CN114813202A - Sampling method of ultra-high purity tellurium - Google Patents
Sampling method of ultra-high purity tellurium Download PDFInfo
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- CN114813202A CN114813202A CN202210527880.2A CN202210527880A CN114813202A CN 114813202 A CN114813202 A CN 114813202A CN 202210527880 A CN202210527880 A CN 202210527880A CN 114813202 A CN114813202 A CN 114813202A
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000005070 sampling Methods 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004857 zone melting Methods 0.000 claims abstract description 30
- 238000004458 analytical method Methods 0.000 claims abstract description 28
- 238000001304 sample melting Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 239000010453 quartz Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 8
- 238000010411 cooking Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 9
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 13
- 239000012535 impurity Substances 0.000 description 8
- 239000000428 dust Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/04—Devices for withdrawing samples in the solid state, e.g. by cutting
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/32—Polishing; Etching
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
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- Molecular Biology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to the technical field of high-purity metal sampling, and discloses a method for sampling ultra-high-purity tellurium, which comprises the following steps: (1) taking out the tellurium ingot from the zone melting furnace, and removing tellurium powder on the surface of the tellurium ingot; (2) transferring the tellurium ingot to a glove box, knocking the tail of the tellurium ingot out, and knocking a tellurium block from the tail-removed position of the tellurium ingot; (3) putting the tellurium blocks into a mold and transferring the tellurium blocks from a glove box to a sample melting furnace; (4) vacuumizing the sample melting furnace, filling high-purity inert gas, and heating to melt the tellurium blocks; (5) cooling, taking out the mold, transferring the mold to a glove box, and taking out the tellurium sheets in the mold; (6) cutting the tellurium sheet into a plurality of sample blocks meeting the detection and analysis specification; (7) and corroding the sample block, and washing the sample block with pure water after the corrosion is finished. The invention not only ensures that the specification of the sample meets the analysis requirement, but also can reduce the pollution of the product in the sampling process, ensure the quality of the reaction product and reduce the analysis error caused by sampling, thereby ensuring the accuracy of analysis.
Description
Technical Field
The invention relates to the technical field of high-purity metal sampling, in particular to a sampling method of ultra-high-purity tellurium.
Background
The purity of the ultra-high pure tellurium reaches 99.99999 percent (7N), and the tellurium-zinc-Cadmium (CZT) nuclear radiation detector and tellurium-cadmium-Mercury (MCT) infrared detector substrate materials prepared from the ultra-high pure tellurium are widely applied to the fields of national defense, security protection, positioning, guidance infrared detection and the like. Impurities in tellurium directly influence the service performance of CZT and MCT crystal materials, and further influence the detection range and the detection precision of the two detectors, so that detection analysis needs to be carried out on products.
At present, the detection and analysis method of products of 7N and above is mainly GDMS. The GDMS has special requirements on the appearance of a sample, and the current GDMS sample introduction has two specifications: 1. sheet-shaped: (10-20) × (2-10) mm, and the surface is flat; 2. needle-shaped: (1.5-3) × (20-30) mm.
At present, the main preparation method of the ultra-high purity tellurium adopts a zone melting method, and the materials are placed in a graphite boat or a carbon-plated quartz boat or a glass carbon boat and are subjected to zone melting production in an induction heating or resistance heating mode.
The sampling of the tellurium ingot after zone melting is as follows: and removing the tail of the zone-melting tellurium ingot, and knocking out a sample at the tail-removed position by using a titanium or zirconium oxide hammer. This sampling method has the following problems: 1) the method has the advantages that the method is difficult to obtain the sheet or needle shape meeting the GDMS detection sample introduction requirement, the sampling time is long, the surface of the sample is uneven, and the pollution is easy to exist; 2) the tellurium surface and the part contacting the container are polluted, so that the sample cannot truly reflect the product quality.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for sampling ultra-high purity tellurium, which reduces the pollution of products in the sampling process, ensures the quality of reaction products, reduces the analysis error caused by sampling and ensures the accuracy of analysis.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a sampling method of ultra-high purity tellurium comprises the following steps:
(1) taking out the tellurium ingot from the zone melting furnace, and removing tellurium powder on the surface of the tellurium ingot;
(2) transferring the tellurium ingot to a glove box, knocking the tail of the tellurium ingot out, and knocking a tellurium block from the tail-removed position of the tellurium ingot;
(3) putting the tellurium blocks into a mold and transferring the tellurium blocks from a glove box to a sample melting furnace;
(4) vacuumizing the sample melting furnace, filling high-purity inert gas, and heating to melt the tellurium blocks;
(5) cooling, taking out the mold, transferring the mold to a glove box, and taking out the tellurium sheets in the mold;
(6) cutting the tellurium sheet into a plurality of sample blocks meeting the detection and analysis specification;
(7) and corroding the sample block, and washing the sample block with pure water after the corrosion is finished.
Preferably, in the step (2), the mass of the tellurium blocks is 50-100 g.
Preferably, the sample melting furnace comprises a quartz tube, the inside of the quartz tube is used for placing the mold, one end of the quartz tube is provided with an inflation inlet, the other end of the quartz tube is provided with a vacuum joint communicated with the inside of the quartz tube, and the outer wall of the quartz tube is provided with a heater.
Preferably, the quartz tube comprises a tube body and a cover body covering the open end of the tube body, a sealing flange is arranged between the tube body and the cover body, the inflation inlet is arranged at the bottom end of the tube body, and the vacuum joint is arranged on the cover body.
Preferably, in the step (4), after the vacuum is pumped to below 0.001Pa, the vacuum system is closed.
Preferably, in the step (4), the heating temperature is 500 ℃, and the heat preservation time is 10-30 min.
Preferably, in the step (6), the tellurium sheet is sliced along the lines on the tellurium sheet when the tellurium sheet is sliced.
Preferably, in the step (6), after the tellurium sheet is cut into sample pieces, the sample pieces are put into a retort pouch and taken out of the glove box after heat sealing.
Preferably, in the step (7), the corrosion process of the sample block is as follows: and putting the tellurium sample into a corrosive liquid for corroding for 10-60 seconds, adding excessive pure water to slow down the speed, and taking out the tellurium sample.
Preferably, the etching solution is prepared by mixing pure water, nitric acid and hydrofluoric acid, and the mass ratio of the etching solution is pure water: nitric acid: the hydrofluoric acid is 2: 0.5-1.5: 0.5 to 1.5.
Compared with the prior art, the sampling method of the ultra-high-purity tellurium has the beneficial effects that: through knocking out great tellurium piece to zone-melting tellurium ingot sample site, then putting into mould internal heating melting, form the sample of suitable size, not only guaranteed that the specification of sample satisfies the analysis requirement, simultaneously because corrode, wash the sample, the operation is all gone on in the glove box moreover, can reduce the pollution of sample in-process product, guarantee the quality of reaction product that can be true, reduce the analysis error that the sample caused to the accuracy of analysis has been guaranteed.
Drawings
FIG. 1 is a schematic structural view of a sample melting furnace according to the present invention.
Fig. 2 is a first structural schematic diagram of the mold.
Fig. 3 is a second structural diagram of the mold.
Wherein: 1-inflation inlet, 2-mould, 3-vacuum joint, 4-cover body, 5-heater and 6-pipe body.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The sampling method of the ultra-high purity tellurium in the preferred embodiment of the invention comprises the following steps:
(1) after zone melting is completed, taking out the tellurium boat from the zone melting furnace, transferring the tellurium boat to a clean platform, turning the tellurium boat, taking out tellurium ingots (not breaking the tellurium ingots in the process), and completely sucking tellurium powder on the surface of the tellurium boat by using a dust collector;
(2) the tellurium ingots were transferred to a glove box to reduce the environmental impact during sampling and to ensure that the water/oxygen was < 1 ppm. The tail is then knocked off and isolated with a titanium or zirconia hammer. Then knocking 50-100 g of tellurium blocks (a whole block comprising the upper surface and the contact surface with a tellurium boat) from the tail removing position of the tellurium ingot by using a titanium or zirconium oxide hammer;
(3) referring to fig. 1, a tellurium block is placed in a mold 2 and transferred from a glove box to a sample melting furnace; the sample melting furnace comprises a quartz tube, the mold 2 is placed in the quartz tube, and an inflation inlet 1 is formed in one end of the quartz tube and used for filling high-purity inert gas into the quartz tube. And the other end of the quartz tube is provided with a vacuum joint 3 communicated with the inside of the quartz tube and used for vacuumizing the quartz tube. And the outer wall of the quartz tube is provided with a heater 5 for heating the mould 2. The mold 2 is preferably a quartz mold.
Meanwhile, for convenient operation, the quartz tube comprises a tube body 6 and a cover body 4 covering the opening end of the tube body 6, the cover body 4 is opened when the mold 2 is required to be placed in the quartz tube, and the cover body 4 is fixed after the mold is placed. Meanwhile, a sealing flange is arranged between the pipe body 6 and the cover body 4, so that the sealing performance of the cover body 4 after being covered is ensured. Inflation inlet 1 sets up the bottom of body 6, vacuum joint 3 sets up on lid 4.
(4) And (3) vacuumizing the sample melting furnace to below 0.001Pa, closing a vacuum system, filling high-purity inert gas (7N), and heating to melt the tellurium blocks. Heating to 500 deg.c and maintaining for 10-30 min to ensure the melting of Te block.
(5) Cooling, taking out the mold 2, transferring the mold 2 to a glove box, and taking out the tellurium sheets in the mold 2;
(6) cutting the tellurium sheets into a plurality of sample blocks meeting the detection analysis specification (GDMS) along the lines on the tellurium sheets, then putting the sample blocks into a cooking bag, carrying out heat sealing, and taking out the glove box;
the detection and analysis method of the products of 7N and above is mainly GDMS. The GDMS has two specifications for the appearance of the sample, namely, sheet shape and needle shape, and in order to facilitate the slicing of the pattern requirement after the tellurium block is re-melted and formed in the mold 2, the bottom surface of the mold 2 can be provided with rectangular corresponding splitting grooves, as shown in figure 2, for manufacturing the sheet sample block; as shown in fig. 3, for making needle-like sample blocks.
(7) And putting the tellurium sample into a corrosive liquid to corrode for 10-60S, adding excessive pure water to slow down the speed, taking out the tellurium sample, and washing the tellurium sample with pure water to be clean, thus performing GDMS analysis. Wherein the corrosive liquid is formed by mixing pure water, nitric acid and hydrofluoric acid, and the mass ratio of the corrosive liquid is that the pure water: nitric acid: the hydrofluoric acid is 2: 0.5-1.5: 0.5 to 1.5.
According to the sampling method of the ultra-high pure tellurium, the large tellurium blocks are knocked from the sampling part of the zone-melting tellurium ingot and then placed into the mold 2 to be heated and melted to form a sample with a proper size, so that the specification of the sample meets the analysis requirement, meanwhile, the sample is corroded and cleaned, and the operation is carried out in a glove box, so that the pollution of the product in the sampling process can be reduced, the quality of a reaction product can be real, the analysis error caused by sampling is reduced, and the accuracy of analysis is guaranteed.
The effects of the present invention will be described below with reference to specific examples and comparative examples.
In the following experiments, the float-zone raw materials were in the same batch and the float-zone process was the same.
Example one
Cleaning a quartz mould by using pure water, and then carrying out carbon plating treatment for later use;
after the zone melting of the ultra-high pure tellurium is finished, taking out the tellurium containing boat from the zone melting furnace, transferring the tellurium containing boat to a clean platform, turning the tellurium containing boat, taking out a tellurium ingot, and completely absorbing tellurium powder on the surface of the tellurium ingot by using a dust collector;
the zone-melting tellurium ingots were transferred to a glove box, and the tails were knocked off with a titanium hammer and isolated. And knocking 60g of tellurium blocks from the tail-removed part of the tellurium ingot by using a titanium hammer, putting the tellurium blocks into a carbon-plated quartz mold, taking out the glove box, and transferring the glove box into a quartz tube of a sample melting furnace. Fixing a quartz tube cover;
and opening a vacuum system, vacuumizing to below 0.001Pa, then closing the vacuum system, and filling high-purity argon gas (7N) to normal pressure. Then heating, raising the temperature to 500 ℃, and preserving the heat for 20 min. After cooling to normal temperature, taking out the mold, transferring into a glove box, taking out the tellurium sheets, dividing the tellurium sheets into a plurality of small blocks along the lines on the tellurium sheets, putting 3 tellurium sheets into a cooking bag, carrying out heat sealing, and taking out the glove box;
respectively corroding the tellurium sheets according to the following methods: putting into 50mL of corrosive liquid (pure water: nitric acid: hydrofluoric acid is 2: 1: 1) for corrosion for 10S, adding 500mL of pure water to slow down the speed, taking out the tellurium wafer, washing with pure water until the conductivity of the pure water after tellurium washing is less than 0.5 mu S/cm, and carrying out GDMS analysis.
Comparative example 1
After the zone melting of the ultra-high pure tellurium is finished, taking out the tellurium containing boat from the zone melting furnace, transferring the tellurium containing boat to a clean platform, turning the tellurium containing boat, taking out a tellurium ingot, and completely absorbing tellurium powder on the surface of the tellurium ingot by using a dust collector;
the zone-melting tellurium ingots were transferred to a glove box, and the tails were knocked off with a titanium hammer and isolated. Then a slice tellurium sample (the contact surface of the tellurium-sample tellurium-containing zone melting ingot and the tellurium-containing boat) is knocked by a titanium hammer from the tail removing position of the tellurium ingot.
And (3) putting the tellurium sheet into 50mL of corrosive liquid (pure water, nitric acid and hydrofluoric acid are in a ratio of 2: 1: 1) for corrosion for 10S, adding 500mL of pure water for slowing down the speed, taking out the tellurium sheet, washing the tellurium sheet by using the pure water until the conductivity of the pure water after the tellurium sheet is washed is less than 0.5 mu S/cm, and carrying out GDMS analysis.
Comparative example 2
After the zone melting of the ultra-high pure tellurium is finished, taking out the tellurium containing boat from the zone melting furnace, transferring the tellurium containing boat to a clean platform, turning the tellurium containing boat, taking out a tellurium ingot, and completely absorbing tellurium powder on the surface of the tellurium ingot by using a dust collector;
the zone-melting tellurium ingots were transferred to a glove box, and the tails were knocked off with a titanium hammer and isolated. Then a flaky tellurium sample (the upper surface of the tellurium-containing zone-melting ingot) is knocked by a titanium hammer from the tail part of the tellurium ingot.
And (3) putting the tellurium sheet into 50mL of corrosive liquid (pure water, nitric acid and hydrofluoric acid are in a ratio of 2: 1: 1) for corrosion for 10S, adding 500mL of pure water for slowing down the speed, taking out the tellurium sheet, washing the tellurium sheet by using the pure water until the conductivity of the pure water after the tellurium sheet is washed is less than 0.5 mu S/cm, and carrying out GDMS analysis.
Comparative example 3
After the zone melting of the ultra-high pure tellurium is finished, taking out the tellurium containing boat from the zone melting furnace, transferring the tellurium containing boat to a clean platform, turning the tellurium containing boat, taking out a tellurium ingot, and completely absorbing tellurium powder on the surface of the tellurium ingot by using a dust collector;
the zone-melting tellurium ingots were transferred to a glove box, and the tails were knocked off with a titanium hammer and isolated. Then a flaky tellurium sample (the tellurium sample is taken from the central part of the tellurium zone-melting ingot) is knocked out from the tail part of the tellurium ingot by a titanium hammer.
And (3) putting the tellurium sheet into 50mL of corrosive liquid (pure water, nitric acid and hydrofluoric acid are in a ratio of 2: 1: 1) for corrosion for 10S, adding 500mL of pure water for slowing down the speed, taking out the tellurium sheet, washing the tellurium sheet by using the pure water until the conductivity of the pure water after the tellurium sheet is washed is less than 0.5 mu S/cm, and carrying out GDMS analysis.
Comparative example 4
Cleaning a quartz mould with pure water for later use;
after the zone melting of the ultra-high pure tellurium is finished, taking out the tellurium containing boat from the zone melting furnace, transferring the tellurium containing boat to a clean platform, turning the tellurium containing boat, taking out a tellurium ingot, and completely absorbing tellurium powder on the surface of the tellurium ingot by using a dust collector;
the zone-melting tellurium ingots were transferred to a glove box, and the tails were knocked off with a titanium hammer and isolated. And knocking 60g of tellurium blocks from the tail-removed part of the tellurium ingot by using a titanium hammer, putting the tellurium blocks into a carbon-plated quartz mold, taking out the glove box, and transferring the glove box into a quartz tube of a sample melting furnace. Fixing a quartz tube cover;
and opening a vacuum system, vacuumizing to below 0.001Pa, then closing the vacuum system, and filling high-purity argon gas (7N) to normal pressure. Then heating, raising the temperature to 500 ℃, and preserving the heat for 20 min. After cooling to normal temperature, taking out the mold, transferring into a glove box, taking out the tellurium sheets, dividing the tellurium sheets into a plurality of small blocks along the lines on the tellurium sheets, putting the tellurium sheets into a cooking bag, carrying out heat sealing, and taking out the glove box;
and (3) putting the tellurium sheet into 50mL of corrosive liquid (pure water, nitric acid and hydrofluoric acid are in a ratio of 2: 1: 1) for corrosion for 10S, adding 500mL of pure water for slowing down the speed, taking out the tellurium sheet, washing the tellurium sheet by using the pure water until the conductivity of the pure water after the tellurium sheet is washed is less than 0.5 mu S/cm, and carrying out GDMS analysis.
And (4) analyzing results:
the table below gives the results of the main impurity analysis (GDMS) of the example and comparative group of ultra-high pure tellurium.
TABLE 1 analysis results (unit ppbw) of major impurities of ultra-high purity tellurium
TABLE 1 analysis results (unit ppbw) of major impurities of ultra-high purity tellurium
TABLE 2 time of knocking tellurium ingot using titanium hammer
| Example one | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Time/ |
5 | 45 | 50 | 100 | 5 |
1) From the embodiment, by adopting the sampling method, the uniformity of the sample can meet the requirement of ultra-high purity tellurium
2) In comparative examples 1, 2 and 3, the impurities in the inner part, the upper surface and the boat contact surface of the same position of the ultra-high pure tellurium are greatly different, and the whole impurity content in the inner part is the lowest. It is difficult to represent the overall impurity level of the zone-melted tellurium ingot.
3) From the examples and comparative example 3, theoretically, the impurity profile of comparative example 3 should be superior to the examples, while the analytical results are reversed. The reason is that: in comparative example 3, when a suitable sample was tapped directly with a titanium hammer, a large amount of tellurium fragments were generated during the process, and contamination was likely to occur.
4) As seen from examples and comparative example 4, the quartz mold was carbon-plated to prevent contamination of the sample with quartz (Si).
In summary, the sampling method of ultra-high purity tellurium provided by the invention is that a large tellurium block is taken from the sampling part of the zone-melting tellurium ingot, then the large tellurium block is put into a mould, heated and melted to form a sample with a proper size, and then the sample is corroded and cleaned, so that GDMS analysis can be carried out. The product pollution in the sampling process can be reduced, the sample representativeness is improved, and the quality of reaction products can be real.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A sampling method of ultra-high purity tellurium is characterized in that: the method comprises the following steps:
(1) taking out the tellurium ingot from the zone melting furnace, and removing tellurium powder on the surface of the tellurium ingot;
(2) transferring the tellurium ingot to a glove box, knocking the tail of the tellurium ingot out, and knocking a tellurium block from the tail-removed position of the tellurium ingot;
(3) putting the tellurium blocks into a mold and transferring the tellurium blocks from a glove box to a sample melting furnace;
(4) vacuumizing the sample melting furnace, filling high-purity inert gas, and heating to melt the tellurium blocks;
(5) cooling, taking out the mold, transferring the mold to a glove box, and taking out the tellurium sheets in the mold;
(6) cutting the tellurium sheet into a plurality of sample blocks meeting the detection and analysis specification;
(7) and corroding the sample block, and washing the sample block with pure water after the corrosion is finished.
2. The method of sampling ultra-high purity tellurium of claim 1, wherein: in the step (2), the mass of the tellurium blocks is 50-100 g.
3. The method of sampling ultra-high purity tellurium of claim 1, wherein: the sample melting furnace comprises a quartz tube, the inside of the quartz tube is used for placing the mold, one end of the quartz tube is provided with an inflation inlet, the other end of the quartz tube is provided with a vacuum joint communicated with the inside of the quartz tube, and the outer wall of the quartz tube is provided with a heater.
4. The method of sampling ultra-high purity tellurium of claim 3, wherein: the quartz tube comprises a tube body and a cover body covering the opening end of the tube body, a sealing flange is arranged between the tube body and the cover body, the inflation inlet is formed in the bottom end of the tube body, and the vacuum joint is arranged on the cover body.
5. The method of sampling ultra-high purity tellurium of claim 1, wherein: in the step (4), after the vacuum is pumped to below 0.001Pa, the vacuum system is closed.
6. The method of sampling ultra-high purity tellurium of claim 1, wherein: in the step (4), the heating temperature is 500 ℃, and the temperature is kept for 10-30 min.
7. The method of sampling ultra-high purity tellurium of claim 1, wherein: in the step (6), the tellurium sheets are cut along the lines on the tellurium sheets when the tellurium sheets are cut.
8. The method of sampling ultra-high purity tellurium of claim 1, wherein: in the step (6), after the tellurium sheets are cut into sample blocks, the sample blocks are put into a cooking bag, and the glove box is taken out after the heat seal.
9. The method of sampling ultra-high purity tellurium of claim 1, wherein: in the step (7), the corrosion process of the sample block is as follows: and putting the tellurium sample into a corrosive liquid for corroding for 10-60 seconds, adding excessive pure water to slow down the speed, and taking out the tellurium sample.
10. The method of sampling ultra-high purity tellurium of claim 9, wherein: the corrosive liquid is formed by mixing pure water, nitric acid and hydrofluoric acid, and the mass ratio of the corrosive liquid is that the pure water: nitric acid: the hydrofluoric acid is 2: 0.5-1.5: 0.5 to 1.5.
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| CN202210527880.2A CN114813202B (en) | 2022-05-16 | Sampling method of ultra-high purity tellurium |
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| CN202210527880.2A CN114813202B (en) | 2022-05-16 | Sampling method of ultra-high purity tellurium |
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|---|---|---|---|---|
| FR2171627A5 (en) * | 1972-02-09 | 1973-09-21 | Decolletage Et Const Meca Ste | Molten metal sampler - contg tellurium powder to ensure homogenous carbon content |
| CN110894065A (en) * | 2019-12-18 | 2020-03-20 | 中南大学 | Equipment and method for preparing high-purity tellurium |
| CN113957543A (en) * | 2021-10-22 | 2022-01-21 | 广东先导微电子科技有限公司 | Method for removing surface impurities of ultra-high-purity tellurium |
| CN215626804U (en) * | 2021-07-21 | 2022-01-25 | 四川孚孚新材料科技有限公司 | High-purity tellurium anaerobic casting device |
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|---|---|---|---|---|
| FR2171627A5 (en) * | 1972-02-09 | 1973-09-21 | Decolletage Et Const Meca Ste | Molten metal sampler - contg tellurium powder to ensure homogenous carbon content |
| CN110894065A (en) * | 2019-12-18 | 2020-03-20 | 中南大学 | Equipment and method for preparing high-purity tellurium |
| CN215626804U (en) * | 2021-07-21 | 2022-01-25 | 四川孚孚新材料科技有限公司 | High-purity tellurium anaerobic casting device |
| CN113957543A (en) * | 2021-10-22 | 2022-01-21 | 广东先导微电子科技有限公司 | Method for removing surface impurities of ultra-high-purity tellurium |
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