CN216801689U - Mould for preparing germanium metal small ball - Google Patents

Abstract

The present disclosure provides a mold for preparing germanium prills, wherein the mold is a plate body, and the plate body is provided with an upper surface and a lower surface which are opposite along the thickness direction; the plate body is provided with a U-shaped hole; the U-shaped hole is provided with an opening positioned on the upper surface of the plate body, a cylinder extending downwards from the upper surface of the plate body and a hemisphere extending downwards from the cylinder; the radius of the cylinder is the same as that of the hemisphere, and the bottom surface of the cylinder and the top surface of the hemisphere are completely overlapped in the thickness direction of the plate body. In the preparation process, a germanium simple substance is obtained through reduction reaction based on germanium oxide, the volume occupied by the germanium simple substance is reduced, gaps among germanium oxide particles of raw materials are eliminated, and then the germanium metal small balls which are approximately spherical can be finally obtained by utilizing hemispheres and combining with cooling volume expansion of the germanium simple substance, so that the mold for preparing the germanium metal small balls can be used for preparing the germanium metal small balls.

Description

Mould for preparing germanium metal small ball

Technical Field

The disclosure relates to the field of germanium metal, in particular to a mold for preparing germanium metal balls.

Background

With the increasing demand of infrared semiconductor laser materials in domestic and foreign markets, the demand of infrared semiconductor materials is diversified. The infrared material is used for coating and extending to improve various properties of the material, and at present, the domestic pure germanium is prepared by high-temperature thermal reduction of germanium oxide, hydrogen is used as a reducing agent, and a high-purity germanium simple substance is obtained by high-temperature zone melting. The reduced germanium in the current market is a massive germanium ingot, and when orders with few materials and a lot of materials are made, the massive germanium ingot needs to be cut, so that the phenomena of prolonged production and processing period, complex production process, increased raw material requirements and the like are caused. The current production process needs production and preparation process equipment aiming at small-particle germanium pellets.

Disclosure of Invention

In view of the problems in the background art, it is an object of the present disclosure to provide a mold for preparing germanium pellets, which can be used to prepare germanium pellets.

Thus, in some embodiments, a mold for preparing germanium beads is a plate body having upper and lower surfaces opposite in thickness; the plate body is provided with a U-shaped hole; the U-shaped hole is provided with an opening positioned on the upper surface of the plate body, a cylinder extending downwards from the upper surface of the plate body and a hemisphere extending downwards from the cylinder; the radius of the cylinder is the same as that of the hemisphere, and the bottom surface of the cylinder and the top surface of the hemisphere are completely overlapped in the thickness direction of the plate body.

In some embodiments, the mold is a graphite plate.

In some embodiments, the ratio of the height of the cylinder to the radius of the hemisphere is 3: 2.

In some embodiments, the plate body has a thickness of 15mm to 20mm, the cylinder has a height of 6mm, and the radius of the hemisphere is 4 mm.

In some embodiments, the U-shaped holes are arranged in an array on the plate body.

In some embodiments, the U-shaped apertures are disposed in a row-column aligned array on the plate body.

In some embodiments, the U-shaped apertures are offset in adjacent rows on the plate body.

In some embodiments, the U-shaped cells are arranged in a honeycomb pattern.

The beneficial effects of this disclosure are as follows: in the preparation process, a germanium simple substance is obtained through reduction reaction based on germanium oxide, the volume occupied by the germanium simple substance is reduced, gaps among germanium oxide particles of raw materials are eliminated, and then the germanium metal small balls which are approximately spherical can be finally obtained by utilizing hemispheres and combining with cooling volume expansion of the germanium simple substance, so that the mold for preparing the germanium metal small balls can be used for preparing the germanium metal small balls.

Drawings

Fig. 1 is a schematic perspective view of an embodiment of a mold for producing germanium beads according to the present disclosure, wherein a portion of one U-shaped hole below an upper surface is shown in phantom.

Fig. 2 is a schematic illustration of the U-shaped hole in the mold of fig. 1 filled with germania, shown in fill color.

Figure 3 is a cross-sectional view of a U-shaped hole in a single mold.

Fig. 4 is a schematic perspective view of another embodiment of a mold for producing germanium beads according to the present disclosure.

Wherein the reference numerals are as follows:

100 mold 32 cylinder

1 height of upper surface H

2 lower surface 33 hemisphere

Radius of 3U-shaped hole R

31 opening

Detailed Description

The accompanying drawings illustrate embodiments of the present disclosure and it is to be understood that the disclosed embodiments are merely examples of the disclosure, which can be embodied in various forms, and therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present disclosure.

Further, the expressions indicating directions (for example, upper and lower) for explaining the operation and configuration of each member in the embodiment are not absolute but relative, and although these indications are appropriate when each member is in the position shown in the drawings, when the position is changed, these directions should be interpreted differently to correspond to the change.

First, a mold 100 for preparing germanium pellets according to the present disclosure is described.

Referring to fig. 1 to 4, the mold 100 is a plate body having an upper surface 1 and a lower surface 2 opposite in a thickness direction; the plate body is provided with a U-shaped hole 3; the U-shaped hole 3 has an opening 31 at the upper surface 1 of the plate body, a cylindrical body 32 extending downward from the upper surface 1 of the plate body, and a hemisphere 33 extending downward from the cylindrical body 32; the radius of the cylindrical body 32 is the same as the radius R of the hemisphere 33, and the bottom surface of the cylindrical body 32 and the top surface of the hemisphere 33 completely overlap in the thickness direction of the plate body. In the preparation process, a germanium simple substance is obtained through reduction reaction based on germanium oxide, the volume occupied by the germanium simple substance is reduced, gaps among germanium oxide particles of the raw material are eliminated, and then the spherical germanium metal balls can be finally obtained by utilizing the hemispheroid 33 and combining with the cooling volume expansion of the germanium simple substance.

In some embodiments, the mold 100 is a graphite plate. In some embodiments, the graphite plates have a gray scale of less than 20 ppm. The graphite plate with the gray level lower than 20ppm is high temperature resistant, single in component, free of participating in reduction reaction, easy to process the U-shaped hole 3 and high in heat conductivity, so that the temperature of the whole graphite plate is uniformly distributed in the heating process. Graphite plates with a gray scale of less than 20ppm are commercially available.

In some embodiments, the ratio of the height H of the cylinder 32 to the radius R of the hemisphere 33 is 3: 2.

In some embodiments, the plate has a thickness of 15mm to 20mm, the height H of the cylinder 32 is 6mm, and the radius R of the hemisphere 33 is 4 mm. A thickness lower than 15mm makes the plate body insufficient in strength and susceptible to damage in production upon accidental impact, in particular at the location of the U-shaped hole 3.

In some embodiments, referring to fig. 1, 2 and 4, U-shaped holes 3 are disposed in an array on the plate body. Therefore, the mold 100 can simultaneously prepare a plurality of germanium metal pellets, thereby improving the production efficiency.

In some embodiments, the radius in the plurality of U-shaped holes 3 is divided into two different radii, thereby enabling the production of germanium metal pellets of different sizes using the same mold 100.

In some embodiments, referring to fig. 1 and 2, U-shaped apertures 3 are provided in a plate body in an array aligned in rows and columns. Thereby simplifying the layout design of the U-shaped holes 3.

In some embodiments, referring to fig. 4, the U-shaped holes 3 are arranged on the plate body in adjacent rows and offset. Thereby making full use of the surface area of the plate body. Further, the U-shaped holes 3 are arranged in a honeycomb shape (as shown by dotted lines in fig. 4, six other U-shaped holes 3 forming a hexagon are surrounded around each U-shaped hole 3 except the U-shaped holes 3 at the periphery of the mold 100), thereby more fully utilizing the surface area of the plate body, increasing the number of U-shaped holes 3, and improving the single production efficiency.

Next, a method for producing germanium metal pellets of the present disclosure is explained.

The disclosed germanium prill comprises the steps of: step one, preparing a mold 100, wherein the mold 100 is a plate body, the plate body is provided with an upper surface 1 and a lower surface 2 which are opposite in thickness direction, the plate body is provided with a U-shaped hole 3, the U-shaped hole 3 is provided with an opening 31 which is positioned on the upper surface 1 of the plate body, a cylinder 32 which extends downwards from the upper surface 1 of the plate body and a hemisphere 33 which extends downwards from the cylinder 32, the radius R of the cylinder 32 is the same as the radius R of the hemisphere 33, and the bottom surface of the cylinder 32 and the top surface of the hemisphere 33 are completely overlapped in the thickness direction of graphite; filling the U-shaped hole 3 with germanium oxide; step three, placing the graphite plate in a graphite boat; step four, placing the graphite boat in a horizontal reduction furnace; introducing nitrogen into the horizontal reduction furnace to remove redundant air in the horizontal reduction furnace; introducing hydrogen into the horizontal reduction furnace, raising the temperature, and preserving the temperature at about 750-780 ℃ to form a germanium simple substance through reduction reaction, wherein water formed in the reduction process overflows in a gaseous state; step seven, keeping introducing hydrogen and keeping normal exhaust of an air outlet of the horizontal reduction furnace, after the reduction reaction is finished, heating to 950-1050 ℃, and preserving heat; and step eight, keeping introducing hydrogen and keeping normal exhaust of an air outlet of the horizontal reduction furnace, gradually cooling to room temperature, and forming a spherical germanium simple substance in the U-shaped hole 3. And normal exhaust refers to opening an air outlet of the horizontal reduction furnace.

In some embodiments, in step two, the germanium oxide is in powder form and has a purity of 6N.

In some embodiments, in step five, the nitrogen gas is introduced into the horizontal reduction furnace at a rate of 15L/min to 20L/min.

In some embodiments, in the sixth step, the flow rate of the hydrogen gas introduced into the horizontal reduction furnace is 10L/min to 15L/min.

In some embodiments, in step six, the ramp rate is from 10 ℃ to 15 ℃/min; the heat preservation time is 20h-25h, so that the reduction reaction between the germanium oxide and the hydrogen is thorough.

In some embodiments, in step seven, the ramp rate is from 10 ℃ to 15 ℃/min; the heat preservation time is 4h-5h, the hydrogen flow rate is controlled at 10L/min-15L/min at constant temperature, and at the moment, the hydrogen is used as protective atmosphere on one hand and is used for thoroughly reducing the germanium oxide in the U-shaped hole on the other hand.

In some embodiments, in the step eight, the cooling rate is 3 ℃/min to 5 ℃/min, and the hydrogen flow rate is controlled to be 5L/min to 10L/min during cooling. The temperature reduction rate in the range is favorable for controlling the cooling expansion process of the germanium simple substance and improving the roundness of the final germanium prill. And the hydrogen flow rate is controlled within the range during temperature reduction, so that the constraint of the hydrogen flow on the cooling expansion of the germanium simple substance is favorably reduced, and the reduction process is completed in the step seven, so that the consumption of hydrogen can be reduced, and the production cost is reduced.

In the preparation method of the germanium prills, germanium oxide in the U-shaped hole 3 obtains a germanium simple substance through a reduction reaction (the germanium oxide obtains the germanium simple substance through the reduction reaction, the volume occupied by the germanium simple substance is reduced, and gaps among the germanium oxide are eliminated at the same time), then the germanium simple substance is melted at a high temperature and then cooled and solidified, and the germanium can expand in volume in the cooling and solidification process, so that the approximately spherical germanium prills are obtained by utilizing the hemispheres 33 of the U-shaped hole 3 and the cooling volume expansion of the germanium. Therefore, germanium ingots in the background art do not need to be formed, and the process is greatly simplified.

Next, specific examples of the production process will be described.

Example 1

Step one, preparing a mold 100, wherein the mold 100 is a graphite plate, the plate body is provided with an upper surface 1 and a lower surface 2 which are opposite in thickness direction, the plate body is provided with a U-shaped hole 3, the U-shaped hole 3 is provided with an opening 31 which is positioned on the upper surface 1 of the plate body, a cylinder 32 which extends downwards from the upper surface 1 of the plate body and a hemisphere 33 which extends downwards from the cylinder 32, the radius R of the cylinder 32 is the same as the radius R of the hemisphere 33, the bottom surface of the cylinder 32 and the top surface of the hemisphere 33 are completely overlapped in the thickness direction of the graphite, the height H of the cylinder 32 is 6mm, the radius R of the cylinder 32 is 4mm, the gray level of the graphite plate is lower than 20ppm, and the thickness of the plate body is 20 mm;

step two, spreading germanium oxide on the mold 100 to fill the mold 100 in the plurality of U-shaped holes 3, wherein except for the existence of the germanium oxide in the plurality of U-shaped holes 3 of the mold 100, the part of the upper surface 1 of the mold 100 except the U-shaped holes 3 does not have the germanium oxide, so that the bonding phenomenon between the adjacent small balls due to the germanium obtained by reducing the residual germanium oxide on the surface in the temperature reduction process of the part of the upper surface 1 of the mold 100 except the U-shaped holes 3 is prevented;

step three, placing the graphite plate in a graphite boat;

step four, placing the graphite boat in a horizontal reduction furnace;

introducing nitrogen into the horizontal reduction furnace to drive away redundant air in the horizontal reduction furnace, wherein the speed of introducing the nitrogen into the horizontal reduction furnace is 15L/min;

introducing hydrogen into the horizontal reduction furnace, raising the temperature at the rate of 10 ℃/min, and keeping the temperature at about 750 ℃ for 20h to form a germanium simple substance through reduction reaction, wherein water formed in the reduction process overflows in a gaseous state;

step seven, keeping introducing hydrogen and keeping normal exhaust of an air outlet of the horizontal reduction furnace, after the reduction reaction is finished, heating up to 950 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 4 h;

and step eight, keeping introducing hydrogen and keeping normal exhaust of an air outlet of the horizontal reduction furnace, gradually cooling to room temperature, controlling the cooling rate at 4 ℃/min, controlling the hydrogen flow rate at 5L/min during cooling, and enabling the germanium simple substance in the U-shaped hole 3 to form a sphere.

The germanium metal pellets prepared in example 1, when viewed from the outside, were reduced to approximately spherical shapes, each pellet having a weight of about 0.3 to 0.4g and a diameter of about 3mm to 5 mm.

The germanium metal pellets discharged from the furnace are subjected to ICP-MS quantitative analysis, and the results of the three-time analysis are shown in Table 1.

TABLE 1 ICP-MS quantitative analysis of germanium metal pellets

From the results of the three parallel analyses in Table 1, it can be seen that the total impurity content is about 1ppm, and the purity requirement is achieved.

The above detailed description is used to describe a number of exemplary embodiments, but is not intended to limit the combinations explicitly disclosed herein. Thus, unless otherwise specified, various features disclosed herein can be combined together to form a number of additional combinations that are not shown for the sake of brevity.

Claims (8)

1. A mould (100) for preparing germanium metal pellets, the mould (100) is a plate body,

the plate body is provided with an upper surface (1) and a lower surface (2) which are opposite in thickness direction;

the plate body is provided with a U-shaped hole (3);

the U-shaped hole (3) is provided with an opening (31) positioned on the upper surface (1) of the plate body, a cylinder (32) extending downwards from the upper surface (1) of the plate body and a hemisphere (33) extending downwards from the cylinder (32);

the radius of the cylinder (32) is the same as the radius (R) of the hemisphere (33), and the bottom surface of the cylinder (32) and the top surface of the hemisphere (33) are completely overlapped in the thickness direction of the plate body.

2. A mould (100) for producing germanium prills according to claim 1, wherein the mould (100) is a graphite plate.

3. The mold (100) for producing germanium prills according to claim 1, wherein the ratio of the height (H) of the cylinder (32) to the radius (R) of the hemisphere (33) is 3: 2.

4. The mold (100) for preparing germanium prills according to claim 3, wherein the plate has a thickness of 15mm-20mm, the cylinder (32) has a height (H) of 6mm, and the hemisphere (33) has a radius (R) of 4 mm.

5. Mould (100) for the preparation of germanium prills according to claim 1, wherein the U-shaped holes (3) are arranged in an array on the plate body.

6. The mold (100) for producing germanium prills according to claim 5, wherein the U-shaped holes (3) are arranged in a plate body in an array aligned in rows and columns.

7. The mold (100) for preparing germanium prills according to claim 5, wherein the U-shaped holes (3) are arranged in the plate body in adjacent rows and offset.

8. The mold (100) for preparing germanium prills according to claim 7, wherein the U-shaped holes (3) are arranged in a honeycomb shape.

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