JPS598623A - Bismuth-niobium amorphous compound and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare a bismuth-niobium amorphous compound having a specific composition, by hot-melting a mixture of Nb2O5 with Bi2O3 in a specific composition ratio, and quenching the resultant hot melt at an ultrahigh quenching rate. CONSTITUTION:A mixture of (Nb2O5)x with (Bi2O3)1-x (1>x>0) is hot molten at a temperature 50-200 deg.C higher than the melting point thereof and quenched at an ultrahigh quenching rate as high as 10<4>-10<6> deg.C/sec by jetting on the surface of a roll rotating at 5-35m/sec peripheral speed by the liquid quenching method in contact with a solid at an ultrahigh quenching rate to give the aimed bismuth-niobium amorphous compound having the composition of the formula (Nb2O5)x.(Bi2O3)1-x (1>x>0). The atomic configurational structure varies with the mixing ratio of the raw materials as follows: When x is within 0.5<=x<1 range, 100% amorphous compound is obtained. When x is within 0.4<=x<0.5 range, a mixture of small amount of a polycrystalline phase of delta- Bi2O3 with the amorphous compound is obtained. When x is within 0<x<0.4 range, a polycrystalline phase of alpha-Bi2O3, a polycrystalline phase of beta-Bi2O3 and delta-Bi2O3 and a mixture of solid solution polycrystalline phase of (Nb2O5)x.(Bi2O3)x-1 with the amorphous compound are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an amorphous compound of hismuth-niobium yarn and a method for producing the same, and more particularly to a novel substance of 12-year-old hismuth yarn that has not been described in the literature and a method for producing the same.

Research on oxide thread ceramics mainly composed of bismuth oxide (Bi203) and its single crystals has been actively conducted in line with the recent development of the electronics field, especially in the areas of photo-electricity, sound-electricity, and atmospheric gas3. - As a conversion element for electricity, photoacoustic deflection, X-ray spectroscopy, etc.
He is also actively researching catalysts and...

As a stable compound of Bi203 and Nb2O5, 2
．． 3 describes only a few types of crystalline forms, and although research into single crystallization has been actively conducted, no research has been conducted on it as an amorphous compound. .

The present invention is a newly synthesized amorphous compound of the same sumasnio-based material, which has not been known in the past.In other words, the present invention is based on (Nb205)jc-(Bi203)1-, (provided that 1''>z>0 ) (New hismuth-niobium thread amorphous compound with composition D and (Nb205 and (B
1203) This relates to a method for producing a di-sma-di-silicon amorphous compound, which is characterized by heating and melting a mixture of y-1 (where I>x>O) and then ultra-quenching it.

The invention will be explained below according to the manufacturing method. The raw material used in the present invention is a mixture of oxidized sumus and niobium oxide, and its composition ratio is 4-(Nb205)z, (B'203)1-x (where I>
1, where X>O), 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, and more preferably 50 to 200°C or higher than the melting temperature, particularly preferably 80 to +
Heat at a temperature higher than 50°C. There is no particular interest in the atmosphere during heating, and heating is usually carried out in air.

Next, the melt of the raw material mixture is ultra-quenched. At this time, it is extremely important to perform ultra-rapid cooling, and only then can a new amorphous compound be obtained. Super rapid cooling is usually 1
This ultra-rapid cooling is performed at a cooling rate of about 0" to 106°C/sec. A wide range of methods can be used for this ultra-rapid cooling as long as it can cool at the above-mentioned cooling rate. A typical method is to A typical example is a method in which a melt of a raw material mixture is sprayed onto the surface of a mold and solidified in the atomic arrangement of the liquid state.This method is explained in more detail below.
As per myself.

An example of a typical apparatus used in carrying out the present invention will be described below with reference to the drawings.

Fig. 7 is a front view of the quenching device, (]) is a rotary tube for quenching, (2) N is a tube with a nozzle for heating the raw material, (
3) shows the electric heating coil. FIG. 8 shows the tube support, (4) shows the needle pulp, (5) the air inlet, (6) the cooling water outlet, and (7) the cooling water inlet. The inside of this support can be cooled with cooling water, and a mechanism (8) for finely adjusting the gap between the surface of the 0-finger and the tube nozzle opening is installed, as well as a mechanism for uniformly extruding the raw material melt. A rectifying perforated plate (9) is attached to the tip. Figure 9 shows a stable quenching type air-cooled 0-roller with fencing installed inside the D-ru and an air inlet at the end of the roll surface for the purpose of efficiently quenching the 0-ru itself and air-cooling the 0-ru itself.
- Figure (a) is a front view of the same, (
2) is a side sectional view, and (c) is an explanatory diagram of the shape of the slit hole.

Figure 10 (a) Kero 11. The counter-current blow-off nozzle for preventing vortex flow during soldering when the tachometer appears on the back side is shown in the same figure (b).
The air nozzle for local cooling in the ゜ section is shown. It is preferable that all of these nozzles are made of quartz tubes.

stomach. Figure 11 shows the nozzle shape of 19c material heating -f-1-1. The nozzle shape is a slit nozzle, ■ is a nozzle with a round hole, ■ is a wide multistage slit, and ■ and [phase] are the inclination angles. It is 1 no.

First, a raw material mixture having a predetermined composition is placed in a tube having a nozzle for blowing out the melt. The tube is made of a material that is sufficiently durable under high temperature oxidizing atmosphere conditions, preferably of platinum, platinum-rhodium, iridium, silicon nitride, nitride boron, or the like. The material of the part that comes into direct contact with the raw material melt may be ceramic, glass, or metal with a high melting point. The shape of the nozzle opening is determined according to the intended product; for example, a round shape is used for thin wire materials, and a slit-like 7-11 shape is used for wide products. The raw material mixture stored in the D-roll is then heated to a temperature higher than its melting point, and then the melt is blown out at a constant gas pressure onto the roll surface rotating at high speed. Let it cool down rapidly. In this case, the blowing angle H+ of the raw material melt between the nozzle opening and the D-rule surface may be perpendicular to the roll surface if the width of the target compound is about 3 mm or less; In the above case, the blowing angle is 0° to 45° with respect to the normal to the roll surface. Although it is possible to incorporate a mechanism for setting a predetermined angle into the device itself, it is preferable to use means for machining the nozzle.

The method of heating 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.3. The raw material mixture is heated and melted by this heating, but the temperature of the raw material melt at this time is 50 to 200 degrees below its melting point.
℃ Preferably, the temperature is about 80 to 150°C higher.

At this time, if the temperature is not higher than the melting point (8--1), the melt may blow out onto the small face (7) and may cool and solidify near the nozzle. The pressurized gas used to blow out the mucus onto the roll surface may preferably be inert gas, such as aluminum, nitrogen, helium, etc.; Dry compressed air is preferable because there is a risk of reinforcing the gas.The gas pressure depends on the thickness of the nozzle opening, but is usually 0.
．． 1-2.0 kg/d preferably 0.5-1.0 k
l;l/c11°. The distance between the nozzle opening and the O-ru surface when blowing out the raw material melt is 0.01-1.0
It is preferably about 11, particularly preferably about 0.05 to 0.5. If the sail 01 cod is also small, the amount of paddle will be very small and uniform material will not be obtained.1. If QIJI or more, the amount of puddles becomes excessive, or if the thickness exceeds the puddle thickness formed by the interfacial tension of the composition melt, it may be difficult to form puddles. The material of the roll is copper with good thermal conductivity and its alloy, the above-mentioned material having a hard D-mmed layer, furthermore, steel, stainless steel, etc.
The target amorphous compound material of good quality can be obtained by rapid cooling at a circumferential speed of 5 η2/sec-35yti 7 seconds, preferably 1 Qyz/sec-20 ηl/sec. In this case, if the roll circumferential speed is 5 m/sec or less, it is not very preferable because it tends to be difficult to become amorphous. Circumferential speed is 3
If the speed exceeds 5 m/sec, the shape of the obtained target material becomes very thin, and it becomes flaky or fine powder-like, but in terms of material structure, it is the amorphous compound material of the present invention. Although it is possible to produce the compounds of the present invention under reduced pressure or high vacuum or in an inert gas atmosphere in an atmosphere in which the melt raw material is blown out onto the rotating facet, Reduction occurs and the number of oxygen atoms in the composition atoms decreases, causing the resulting material to be colored purple or black. However, it is possible to extract the material VC &- from the big explanation.

Furthermore, when heating and melting the raw material mixture in a tube, it is necessary to completely melt the mixture. [7] However, before the mixture is completely molten, there is a risk that 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 prevent this. A typical means for locally cooling the nozzle is to blow a cooling gas onto the tip of the nozzle.The gas may be an inert gas such as argon, helium, or nitrogen, but dry, cold compressed air is preferred. stomach.

The novel amorphous compound abrasive material according to the present invention is usually 50 to 1
It has a thickness of about 0 μm and is a very fragile material. For this reason, it is preferable that no stress is applied to the material as much as possible after it is rapidly cooled and solidified on the 0-rule plane. The cause of the stress addition is the large turbulent flow in the air layer on the surface of the roll due to the wind blowing phenomenon that often occurs when the roll is rotated in the atmosphere.

This turbulence prevention e; 1 is necessary, and for this purpose and to improve the adhesion between the bath molten raw material mixture to be rapidly cooled and the roll surface, a countercurrent blowing nozzle for preventing circumferential cutting is installed, or 0-Fix the facil inside the wheel. In the latter case, as the roll rotates, the turbulent flow generated inside the roll is absorbed through the variable-diameter air inlet provided at the end of the D-ru surface and discharged from the front of the roll axis. The air above is moved into the interior of the tube, which removes the molten material.
] - The roll itself can be air-cooled by pressing the roll more closely against the roll surface and moving the roll by blowing air into it. In addition, in order to maintain the dimensional uniformity of the obtained material, 0-
If grooves for cutting the material are provided on the surface of the tool at right angles to the direction of rotation, the material can be cut to a constant length and a cut material can be obtained.

The atomic arrangement structure of the di-suma-niop yarn compound of the present invention changes greatly depending on the mixing ratio of raw materials, and can be roughly divided into three types. First, when 0.5≦χ<1, the amorphous compound is 100%, and when 0.4≦X<0.5, it is a mixture of δ-B+203 polycrystalline phase and amorphous compound. However, for 0 < r < 0.4, δ-Bt
203 Polycrystalline Phase An amorphous compound containing a polycrystalline phase of δ-Bi203 and α-B1203, and a (Nb205)-(Bi20.)1-□ solid bath polycrystalline phase is obtained. The production range of the compound of the present invention is shown in FIG. Further, when the rotational speed of the roll changes, that is, the circumferential speed changes in the range of 5 m/sec to 35 m/sec, there is no significant difference in the structural changes of the material obtained with each composition change. This is shown in Figure 2 ((a) to (c))
Shown below. In addition, Fig. 2 U) is (Nb205), c・(Bi2
03) In 1-□, X is 0.25, the same figure P) C is 14.29 and the circumferential speed is 17.27 m/sec, and the same figure (C) shows the case where X is 0.33 and various circumferential speeds. The case of speed is shown.

As a means of identifying the structure of the material obtained by the present invention,
Linear diffraction and polarization microscopy were performed using a polycrystalline electron microscope.

A photograph of a representative amorphous compound of the present invention, Te5tA9 in the Examples described later, is shown in FIG. 3, and Text//aI.

The fourth scanning electron micrograph (12,000x) of the object
As shown in the figure. Similarly, Fig. 5 shows the results of water source thermal analysis. The infrared absorption spectrum is shown in FIG. In addition, in Figure 6 (
(a) is for Te5tA9, (b) is for Ttst42.

Examples are shown below (- indicates the present invention in detail.

Example: Using Bs203 (purity 99.996) and Nb205 (purity 99.999999%) as raw materials,
After uniformly mixing at a predetermined blending ratio, the mixture was calcined at 850° C. for 30 minutes, taken out, allowed to cool, and ground and mixed again to obtain a composition raw material. This composition raw material is called platinum 1-zu (φlQg*).
<Length 150~m), set voltage in M electric heating coil 10 KV, bean paste current +2020-15O,
At an anode current of 1.2 to 1.8[Delta], the raw material having a different composition was molten and quenched by blowing it out with dry compressed air from the surface of the rotating O-ru. Tables 1 and 2 show the condition values and the resulting hits. Te5t/Pal~20 is a condition that satisfies the requirements of the present invention, 'I'tsl庖21~29 +:j: 1° is an unsuitable condition.

[Brief explanation of the drawing]

Figure 1 is a drawing showing the composition range of the compound of the present invention, Figure 2 is its X-ray diffraction diagram, Figure 3 is its external appearance photograph, Figure 4 is its scanning electron micrograph, and Figure 5 is its differential thermal analysis. Figure, 6th
The figure shows its infrared absorption spectrum; 1. -1 7th
-11 are drawings showing examples of various devices used for the compound of the present invention, in which FIG. 7 shows a quenching device, FIG. 8 shows a tube support, and FIG. 9 shows a quenching roll. Further, FIG. 10 shows the blowing nozzle, and FIG. 11 shows the shapes of various nozzles. (Above) Figure 1 Figure 5 x 100 BI20 Fire crystal Nb205x Figure 3 Time (intermediate) JP-A-59-8623 (9) JP-A-59-8G23 (10) JP-A-59-8G23 (11) Patent Agency Commissioner Kazuo Wakasugi 1. Indication of the incident 1982 Patent Application No. 4652 No. 2 Invention (
7) Name Bismuth-niobium amorphous compound and relationship to the incident Patent applicant New Technology Development Corporation (and 2 others) 4. Agent Telephone number 06-203 in Heiwa Building, 2-10 Hirano-cho, Higashi-ku, Osaka City
-0941 (Main) Contents of the correction as shown in the attached sheet Figures 1 to 6 are corrected as shown in the attached sheet. 2 Delete Figures 7 to 11 0 3 Add “Reference drawing 1” and “Reference drawing ■” ■ 4 Ming#ilQiaochu, page 24, lines 2 to 10 (brief explanation of drawings) [ Figure 1 shows the shape of a circle.The statement - is corrected as follows. "Figure 1 is a diagram showing the composition range of the compound of the present invention, Figure 2 is a diagram showing the composition range of the compound of the present invention.
The figure is its X-ray diffraction diagram, Figure 3 is its differential thermal analysis diagram, and Figure 4 is its X-ray diffraction diagram.
The figure shows its infrared absorption spectrum. Further, Figures M5 and M6 are drawings showing examples of various devices used for the compound of the present invention, Figure 5 is a front view of the quenching apparatus, and Figure 6 is a vertical to one side view of the tube support. ” (and above) 1-

Claims (1)

[Claims] ■ (Nb205)! '("203)1-ff (
However, a new amorphous compound having a composition of (I>X>O). (2) A homogeneous mixture of 203 g of δ-Bi crystals and the amorphous compound described in claim 1 above. ■ Polycrystalline phase of α-Bi203, β-Bi203 and δ
-Bi203 polycrystal and (Nb205)□・(Bi
203) A homogeneous mixture of the solid solution polycrystalline phase of 1a and the amorphous compound according to claim 1 above. (2) The amorphous compound according to claim 1, wherein X is 0.5≦r<+. ■ X is 0. A mixture according to claim 2, wherein X < 0.5. ■ A compound according to claim 3, iF1'', in which X is o < x < 0.4. ■ A mixture of (Nb205) and (B; An amorphous compound obtained by ultra-quenching a melt, or a mixture mainly composed of it. ■ A mixture of (Nb205) and (Bi203) 1-, (where I>J>O) A method for producing an amorphous compound of Sumassunioff yarn, which is characterized by heating and melting the compound and then ultra-quenching it. ■ Production according to claim 8, which is characterized by ultra-cooling at a rate of 104 to IQ67 set. [Phase] The manufacturing method according to claim 8, characterized in that the ultra-quenching is carried out by a solid-contact liquid ultra-quenching method. ■ A slit-shaped, round, or oval hole is provided at the bottom of the manufacturing method. 1iLIM [Free: 5rn/2
9. The manufacturing method according to claim 8, characterized in that the cooling is rapidly performed by blowing onto the surface of the cylinder. [Phase] Consists of a material that is stable in a high-temperature oxidizing atmosphere with a temperature below the melting temperature of the raw material mixture, and the molten liquid of the raw material mixture is dripped from the tip of the nozzle when not required. The manufacturing method according to claim 8, characterized in that a nozzle designed so that only the tip of the nozzle can be cooled with gas (step 7) performs ultra-rapid cooling.