CN116143499A - Barium technetiate ceramic solidified body for solidifying technetium and preparation method and application thereof - Google Patents
Barium technetiate ceramic solidified body for solidifying technetium and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 49
- 229910052713 technetium Inorganic materials 0.000 title claims abstract description 21
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052788 barium Inorganic materials 0.000 title claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 230000006698 induction Effects 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 13
- PYHBIWVCLFQOQX-UHFFFAOYSA-N [Tc][Ba] Chemical compound [Tc][Ba] PYHBIWVCLFQOQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- -1 barium technetium oxide Chemical compound 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 2
- 239000011224 oxide ceramic Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 9
- 238000000280 densification Methods 0.000 abstract description 9
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 230000005303 antiferromagnetism Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BWUXDKMMCZJFAB-UHFFFAOYSA-N oxotechnetium Chemical group [Tc]=O BWUXDKMMCZJFAB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium oxides or oxide-forming salts thereof
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
Abstract
The invention belongs to the technical field of high-radioactivity nuclear waste treatment, and discloses a technetium barium titanate ceramic (BaTcO) for solidifying technetium (Tc) 3 ) And a preparation method and application thereof, wherein the method is to make NH 4 TcO 4 Calcining at 600-800 ℃ to obtain TcO 2 Powder, tcO 2 Mixing with Ba source powder uniformly, pressing the mixed powder into green body, sintering at 900-1300 ℃ by using induction heating to obtain BaTcO 3 And (3) a ceramic solidified body. The BaTcO 3 The ceramic solidified body has good thermal stability, effectively reduces the volatilization of technetium, is beneficial to densification of the ceramic solidified body in a short time, has simple preparation process and is suitable for large-scale preparation. The barium technetium ceramic solidified body is applied to the volatile nuclide technetium in solidified nuclear waste.
Description
Technical Field
The invention belongs to the technical field of high-radioactivity nuclear waste treatment, and in particular relates to a technetium barium titanate ceramic solidified body for solidifying technetium, and a preparation method and application thereof.
Background
Technetium (Tc) is an important contaminating element in nuclear waste, 99 tc has a half-life as long as 2.13×10 5 Year mainly by 235 U or 239 Pu is fissiled with a yield of about 6% of which only a small fraction is used for commercial purposes. Under normal conditions, tc is TcO in pertechnetate radical 4 - In the form of (a) TcO 4 - Is easy to dissolve in water, is not easy to be adsorbed by soil, rock and the like, is easy to enter water body to migrate, and damages ecological environment to cause huge secondary disasters. Thus, the first and second substrates are bonded together, 99 the safe handling and disposal of Tc has been an important concern in the area of radioactive waste treatment and disposal.
In practical engineering applications, tc nuclides are generally treated in a glass-cured form and dissolved in a glass matrix for curing. But glass is opposite to pertechnetate TcO 4 - The inclusion of the equal-height radioactive nuclear waste is poor, the solid solution quantity is generally about 4wt% according to the records of Glass, glass-Ceramics and Ceramics for Immobilization of Highly Radioactive Nuclear Wastes by Caurant, the overall leaching rate is high, after the nuclear radiation is carried out, the coordination number of a silica network in the Glass is reduced, even the leaching rate is broken, the leaching rate is reduced by 1-2 orders of magnitude, and the reliability of the design service period of the Glass solidified body is reduced.
The ceramic solidified body is formed by sintering nuclear waste and ceramic powder at high temperature, and realizing lattice solidification by utilizing solid solution reaction of the nuclear waste and ceramic lattice on an atomic scale; represented by perovskite ceramic solid body (chemical formula ABO 3 ) Ceramic cured bodies not only cure more nuclear waste, but also have superior thermal stability, radiation resistance, and leaching resistance, and have been considered as one of the best forms of treating nuclear waste. The literature on perovskite structure ceramic cured bodies with cured Tc reports CaTcO 3 And SrTcO 3 As published in 2012, fabrication and properties of technetium-bearing pyrochlores and perovskites as potential waste forms discloses a SrTcO 3 Preparation method of powder comprises mixing SrO and TcO 2 The mixed powder is kept at 770 ℃ for 7 days to obtain SrTcO 3 Powder, the contact area of the powder and the outside is far larger than that of the ceramic blockThe body can bring the result of obviously reduced leaching performance, is not suitable for being used as a solidified body, has sintering time as long as 7 days, and is unfavorable for process popularization due to long heat treatment time. Antiferromagnetism in a technetium oxide Structure of CaTcO published 2022 3 The CaTcO is disclosed in 3 Solid phase reaction preparation method of (2), NH 4 TcO 4 With Ca (NO) 3 ) 2 ·4H 2 Calcining at 700 deg.C for 1 hr after mixing O, grinding, mixing again, and maintaining at 1150 deg.C for 4 hr to obtain CaTcO 3 The ceramic solidified body is formed by the preparation method without applying pressure, which is unfavorable for sample densification, and the porous microstructure increases the contact area with the outside, so that the leaching performance of the sample is reduced.
Currently, baTcO is not seen 3 The relevant preparation of cured bodies has been reported in only one conference paper structure, electronic and Ferroelectric Properties of BaTcO 3 Calculating BaTcO using density functional theory 3 The crystal structure and antiferroelectric properties of (a). With reference to the law of variation of physical properties of alkaline earth compounds (e.g. CaCO) 3 、SrCO 3 、BaCO 3 The decomposition temperature is 900 ℃, 1100 ℃ and 1360 ℃ in sequence, the influence of electronegativity of A-site element in perovskite ceramic on heat stability can be deduced to be BaTcO 3 The high-temperature stability of the (C) is better, and the densification of the structure of the solidified body and the minimization of volatile components are facilitated. The traditional heating mode has slow heating rate and long heat preservation time, and can promote more TcO 2 Volatilizing.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the primary aim of the invention is to provide a preparation method of a barium technetium oxide ceramic solidified body for solidifying technetium, which adopts the composition design BaTcO 3 Combined with a rapid heating method by induction heating, the BaTcO is prepared 3 The preparation time of the ceramic solidified body is greatly shortened, and the process flow is simple, thereby being suitable for mass preparation.
It is another object of the present invention to provide a barium technetium ceramic solidified body for solidifying technetium produced by the above method. The cured body has more excellent comprehensive performance.
It is a further object of the present invention to provide the use of the above-described barium technetiate ceramic solidified body for solidifying technetium.
The aim of the invention is achieved by the following technical scheme:
a method for preparing a barium technetiate ceramic solidified body for solidifying technetium, comprising the steps of:
s1, NH is carried out 4 TcO 4 Calcining at 600-800 ℃ by using induction heating under flowing protective atmosphere, naturally cooling, grinding and sieving to obtain TcO 2 Powder;
s2, tcO is carried out 2 Mixing the powder with Ba source powder to make the molar ratio of Tc to Ba element in the raw material be 1:1, adding a ball milling medium for ball milling, drying and sieving to obtain mixed powder;
s3, dry-pressing the mixed powder, placing the mixed powder into a boron nitride crucible, heating to 900-1300 ℃ by using induction heating under a flowing protective atmosphere, sintering, cooling the furnace chamber in a water circulation manner while heating, and then naturally cooling to obtain BaTcO 3 And (3) a ceramic solidified body.
Preferably, the protective atmosphere in the step S1 is Ar or He; the calcination time is 0.5-2 h; the heating rate of the induction heating is 50-200 ℃/min.
Preferably, in step S2, the Ba source powder is BaCO 3 、Ba(OH) 2 、Ba(NO 3 ) 2 Or BaO.
Preferably, the rotating speed of the ball milling in the step S2 is 150-350 r/min, the ball milling time is 6-12 h, and the ball milling medium is more than one of absolute ethyl alcohol, ethylene glycol, cyclohexane and n-hexane; the drying temperature is 80-120 ℃, and the drying time is 12-18 h.
Preferably, the dry press molding pressure in the step S3 is 50-80 MPa, and the press molding time is 15-30S; the heating rate of the induction heating is 50-200 ℃/min, and the calcining time is 0.5-2 h.
Preferably, the temperature of the water circulation cooling in the step S3 is 10-25 ℃, the wall temperature outside the furnace chamber is ensured to be lower than 30 ℃, and the protective atmosphere is Ar or He.
A barium technetium ceramic solidified body prepared by the method.
The application of the barium technetium ceramic solidified body in solidifying volatile nuclide technetium in nuclear waste.
Compared with the prior art, the invention has the following beneficial effects:
1. BaTcO prepared by the invention 3 The ceramic solidified body has good high-temperature stability, is more beneficial to the sintering densification of ceramic and reduces the volatilization of technetium (Tc) at high temperature.
2. Compared with the traditional method for preparing the ceramic solidified body for solidifying the Tc, the method adopts induction heating rapid heating calcination and sintering treatment, and the time of the whole heat treatment process is greatly shortened compared with the traditional heating method, so that the volatilization amount of the Tc at high temperature is reduced. Meanwhile, the shorter sintering time can avoid generating pyrochlore structure with poor chemical stability, and is beneficial to long-term placement of the solidified body in deep ground.
3. BaTcO prepared by the invention 3 The ceramic cured body had a higher solid solution amount (Tc at BaTcO) than the glass cured body (Tc at about 4wt% in the glass cured body) 3 34.5 wt%) and the structural integrity and densification, can reduce the contact area with the outside, is beneficial to reducing the leaching of nuclide Tc, thereby improving the leaching resistance of the nuclide Tc, has simple preparation process and is suitable for mass production.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1. Weigh 15gNH 4 TcO 4 Pouring into boron nitride crucible, placing in the middle of heating element of induction heating furnace, continuously washing with Ar gas for 3 times, controlling Ar gas flow at 200mL/min, and induction heatingSetting the heating rate of the heating furnace to 150 ℃/min, heating to 700 ℃ for calcination and heat preservation for 1h, then naturally cooling, taking out, pouring into an agate grinding pot for manual grinding, and sieving by using a 100-mesh screen to obtain the TcO 2 And (3) powder.
2. Weigh TcO 2 And BaCO 3 15g in total (molar ratio 1:1), pouring the mixture into a nylon ball milling tank, adding 30g of silicon nitride grinding balls and 50mL of absolute ethyl alcohol, and performing ball milling for 6 hours at a rotating speed of 150-350 r/min; the mixture after ball milling was poured into a flask for rotary evaporation, then dried in a constant temperature oven at 80 ℃ for 18 hours, then manually ground by using an agate grinding bowl, poured into a 100 mesh screen and sieved to obtain mixed powder.
3. Weighing 2g of mixed powder, pouring into a stainless steel die, performing axial dry pressing under 80MPa for 15s, placing the pressed sample green body into a boron nitride crucible, washing with Ar gas for 3 times, controlling Ar gas flow to be 200mL/min, setting the heating rate of an induction heating furnace to be 150 ℃/min, calcining at 1300 ℃ and preserving heat for 1h, and naturally cooling to obtain BaTcO 3 Ceramic solidified body, tc is BaTcO 3 The mass ratio of the (B) to the (C) reaches 34.56wt percent, which indicates that the prepared BaTcO 3 The ceramic solidified body has higher solid solution quantity, structural integrity and densification, can reduce the contact area with the outside, and is beneficial to reducing the leaching of nuclide Tc, thereby improving the leaching resistance of the ceramic solidified body.
Example 2
1. Weigh 15gNH 4 TcO 4 Pouring the mixture into a boron nitride crucible, placing the crucible in the middle of a heating body of an induction heating furnace, continuously washing the crucible with Ar gas for 3 times, controlling the Ar gas flow to be 200mL/min, setting the heating rate of the induction heating furnace to be 50 ℃/min, calcining at 600 ℃ and preserving the temperature for 2 hours, and naturally cooling; taking out, pouring into an agate grinding pot, manually grinding, and sieving with a 100-mesh screen to obtain TcO 2 And (3) powder.
2. Weigh TcO 2 And BaO (molar ratio 1:1) 15g in total, pouring into a nylon ball milling tank, adding 30g silicon nitride grinding balls and 50mL absolute ethyl alcohol, ball milling for 6 hours at a rotating speed of 150-350 r/min, pouring the ball-milled mixture into a flask for rotary evaporation, drying for 18 hours at 80 ℃ in a constant-temperature oven, and then usingThe agate grinding pot is manually ground, poured into a 100-mesh screen and screened to obtain mixed powder.
3. Weighing 2g of mixed powder, pouring into a stainless steel die, performing axial dry pressing under 50MPa for 15s, placing the pressed sample green body into a boron nitride crucible, washing with Ar gas for 3 times, controlling Ar gas flow to be 200mL/min, setting the heating rate of an induction heating furnace to be 50 ℃/min, calcining at 900 ℃ and preserving heat for 2h, and naturally cooling to obtain BaTcO 3 Ceramic solidified body, tc is BaTcO 3 The mass ratio of the (B) to the (C) reaches 34.56wt percent, which indicates that the prepared BaTcO 3 The ceramic solidified body has higher solid solution quantity, structural integrity and densification, can reduce the contact area with the outside, and is beneficial to reducing the leaching of nuclide Tc, thereby improving the leaching resistance of the ceramic solidified body.
Example 3
1. Weigh 15gNH 4 TcO 4 Pouring into a boron nitride crucible, placing in the middle of a heating element of an induction heating furnace, continuously washing with He gas for 3 times, controlling the He gas flow to be 200ml/min, setting the heating rate of the induction heating furnace to be 200 ℃/min, calcining at 800 ℃ and preserving heat for 0.5h, and naturally cooling; taking out, pouring into an agate grinding pot, manually grinding, and sieving with a 100-mesh screen to obtain TcO 2 And (3) powder.
2. Weigh TcO 2 And Ba (OH) 2 (molar ratio 1:1) 15g in total, pouring into a nylon ball milling tank, adding 30g of silicon nitride grinding balls and 50mL of absolute ethyl alcohol, and ball milling for 6 hours at a rotating speed of 150-350 r/min. And pouring the ball-milled mixed liquid into a flask for rotary evaporation, drying the mixed liquid at the constant-temperature oven at 80 ℃ for 18 hours, manually grinding the mixed liquid by using an agate grinding pot, pouring the mixed liquid into a 100-mesh screen, and sieving the mixed liquid to obtain mixed powder.
3. Weighing 2g of mixed powder, pouring into a stainless steel die, performing axial dry pressing under the pressure of 70MPa for 15s, placing the pressed sample green body into a boron nitride crucible, washing with He gas for 3 times, controlling the He gas flow to be 200mL/min, setting the heating rate of an induction heating furnace to be 200 ℃/min, preserving heat at 1000 ℃ for 0.5h, and naturally cooling to obtain BaTcO 3 Ceramic solidified body, tc is BaTcO 3 The mass ratio of the (B) to the (C) reaches 34.56wt percent, which indicates that the prepared BaTcO 3 The ceramic solidified body has higher solid solution quantity, structural integrity and densification, can reduce the contact area with the outside, and is beneficial to reducing the leaching of nuclide Tc, thereby improving the leaching resistance of the ceramic solidified body.
Example 4
1. Weigh 15gNH 4 TcO 4 Pouring the mixture into a boron nitride crucible, placing the crucible in the middle of a heating body of an induction heating furnace, continuously washing gas for 3 times by using He gas, controlling the He gas flow to be 200mL/min, setting the heating rate of the induction heating furnace to be 150 ℃/min, calcining at 700 ℃ and preserving heat for 1h, and naturally cooling; taking out, pouring into an agate grinding pot, manually grinding, and sieving with a 100-mesh screen to obtain TcO 2 And (3) powder.
2. Weigh TcO 2 And Ba (NO) 3 ) 2 (molar ratio 1:1) is 15g in total, poured into a nylon ball milling tank, 30g of silicon nitride grinding balls and 50mL of absolute ethyl alcohol are added, and ball milling is carried out for 6 hours at a rotating speed of 150-350 r/min. The mixture after ball milling was poured into a flask for rotary evaporation, then dried in a constant temperature oven at 80 ℃ for 18 hours, then manually ground by using an agate grinding bowl, poured into a 100 mesh screen and sieved to obtain mixed powder.
3. Weighing 2g of mixed powder, pouring into a stainless steel die, performing axial dry pressing under 80MPa for 15s, placing the pressed sample green body into a boron nitride crucible, washing with He gas for 3 times, controlling the He gas flow to be 200ml/min, setting the heating rate of an induction heating device to be 150 ℃/min, calcining at 1150 ℃ and preserving heat for 1h, and naturally cooling to obtain BaTcO 3 Ceramic solidified body, tc is BaTcO 3 The mass ratio of the (B) to the (C) reaches 34.56wt percent, which indicates that the prepared BaTcO 3 The ceramic solidified body has higher solid solution quantity, structural integrity and densification, can reduce the contact area with the outside, and is beneficial to reducing the leaching of nuclide Tc, thereby improving the leaching resistance of the ceramic solidified body.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A method for preparing a barium technetiate ceramic solidified body for solidifying technetium, comprising the steps of:
s1, NH is carried out 4 TcO 4 Calcining at 600-800 ℃ by using induction heating under flowing protective atmosphere, naturally cooling, grinding and sieving to obtain TcO 2 Powder;
s2, tcO is carried out 2 Mixing the powder with Ba source powder to make the molar ratio of Tc to Ba element in the raw material be 1:1, adding a ball milling medium for ball milling, drying and sieving to obtain mixed powder;
s3, dry-pressing the mixed powder, placing the mixed powder into a boron nitride crucible, heating to 900-1300 ℃ by using induction heating under a flowing protective atmosphere, sintering, heating while carrying out water circulation cooling on a furnace chamber, and then naturally cooling to obtain BaTcO 3 And (3) a ceramic solidified body.
2. The method for producing a barium technetium ceramic solidified body for solidifying technetium according to claim 1, characterized in that the protective atmosphere in step S1 is Ar or He; the calcination time is 0.5-2 h; the heating rate of the induction heating is 50-200 ℃/min.
3. The method for producing a barium technetium ceramic solidified body for solidifying technetium according to claim 1, characterized in that the Ba source powder in step S2 is BaCO 3 、Ba(OH) 2 、Ba(NO 3 ) 2 Or BaO.
4. The method for preparing a barium technetium ceramic solidified body for solidifying technetium according to claim 1, wherein the rotation speed of ball milling in the step S2 is 150-350 r/min, the ball milling time is 6-12 h, and the ball milling medium is one or more of absolute ethyl alcohol, ethylene glycol, cyclohexane and n-hexane; the drying temperature is 80-120 ℃, and the drying time is 12-18 h.
5. The method for producing a barium technetium ceramic solidified body for solidifying technetium according to claim 1, characterized in that the dry press molding pressure in step S3 is 50 to 80MPa and the press molding time is 15 to 30S; the heating rate of the induction heating is 50-200 ℃/min, and the calcining time is 0.5-2 h.
6. The method for preparing a barium technetium ceramic solidified body for solidifying technetium according to claim 1, wherein the temperature of water circulation cooling in step S3 is 10-25 ℃, and the wall temperature outside the furnace chamber is ensured to be lower than 30 ℃; the protective atmosphere is Ar or He.
7. A barium technetium ceramic solidified body prepared by the method of any one of claims 1-6.
8. Use of the barium technetium oxide ceramic solidified body of claim 7 to solidify volatile nuclide technetium in nuclear waste.
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| CN1254191A (en) * | 1998-11-12 | 2000-05-24 | 潘树明 | Production method of high-temp. superconducting film |
| CN102272859A (en) * | 2008-12-30 | 2011-12-07 | 阿雷瓦核废料回收公司 | Alumino-borosilicate glass for confining radioactive liquid effluents, and method for processing radioactive effluents |
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