if it is larger than 1.0 mm, the puddle amount becomes excessive, or if it exceeds the puddle thickness formed by the interfacial tension of the composition melt. In some cases, a puddle tends to be difficult to form. The material of the roll includes copper and its alloy with good thermal conductivity, the above-mentioned materials having a hard chrome plating layer, steel, stainless steel, and the like. The circumferential speed of the roll is 5 m/sec to 35 m/sec, preferably 10 m/sec.
The target amorphous compound material of high quality can be obtained by rapidly cooling the raw material melt at a speed of 20 m/sec to 20 m/sec. In this case, if the peripheral speed of the roll is 5 m/sec or less, it is not very preferable because it tends to be difficult to become amorphous. When the peripheral speed of the roll is greater than 35 m/s, the shape of the target material obtained becomes extremely thin, and all of it becomes scaly or fine powder-like.
In terms of material structure, it is still an amorphous compound material of the present invention. The compound of the present invention is produced under reduced pressure to high vacuum or in an inert gas atmosphere as an atmosphere in which the melt raw material is blown onto the rotating roll surface. When heating and melting the raw material mixture in a tube, it is necessary to completely melt the mixture. However, before the mixture is completely molten, some of the molten material may flow out from the nozzle tip, so the nozzle tip is locally cooled to prevent the melt from flowing out. It is preferable to do so. A typical means for locally cooling the nozzle is to blow a cooling gas onto the tip of the nozzle, and the gas is preferably an inert gas such as argon, helium, or nitrogen. The novel amorphous compound material according to the present invention usually has a thickness of about 50 to 10 μm and is a very brittle material. For this reason, after the material is rapidly cooled and solidified on the roll surface, it is preferable that stress is not applied to the material as much as possible. One of the causes of stress addition is the large turbulent flow in the air layer on the roll surface caused by the wind phenomenon caused by roll rotation in the atmosphere. In order to prevent this turbulent flow and to improve the adhesion between the molten raw material mixture to be rapidly cooled and the roll surface, a countercurrent blowout nozzle for preventing wind blowing, that is, a swirl prevention nozzle 17 shown in FIG. 1 is installed. , a fan is fixedly installed inside the roll. In the latter case, the turbulent flow generated inside the roll due to rotation of the roll is absorbed into the roll through a variable-diameter gas inlet provided at the end of the roll surface, and is discharged from the front of the roll axis, allowing the gas to flow on the roll surface. This allows the melt to be pressed more tightly against the roll surface, and furthermore, the roll itself can be cooled by blowing and moving the gas. Further, in order to maintain the dimensional uniformity of the obtained material, if grooves for cutting the material are provided on the roll surface at right angles to the rotation direction, the material can be cut to a constant size. In the iron-lead compound of the present invention containing at least one of Co, Ni, Mn and Zn as the third component, an amorphous compound material can be obtained in all composition ranges. The peripheral speed of the cooling roll of the quenching device used is
Within the range of 5 m/sec to 35 m/sec, no major changes are observed in the structure of the material obtained in each composition range. In order to identify the structure of the material of the present invention, the presence or absence of crystallinity was confirmed and structural analysis was performed using X-ray diffraction and a polarizing microscope, and the extremely small portion was observed using a scanning electron microscope. The features of the present invention will be further clarified by examples below. Example 1 Fe ₃ O ₄ (99.9% purity) and PbO (99.9% purity) and Co ₂ O ₃ (99.9% purity) or NiO (99.9% purity)
After blending with the specified composition and mixing uniformly, 850
It was calcined at ℃ for 30 minutes and used as a composition raw material. The obtained composition raw material was placed in a platinum tube (diameter 10 mm x length 150 mm).
mm), installed in the dielectric heating coil, oscillator tube fiber voltage 13V, anode voltage 10KV, grid current 120
Dielectric heating was performed under conditions of ~150 mA and anode current of 1.2 to 1.8 A. The completely molten raw material was blown out onto the surface of a rotating rapid cooling roll using dry compressed air to rapidly cool it. Tables 1 and 2 show the composition and manufacturing conditions. Note that nozzle shape A indicates a 0.2 mm x 4 mm slit-shaped nozzle.

【table】

[Table] Reference Example 1 The magnetization curves of Samples No. 1, 2, and 3 of Example 1 at room temperature are shown in FIG. 3. Curve A~C
The composition (molar ratio) and crystal form of the compound represented by are as follows. A: Fe ₃ O ₄ /PbO/Co ₂ O ₃ = 1/2/0.5 Amorphous material (Sample No. 2) B: Fe ₃ O ₄ /PbO/NiO = 1/2/0.1 Amorphous material ( Sample No. 3) C: Fe ₃ O ₄ /PbO/Co ₂ O ₃ = 1/2/0.1 Amorphous material (Sample No. 1) Reference example 2 Samples No. 1, 2 and 3 of Example 1 Table 3 shows the physical properties as a magnetic material.

[Table] Reference example 3 (Fe ₃ O ₄ ) _1-xy・(PbO) _x・(NiO) _y ,
Sample No. of Example 1 corresponding to X=0.65, y=0.03.
The differential thermal analysis results of No. 3 are shown in FIG. Reference Example 4 The X-ray diffraction results for Samples No. 1 and 3 of Example 1 are shown in FIG. From the results shown in FIG. 5, it is clear that the compound material according to the present invention has an amorphous structure.

[Brief explanation of drawings]

FIG. 1 is a front view of an example of a cooling device for melted raw materials used in the method of the present invention, and FIG.
FIG. 3 is a graph showing the magnetization curves of several materials according to the invention;
FIG. 4 shows differential thermal analysis diagrams of one material according to the present invention. Moreover, FIG. 5 is a drawing showing the results of X-ray diffraction of the amorphous compound obtained in the example of the present invention. DESCRIPTION OF SYMBOLS 1... Frame, 3... Rapid cooling device main body, 5... Dielectric heating coil, 7... Raw material heating tube, 9...
...Support for raw material heating tube, 11... Nozzle for spouting molten raw material, 13... Roll for rapid cooling, 15...
... Cooling nozzle for nozzle 11, 17 ... Eddy current prevention air nozzle, 19 ... Fine adjustment mechanism for nozzle 11,
21...Air cylinder, 23...Cooled material receiving box, 25...Cooled material outlet, 27...
... Valve, 29 ... Cooling water introduction path, 31 ... Cooling water discharge path, 33 ... Needle valve, 35 ... Blow air introduction path, 37 ... Roll 13 and nozzle 1
Fine adjustment mechanism for spacing with 1, 39... perforated plate for rectification.

Claims (1)

[Claims] 1 (Fe ₃ O ₄ ) _1-xy・(PbO) _x・(M) _y (where M is
At least one kind of oxide of Co, Ni, Mn and Zn, 0.30≦x≦0.70, 0<y≦0.50)
An iron-lead amorphous compound material having the following composition. 2. After heating and melting a mixture consisting of at least one of cobalt oxide, nickel oxide, manganese oxide and zinc oxide, iron oxide and lead oxide in an inert atmosphere or in a vacuum, the melt is heated in an inert atmosphere or in a vacuum. (Fe ₃ O ₄ ) _1-x- characterized by ultra-rapid cooling
_y・(PbO) _x・(M) _y (where M is Co, Ni, Mn and
Indicates at least one type of Zn oxide, 0.30≦x≦
0.70, 0<y≦0.50). 3. The method for producing an iron-lead amorphous compound material according to claim 2, wherein the material is ultra-rapidly cooled at a cooling rate of ³¹⁰⁴ to ¹⁰⁶ °C/sec. 4. The method for producing an iron-lead amorphous compound material according to claim 2 or 3, wherein the raw material melt is ultra-quenched by contacting it with a solid. 5. The raw material mixture is put into a heating tube equipped with a nozzle equipped with a slit-shaped, circular or elliptical outlet, heated and melted at a temperature 50 to 200°C higher than the melting point of the mixture, and then heated for 5 to 35 m. Claim 2: The melt is blown out through the nozzle onto the surface of a roll rotating at a circumferential speed of 1/2 to cool it super rapidly.
A method for producing an iron-lead amorphous compound material according to items 4 to 4.