JPS59203730A - Material and preparation of fe-v amorphous compound - Google Patents

Abstract

PURPOSE:To prepare the suitable titled material for magnetic materials, photoresponsive magnetic element, heat-electricity switching element, etc. by cooling superquickly a molten mixture of iron oxide and vanadium oxide. CONSTITUTION:A mixture of iron oxide and vanadium oxide of a specified ratio is charged in a tube 7, and its temp. is held at a temp. by ca. 50-200 deg.C higher than its m.p. by energizing an induction heating coil 5. Obtd. melt of the starting materials is then ejected from a nozzle 11 (15 in the drawing is a cooling nozzle for the nozzle 11; 17 is an air nozzle for preventing vortex flow) onto a roll 13 rotated in the direction of an arrow mark with ca. 5-35m/sec peripheral velocity by dry compressed air and is cooled superquickly with ca. 10<4>-10<6> deg.Csec cooling rate. By this method, a belt-shaped product having 50-10mu thickness consisting of Fe-V amorphous compd. having a compsn. expressed by the formula (wherein x is 1-0.2) is obtd. out of a discharge port 25.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel iron-vanadium 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 (Fe208) and their single crystals. - Research is being conducted as a conversion element material in fields such as electricity, photoacoustic polarization, and X-ray spectroscopy, as well as as a catalyst material, magnetic material, etc. Fe20B
As stable compounds of v2 and o5, only a few types of crystalline forms have been described in a few documents, and although research on the single crystallization of these compounds has been actively conducted, amorphous No studies have been conducted on the compound.

The present invention provides an iron-vanadium amorphous oxide that has been completely unknown heretofore. That is, the present invention provides (F
e20a)x -x ・(V2O3)X (However, 1.o
o) A novel iron having the composition x≧0.20)
Vanadium-based amorphous compound material and (Fe20a)t
The present invention relates to a method for producing an iron-vanadium amorphous compound material, which comprises heating and melting a mixture with -x(V2O3)x vanadium and then ultra-quenching the mixture.

The iron-vanadium amorphous oxide of the present invention is a magnetic material,
It is useful as a photo-responsive magnetic element, a temperature-responsive magnetic element, a magnetic memory material, an ion-conducting material, a magnetic tape, a catalyst, a light-transparent conductive material, a dielectric material, an opto-electrical switching element, a thermo-electrical switching element, etc. be.

The present invention further provides (Fe20a)x−x・(V2O3)
A method for producing an oriented polycrystalline thin film material, which comprises heat-treating an iron-vanadium amorphous compound material having a composition of x (1.00>x≧0.20) at a temperature below its crystallization temperature. It also provides the following.

The oriented polycrystalline thin film material obtained in this way can be used for optical memory materials, magneto-optical memory materials, optical waveguide elements, optical mirrors, surface wave devices, photoacoustic devices, piezoelectric transducers, pyroelectric elements, photoelectric elements, transparent It is useful as an electrode material, bypass capacitor, optical switch, electrochromic device, light modulation device, humidity sensor, temperature sensor, chemical sensor, catalyst, etc.

In the present invention, the amorphous iron-vanadium compound PA includes not only the case where the compound is amorphous alone, but also the case where the amorphous state contains a polycrystalline phase.

The iron-vanadium amorphous oxide of the present invention is produced as follows.

The raw material used in the present invention is a mixture of iron oxide and vanadium oxide, and its composition ratio is (Fe205)
t-x・(V2O3)x (However, 1.00')x≧0.
20). A raw material mixture having the above composition ratio is heated and melted, and then cooled extremely rapidly. The heating and melting may be carried out at a temperature higher than the temperature at which these raw material mixtures are sufficiently melted, preferably in a temperature range of about 50 to 200°C higher than the melting temperature, particularly preferably in a temperature range of about 80 to 150°C higher than the melting temperature. . There are no particular restrictions on the atmosphere during heating, and heating is usually performed in air. 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. Ultra-quenching is usually carried out at a cooling rate of about 104 to 106''C/sec.

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 ejected onto the surface of the 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.

Figure 1 shows the main body of the rapid cooling device (3
) is shown. The quenching device consists of a dielectric heating coil (5
), (5)..., a tube for heating the raw material (7), a support body (9) for the tube (7), a nozzle for spouting the molten raw material (
11), quenching roll (1), cooling nozzle (15) for nozzle (11), swirl prevention air nozzle (1), nozzle (1),
l+) fine adjustment mechanism (19), air cylinder (21)
, the receptacle for the cooled material is the box (23), and the cooled material outlet (
25) etc. are the main components. Cooling roll (13
) by installing a fan for cooling the roll and providing an air blowing port at the end of the roll surface, the molten raw material can be rapidly cooled stably. Figure 2 shows details of the support (9).

In FIG. 2, the support body (9) includes a cooling water inlet passage (9) equipped with a valve (27), a cooling water discharge passage (31), and a blow air inlet passage (3) equipped with a needle valve (33).
Fine adjustment mechanism for the distance between the surface of the roll and the nozzle (11) (
37) and a rectifying perforated plate (3) for uniformly extruding the raw material melt.
9).

When carrying out the method of the present invention using the quenching device (3) shown in FIGS. 1 and 2, first, a raw material mixture of a predetermined composition is stored in a tube (7) having a nozzle (11) for blowing out the melt. do. The tube (7) is preferably made of a material that is sufficiently durable under high-temperature oxidizing atmosphere conditions, such as platinum, platinum-rhodium, iridium, silicon nitride, boron nitride, or the like.

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 appropriately determined depending on the target product; for example, a round shape is used for a thin linear material, and a slit-like shape is used for a wide product. The shape of the nozzle opening may be oval or other shapes. The raw material mixture housed in the tube (7) is then heated to a temperature higher than its melting point to form a melt, and then is poured onto the surface of the roll (+3) rotating at high speed from the mouth of the nozzle (Il). The gas is then blown out at a constant gas pressure 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 if the width is approximately 3 mm or more, it may be perpendicular to the roll surface. σ~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 about 50 to 200°C, preferably 80 to 150°C higher than its melting point.

If the temperature is too close to the melting point, there is a risk that the melt will cool and solidify near the nozzle while it is being blown onto the roll surface.On the other hand, if it is too high, it will be difficult to rapidly cool the melt on the roll surface. Tend.

The pressurizing gas used to blow out the melt onto the roll surface is preferably an inert gas, such as argon,
Although nitrogen, helium, etc. may be used, dry compressed air is preferable in order to maintain the melt raw material in an oxidized state. Although the gas pressure depends on the size of the nozzle opening, it is usually 0.1 to 2. OK
/cm2 is preferably about 0.5 to 1.0 ky/cm". Also, the distance between the nozzle opening and the roll surface when blowing out the raw material melt is 0.01 to 1.0 ky/cm2.

Approximately mm, more preferably 0.05 to 0.5 m
There are about m. If it is smaller than 0.01 mm, the amount of puddles will be very small and a uniform material cannot be obtained, while if it is larger than 1.0 mm, the amount of puddles will be excessive or the interfacial tension of the composition melt will increase. If the thickness is greater than the thickness of the paddle formed by the above, there may be a tendency for the paddle to be difficult to form.

The material of the roll is 5, copper with good thermal conductivity and its alloy, the above-mentioned materials having a hard chrome plating layer, steel, stainless steel, etc. The circumferential speed of the roll is 5 m/
The target amorphous compound material of good quality can be obtained by rapidly cooling the raw material melt at a rate of 10 m/sec to 35 m/sec, preferably 10 m/sec to 20 m/sec. At this time, the roll peripheral speed is 5
If m is 7 seconds or less, it tends to be difficult to become amorphous, which is not very preferable. When the peripheral speed of the roll is higher than 35 m/sec, the shape of the target material obtained becomes extremely thin and becomes scaly or fine powder, but in terms of material structure, it is still the amorphous compound material of the present invention. It is.

When producing the compound of the present invention under reduced pressure or high vacuum or in an inert gas atmosphere as the atmosphere in which the melt raw material is blown onto the rotating roll surface, reduction of the raw material melt at high temperature occurs, Oxygen atoms in the composition atoms decrease, and the resulting material becomes colored purple or black. However, this colored product is also a compound of the present invention physically and can be used in a colored state.

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 may be an inert gas such as argon, helium, nitrogen, etc., but dry, cold compressed air is more preferable.

The novel amorphous compound material according to the present invention usually has a
It has a thickness of about 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 blowing nozzle for preventing wind blowing, that is, a first
Install an anti-eddy air nozzle (17) as shown in the figure, or install a fan fixedly inside the roll. In the latter case, the turbulent flow generated inside the roll due to the rotation of the roll is absorbed into the roll through the Nikkei variable air inlet provided at the end of the roll surface, and is discharged from the front of the roll axis, causing air to flow over the roll surface. By moving the melt into the interior, the molten material is pressed more tightly against the roll surface, and the roll itself can also be cooled by air blowing and movement. Further, in order to maintain the dimensional uniformity of the obtained material, if grooves for cutting the material are provided on the surface of the roll at right angles to the direction of rotation, the material can be cut to a constant size.

The iron-vanadium compound of the present invention has an atomic arrangement structure that changes greatly depending on the mixing ratio of raw materials, and can be broadly classified into the following types. First, 1.00)x≧0.2
In the case of 5, a 100% amorphous compound is obtained, and 0
．． 25) In the range of x≧0.20, an oriented polycrystalline mixed amorphous material containing Fe20B crystals is obtained;
)x, a material mainly consisting of Fe20B crystal phase is obtained.

FIG. 3 shows the production range of the material of the present invention.

The peripheral speed of the quenching roll of the quenching device used is 5 m.
Within the range of m/sec to 35 m/sec, no major changes are observed in the structure of the material obtained in each composition range.

The oriented polycrystalline thin film material of the present invention is obtained as described above (Fe20a)t-x/(V2O3)x (where 1
．． 00>x, 70.20) was subjected to thermal analysis to determine its crystallization temperature (T
After determining c), it is obtained by heat-treating the compound material at a temperature below the crystallization temperature for a predetermined period of time. Note that if the heat treatment time is too long even below the crystallization temperature, a non-oriented polycrystalline material will result, so care must be taken in this regard.

For example, in CFe20a)1-x・(V2O3)x, X=0.50. The crystallization temperature of the iron-vanadium amorphous compound material is 439°C, and when this is heat-treated in the atmosphere, the following materials can be obtained depending on the conditions.

1. 435°C x 10 minutes: oriented polycrystalline material 2. 43
5°C x 30 minutes: Polycrystalline material 8, 400°C x 10 minutes: Amorphous material 4, 400°C
x 30 minutes: Oriented polycrystalline body 6, 400°C x 60 minutes:
Polycrystalline body When identifying 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 a very small portion was observed using a scanning electron microscope.

Below, the features of the present invention will be explained in more detail through Examples-1.
-to clarify.

Example 1 Fe20B (purity 99°9%) and V2O5 (purity 9%)
9.9%) in a predetermined composition and mixed uniformly,
It was calcined at 850°C for 30 minutes and used as a raw material for a composition. The obtained composition raw material was placed in a platinum tube (diameter 1077Z77Z).
x length 150mm), installed in a dielectric heating coil, oscillating tube fiber pressure 13V, anode voltage 10KV, grid current 120-150mA, anode current 1.2-1.8A
The mixture was heated for 14 hours under the following conditions. The completely molten raw material is blown onto the surface of a rapidly cooling rotating roll using dry compressed air.
Cooled rapidly.

Tables 1 and 2 show the composition and manufacturing conditions. Sample No. 1 to 20.25 and 29 in Tables 1 and 2
shows the amorphous oxide material of the present invention in the form of a ribbon. or,
No. 24 is a thin piece because the rotation speed of the roll is high, but it can be used in fields such as catalysts where there are no restrictions on shape.

Note that nozzle shape A indicates a slit-like nozzle of 0.2 mm x 4 nm, and nozzle shape B indicates a circular nozzle with a diameter of 0.2 mm. .

-28- Reference example 1 (Fe20a)x-x・(V20s)x=0
．． Sample No. 8.10 of the above Example 1 corresponding to 50,
The X-ray diffraction results for 12.13 and 15 are shown in FIG. The peripheral speed of the quenching roll was 5.18 m 7 seconds (N
It is clear that there is no significant change in the atomic arrangement structure of the material obtained within the range from 34.54 m/s (No. 15) to 34.54 m/s (No. 15).

Reference example 2 In (Fe20B)1-x・(V2O3)x, x =
The differential thermal analysis results of Sample No. 10 of Example 1, which corresponds to 0.50, are shown in FIG.

In FIG. 5, Tc represents the crystallization temperature, Tg represents the glass transition point, and mp represents the melting point.

Reference example 3 (Fe20B)1-x(V2O3)x where X=0
．． A photograph showing the external appearance of sample N007 of Example 1, which corresponds to No. 25 D, is shown as reference drawing (■).

24- Reference Example 4 Scanning electron micrographs (20,000x and 880x) of Sample No. 7 of Example 1 above are shown in Reference Drawings ■ and I, respectively.
Shown as II.

Reference example 5 (Fe20a)t-x・(V2O3)x, x=0
．． The infrared absorption spectrum of Sample No. 13 of Example 1, which corresponds to No. 50, is shown in FIG.

Reference example 6 In (Fe20a)x−x(V2O3)x, x=o,
Sample No. 17-15 of the above Example 1 corresponding to go
．． The DC electrical conductivity at 6°C is shown in Figure 7, and 1
Figure 8 shows the dielectric constant and dielectric loss versus frequency at 5.6°C. Note that the thickness of the sample was 0.0019 cm, and the electrode area was 0.0491 cm.

Reference example 7 (Fe20a)t-x・(V2O3)x
Figure 9 shows the change in magnetization at room temperature (26°C) when the force changes.

Example 2 Sample No. 17 of Example 1 was heated in air at 400°C for 30 minutes.
After heat treatment for a minute, X-ray diffraction was performed, and a sharp diffraction peak of one in two diffraction angles was observed, confirming a change from an amorphous structure to an oriented polycrystalline structure.

In addition, electric genital tube (frequency IKHz) before and after heat treatment
) were as follows.

Before heat treatment After heat treatment Dielectric constant (ε) 285 455 Dielectric loss (tan δ) 75 0.85

[Brief explanation of the drawing]

FIG. 1 is a front view of an example of a quenching device for molten raw materials used in the method of the present invention, FIG. 2 is a partially enlarged detailed drawing of the quenching device in FIG. 1, and FIG. Drawings showing the composition range; FIG. 4 is an X-ray diffraction diagram of some materials of the present invention; FIG. 5 is a differential thermal analysis diagram of one material according to the present invention; FIG.
FIG. 8 is a graph showing the DC electrical conductivity of another material according to the invention, and FIG. 8 is a graph showing the dielectric constant and dielectric loss versus frequency of a material similar to that shown in FIG. 7. Figure 9 shows (Fe20a)t-x・(V2O3)x
Graphs showing changes in the amount of magnetization when X changes in D and D are shown, respectively. (1)... Frame, (3)... Rapid cooling device main body, (5), (5)... Dielectric heating coil, (7)
... tube for heating raw material, (9) ... support for tube for heating raw material, (11).
... Nozzle for spouting molten raw material, (1 sai... Roll for rapid cooling, (Country... Nozzle for cooling nozzle (11), (17)
... Eddy current prevention air nozzle, (19) ... Fine adjustment mechanism for nozzle (0), (21).
...Air cylinder, (23)...The container for the cooled material is a box, (25)...
・Cooling material outlet, (27)...Valve, (29)
...Cooling water introduction channel, (31)...Cooling water discharge channel,
(33)...21 dollar valve, (3 (to)...blow air introduction path, 0η...roll (1 sai) and nozzle (ll
), (39)... perforated plate for rectification. (The above) and Agent: Eiji Saegusa, Patent Attorney (1st year). JP-A-59-203730 (10) Continued from page 1 0 Inventor: Shuji Masuda 27-8 Miyanomoto, Ejiri, Kitajima-cho, Itano-gun, Tokushima Prefecture 0 Author: Ota Oikei 86, Nagae Soji, Higashinakatomi, Aizumi-cho, Itano-gun, Tokushima Prefecture, Nakatomi Danchi F8-148 0 Author: Mika Okubo, 3-20, Sako Rokuban-cho, Tokushima City, 0 Author: Ken Masumoto 3, Uesugi, Sendai City No. 8-22 @ Applicant: Kenji Suzuki Izumi City General Manager 11-12-11 No. 0 Applicant: Shuji Masuda 27-8 Miyanomoto, Ejiri, Kitajima-cho, Itano-gun, Tokushima Prefecture ■ Applicant: Osei Ota, Tokushima Prefecture F8-148, Nakatomi Danchi, 86 Nagae Soji, Aizumi-cho, Itano-gun

Claims (1)

[Claims] (1) An iron-vanadium amorphous compound material having the following composition: (Fe20a)t -x .(V2O3)X (where 1.00)x≧0.20). ■ 1.00) The first claim where x≧0.25
Iron-vanadium amorphous compound material. ■ 0.25) Claim 1 where x≧0.20
Iron-vanadium amorphous compound material. ■ It is characterized by heating and melting a mixture of iron oxide and vanadium oxide and then ultra-quenching the melt (Fe20a
)t-x(V2O3)x (1.00)x≧0.2
0) A method for producing an iron-vanadium amorphous compound material having the composition. (104-b) A method for producing an iron-vanadium amorphous compound material according to claim 4. (2) A method for producing an iron-vanadium amorphous compound material according to claim 4 or 5, wherein the raw material melt is ultra-quenched by contacting it with a solid. ■ The raw material mixture is put into a heating tube equipped with a nozzle equipped with a slit-shaped, circular or oval outlet, and after heating and melting at a temperature 50 to 200°C higher than the melting point of the mixture, 5 m / The iron-vanadium non-containing material according to any one of claims 4 to 6, wherein the melt is blown out through the nozzle onto the surface of a roll rotating at a circumferential speed of 35 m/sec to 35 m/sec for ultra-quenching. Method for producing crystalline compound materials. ■ Orientation characterized by heat-treating an iron-vanadium amorphous compound material having the composition (Fe20a)t x ・(V2O3)X (1.00 > A method for producing polycrystalline thin film materials.