CN113102763A - Preparation method of high-purity gallium particles - Google Patents
Preparation method of high-purity gallium particles Download PDFInfo
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- CN113102763A CN113102763A CN202110387746.2A CN202110387746A CN113102763A CN 113102763 A CN113102763 A CN 113102763A CN 202110387746 A CN202110387746 A CN 202110387746A CN 113102763 A CN113102763 A CN 113102763A
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- coolant
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 157
- 239000002245 particle Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002826 coolant Substances 0.000 claims abstract description 80
- 238000005469 granulation Methods 0.000 claims abstract description 51
- 230000003179 granulation Effects 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 230000007704 transition Effects 0.000 claims abstract description 13
- 239000008187 granular material Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 238000004062 sedimentation Methods 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims description 18
- 239000003507 refrigerant Substances 0.000 claims description 12
- 238000005057 refrigeration Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 230000003134 recirculating effect Effects 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 description 19
- -1 polytetrafluoroethylene Polymers 0.000 description 18
- 238000001514 detection method Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000011868 grain product Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F2009/0804—Dispersion in or on liquid, other than with sieves
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to the technical field of high-purity metal, and discloses a preparation method of high-purity gallium particles. The method specifically comprises the following steps: (1) providing a device for preparing high-purity gallium particles; (2) putting high-purity gallium into a glove box, and placing on a heating plate to melt the gallium for later use; (3) vacuumizing the granulation tube, filling nitrogen or inert gas, taking down a blind plate at the top of the granulation tube, and then placing a funnel at the top of the granulation tube; (4) starting a circulating cooling system to enable the liquid coolant to fill the product collecting tank and the granulating pipe; (5) pouring the gallium liquid into a funnel in a glove box, dripping the gallium liquid into a coolant, and condensing the gallium liquid into granules in the process of sedimentation; (6) after granulation is finished, gallium particles in the product collecting tank are separated from the coolant, the gallium particles are placed in a glove box transition bin for vacuumizing and drying, and then the gallium particles enter a main box body for packaging, so that a high-purity gallium particle product is obtained. By adopting the method, high-purity gallium particles with oxygen content lower than 1ppm, particle size of 1-10 mm and uniform size and meeting the semiconductor doping requirement can be prepared.
Description
Technical Field
The invention relates to the technical field of high-purity metal, in particular to a preparation method of high-purity gallium particles.
Background
At present, the main preparation method of high-purity gallium particles is to put gallium liquid in a dropping device in an air environment, drop the gallium liquid into a coolant to solidify the gallium, and then clean and dry the gallium, so that the gallium particles are prepared. The main defects of the method are as follows: (a) liquid such as glycerin, hydrochloric acid and the like which is difficult to clean is used as a coolant, and C, Cl and other impurities are introduced; (b) the product must be washed with a large amount of pure water and dried, which increases the oxygen content of the product.
The invention patent CN103157799B provides a method for preparing gallium particles, which is to drop gallium liquid into a coolant containing glycerol and water or mixed solution of alcohol and water, thereby obtaining gallium particles. This method has the following drawbacks: (a) the glycerol is used as a cooling agent, and is easy to attach to gallium particles, so that the cleaning cost of the product is increased, and impurities (such as C) are introduced; (b) the coolant temperature is unstable, and the gallium particles can be irregular in shape and even conglomerated; (c) the coolant and the heat preservation agent both contain water, and subsequent processes such as cleaning, drying and the like are needed, so that the oxygen content of the product can be increased.
The invention patent CN111659897A provides a process for producing high-purity gallium particles. The method drops the gallium liquid raw material into deionized exchange water added with concentrated hydrochloric acid to prepare high-purity gallium particles. This method has the following drawbacks: (a) the dropping bottle needs to be moved ceaselessly in the process, and the granulating process is difficult to control stably; (b) in the process, concentrated hydrochloric acid is used, impurity ions are introduced, the cost of product cleaning, equipment maintenance and the like is increased, and operators are possibly injured; (c) the product needs to be cleaned and dried, and the oxygen content of the product can be increased in the process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of high-purity gallium particles, and the high-purity gallium particles which have the oxygen content lower than 1ppm, the particle size of 1-10 mm and uniform size and meet the semiconductor doping requirement can be prepared by adopting the method.
In order to realize the purpose of the invention, the specific technical scheme is as follows:
a preparation method of high-purity gallium particles comprises the following steps:
(1) providing an apparatus for producing high purity gallium particles, the apparatus comprising: the glove box comprises a main box body and a transition bin, the main box body is of a sealed box body structure, the side face of the main box body is provided with a manual operation hole for operating gloves in sealing connection, and a heating plate is arranged in the glove box; the device comprises a granulation pipe, a glove box and a control system, wherein the granulation pipe vertically penetrates through the bottom of the glove box, so that the upper part of the granulation pipe is positioned in a main box body of the glove box, the lower part of the granulation pipe is positioned outside the main box body of the glove box, a detachable blind plate for sealing the opening is arranged at an opening at the upper part of the granulation pipe, and a product collecting tank is arranged at an opening at the lower part of the; the funnel is matched with an opening at the upper part of the granulating pipe; a recirculating cooling system configured to recirculate liquid coolant to cool the product in the pelletization tube; the vacuumizing system is connected with the granulating pipe and/or the glove box; and the gas supply system is connected with the granulating pipe and/or the glove box, and the supplied gas is nitrogen or inert gas.
(2) Installing a top blind plate of the granulation tube, keeping the atmosphere of nitrogen or inert gas in the glove box main box body, putting high-purity gallium into the glove box, and placing the glove box on a heating plate to melt the gallium for later use;
(3) vacuumizing the granulation tube, filling nitrogen or inert gas, taking down a blind plate at the top of the granulation tube, and then placing a funnel at the top of the granulation tube;
(4) starting a circulating cooling system to enable a liquid coolant to fill the product collecting tank and the granulating pipe, and controlling the temperature of the coolant to be-10 to-30 ℃;
(5) pouring the gallium liquid into a funnel in a glove box, dripping the gallium liquid into a coolant through the funnel, and condensing the gallium liquid into granules in the process of sedimentation;
(6) after granulation is finished, gallium particles in the product collecting tank are separated from the coolant, the gallium particles are placed in a glove box transition bin for vacuum drying, and then the gallium particles enter a main box body for packaging, so that a high-purity gallium particle product is obtained.
The method combines the device for preparing the high-purity gallium granules, creatively connects the granulation tube with the glove box in a sealing way, melts, granulates, dries and packages the materials in the device for preparing the high-purity gallium granules, greatly reduces the contact time of the gallium granules and the air, and simultaneously ensures the stability of the temperature and the liquid level of the coolant by adopting a coolant circulating refrigeration mode for the granulation tube.
Further, in the step (2), the raw material of the invention is 5-8N high-purity gallium.
Further, in step (1), the circulation cooling system includes: the refrigerator, the refrigerant, the coolant outlet and the coolant inlet are respectively arranged at two ends of the outside part of the glove box main box body of the granulation tube, and the refrigerator is respectively communicated with the cooler outlet and the coolant inlet through pipelines to form a refrigeration cycle.
Further, in the steps (1) and (4), the refrigerant is alcohol or isopropanol.
Further, in the step (1), control valves are respectively arranged at the coolant outlet and the coolant inlet.
Further, in the step (1), a vacuum port is arranged on the pipe wall of the granulating pipe, which is positioned at the outer part of the glove box main box body, and a valve is arranged on the vacuum port.
Further, in the step (1), an opening is formed in the product collecting tank, and an opening in the lower portion of the granulating pipe is communicated with the opening of the product collecting tank.
Further, in the step (1), an opening at the lower part of the granulating pipe is connected with an opening of the product collecting tank through a sealing flange.
The method aims to solve the problem that a quartz and common plastic funnel is easy to cause gallium adhesion, so that a funnel mouth is blocked. According to the invention, in the steps (1), (3) and (5), the funnel is preferably a polytetrafluoroethylene funnel. Polytetrafluoroethylene is used as a funnel, and the aperture of a funnel mouth of the funnel is preferably 0.5-1.5 mm.
Further, in the step (3), the blind plate at the opening at the top of the granulating pipe is taken down, the funnel is placed at the opening at the top of the granulating pipe, and the liquid level of the coolant in the granulating pipe is controlled to be 0-3 cm higher than the mouth of the funnel.
Further, in the step (2), the temperature of the heating plate is set to be 35-50 ℃, and the constant temperature is kept for 0.5-3 hours, so that the gallium is melted for standby application.
Further, in the step (3), the granulation tube is vacuumized, the vacuum degree reaches below 10Pa, and the vacuumizing is finished.
In the step (6), the gallium particles are separated by a screen before being placed into a glove box, and the gallium particles are leached until no linear liquid flows down, wherein the size of the screen is determined according to the particle size of granulation.
And (6) further, putting the gallium particles after separation into a glove box transition bin, vacuumizing and drying until the pressure is below 10Pa, and keeping for 3-6 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention, raw materials are melted, granulated, dried and packaged in the device for preparing high-purity gallium particles, so that the contact time of the gallium particles and air is greatly reduced; meanwhile, high-purity alcohol or isopropanol is used as a coolant, and gallium particles do not contact water in the whole production process. The effect of preventing gallium particles from being oxidized is well achieved, the surfaces of the produced gallium particles are bright, the oxygen content is less than 1ppm, and the using requirements of customers are met.
(2) The invention adopts a coolant circulating refrigeration mode, ensures the stability of the temperature and the liquid level of the coolant, and ensures that the prepared gallium has uniform particle size and the product sphericity rate is 90-95%.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic view of an apparatus for producing high-purity gallium fine particles according to example 1 of the present invention.
FIG. 2 is a schematic cross-sectional view of a PTFE funnel in an apparatus for preparing high-purity gallium particles according to example 1 of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, features from embodiments in this document and from different embodiments may be combined accordingly by a person skilled in the art from the description in this document.
Example 1
The embodiment provides a high-purity gallium particle preparation device. Referring to fig. 1 and 2, the apparatus includes:
the glove box 1 comprises a main box body and a transition bin 2, the main box body is of a sealed box body structure, a manual operation hole of an operation glove in sealing connection is formed in the side face of the main box body, and a heating plate is arranged in the glove box 1; in the embodiment, the heating plate is preferably a constant-temperature heating plate, and the constant temperature range comprises 35-50 ℃;
the device comprises a granulation pipe 4, wherein the granulation pipe 4 vertically penetrates through the bottom of a glove box 1, the upper portion of the granulation pipe 4 is located in a main box body of the glove box 1, the lower portion of the granulation pipe 4 is located outside the main box body of the glove box 1, a detachable sealing blind plate 7 is arranged at an opening of the upper portion of the granulation pipe 4, a product collecting tank 6 is arranged at an opening of the lower portion of the granulation pipe 4, an opening of the lower portion of the granulation pipe 4 is communicated with an opening of the product collecting tank 6, and the opening of the lower portion of the granulation pipe 4 is connected with the opening of the product collecting tank 6 through a. In the embodiment, a vacuum port 3 is arranged on the wall of the granulation tube 4 positioned outside the main box body of the glove box 1, and a valve is arranged on the vacuum port 3.
The polytetrafluoroethylene funnel 7 is matched with an opening at the upper part of the granulating pipe 4; in the embodiment, the aperture of the funnel mouth of the funnel is 0.5-1.5 mm;
a hydronic cooling system, the hydronic cooling system comprising: the device comprises a refrigerating machine 9, a refrigerant outlet 8 and a refrigerant inlet 9, wherein the refrigerant outlet 8 and the refrigerant inlet 9 are respectively arranged at two ends of the granulation tube 4, which are positioned at the outer part of the main box body of the glove box 1, the refrigerating machine 9 is respectively communicated with the refrigerant outlet 8 and the refrigerant inlet 10 through pipelines to form a refrigerating cycle, and control valves are respectively arranged at the refrigerant outlet 8 and the refrigerant inlet 10.
The vacuumizing system is connected with the granulating pipe 4 and/or the glove box 1;
and the gas supply system is connected with the granulating pipe 4 and/or the glove box 1, and the supplied gas is nitrogen or inert gas.
Example 2
The embodiment discloses a preparation method of high-purity gallium particles, which comprises the following steps:
(1) the apparatus for producing high purity gallium pellets as described in example 1 was used.
(2) And (3) installing a top blind plate of the granulation tube 4, keeping the nitrogen atmosphere in the main box body of the glove box 1, and putting bottled 5-8N high-purity gallium into the glove box 1, wherein 5N high-purity gallium is preferably adopted in the embodiment, and the bottled high-purity gallium is placed on a constant-temperature heating plate, the temperature is set to be 50 ℃, and the constant temperature is kept for 0.5h to melt the gallium for later use.
(3) Connecting a product collecting tank 6 with a granulating pipe 4 by using a sealing flange 5, closing valves of a coolant inlet 8 and a coolant outlet 10, opening a valve at a vacuum interface 3, vacuumizing the granulating pipe 4 until the vacuum degree reaches below 10Pa, finishing vacuumizing, filling nitrogen to normal pressure, closing the valve at the vacuum interface 3, taking down a blind plate at the top of the granulating pipe 4, and placing a polytetrafluoroethylene funnel 7 at the top of the granulating pipe 4.
(4) Starting a circulating cooling system, adopting high-purity alcohol as a coolant, opening an inlet valve and an outlet valve of the coolant, performing circulating refrigeration, filling the product collecting tank and the granulating pipe with the coolant, and controlling the temperature to be-15 ℃; and the liquid level of the coolant is controlled to be maintained to be 2cm higher than the bottom of the funnel mouth by adjusting the circulation flow of the coolant.
(5) Pouring gallium liquid into a polytetrafluoroethylene funnel 7 with a funnel mouth aperture of 0.5mm in the glove box 1, dripping the gallium liquid into a coolant through the polytetrafluoroethylene funnel 7, and condensing into granules in the process of sedimentation;
(6) and after granulation is finished, discharging the coolant, loosening the sealing flange 5, taking down the product collecting tank 6, taking out gallium particles, immediately pouring the gallium particles into a screen, and draining the gallium particles until no linear liquid flows down. Immediately putting gallium particles into a transition bin of a glove box 1, vacuumizing to below 10Pa, and keeping for 6 hours. And then the gallium particles are transferred to a glove box for packaging, and a high-purity gallium particle product is obtained and is subjected to particle size detection and oxygen content detection.
Example 3
The embodiment discloses a preparation method of high-purity gallium particles, which comprises the following steps:
(1) the apparatus for producing high purity gallium pellets as described in example 1 was used.
(2) And (3) installing a top blind plate of the granulation tube 4, keeping the nitrogen atmosphere in the main box body of the glove box 1, and putting bottled 5-8N high-purity gallium into the glove box 1, wherein 5N high-purity gallium is preferably adopted in the embodiment, and the bottled high-purity gallium is placed on a constant-temperature heating plate, the temperature is set to be 40 ℃, and the constant temperature is kept for 1.5 hours to melt the gallium for later use.
(3) Connecting a product collecting tank 6 with a granulating pipe 4 by using a sealing flange 5, closing valves of a coolant inlet 8 and a coolant outlet 10, opening a valve at a vacuum interface 3, vacuumizing the granulating pipe 4 until the vacuum degree reaches below 10Pa, finishing vacuumizing, filling nitrogen to normal pressure, closing the valve at the vacuum interface 3, taking down a blind plate at the top of the granulating pipe 4, and placing a polytetrafluoroethylene funnel 7 at the top of the granulating pipe 4.
(4) Starting a circulating cooling system, adopting high-purity alcohol as a coolant, opening an inlet valve and an outlet valve of the coolant, performing circulating refrigeration, filling the product collecting tank and the granulating pipe with the coolant, and controlling the temperature to be-20 ℃; and the liquid level of the coolant is controlled to be maintained to be 1.5cm over the bottom of the funnel mouth by adjusting the circulation flow of the coolant.
(5) Pouring gallium liquid into a polytetrafluoroethylene funnel 7 with a funnel mouth aperture of 0.8mm in the glove box 1, dripping the gallium liquid into a coolant through the polytetrafluoroethylene funnel 7, and condensing into granules in the process of sedimentation;
(6) and after granulation is finished, discharging the coolant, loosening the sealing flange 5, taking down the product collecting tank 6, taking out gallium particles, immediately pouring the gallium particles into a screen, and draining the gallium particles until no linear liquid flows down. Immediately putting gallium particles into a transition bin of a glove box 1, vacuumizing to below 10Pa, and keeping for 5 hours. And then the gallium particles are transferred to a glove box for packaging, and a high-purity gallium particle product is obtained and is subjected to particle size detection and oxygen content detection.
Example 4
The embodiment discloses a preparation method of high-purity gallium particles, which comprises the following steps:
(1) the apparatus for producing high purity gallium pellets as described in example 1 was used.
(2) And (3) installing a top blind plate of the granulation tube 4, keeping the nitrogen atmosphere in the main box body of the glove box 1, and putting bottled 5-8N high-purity gallium into the glove box 1, wherein 5N high-purity gallium is preferably adopted in the embodiment, and the bottled high-purity gallium is placed on a constant-temperature heating plate, the temperature is set to be 35 ℃, and the constant temperature is kept for 3 hours to melt the gallium for standby.
(3) Connecting a product collecting tank 6 with a granulating pipe 4 by using a sealing flange 5, closing valves of a coolant inlet 8 and a coolant outlet 10, opening a valve at a vacuum interface 3, vacuumizing the granulating pipe 4 until the vacuum degree reaches below 10Pa, finishing vacuumizing, filling nitrogen to normal pressure, closing the valve at the vacuum interface 3, taking down a blind plate at the top of the granulating pipe 4, and placing a polytetrafluoroethylene funnel 7 at the top of the granulating pipe 4.
(4) Starting a circulating cooling system, adopting high-purity alcohol as a coolant, opening an inlet valve and an outlet valve of the coolant, performing circulating refrigeration, filling the product collecting tank and the granulating pipe with the coolant, and controlling the temperature to be-25 ℃; and the liquid level of the coolant is controlled to be 0.5cm over the bottom of the funnel nozzle by adjusting the circulation flow of the coolant.
(5) Pouring gallium liquid into a polytetrafluoroethylene funnel 7 with a funnel mouth with the aperture of 1.5mm in the glove box 1, dripping the gallium liquid into a coolant through the polytetrafluoroethylene funnel 7, and condensing into granules in the process of sedimentation;
(6) and after granulation is finished, discharging the coolant, loosening the sealing flange 5, taking down the product collecting tank 6, taking out gallium particles, immediately pouring the gallium particles into a screen, and draining the gallium particles until no linear liquid flows down. Immediately putting gallium particles into a transition bin of a glove box 1, vacuumizing to below 10Pa, and keeping for 3 hours. And then the gallium particles are transferred to a glove box for packaging, and a high-purity gallium particle product is obtained and is subjected to particle size detection and oxygen content detection.
Example 5
The embodiment discloses a preparation method of high-purity gallium particles, which comprises the following steps:
(1) the apparatus for producing high purity gallium pellets as described in example 1 was used.
(2) And (3) installing a top blind plate of the granulation tube 4, keeping the nitrogen atmosphere in the main box body of the glove box 1, and putting bottled 5-8N high-purity gallium into the glove box 1, wherein 5N high-purity gallium is preferably adopted in the embodiment, and the bottled high-purity gallium is placed on a constant-temperature heating plate, the temperature is set to be 45 ℃, and the constant temperature is kept for 1 hour to melt the gallium for standby.
(3) Connecting a product collecting tank 6 with a granulating pipe 4 by using a sealing flange 5, closing valves of a coolant inlet 8 and a coolant outlet 10, opening a valve at a vacuum interface 3, vacuumizing the granulating pipe 4 until the vacuum degree reaches below 10Pa, finishing vacuumizing, filling nitrogen to normal pressure, closing the valve at the vacuum interface 3, taking down a blind plate at the top of the granulating pipe 4, and placing a polytetrafluoroethylene funnel 7 at the top of the granulating pipe 4.
(4) Starting a circulating cooling system, adopting high-purity alcohol as a coolant, opening an inlet valve and an outlet valve of the coolant, performing circulating refrigeration, filling the product collecting tank and the granulating pipe with the coolant, and controlling the temperature to be-20 ℃; and the liquid level of the coolant is controlled to be maintained to be 3cm over the bottom of the funnel mouth by adjusting the circulation flow of the coolant.
(5) Pouring gallium liquid into a polytetrafluoroethylene funnel 7 with a funnel mouth with the aperture of 1mm in the glove box 1, dripping the gallium liquid into a coolant through the polytetrafluoroethylene funnel 7, and condensing into particles in the process of sedimentation;
(6) and after granulation is finished, discharging the coolant, loosening the sealing flange 5, taking down the product collecting tank 6, taking out gallium particles, immediately pouring the gallium particles into a screen, and draining the gallium particles until no linear liquid flows down. Immediately putting gallium particles into a transition bin of a glove box 1, vacuumizing to below 10Pa, and keeping for 4 hours. And then the gallium particles are transferred to a glove box for packaging, and a high-purity gallium particle product is obtained and is subjected to particle size detection and oxygen content detection.
Example 6
The embodiment discloses a preparation method of high-purity gallium particles, which comprises the following steps:
(1) the apparatus for producing high purity gallium pellets as described in example 1 was used.
(2) And (3) installing a top blind plate of the granulation tube 4, keeping the nitrogen atmosphere in the main box body of the glove box 1, and putting bottled 5-8N high-purity gallium into the glove box 1, wherein 5N high-purity gallium is preferably adopted in the embodiment, and the bottled high-purity gallium is placed on a constant-temperature heating plate, the temperature is set to be 45 ℃, and the constant temperature is kept for 0.5h to melt the gallium for later use.
(3) Connecting a product collecting tank 6 with a granulating pipe 4 by using a sealing flange 5, closing valves of a coolant inlet 8 and a coolant outlet 10, opening a valve at a vacuum interface 3, vacuumizing the granulating pipe 4 until the vacuum degree reaches below 10Pa, finishing vacuumizing, filling nitrogen to normal pressure, closing the valve at the vacuum interface 3, taking down a blind plate at the top of the granulating pipe 4, and placing a polytetrafluoroethylene funnel 7 at the top of the granulating pipe 4.
(4) Starting a circulating cooling system, adopting high-purity alcohol as a coolant, opening an inlet valve and an outlet valve of the coolant, performing circulating refrigeration, filling the product collecting tank and the granulating pipe with the coolant, and controlling the temperature to be-25 ℃; and the liquid level of the coolant is controlled to be maintained to be 1.5cm over the bottom of the funnel mouth by adjusting the circulation flow of the coolant.
(5) Pouring gallium liquid into a polytetrafluoroethylene funnel 7 with a funnel mouth with the aperture of 1.2mm in the glove box 1, dripping the gallium liquid into a coolant through the polytetrafluoroethylene funnel 7, and condensing into granules in the process of sedimentation;
(6) and after granulation is finished, discharging the coolant, loosening the sealing flange 5, taking down the product collecting tank 6, taking out gallium particles, immediately pouring the gallium particles into a screen, and draining the gallium particles until no linear liquid flows down. Immediately putting gallium particles into a transition bin of a glove box 1, vacuumizing to below 10Pa, and keeping for 3 hours. And then the gallium particles are transferred to a glove box for packaging, and a high-purity gallium particle product is obtained and is subjected to particle size detection and oxygen content detection.
Analysis of test results
The results of particle size and oxygen content measurements of the high purity gallium grain products obtained in examples 2-6 are shown in tables 1 and 2.
TABLE 1 statistical table of gallium particle size
TABLE 2 statistical table of oxygen content of gallium particles (unit ppm)
As can be seen from tables 1 and 2, the high-purity gallium particles prepared by the method 2-6 have the particle size of 1-10 mm, the sphericity rate of 90-95% and the oxygen content of less than 1ppm, and meet the use requirements of customers in the fields of semiconductor doping and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-purity gallium particles is characterized by comprising the following steps of:
(1) providing an apparatus for producing high purity gallium particles, the apparatus comprising: the glove box comprises a main box body and a transition bin, the main box body is of a sealed box body structure, the side face of the main box body is provided with a manual operation hole for operating gloves in sealing connection, and a heating plate is arranged in the glove box; the device comprises a granulation pipe, a glove box and a control system, wherein the granulation pipe vertically penetrates through the bottom of the glove box, so that the upper part of the granulation pipe is positioned in a main box body of the glove box, the lower part of the granulation pipe is positioned outside the main box body of the glove box, a detachable blind plate for sealing the opening is arranged at an opening at the upper part of the granulation pipe, and a product collecting tank is arranged at an opening at the lower part of the; the funnel is matched with an opening at the upper part of the granulating pipe; a recirculating cooling system configured to recirculate liquid coolant to cool the product in the pelletization tube; the vacuumizing system is connected with the granulating pipe and/or the glove box; the gas supply system is connected with the granulating pipe and/or the glove box, and the supplied gas is nitrogen or inert gas;
(2) installing a top blind plate of the granulation tube, keeping the atmosphere of nitrogen or inert gas in the glove box main box body, putting high-purity gallium into the glove box, and placing the glove box on a heating plate to melt the gallium for later use;
(3) vacuumizing the granulation tube, filling nitrogen or inert gas, taking down a blind plate at the top of the granulation tube, and then placing a funnel at the top of the granulation tube;
(4) starting a circulating cooling system to enable a liquid coolant to fill the product collecting tank and the granulating pipe, and controlling the temperature of the coolant to be-10 to-30 ℃;
(5) pouring the gallium liquid into a funnel in a glove box, dripping the gallium liquid into a coolant through the funnel, and condensing the gallium liquid into granules in the process of sedimentation;
(6) after granulation is finished, gallium particles in the product collecting tank are separated from the coolant, the gallium particles are placed in a glove box transition bin for vacuum drying, and then the gallium particles enter a main box body for packaging, so that a high-purity gallium particle product is obtained.
2. The method for preparing high-purity gallium particles according to claim 1, wherein in step (1), the circulating cooling system comprises: the refrigerator, the refrigerant, the coolant outlet and the coolant inlet are respectively arranged at two ends of the outside part of the glove box main box body of the granulation tube, and the refrigerator is respectively communicated with the cooler outlet and the coolant inlet through pipelines to form a refrigeration cycle.
3. The method for preparing high-purity gallium particles according to claim 1, wherein in steps (1) and (4), the refrigerant is alcohol or isopropanol.
4. The method of claim 1, wherein in steps (1), (3) and (5), the funnel is a teflon funnel.
5. The method for preparing high-purity gallium particles according to claim 1, wherein in steps (1), (3) and (5), the aperture of the funnel mouth of the funnel is 0.5-1.5 mm.
6. The method for preparing high-purity gallium particles according to claim 1, wherein in the step (3), the blind plate at the opening at the top of the granulating tube is removed, the funnel is placed at the opening at the top of the granulating tube, and the coolant liquid level in the granulating tube is controlled to be 0-3 cm higher than the funnel nozzle.
7. The method for preparing high-purity gallium particles according to claim 1, wherein in the step (2), the temperature of the heating plate is set to be 35-50 ℃, and the gallium is melted for standby by keeping the temperature constant for 0.5-3 hours.
8. The method for preparing high purity gallium pellets according to claim 1, wherein in step (3), the granulation tube is evacuated to a vacuum degree of less than 10Pa, and the evacuation is terminated.
9. The process according to claim 1, wherein in the step (6), the gallium particles are separated from the coolant by a screen before being placed in the glove box, and the gallium particles are drained until no linear liquid flows down.
10. The method for preparing high-purity gallium particles according to claim 1, wherein in the step (6), the separated gallium particles are placed in a glove box transition bin for vacuum drying until the pressure is below 10Pa, and the gallium particles are kept for 3-6 hours.
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| CN114212816A (en) * | 2021-12-13 | 2022-03-22 | 山东大学 | A kind of rapid preparation method of ultra-thin gallium oxide film |
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