CN111910086A - Device for preparing ultrapure indium and method for preparing ultrapure indium by adopting device - Google Patents
Device for preparing ultrapure indium and method for preparing ultrapure indium by adopting device Download PDFInfo
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- CN111910086A CN111910086A CN202010755349.1A CN202010755349A CN111910086A CN 111910086 A CN111910086 A CN 111910086A CN 202010755349 A CN202010755349 A CN 202010755349A CN 111910086 A CN111910086 A CN 111910086A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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Abstract
The invention discloses a top-end self-suction type vertical zone-melting purification device and a method for preparing ultrapure indium, wherein the device comprises a vacuum cavity, a vertical zone-melting system arranged in the vacuum cavity and a self-suction system arranged at the upper end of the vacuum cavity; installing a quartz tube filled with 4N/5N-grade indium raw materials into a vertical zone melting system, respectively setting heating temperature and cold trap temperature, driving the quartz tube to move up and down through a guide rod, carrying out multi-pass vertical zone melting, carrying out N (N is 5-10) pass vertical zone melting purification in each cycle, melting indium metal of 10-20% volume fraction of a sample at the top end in the quartz tube, and sucking out the indium metal through a self-absorption system. Followed by replenishing the same mass of indium starting material. And after 3 cycles of 3n times of vertical zone-melting purification processes are completed, taking out and intercepting samples with volume fractions of 5-15% at two ends of the quartz tube respectively, and remelting and sample preparation are carried out on the samples in the residual middle area. The invention can realize the high-efficiency and stable production of 6N-grade and above ultra-pure indium products with different grades of purity by the top-end self-suction type vertical zone melting device and method.
Description
Technical Field
The invention belongs to the field of preparation of ultrapure indium, and particularly relates to a device for preparing ultrapure indium and a preparation method adopting the device.
Background
The metal indium has unique and excellent physical and chemical properties, is widely applied to high-tech fields such as energy, national defense and military, aerospace, nuclear industry, modern information industry and the like, and has increasingly important function in national economy. However, the introduction of trace impurities can seriously affect the performance of the material, so the purity of the metal indium directly determines the performance of the material synthesized subsequently. For example, an indium phosphide semiconductor material prepared by adopting ultra-pure indium is widely applied to the top fields of 5G communication, infrared detection, image transmission and the like. The method for purifying indium metal includes mainly chemical electrolysis, vacuum distillation, zone melting, ion exchange, and low-halogen compound methods. The process route commonly adopted by indium production enterprises is 'industrial refined indium → chemical impurity removal → electrolytic refining → low-temperature vacuum distillation → high-temperature vacuum distillation → electrolytic refining', but from the perspective of practical production benefits, the vacuum distillation in the high-temperature stage greatly reduces the yield of products, the long-period electrolytic refining chemical method treatment in the two stages easily causes the difficulty in stabilizing the quality of terminal products, and the existing production process is difficult to prepare the ultrapure indium with stable quality.
At present, the purification work of the ultra-pure metal is more and more emphasized, and related scientific research and patent invention are rapidly increased. For example, the invention with the application number of CN201711305879.0 and the name of 'a method for purifying indium' discloses a device and a method for preparing ultrapure indium, and explains that 6N-grade ultrapure indium is obtained by using 6N-7N-grade high-purity indium as seed crystals and adopting a suspension zone melting method, but because the surface tension of an indium melt is small, the yield per time is small, and the large-scale production cannot be realized. The invention with the application number of CN201711441250.9 and the name of 'a high-purity indium purification device and method' discloses a horizontal zone melting method, which describes that a plurality of resistance heaters are sequentially arranged on the outer side of a quartz tube along the horizontal direction, and 6N-7N-grade ultra-pure indium is obtained by controlling the temperature of the resistance heaters to realize multi-stage heating, but the solid-liquid interface of indium metal in a quartz boat in a horizontal zone melting method is inclined, so the yield is generally lower than 60%; and the horizontal zone melting method is difficult to apply a cooling system, and the width of a melting zone is difficult to control, so that the purification efficiency is low. The invention with the application number of CN201910606312.X and the name of 'a device for preparing ultrapure indium and a preparation method thereof' discloses a device integrating vacuum distillation and vertical zone melting and a preparation method thereof, wherein precise control of a temperature zone is realized by combining resistance wire heating and cooling devices, but in the zone melting process, a multi-pass repeated pulling process is required, impurity enrichment areas at two ends are removed after a sample is taken out, and then multi-pass zone melting is carried out repeatedly to purify indium to 7N grade, so that the time cost required is relatively high. On the basis, the invention provides a top-end self-suction type vertical zone melting device and a method thereof, aiming at 4N-grade or 5N-grade indium raw materials, different-pass vertical zone melting purification is carried out, an additional self-suction system is directly adopted in the vertical zone melting system, a sample of an impurity enrichment zone at the top end of the sample is remelted and sucked out, then indium raw materials with the same quality as the sucked out indium raw materials are supplemented, the next round of multi-pass vertical zone melting purification is directly and circularly carried out, and 6N-grade or above ultra-pure indium products with different grades of purity can be efficiently prepared by adjusting the single-cycle internal zone melting pass and the impurity amount of each self-suction.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above problems, the present invention provides an apparatus and a method for producing ultrapure indium, which are capable of achieving efficient and stable production of ultrapure indium having a purity of 6N grade or higher.
The technical scheme is as follows: in order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: a top end self-suction type vertical zone melting device for preparing ultrapure indium comprises a vacuum cavity (14), a vertical zone melting system arranged in the vacuum cavity (14) and a self-suction system positioned above the vertical zone melting system;
the vertical zone melting system comprises a quartz tube (16), a heating device, a guide rod (22) and a cold trap device (20), wherein the guide rod (22) is arranged at the lower end of the quartz tube (16) and can move up and down; the guide rod (22) is fixedly connected with the quartz tube (16), the cold trap device (20) is positioned below the heating device (17), the outer sides of the heating device (17) and the cold trap device (20) are wrapped by heat insulation materials (18), and the guide rod (22) can sequentially penetrate through the heating device (17) and the cold trap device (20) to move up and down;
from inhaling the system including be located vacuum cavity (14) upper end outside cutting ferrule formula needle valve (1) and steel from inhaling pipe box (12), inhale glass pipe (13) certainly, the steel is connected with cutting ferrule formula needle valve (1) from inhaling pipe box (12) one end that is located vacuum cavity (14) outer, and the one end that is located vacuum cavity (14) is connected from inhaling glass pipe (13), from inhaling cutting ferrule formula needle valve (1) of system and vacuum tank (4) and being connected with the hose, control from inhaling glass pipe (13) internal pressure, from inhaling the system and can reciprocate and spin.
Furthermore, the lower end of the guide rod (22) is provided with a motor which can move the guide rod (22), so that the guide rod (22) can move up and down.
Furthermore, the heating device is connected with a temperature controller (7), and the temperature is set through the temperature controller (7).
Furthermore, circulating cooling liquid is introduced into the cold trap device (20), and the temperature of the cooling liquid is regulated by the cold trap control device (8).
Further, vacuum cavity (14) and vacuum tank (4) are connected with mechanical pump and vacuum pump tandem arrangement (6), and control vacuum cavity (14) and vacuum tank (4) internal pressure respectively through different valves, and vacuum cavity (14) are connected with gas cylinder (9), provide protective gas environment for the device, and vacuum cavity (14) internal pressure is monitored by first vacuum meter (1), and vacuum tank (4) internal pressure is monitored by second vacuum meter (2).
Furthermore, an observation window (10) is arranged above the vacuum cavity (14).
Furthermore, the guide rod (22) and the quartz tube (16) are fixedly connected through a clamping sleeve (21).
The invention also provides a method for preparing ultrapure indium by the device, which comprises the following steps:
(a) the preset environment is as follows:
putting 4N-grade or 5N-grade indium raw materials into a quartz tube, and vacuumizing a vacuum cavity (14) to N1After Pa, back-filling protective gas to N2 Pa；
(b) The process flow is as follows:
(1) vertical zone melting purification: moving the quartz tube to an initial position, namely the position where the bottom end of the quartz tube is flush with the top end of the heating device, setting the heating temperature, the cold trap temperature and the moving speed of the guide rod, under the parameters, moving the quartz tube from the initial position to the position where the top end of the quartz tube is flush with the top end of the cold trap device, or moving the top end of the quartz tube to the position below the top end of the cold trap device, then closing the heating device and the cooling device, returning the quartz tube to the initial position after cooling to room temperature, starting the next zone melting process, and sequentially carrying out n-pass vertical zone melting purification according to different process parameters, wherein n is 5-10;
(2) top remelting self-absorption and raw material supplement:
(2.1) starting a mechanical pump and vacuum pump series connection device, and vacuumizing the vacuum tank to N3Pa，N3<N2(ii) a Moving the quartz tube to the position where the top end of the sample in the quartz tube is flush with the top end of the heating deviceSetting heating temperature and cold trap temperature, melting 10-20% volume fraction area of the top end of the sample, rotating a self-suction device to the same vertical central position of a self-suction glass tube and a quartz tube, moving the self-suction device downwards to a proper position in the self-suction glass tube, starting the self-suction device, sucking remelted indium, moving the quartz tube downwards to leave a heating area after self-suction is finished, and sequentially restoring the self-suction device and the quartz tube to initial positions;
(2.2) setting the heating temperature and the cold trap temperature to be room temperature, and supplementing indium raw materials with the same absorption quality after the temperature is reduced to the room temperature;
(3) circularly performing the step (1) and the step (2) once respectively;
(4) and (2) performing the step (1) again, taking out the metal indium from the quartz tube after the step is finished, intercepting 5-15% of each of two ends of the sample, and remelting and pouring the samples in the rest areas to obtain the finally purified high-purity metal indium.
Further, the heating device and the cold trap device are respectively set to have the heating temperature of 200-800 ℃, the cold trap temperature of-60-room temperature, and the up-down moving speed of the guide rod of 1-1000 μm/s.
Furthermore, the device for preparing the ultrapure indium also comprises a temperature control device for monitoring and feeding back the temperature of the heating device, wherein the temperature monitoring range is 0-1300 ℃, and the error between the monitored temperature and the actual temperature is +/-1 ℃.
The self-suction system comprises a ferrule type needle valve and a steel self-suction pipe sleeve connected with the ferrule type needle valve, and a self-suction quartz pipe is connected below the steel self-suction pipe sleeve.
Furthermore, the self-priming system of the device for preparing the ultrapure indium can be manually operated and can move up and down and spin. The initial position (0 position) of the self-absorption system is positioned above the heating device, the distance between the lower end of the self-absorption glass tube and the upper end of the heating device is 100mm, the distance between the self-absorption glass tube and the central line of the quartz tube is 90 degrees, and the moving distance interval is-300-200 mm. The maximum spinning angle can be rotated by 90 degrees clockwise/anticlockwise.
Has the advantages that: compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
according to the technical scheme disclosed by the invention, on one hand, the vertical zone melting method can effectively ensure that the temperature field in the melt is uniform and stable in the vertical zone melting pulling process, the height of the melting zone of metal indium in the vertical zone melting process can be flexibly regulated, and the indium purification efficiency is higher by the single-cycle internal combined zone melting process. On the other hand, after each single-cycle vertical zone melting purification process is completed, the top end area sample enriched with impurities is directly sucked out through the self-suction system, so that the production efficiency can be obviously improved, and the production period can be shortened. The time required for the present invention is usually within 7 days. The qualification rate of the 6N grade and above ultra-pure indium product is higher than 95%. The invention does not relate to a chemical reaction process and has no problem of environmental pollution. The top-end self-suction type vertical zone melting device and the method can realize the high-efficiency and stable production of 6N-grade and above ultra-pure indium products with different grades of purity.
Drawings
FIG. 1 is a schematic view of the structure of the apparatus of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
As shown in fig. 1, the apparatus of the present invention is a self-priming vertical zone-melting apparatus, and comprises a vacuum chamber 14, a vertical zone-melting system disposed in the vacuum chamber 14, and a self-priming system disposed above the vertical zone-melting system.
The vertical zone melting system comprises a quartz tube 16, a cutting sleeve 21 and a guide rod 22 which are arranged at the lower end of the quartz tube 16, wherein the guide rod 22 is connected with a motor to realize the up-and-down movement of the guide rod 22. The outside of the quartz tube 16 is sleeved with a heating device, the lower end of the heating device is provided with a cold trap device 20 and a corresponding cold trap control system 8, the cold trap device 20 is preferably a copper cold trap, and circulating cooling liquid is introduced into the cold trap to realize environment refrigeration from minus 60 ℃ to room temperature. The inner diameter of the heating device is 20mm, the inner diameter of the cold trap device is 23mm, and the distance between the heating device and the cold trap device is 1.5 mm. The temperature of the inner wall surface of the heating device 17 is stable and uniform. And the heating device 17 is connected with the temperature control device 7, feeds back and detects the temperature, and the precision is 1K.
The self-priming system comprises a ferrule type needle valve 1, a steel self-priming pipe sleeve 12 connected with the ferrule type needle valve 1, and a self-priming glass pipe 13 connected below the steel self-priming pipe sleeve 12. Wherein the self-sucking device can be manually moved up and down and can be rotated clockwise/anticlockwise in a two-way mode. The initial position (0 position) of the self-absorption system is positioned above the heating device, the distance between the lower end of the self-absorption glass tube and the upper end of the heating device is 100mm, the distance between the self-absorption glass tube and the central line of the quartz tube is 90 degrees, and the maximum moving distance is-300-200 mm. The maximum spinning angle can be rotated by 90 degrees clockwise/anticlockwise.
The device also comprises a vacuumizing device 6 for connecting the molecular pump and the mechanical pump of the vacuum system in series, a vacuum tank 4 connected with the self-priming system, pressure gauges 2 and 10 and the like, wherein the pressure gauge 2 can accurately monitor the pressure in the vacuum tank 4, and the pressure gauge 9 can accurately monitor the pressure in the vacuum cavity 1. The protective gas conveying system comprises a nitrogen cylinder 9, a conveying pipeline and a gas valve. The connection between the wall of the vacuum chamber 14 and other devices involved in the present invention is sealed with teflon.
The method for preparing the ultrapure indium by adopting the device comprises the following steps:
putting the quartz tube filled with 4N-grade or 5N-grade indium raw material into a zone melting furnace, and vacuumizing to 1 × 10-5And after Pa, reversely filling high-purity argon to 0.03MPa, respectively setting the heating temperature of 200-800 ℃ and the cold trap temperature of-60-room temperature for the heating device 17 and the cold trap device 20, and setting the up-down moving speed of 1-1000 mu m/s through the guide rod 22. The process flow is as follows:
the quartz tube filled with 4N-grade or 5N-grade indium raw materials is put into a zone melting system, and a vacuum cavity (14) is vacuumized to N1After Pa, back-filling protective gas to N2 Pa；
The heating device 17 and the cold trap device 20 are respectively set to have the heating temperature of 200-800 ℃ and the cold trap temperature of-60-room temperature, and the up-down moving speed of 1-1000 mu m/s is set through the guide rod 22;
the process flow is as follows:
(1) vertical zone melting purification: and moving the quartz tube to an initial position, namely, the bottom end of the quartz tube is flush with the top end of the heating device, setting the heating temperature, the cold trap temperature and the moving speed of the guide rod, moving the quartz tube from the initial position to a position where the top end of the quartz tube is flush with or below the cold trap device, closing the heating device and the cooling device, and returning the quartz tube to the initial position after cooling to room temperature. Sequentially carrying out n (n is 5-10) pass vertical zone melting purification according to different process parameters;
(2) top remelting self-absorption and raw material supplement:
(2.1) starting a mechanical pump and vacuum pump series connection device, and vacuumizing the vacuum tank to N3 Pa(N3<N2). Moving the quartz tube to the position where the top end of the sample in the quartz tube is flush with the top end of the heating device, setting the heating temperature and the cold trap temperature, melting a volume fraction area of 10% -20% of the top end of the sample, rotating the self-suction device to the position where the self-suction glass tube and the quartz tube are at the same vertical center, moving the self-suction device downwards to a proper position, starting the self-suction device, sucking remelted indium, moving the quartz tube downwards to leave a heating area after the self-suction is finished, and sequentially restoring the self-suction device and the quartz tube to the initial position;
(2.2) setting the heating temperature and the cold trap temperature to be room temperature, and supplementing indium raw materials with the same absorption quality after the temperature is reduced to the room temperature;
(3) step 1 and step 2 are carried out in a circulating mode once respectively;
(4) step 1 is carried out once again, and after completion, the metal indium is taken out of the quartz tube. And intercepting 5% -15% of each of two ends of the sample, remelting and pouring the samples in the rest areas to obtain finally purified high-purity metal indium.
Example 1
Putting the quartz tube filled with 4N-grade indium raw material into a zone melting furnace, and vacuumizing to 1 x 10-5And (4) after Pa, reversely filling high-purity argon to 0.03MPa, and purifying according to the following process flow.
1. Vertical zone melting purification: and moving the quartz tube to an initial position, and sequentially carrying out 5 times of vertical zone melting purification according to the following process parameters.
1 st pass zone melting parameters: the heating temperature is 400 ℃, the cold trap temperature is 25 ℃, and the moving speed is 50 mu m/s;
the parameters of the zone melting of the 2 nd pass are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 3 rd pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 4 th pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of the zone melting of the 5 th pass: the heating temperature was 300 ℃, the cold trap temperature was 25 ℃, and the moving speed was 10 μm/s.
2. Top remelting self-absorption and raw material supplement:
1) starting a mechanical pump and vacuum pump series device, and vacuumizing the vacuum tank to 0.01 MPa. And moving the quartz tube to the position where the upper end area of the sample is flush with the upper end of the heating device, setting the heating temperature to be 290 ℃ and the cold trap temperature to be 0 ℃, and melting the 10% volume fraction area at the top end of the sample. And rotating the self-suction device to the same vertical central position of the self-suction glass tube and the quartz tube, moving the self-suction device downwards to a proper position, starting the self-suction device, and sucking the remelted indium. After the self-suction is finished, the quartz tube is moved downwards to leave the heating area, and the self-suction system and the quartz tube are sequentially restored to the initial position.
2) Setting the heating temperature and the cold trap temperature as room temperature, opening the furnace door after the temperature is reduced to the room temperature, replenishing raw materials, replacing the self-absorption glass tube, and replenishing indium raw materials with the same quality as the absorbed indium raw materials.
3. And (5) circularly performing the step 1 and the step 2.
4. Step 1 is carried out once again, and after completion, the metal indium is taken out of the quartz tube. And cutting 10% of each of two ends of the sample, remelting and pouring the samples in the rest areas to obtain finally purified high-purity metal indium. The detection proves that the impurity content meets the standard of 6N 5-grade ultrapure indium.
Example 2
Putting a quartz tube filled with 4N-grade raw materials into a zone melting furnace, and vacuumizing to 1 x 10-5And (4) after Pa, reversely filling high-purity argon to 0.03MPa, and purifying according to the following process flow.
1. Vertical zone melting purification: and moving the quartz tube to an initial position, and sequentially carrying out 7-pass vertical zone melting purification according to the following process parameters.
1 st pass zone melting parameters: the heating temperature is 600 ℃, the cold trap temperature is 25 ℃, and the moving speed is 50 mu m/s;
the parameters of the zone melting of the 2 nd pass are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 3 rd pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 4 th pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of the zone melting of the 5 th pass: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 6 th pass zone melting parameters are as follows: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 10 mu m/s;
and 7, pass zone melting parameters: the heating temperature was 300 ℃, the cold trap temperature was-10 ℃, and the moving speed was 10 μm/s.
2. Top remelting self-absorption and raw material supplement:
1) starting a mechanical pump and vacuum pump series device, and vacuumizing the vacuum tank to 0.01 MPa. And moving the quartz tube to the position where the upper end area of the sample is flush with the upper end of the heating device, setting the heating temperature to be 290 ℃ and the cold trap temperature to be 0 ℃, and melting the 10% volume fraction area at the top end of the sample. And rotating the self-suction device to the same vertical central position of the self-suction glass tube and the quartz tube, moving the self-suction device downwards to a proper position, starting the self-suction device, and sucking the remelted indium. After the self-suction is finished, the quartz tube is moved downwards to leave the heating area, and the self-suction system and the quartz tube are sequentially restored to the initial position.
2) Setting the heating temperature and the cold trap temperature as room temperature, opening the furnace door after the temperature is reduced to the room temperature, replenishing raw materials, replacing the self-absorption glass tube, and replenishing indium raw materials with the same quality as the absorbed indium raw materials.
3. And (5) circularly performing the step 1 and the step 2.
4. Step 1 is carried out once again, and after completion, the metal indium is taken out of the quartz tube. And cutting 10% of each of two ends of the sample, remelting and pouring the samples in the rest areas to obtain finally purified high-purity metal indium. Through detection, the impurity content meets the standard of 7N-grade ultrapure indium.
Example 3
Putting the quartz tube filled with 5N-grade indium raw material into a zone melting furnace, and vacuumizing to 1 x 10-5And (4) after Pa, reversely filling high-purity argon to 0.03MPa, and purifying according to the following process flow.
1. Vertical zone melting purification: and moving the quartz tube to an initial position, and sequentially carrying out 7-pass vertical zone melting purification according to the following process parameters.
1 st pass zone melting parameters: the heating temperature is 400 ℃, the cold trap temperature is 25 ℃, and the moving speed is 50 mu m/s;
the parameters of the zone melting of the 2 nd pass are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 3 rd pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 4 th pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of the zone melting of the 5 th pass: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 6 th pass zone melting parameters are as follows: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 10 mu m/s;
and 7, pass zone melting parameters: the heating temperature was 300 ℃, the cold trap temperature was 25 ℃, and the moving speed was 10 μm/s.
2. Top remelting self-absorption and raw material supplement:
1) starting a mechanical pump and vacuum pump series device, and vacuumizing the vacuum tank to 0.01 MPa. And moving the quartz tube to a position where the upper end area of the sample is flush with the upper end of the heating device, setting the heating temperature to be 300 ℃ and the cold trap temperature to be 0 ℃, and melting the 15% volume fraction area at the top end of the sample. And rotating the self-suction device to the same vertical central position of the self-suction glass tube and the quartz tube, moving the self-suction device downwards to a proper position, starting the self-suction device, and sucking the remelted indium. After the self-suction is finished, the quartz tube is moved downwards to leave the heating area, and the self-suction system and the quartz tube are sequentially restored to the initial position.
2) Setting the heating temperature and the cold trap temperature as room temperature, opening the furnace door after the temperature is reduced to the room temperature, replenishing raw materials, replacing the self-absorption glass tube, and replenishing indium raw materials with the same quality as the absorbed indium raw materials.
3. And (5) circularly performing the step 1 and the step 2.
4. Step 1 is carried out once again, and after completion, the metal indium is taken out of the quartz tube. And cutting 10% of each of two ends of the sample, remelting and pouring the samples in the rest areas to obtain finally purified high-purity metal indium. The detection proves that the impurity content meets the standard of 7N 5-grade ultrapure indium.
Example 4
Putting the quartz tube filled with 5N-grade indium raw material into a zone melting furnace, and vacuumizing to 1 x 10-5And (4) after Pa, reversely filling high-purity argon to 0.03MPa, and purifying according to the following process flow.
1. Vertical zone melting purification: the quartz tube is moved to the initial position, and 10 times of vertical zone melting purification are sequentially carried out according to the following process parameters.
1 st pass zone melting parameters: the heating temperature is 800 ℃, the cold trap temperature is 0 ℃, and the moving speed is 50 mu m/s;
the parameters of the zone melting of the 2 nd pass are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 3 rd pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 4 th pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of the zone melting of the 5 th pass: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 6 th pass zone melting parameters are as follows: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and 7, pass zone melting parameters: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 8 th pass zone melting parameters are as follows: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of pass 9 zone melting: the heating temperature is 300 ℃, the cold trap temperature is 10 ℃, and the moving speed is 10 mu m/s;
the 10 th pass zone melting parameters are as follows: the heating temperature was 300 ℃, the cold trap temperature was 10 ℃, and the moving speed was 10 μm/s.
2. Top remelting self-absorption and raw material supplement:
1) starting a mechanical pump and vacuum pump series device, and vacuumizing the vacuum tank to 0.01 MPa. And moving the quartz tube to a position where the upper end area of the sample is flush with the upper end of the heating device, setting the heating temperature to be 310 ℃ and the cold trap temperature to be 0 ℃, and melting the 20% volume fraction area at the top end of the sample. And rotating the self-suction device to the same vertical central position of the self-suction glass tube and the quartz tube, moving the self-suction device downwards to a proper position, starting the self-suction device, and sucking the remelted indium. After the self-suction is finished, the quartz tube is moved downwards to leave the heating area, and the self-suction system and the quartz tube are sequentially restored to the initial position.
2) Setting the heating temperature and the cold trap temperature as room temperature, opening the furnace door after the temperature is reduced to the room temperature, replenishing raw materials, replacing the self-absorption glass tube, and replenishing indium raw materials with the same quality as the absorbed indium raw materials.
3. And (5) circularly performing the step 1 and the step 2.
4. Step 1 is carried out once again, and after completion, the metal indium is taken out of the quartz tube. And cutting 10% of each of two ends of the sample, remelting and pouring the samples in the rest areas to obtain finally purified high-purity metal indium. Through detection, the impurity content meets the standard of 8N-grade ultrapure indium.
Example 5
Putting the quartz tube filled with 5N-grade indium raw material into a zone melting furnace, and vacuumizing to 1 x 10-5And (4) after Pa, reversely filling high-purity argon to 0.03MPa, and purifying according to the following process flow.
1. Vertical zone melting purification: the quartz tube is moved to the initial position, and 10 times of vertical zone melting purification are sequentially carried out according to the following process parameters.
1 st pass zone melting parameters: the heating temperature is 800 ℃, the cold trap temperature is-50 ℃, and the moving speed is 50 mu m/s;
the parameters of the zone melting of the 2 nd pass are as follows: the heating temperature is 400 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 3 rd pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 4 th pass zone melting parameters are as follows: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of the zone melting of the 5 th pass: the heating temperature is 310 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 6 th pass zone melting parameters are as follows: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and 7, pass zone melting parameters: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
the 8 th pass zone melting parameters are as follows: the heating temperature is 300 ℃, the cold trap temperature is 25 ℃, and the moving speed is 25 mu m/s;
and (3) the parameters of pass 9 zone melting: the heating temperature is 200 ℃, the cold trap temperature is 25 ℃, and the moving speed is 8 mu m/s;
the 10 th pass zone melting parameters are as follows: the heating temperature was 200 ℃, the cold trap temperature was 25 ℃ and the moving speed was 8 μm/s.
2. Top remelting self-absorption and raw material supplement:
1) starting a mechanical pump and vacuum pump series device, and vacuumizing the vacuum tank to 0.01 MPa. And moving the quartz tube to a position where the upper end area of the sample is flush with the upper end of the heating device, setting the heating temperature to be 310 ℃ and the cold trap temperature to be 0 ℃, and melting the 20% volume fraction area at the top end of the sample. And rotating the self-suction device to the same vertical central position of the self-suction glass tube and the quartz tube, moving the self-suction device downwards to a proper position, starting the self-suction device, and sucking the remelted indium. After the self-suction is finished, the quartz tube is moved downwards to leave the heating area, and the self-suction system and the quartz tube are sequentially restored to the initial position.
2) Setting the heating temperature and the cold trap temperature as room temperature, opening the furnace door after the temperature is reduced to the room temperature, replenishing raw materials, replacing the self-absorption glass tube, and replenishing indium raw materials with the same quality as the absorbed indium raw materials.
3. And (5) circularly performing the step 1 and the step 2.
4. Step 1 is carried out once again, and after completion, the metal indium is taken out of the quartz tube. And cutting 10% of each of two ends of the sample, remelting and pouring the samples in the rest areas to obtain finally purified high-purity metal indium. Through detection, the impurity content meets the standard of 8N-grade ultrapure indium.
Claims (9)
1. The top end self-suction type vertical zone melting device for preparing the ultrapure indium is characterized by comprising a vacuum cavity (14), a vertical zone melting system arranged in the vacuum cavity (14) and a self-suction system positioned above the vertical zone melting system;
the vertical zone melting system comprises a quartz tube (16), a heating device (17), a guide rod (22) and a cold trap device (20), wherein the guide rod (22) and the cold trap device are arranged at the lower end of the quartz tube (16) and can move up and down; the guide rod (22) is fixedly connected with the quartz tube (16), the cold trap device (20) is positioned below the heating device (17), the outer sides of the heating device (17) and the cold trap device (20) are wrapped by heat insulation materials (18), and the guide rod (22) can sequentially penetrate through the heating device (17) and the cold trap device (20) to move up and down;
from inhaling the system including be located vacuum cavity (14) upper end outside cutting ferrule formula needle valve (1) and steel from inhaling pipe box (12), inhale glass pipe (13) certainly, the steel is connected with cutting ferrule formula needle valve (1) from inhaling pipe box (12) one end that is located vacuum cavity (14) outer, and the one end that is located vacuum cavity (14) is connected from inhaling glass pipe (13), from inhaling cutting ferrule formula needle valve (1) of system and vacuum tank (4) and being connected with the hose, control from inhaling glass pipe (13) internal pressure, from inhaling the system and can reciprocate and spin.
2. The top-end self-suction type vertical zone melting device for preparing the ultrapure indium according to claim 1, is characterized in that: the lower end of the guide rod (22) is provided with a motor which can move the guide rod (22), so that the guide rod (22) can move up and down.
3. The top-end self-suction type vertical zone melting device for preparing the ultrapure indium according to claim 1 or 2, wherein: the heating device is connected with the temperature controller (7), and the temperature is set through the temperature controller (7).
4. The top-end self-suction type vertical zone melting device for preparing the ultrapure indium according to claim 1, is characterized in that: circulating cooling liquid is introduced into the cold trap device (20), and the temperature of the cooling liquid is adjusted by the cold trap control device (8).
5. The top-end self-suction type vertical zone melting device for preparing the ultrapure indium according to claim 1, is characterized in that: vacuum cavity (14) and vacuum tank (4) are connected with mechanical pump and vacuum pump tandem arrangement (6), and control vacuum cavity (14) and vacuum tank (4) internal pressure respectively through different valves, and vacuum cavity (14) are connected with gas cylinder (9), for the device provides protective gas environment, and vacuum cavity (14) internal pressure is monitored by first vacuum meter (1), and vacuum tank (4) internal pressure is monitored by second vacuum meter (2).
6. The top-end self-suction type vertical zone melting device for preparing the ultrapure indium according to claim 1, wherein an observation window (10) is arranged above the vacuum cavity (14).
7. The top end self-suction type vertical zone melting device for preparing the ultrapure indium according to claim 1, wherein a guide rod (22) is fixedly connected with a quartz tube (16) through a clamping sleeve (21).
8. A method for preparing ultrapure indium using the apparatus of any one of claims 1 to 7, characterized in that the method comprises the steps of:
(a) the preset environment is as follows:
putting 4N-grade or 5N-grade indium raw materials into a quartz tube, and vacuumizing a vacuum cavity (14) to N1After Pa, back-filling protective gas to N2 Pa；
(b) The process flow is as follows:
(1) vertical zone melting purification: moving the quartz tube to an initial position, namely the position where the bottom end of the quartz tube is flush with the top end of the heating device, setting the heating temperature, the cold trap temperature and the moving speed of the guide rod, under the parameters, moving the quartz tube from the initial position to the position where the top end of the quartz tube is flush with the top end of the cold trap device, or moving the top end of the quartz tube to the position below the top end of the cold trap device, then closing the heating device and the cold trap device, returning the quartz tube to the initial position after cooling to the room temperature, starting the next zone melting process, and sequentially carrying out n-pass vertical zone melting purification according to different process parameters, wherein n is 5-10;
(2) top remelting self-absorption and raw material supplement:
(2.1) starting a mechanical pump and vacuum pump series connection device, and vacuumizing the vacuum tank to N3Pa，N3<N2(ii) a Moving the quartz tube to the position where the top end of a sample in the quartz tube is flush with the top end of the heating device, setting the heating temperature and the cold trap temperature, melting a volume fraction area of 10-20% of the top end of the sample, rotating the self-suction device to the position where the self-suction glass tube and the quartz tube are at the same vertical center, moving the self-suction device downwards to a proper position in the self-suction glass tube, starting the self-suction device, sucking remelted indium, moving the quartz tube downwards to leave a heating area after self-suction is finished, and sequentially restoring the self-suction device and the quartz tube to initial positions;
(2.2) setting the heating temperature and the cold trap temperature to be room temperature, and supplementing indium raw materials with the same absorption quality after the temperature is reduced to the room temperature;
(3) circularly performing the step (1) and the step (2) once respectively;
(4) and (2) performing the step (1) again, taking out the metal indium from the quartz tube after the step is finished, intercepting 5-15% of each of two ends of the sample, and remelting and pouring the samples in the rest areas to obtain the finally purified high-purity metal indium.
9. The method for preparing ultrapure indium according to claim 8, wherein the heating device and the cold trap device are set to a heating temperature of 200 to 800 ℃, a cold trap temperature of-60 ℃ to room temperature, respectively, and a guide rod is set to move up and down at a speed of 1 to 1000 μm/s.
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| CN1388259A (en) * | 2002-04-12 | 2003-01-01 | 上海交通大学 | Continuous vacuum purifier for producing high-purity aluminium |
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