JPS58167429A - Amorphous material of bismuth-germanium type oxide and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain an amorphous material having improved mutual exchangeability of various kinds of energy or catalytic ability, by heating a compound of bismuth oxide with germanium oxide expressed by a specific general formula, etc., and quenching the resultant melt. CONSTITUTION:A compound of bismuth oxide with germanium oxide expressed by the general formula (Bi2O3)x.(GeO2)(1-x) (1>x>0) or a mixture or both are heated to prepare a melt at 50-300 deg.C higher than the melting points thereof. The resultant melt is then fed to the surface of a roll rotating at room temperature or below, quenched and solidified. Thus, the aimed amorphous material having improved mutual exchangeability of various kinds of energy and catalytic ability is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bis-germaeum oxide amorphous material and a method for producing the same. In addition, it is highly praised for the material called New Seven Uden Tutus, which is an amorphous material that is dissolved in bismuth, germanium, and oxygen, and has excellent interconvertibility of number energy or saponifying power, and its manufacturing method. There are great expectations for this, and its research is being carried out with various public technical funds. Bismuth oxide and germanium oxide are also being considered as one of the two types of materials.

However, an amorphous compound consisting of bismuth oxide and germanium oxide is not known. As a stable compound consisting of bismuth oxide and germaella oxide,! l
12G・30. (Japanese Patent Application Laid-Open No. 5195624), B
t4o・,0yu [Tsian Journal Op Inno-
Russian Iour
n&1 of engineering norganio Ghamst
r7)? (2) PP226-250 (196
4)), 11112G・Og. [Journal of R@s@aroh of t
hs Natlcmal Bureau of 5tan
ilards-mu, Physias-01umist
ry) 6・mu [2] PP197-204 (1?+6
4)) are known, but all of them have been reported as single crystals.

As a result of intensive research to develop a stable, amorphous material consisting of bismuth oxide and germanium oxide, Akira Motoya et al. heated a mixture of bismuth oxide and germanium oxide above its melting point. It has been discovered that this goal can be achieved by rapidly cooling and solidifying the resulting molten liquid, and based on this knowledge, the present invention has been completed.

That is, the present invention provides a compound of bismuth oxide and germanium oxide whose composition ratio is represented by the general formula (Bt,03)(G・0□)(,-E) (where 1>x>0) and ( or) the mixture is heated and melted so that it is below its melting point.
-Boo@o A screw formed by rapidly cooling and solidifying a high-temperature molten liquid on a cooling surface! When heating and melting the amorphous germanium oxide material and the compound and/or mixture of bismuth oxide and germanium oxide having a composition ratio within the above range, (a
)Use a heat-resistant container with a blowout port, and set the temperature of the ill melt in a range of SO to 00oo higher than its melting point.
o) Provides a method for producing a bismuth-germanium-based compound amorphous material, characterized in that both sides of a roll rotating at a temperature below room temperature are used as cooling surfaces. The bismuth oxide used in the amorphous material is not limited to <&:lI, and a commercially available conductive product can be used as is.

Further, as for germanium oxide, ordinary commercially available products can be used as they are.

The content ratio of bismuth, germanium and oxygen in the amorphous material of the present invention is expressed by the general formula (mt2o8・←・0&(x-
x) ('' is the same as above).

1. The amorphous material of the present invention is composed of bismuth, germanium, and oxygen, which are formed by almost fixing the atomic arrangement of the aqueous liquid within the above-mentioned composition ratio range. However, this is a known compound of bismuth oxide and germanium oxide, a mixture of bismuth oxide and germanium oxide, or a mixture of the above-mentioned compounds (hereinafter collectively referred to as a mixture). was prepared so that the composition ratio of
It is formed by rapidly cooling and solidifying a molten liquid heated to a temperature of 000 degrees on a cooling surface.

In the present invention, the melting point refers to a compound phase, a mixture of bismuth oxide and germanium oxide, etc., depending on the composition ratio.
(Compound child raw material) phase, (10 chemical compound raw materials + 1 Ifl I form)
Phase II, the melt phase and the (solid solution phase + raw material) phase are generated, and it refers to the temperature at which all of these phases become liquid.

The melting point of the mixture used in the present invention is approximately 890 to 110.
It is within 1m8 of 0'O.

In the process of producing the amorphous material of the present invention by heating and melting the mixture, etc., the heating tank method is not limited to the method, but includes, for example, a high-temperature furnace method, a dielectric heating method, a collection method, etc. A light heating method can be used. The temperature of the molten liquid such as a heated and molten mixture must be higher than its melting point before it is rapidly cooled and opened on the cooling surface. .

The temperature is determined by the conditions for rapidly cooling the melt, and is selected within the range of 60 to 100 qo.

In the method of the present invention, the temperature is selected within the range of (b) 5O-500QO higher than the melting point, preferably 80-260°0. If the height of the concentration of the melt from the melting point is less than 50°O, the fIIj melt will solidify and form a crystalline phase before contacting the cooling surface, which is undesirable as it will hinder the uniformity of the product. In addition, if the height of this temperature from the melting point exceeds &00°0, it is not enough to remove heat from the cooling surface, and a considerable amount of heat remains in the solidified material, which is converted to crystalline material when the bale is air-cooled. Therefore, an amorphous compound is not formed uniformly, which is not preferable.

In the present invention, this heating and melting operation is applied to a mixture filled in a heat-resistant container having an air outlet. The material of the heat-resistant container used in this case is as follows:
It is preferable that it is stable and durable even in high-temperature oxidation IFIjlL, for example, platinum, platinum-p
Suitable materials include a dium alloy, iridium, silicon nitride, and boron nitride. However, there is no problem in the method of the present invention even if the container is a heat-resistant container in which these two materials are used only in the parts that come into direct contact with the molten liquid. In that case, the material that may be used for the part of the container that is not directly connected to the molten liquid is, for example, a high melting point alumina, a metal such as quartz, or a metal such as stainless steel.

The outlet of this heat-resistant container is for supplying the molten liquid that has reached a predetermined temperature onto the cooling surface. There are no particular limitations on the outlet. The next outlet is determined by the form of the product. For example, if a thin product is required, a round hole is usually selected, and if a strip-shaped product is required, a slit-shaped hole is usually selected.

On the other hand, the molten liquid raised to a predetermined temperature in the warehouse is fed onto the cold 1Wj, where it is rapidly quenched and expanded.

The cooling surface used in this case is, for example, steel with good thermal conductivity. : Steel, steel, stainless steel, or those with hard gold plating can be mentioned.

In the method of the present invention, the quenching stratification operation is carried out by supplying the melt that has reached a predetermined temperature onto the surface of a roll rotating at a temperature below the mold temperature.

At that time, the temperature on the surface of the rotating roll is 100
If it exceeds 00, the time required for solidification becomes longer and the degree of occupancy of the amorphous portion of the obtained amorphous material decreases, which is not preferable.

In the method of the present invention, in order to obtain a better amorphous material, the melt at a predetermined temperature is heated for 5 to 55 minutes, preferably 10 to It may be supplied onto the surface of a four wheel rotating at a circumferential speed of 20111/sec.

At that time, if the peripheral speed of rotation of the roll surface is less than 5117 seconds, the cooling capacity will be too low for one supply amount, and the solidified material will become a solid solution of multiphase crystals and will not become an amorphous material. There is no dissatisfaction with the degree of occupancy of the amorphous part of the assimilate when the velocity exceeds 8511/sec, but the WIS of the product resulting from poor shaping properties may be flaky or fine powder-like or excessively thin film-like. Become.

Further, the supply of the melt onto the roll surface is carried out by pressing the melt with a pressurizing gas in addition to the outflow force of one cylinder. As the pressurizing gas 61, for example, an inert gas such as argon-helium monoxide gas, air, or the like is used. Dry compressed air is particularly suitable as a pressurizing gas because it does not reduce the melt. The pressure of the pressurizing gas depends on the viscosity of the melt, the amount of supply, the speed of the reel surface, the melting temperature, and the air outlet. It is selected appropriately depending on the quenching conditions such as the opening temperature and the spatial distance between the nozzle tip and the round surface, but generally 0.1 to 2.0 k/ad.
, preferably within the range of 0.5 to 1.0 kg/clI12. If the pressure of this pressurizing gas is too low, the amount of melt supplied will not be uniform, while if it is too high, the amount of melt supplied will be excessive and the quality and shape of the solidified material will be inconsistent. Undesirable.

In addition, by replacing the atmosphere surrounding the roll surface for cooling the all liquid with air under atmospheric pressure, under reduced pressure or high vacuum, or with an inert gas similar to the above-mentioned pressurizing gas, Compared to the amorphous material obtained in an air atmosphere under atmospheric pressure, a material with a reduced number of oxygen atoms in its molecules, that is, a composition in a reduced state, can be obtained. The latter is more purplish or black than the former (atmospheric).

According to the method of the present invention, by appropriately selecting the rapid solidification conditions or the composition ratio of bismuth oxide and germanium oxide, 4-ML
20. Those containing a trace amount of fine crystalline parts in a uniformly dispersed state, furthermore, a-Mlo r-11i O and -Bi20. 23% fine crystal part, B12.0. It is possible to prepare a solid solution of G·0□ in which polycrystalline portions and amorphous portions are almost uniformly dispersed.

The amorphous material of the present invention has excellent energy mutual conversion power such as light-electricity, sound-electricity, and atmospheric gas-electricity, so it can be used for various energy conversion element materials, photoacoustic deflection materials 5X1
It can be suitably used as an 8-spectroscopic material, solid-state display element material, etc., and also as a catalyst due to its excellent catalytic power.

Next, the present invention will be explained in more detail by way of an example.

First, an example of an apparatus that can be used in the method of the present invention will be schematically described.

151m is a schematic front view of the equipment, in which (5) is a roll for rapid solidification, trout is a tube-shaped heat-resistant container with an outlet for storing raw materials, and (2) is a dielectric heating type for melting raw materials. The coil and ■ are support rods for heat-resistant containers. J1211 is a schematic vertical cross-sectional view of this support rod (2). Inside this support rod, a pipe 1- for letting cooling water in and out is provided, and a communication pipe for blowing out the molten liquid is also provided. A perforated plate for rectification is attached to the mouth to feed the melt in increasing amounts.

The figure is a longitudinal cross-sectional view of a heat-resistant container U, in which the part (loa) in direct contact with the melt (b) is made of platinum, and the other part (lob) is made of quartz. Figures 4 to 6 are respectively heat-resistant This is a schematic view showing the configuration of an air outlet (Figure #+6) provided at one end of the container so that the molten liquid can be supplied at an angle to the axial direction of the container.

In addition, Fig. 7 is a side view for explaining the main part of the structure of the roll (6) made of #I, and Fig. JIIa is a sectional view of the end of the roll for explaining the internal structure of the roll. Inside the tube, there is a mechanism that prevents the generation of turbulent air on the four-wheel surface caused by its rotation under atmospheric pressure to prevent deterioration during the rapid cooling and solidification process of the melt and the crushing of the product after solidification, and also to suck air. A fan (6
) is fixed, and the roll printing plate is provided with an air suction port (7). jl! ? Figure-11 is an explanatory diagram illustrating the form of this air suction port (TE). Furthermore, although not shown, grooves are provided on the surface of the roll in the axial direction to allow the product to be cut to a predetermined size.

In addition, this device is equipped with a heat-resistant container near the container to prevent turbulence on the roll surface and to improve heat circulation.
In order to improve the adhesion of the melt and its solidified material onto the roll, a countercurrent air blowing nozzle is used to prevent wind blowing, and the raw material is heated and melted in a heat-resistant container and subjected to a homogeneous phase ratio. In order to prevent the melted material from flowing out from the outlet during the process, there is a cold gas nozzle (2) that can blow cooling gas to a local area at the tip of the outlet. As this cooling gas, an inert gas such as argon, helium, or nitrogen, or air is used. Further, the blowing of the cold gas is stopped immediately before the molten liquid heated to a predetermined temperature is supplied onto the roll.

In this device, when supplying the melt, the distance between the outlet and the roll surface must be 0.01 to 1 inch, preferably 0.05 to 0.5!1111 degrees. This distance is 0. (If it is less than Nm, it will not be possible to supply the melt smoothly, and if it exceeds 1 m, there will be too many melt puddles (puddles) formed between them, or the puddles will not be formed, resulting in a product of the same quality. I can't hang it.

In addition, the melt can be supplied perpendicularly to the reel surface if the width of the product to be produced is less than 6 mm, but if the width exceeds 6 mm, It is necessary to adjust the angle appropriately within the range of 45 degrees or less based on the supply conditions. Example 1 - Various amounts of 11203 powder, rumored to have a purity of 99.0, and G-02 powder, rumored to have a purity of 99.9, were used. Change the total amount to 30
9, the composition ratio Bt zo310 @ O$1 is Vl,
Prepare 1/1 and 1/2 pieces, calcinate each at 850 Qa for 50 minutes, let it cool, grind again, and cut into slits with a diameter of 0.2 mm and a length of 4-1. A platinum tube (inner diameter 20 cm, length 150 cm) with a blow-out port was filled with the mixture, placed inside a dielectric heating coil, and heated and melted.

Dielectric heating conditions are oscillation fiber voltage 1jSV% anode voltage 10k
Vs Lattice current 120~15011A s Anode current 1.
It is 2 to 1.8 mm. In addition, in order to prevent the melt from flowing out from the outlet during that time, air was blown through the outlet to locally solidify the melt.

Next, after stopping the blowing of the molten liquid to the blow-out port after reaching a predetermined temperature, 0.5 kp/a- dry compressed air was applied to the melt for 10 minutes.
The molten liquid is pressed by blowing air at a rate of U%, and the temperature is kept below 25aO using a hard chrome-plated steel plate rotating at an opening speed of 17.27"/i!l) from the blower outlet. The material was supplied onto the surface of a roll and rapidly cooled and solidified under atmospheric pressure.At this time, the supply rate was 25 to 40 g/sec, and the distance between the shortest part of the air outlet and the sealing surface was 0.05 cm. did.

The dimensional characteristics of the ribbon-like products observed are shown in Table 1.

iml Regarding the obtained product, its structure is powder Xl! A diffraction device (RAD-11 [manufactured by Rigaku Denki ■) and a Mitaro* structure were examined using a scanning electron microscope (■S-4501 [manufactured by Hitachi Seisakusho Co., Ltd.]).

As a result, the general formula (Bi203), ・(G・0□)(,
−〇) (X is the same as above), where X is 0.5≧x
) No crystalline parts were found in the composition ratios in the range of 0, and in the composition ratios in the range of 0.65≧1>0.5, J-Bi, O,
It consisted of an amorphous material containing polycrystalline parts almost uniformly dispersed. 1>) Those in the range of C>0.65 are δ-1i120. Polycrystalline part, α・l1i20. Polycrystalline part, 7-Bi2O, polycrystalline part, BizOs and G@
The solid solution polycrystalline portion with Oai and the amorphous portion were almost uniformly dispersed. Figure 12 shows these results as an S cabinet.

In addition, J111-1581 is a diagram showing the results of differential thermal analysis of the amorphous bodies found in Examples 1.2 and 6, respectively. This is an infrared absorption spectrum charge in infrared spectroscopic analysis of a particle.

11171m is an electronic micrograph (50,000 times) of the material obtained in Example 2, which shows that it is an amorphous material in a nearly uniform state.

Examples 4 to 10 Bi, O, powder with a purity of 99.9% $24.69 and G. ) The total amount of gog was mixed uniformly, calcined at 850 qO for sO minutes, left to cool, and ground again.
5Qm), placed in a dielectric heating coil, and heated and melted.The melting point of the mixture at this composition ratio is 102B.
'It was O. The dielectric heating conditions are: oscillation tube fiber voltage 1! ■
1 anode voltage 10 kV% grid current 120-150 mm, anode current 1.2-1.8 mm.

Next, after stopping the supply of dry air to the outlet of the platinum tube, the molten liquid that has reached a predetermined temperature is pressed with dry compressed air (0.5kp10III2.10t/min) and the rotating hard tube is passed through the outlet. 25 made of chrome-plated copper
The mixture was extruded onto the surface of a roll maintained at a temperature below 0, and rapidly cooled and solidified under atmospheric pressure. #l speed of roll JI
An amorphous material was obtained in the same manner with the changes shown in No. 211.

Other manufacturing conditions are shown below.

The shape of the outlet: the distance between the slit outlet with a radius of 0.2 mm and the length of 4 mm and the shortest part to the roll surface is 2Q, Q5 mm.The results obtained are shown in Table 12. Note that all of the ribbon-like products obtained were transparent glass-like products.

From Table 12 and Table 2, it can be seen that the thickness of the product seen decreases with increasing circumferential speed.

Examples 12 to 2+5 Bt207G. The distance of the shortest part, row-
We investigated products obtained by varying the gas pressure for liquid pressing and the melt temperature. In Examples 11.14 to 18, copper rolls not plated with hard chrome were used.

The results are shown in Table 3.

In addition, the melting point of the composition ratio B1□o, 7a s o, is 1A is 1052'Ora'), 2/1 (7) Mono 4
1985aOte2btsu. Furthermore, all the products obtained were ribbon-like or transparent glass-like.

Comparative Examples 1 to 9 For comparison, the measurement results for samples prepared according to the conditions shown in Table 94 are shown in open bags.

In addition, in Comparative Example 9, the distance t-0 between the air outlet and the roll surface at the shortest point from the air outlet of the round hole (diameter Q, 2 holes),
The melt was supplied as 1 mm.

Incidentally, it was investigated by powder X-ray diffraction analysis how the amorphous occupancy of the obtained material changes with changes in the circumferential velocity of %4.

Example 4.5 in Figure 1I1118! and 7.1119
Examples 2.8.10 and 11.120 in Figures Example 12!5 Yohi 1B, j12[1&:, Example 19 Oyohi 20.422 What was seen in Examples 1.22 and 2M, respectively About Powder X! A 1m fold chart is shown.

[Brief explanation of the drawing]

Figure 1111 is a schematic front view of an apparatus that can be used when carrying out the method of the present invention, Figure 2 is a longitudinal cross-sectional view of a support rod for a heat-resistant container, Figure JI is a longitudinal cross-sectional view of a heat-resistant container, Figure J114, Figures 5 and 11116 are explanatory diagrams illustrating the configuration of the air outlet of a heat-resistant container, respectively, Figure jlK7 is a side view of the roll, Figure 1118 is a sectional view of the end of the roll, Figure JI9,
Figure J110 and Figure 11 are explanatory diagrams illustrating the form of the air suction port provided on the outer periphery of the four-ring, Figure J112 is a phase diagram showing the relationship between the composition ratio and crystal structure, and Figures 1115 to 15 are examples, respectively. 1.2, and the chart obtained by differential thermal analysis of the amorphous material obtained in 6, 1s16 figure is Example 1.2,
and infrared absorption spectrum of amorphous material obtained with black ink), JIH7W! 18 to 22 are electron micrographs of the amorphous material obtained in Example 2, and FIGS. 18 to 22 are those of Example 4, respectively.
5, 6 and 7, Examples 2.810 and 11, Examples 12 and 1iS, Examples 19 and 20 and Examples 1S22 and 26. (Major symbols in the drawing) (5): 1. Heat-resistant container 1. Melt liquid 1.
1%) (3eOxBi20sX G
eOx(1-X)

Claims (1)

[Claims] 1 A compound and/or mixture of bismuth oxide and germanium oxide whose composition ratio is represented by the general formula: % formula % (1) (& stock, 1>!>O) is heated and melted. A screw is formed by rapidly cooling and solidifying a helical wave heated to an ioo ao higher temperature than that one point on a cold surface! Sugel! Ni-based oxide amorphous material. A compound of bismuth oxide and layered germanium and (or ) Fill the mixture into a heat-resistant container with an air outlet, heat and melt the mixture to form a molten liquid at a temperature of lsO to 800 oa higher than its melting point, (a) Rotate this liquid at a temperature below room temperature. The seal that is
A bis that is characterized by being supplied on top of the 1IIWJ and rapidly cooled, making it less viscous! Sugel! A method for manufacturing nium-based oxide amorphous materials.