CN116283277A - Method for loading cesium nitrate on ceramic microspheres - Google Patents
Method for loading cesium nitrate on ceramic microspheres Download PDFInfo
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- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000004005 microsphere Substances 0.000 title claims abstract description 164
- 239000000919 ceramic Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011068 loading method Methods 0.000 title claims abstract description 27
- 239000000499 gel Substances 0.000 claims abstract description 66
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011240 wet gel Substances 0.000 claims abstract description 16
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 25
- 238000001179 sorption measurement Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052792 caesium Inorganic materials 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 229920002545 silicone oil Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007603 infrared drying Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 2
- -1 nitroamino Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- C04B35/48—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 based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention belongs to the technical field of ceramic preparation, and particularly relates to a method for loading cesium nitrate on ceramic microspheres. The invention provides a method for loading cesium nitrate by ceramic microspheres, which comprises the following steps: (1) Sequentially performing trichloroethylene washing and ammonia water washing treatment on the gel microspheres to obtain wet gel microspheres; (2) Placing the wet gel microspheres obtained in the step (1) in cesium nitrate solution for soaking and adsorbing; (3) And (3) soaking the gel microsphere adsorbed with cesium nitrate obtained in the step (2) in propylene glycol methyl ether, and then drying and calcining. The ceramic microsphere obtained by the method has large metal cesium loading capacity, smooth surface, no cracking and simple operation.
Description
Technical Field
The invention belongs to the technical field of ceramic preparation, and particularly relates to a method for loading cesium nitrate on ceramic microspheres.
Background
The conventional radioactive material is treated by solidification of glass, for example, cesium nitrate containing Cs137 in yttrium stabilized zirconia (abbreviated as YSZ). Moreover, cesium nitrate is supported in yttrium-stabilized zirconia, which is of great research value for observing the release behavior of fission products. However, nuclear glass corrosion caused by aqueous medium easily occurs in the glass treatment process, so that cesium nitrate migrates to the biosphere, and life safety of people is threatened.
Since cesium compounds are generally soluble in water, researchers have commonly used "dry" to load cesium nitrate in zirconia, such as by using zirconia, cesium carbonate or cesium nitrate powders in combination with classical ceramic processes (powder milling-granulation-sintering in air), to load cesium nitrate in zirconia. The cesium nitrate is unevenly distributed by the method, and the prepared ceramic microspheres have uniform size. Some researchers load cesium nitrate by ion implantation, namely, a cesium source is implanted into zirconia microspheres in the form of ions and then heat treatment is carried out, and the method is simple to operate, but the implantation depth is shallow, only a few micrometers, and the cesium nitrate load is not high. Some researchers load cesium nitrate by immersing zirconia microspheres in cesium salt, and then calcining, but the adsorption capacity of cesium nitrate is poor and the load of cesium nitrate is not large because the pore channels of zirconia microspheres are basically closed.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems:
cesium nitrate is readily soluble in water and direct loading of cesium nitrate in sol gel processes is not feasible, and cesium nitrate is lost in large amounts in water. And the adsorption method is adopted, the cesium nitrate solution is impregnated with the dried gel microspheres to adsorb cesium nitrate, the dried gel microspheres need to be dried for the second time after adsorbing cesium nitrate, the pore channels of the gel microspheres after the second drying are basically closed, and the gas decomposed by organic matters in the gel microspheres in the high-temperature calcination process can not be discharged, so that the microspheres can be cracked due to excessive internal pressure.
The existing treatment method has the defects of uneven cesium nitrate distribution or low cesium nitrate load, and is difficult to obtain the YSZ ceramic microspheres with smooth surfaces, no cracking and high cesium nitrate load. In order to obtain cesium nitrate-loaded ceramic microspheres without cracking, a method for loading cesium nitrate to ceramic microspheres is needed to solve the difficulty of ceramic curing cesium nitrate.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a method for loading cesium nitrate on ceramic microspheres, wherein the cesium nitrate loaded ceramic microspheres are successfully obtained by the method, the cesium nitrate is uniformly distributed in the ceramic microspheres, the cesium nitrate load is high, and the surfaces of the obtained ceramic microspheres are smooth and have no cracks.
The method for loading cesium nitrate on the ceramic microspheres comprises the following steps:
(1) Sequentially performing trichloroethylene washing and ammonia water washing treatment on the gel microspheres to obtain wet gel microspheres;
(2) Placing the wet gel microspheres obtained in the step (1) in cesium nitrate solution for soaking and adsorbing;
(3) And (3) soaking the gel microsphere adsorbed with cesium nitrate obtained in the step (2) in propylene glycol methyl ether, and then drying and calcining.
The method for loading cesium nitrate on the ceramic microspheres has the advantages and technical effects that 1, the method provided by the embodiment of the invention can remove residual silicone oil on gel microspheres by washing with trichloroethylene because trichloroethylene and silicone oil are mutually soluble; 2. according to the method provided by the embodiment of the invention, the nitroaniline in the gel microsphere is easy to dissolve in water, and can be decomposed and exploded at 400 ℃ to seriously damage the morphology of the microsphere, and ammonia water is adopted to remove the residual nitroaniline in the gel microsphere, so that the microsphere without cracking is obtained; 3. according to the method provided by the embodiment of the invention, the wet gel microspheres are adopted to soak and adsorb cesium nitrate, so that compared with the traditional dry microspheres, the adsorption capacity is large, and the purpose of loading cesium nitrate by the ceramic microspheres is successfully realized; 4. according to the method provided by the embodiment of the invention, after the wet gel microspheres are soaked and adsorbed with cesium nitrate, in order to reduce the capillary force of the wet gel microspheres in the drying process, the gel microspheres are soaked with propylene glycol methyl ether and then dried, the gel microspheres do not need to be dried for the second time, and the gel microspheres also retain rich pore channel structures, so that the ceramic particles without cracking are obtained; 5. according to the method provided by the embodiment of the invention, propylene glycol methyl ether is adopted for soaking treatment, and because the propylene glycol methyl ether and water are mutually soluble and the volatilization speed is moderate, the water in the gel microspheres can be removed, and the surface tension of the propylene glycol methyl ether is small, so that the capillary force generated in the drying process of the gel microspheres can be effectively reduced, and the pore channel structure of the gel microspheres can be reserved as much as possible.
In some embodiments, in step (1), the trichloroethylene is washed at a temperature of 60 to 80 ℃ for a time of 80 to 120 minutes.
In some embodiments, in the step (1), the temperature of the ammonia water washing is 60-80 ℃, and the concentration of the ammonia water is 0.5M.
In some embodiments, the conductivity of the wash solution decreases to 700 μs/cm after the aqueous ammonia wash.
In some embodiments, in step (1), the gel microspheres are yttrium stabilized zirconia gel microspheres.
In some embodiments, in step (2), the cesium nitrate solution has a concentration of 0.1 to 0.2M; and/or, the cesium nitrate solution is an aqueous solution of cesium nitrate.
In some embodiments, in the step (2), the soaking adsorption is performed at a temperature of 60 to 80 ℃ for 3 to 12 hours.
In some embodiments, in the step (3), the soaking treatment in the propylene glycol methyl ether is performed at a temperature of 60-80 ℃ for a time of 10-20 min.
In some embodiments, in the step (3), the drying treatment is performed at a temperature of 60 to 80 ℃ for a time of 10 to 30 hours.
In some embodiments, in the step (3), the calcination treatment is performed at a temperature of 400 to 600 ℃ for a time of 2 to 4 hours.
Drawings
FIG. 1 is a flow chart of cesium nitrate loading of ceramic microspheres in example 1;
FIG. 2 shows gel microspheres (a) and ceramic microspheres (b) prepared in example 1;
FIG. 3 is an XRD spectrum of cesium nitrate-loaded ceramic microspheres prepared in example 1;
FIG. 4 is a diagram showing the morphology of ceramic microspheres obtained according to the present invention: (a) a surface topography; (b) surface topography energy spectrum analysis; (c) cross-sectional morphology; and (d) analyzing the profile energy spectrum of the section.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The method for loading cesium nitrate on the ceramic microspheres comprises the following steps:
(1) Sequentially performing trichloroethylene washing and ammonia water washing treatment on the gel microspheres to obtain wet gel microspheres;
(2) Placing the wet gel microspheres obtained in the step (1) in cesium nitrate solution for soaking and adsorbing;
(3) And (3) soaking the gel microsphere with cesium nitrate adsorbed in the step (2) in propylene glycol methyl ether, and then drying and calcining.
According to the method for loading cesium nitrate on the ceramic microspheres, disclosed by the embodiment of the invention, as trichloroethylene and silicone oil are mutually dissolved, residual silicone oil on the gel microspheres can be removed by washing with trichloroethylene; the nitroamino acid in the gel microsphere is easy to dissolve in water, can be decomposed and exploded at 400 ℃ and seriously damages the morphology of the microsphere, and ammonia water is adopted to remove the residual nitroamino acid in the gel microsphere, thereby being beneficial to obtaining the microsphere without cracking; the wet gel microspheres are adopted to soak and adsorb cesium nitrate, so that compared with the traditional dry microspheres, the adsorption capacity is large, and the purpose of loading cesium nitrate by the ceramic microspheres is successfully realized; after the wet gel microspheres are adopted to soak and adsorb cesium nitrate, in order to reduce the capillary force of the wet gel microspheres in the drying process, the gel microspheres are soaked in propylene glycol methyl ether and then dried, the gel microspheres do not need to be subjected to secondary drying, and the gel microspheres also retain rich pore channel structures, so that the ceramic particles without cracking are obtained; the propylene glycol methyl ether is adopted for soaking treatment, and because the propylene glycol methyl ether and water are mutually soluble and the volatilization speed is moderate, the water in the gel microsphere can be removed, and the surface tension of the propylene glycol methyl ether is small, the capillary force generated by the gel microsphere in the drying process can be effectively reduced, so that the pore channel structure of the gel microsphere is reserved as much as possible.
In some embodiments, preferably, in the step (1), the trichloroethylene is washed at a temperature of 60 to 80 ℃ for a time of 80 to 120min. Further preferably, in the step (1), the temperature of the aqueous ammonia washing is 60 to 80 ℃, and the concentration of the aqueous ammonia is 0.5M. More preferably, after the aqueous ammonia wash, the conductivity of the wash solution is reduced to 700. Mu.s/cm. In the embodiment of the invention, the parameter setting in the washing process is optimized, and silicone oil, ammonium nitrate and other impurities on the surface of the gel microsphere can be quickly and efficiently washed out.
In some embodiments, preferably, in step (1), the gel microspheres are yttrium stabilized zirconia gel microspheres.
In some embodiments, preferably, in the step (2), the cesium nitrate has a concentration of 0.1 to 0.2M; and/or, the cesium nitrate solution is an aqueous solution of cesium nitrate. Further preferably, in the step (2), the soaking adsorption temperature is 60-80 ℃ and the soaking adsorption time is 3-12 h. In the embodiment of the invention, the pore canal of the microsphere is closed due to too high volatilization rate or too high surface tension of the alcohol solution of cesium nitrate, and the ceramic microsphere is seriously cracked in the subsequent drying and calcining processes, so that the problems can be avoided when the adopted cesium nitrate solution is an aqueous solution of cesium nitrate, and the ceramic microsphere without cracking is obtained; the temperature and time of soaking adsorption are optimized, the requirement of adsorption capacity can be rapidly met, and the treatment efficiency is improved; in addition, cesium nitrate can also act as a detergent for the gel microspheres, further removing ammonium nitrate from the gel microspheres.
In some embodiments, preferably, in the step (3), the soaking treatment in the propylene glycol methyl ether is performed at a temperature of 60 to 80 ℃ for a time of 10 to 20 minutes. Further preferably, the gel microsphere soaked in propylene glycol methyl ether is directly sent into a far infrared drying oven for drying treatment. In the embodiment of the invention, propylene glycol methyl ether is adopted for soaking treatment, so that the gel microspheres do not need to be subjected to propylene glycol methyl ether washing operation, the experimental time is shortened, and the experimental efficiency is improved.
In some embodiments, preferably, in the step (3), the drying treatment is performed at a temperature of 60 to 80 ℃ for a time of 10 to 30 hours. Further preferably, in the step (3), the calcination treatment is performed at a temperature of 400 to 600 ℃ for a time of 2 to 4 hours. In the embodiment of the invention, the volatilization rate of the water in the gel microsphere is slower, and the water vapor dried at 60-80 ℃ can slowly escape from the pore canal of the gel microsphere, so that the cracking condition caused by the overlarge internal pressure of the microsphere is prevented, and the cracking rate of the ceramic microsphere is effectively reduced; cesium nitrate in the gel microspheres is basically completely volatilized at a temperature of 600 ℃ or higher, so that cesium nitrate is kept in the ceramic microspheres as much as possible in order to prevent volatilization of cesium nitrate, and the calcination temperature is controlled to be in the range of 400-600 ℃; in addition, calcination at this temperature can produce low thermal conductivity cubic phase YSZ ceramic microspheres.
The following describes the embodiments of the present invention in detail with reference to specific examples and drawings.
Example 1
The flow of cesium nitrate loading of the ceramic microspheres in this embodiment is shown in fig. 1:
(1) 1.15mL of concentrated nitric acid was added to 14.37mL of 1.6M ZrO (NO 3 ) 2 And 0.36M Y (NO 3 ) 3.6 H 2 Preparing Zr/Y solution in the precursor mixed solution of O; 10mL of a mixed solution of 3mol/L hexamethylenetetramine and 2.625mol/L urea was prepared and designated as HMUR solution;
(2) Cooling the HMUR solution and the Zr/Y solution for 0.5h at the temperature of 5 ℃, slowly adding the HMUR solution into the Zr/Y solution, and mixing to obtain a clear and transparent solution, namely the zirconium glue solution;
(3) Dispersing the zirconium glue solution in dimethyl silicone oil at 90 ℃, and rapidly decomposing ammonia under the condition of 90 ℃ due to the thermal instability of hexamethylenetetramine, so that the pH value in sol drops rapidly rises, and the sol drops are rapidly solidified into gel microspheres;
(4) Aging the gel microspheres in dimethyl silicone oil for 2 hours, firstly removing residual silicone oil of the gel microspheres by trichloroethylene, and washing for 4 times each time for 30 min; then removing ammonium nitrate in the gel microspheres by using 0.5M ammonia water until the conductivity of the waste liquid obtained after washing is less than 700 mu s/cm;
(5) Then weighing 4g of wet gel microspheres washed by ammonia water, soaking in 10mL of 2M cesium nitrate solution, and keeping the temperature of the cesium nitrate solution at 60 ℃ for 3 hours; and then fishing out the gel microspheres adsorbed with cesium nitrate, soaking the gel microspheres with propylene glycol methyl ether, then sending the gel microspheres into a far infrared drying oven at 80 ℃ for drying for 24 hours, placing the fully dried gel microspheres into a muffle furnace for heat treatment, and calcining the fully dried gel microspheres for 2 hours at 400 ℃ in an air atmosphere to finally obtain the YSZ ceramic microspheres with high cesium nitrate load and no cracking.
The gel microspheres and ceramic microspheres prepared in this example are shown in fig. 2 (a) and fig. 2 (b), respectively, and it can be seen from the figures that the gel microspheres and ceramic microspheres loaded with cesium nitrate have good sphericity and substantially no cracking.
XRD characterization is carried out on the cesium nitrate-loaded ceramic microspheres prepared in the embodiment, the obtained XRD spectrogram is shown in figure 3, and from the figure, the wet gel microspheres are obviously adsorbed on cesium nitrate after being soaked and adsorbed in cesium nitrate solution, the adsorbed gel microspheres have obvious crystallization peaks of cesium nitrate, and the gel microspheres after adsorbing cesium nitrate are calcined at 400 ℃ to obtain cubic-phase YSZ ceramic microspheres loaded with cesium nitrate, so that the successful loading of cesium nitrate on the ceramic microspheres is demonstrated.
The ceramic microspheres at 400 ℃ obtained by the invention are observed under a scanning electron microscope, the result is shown in fig. 4, fig. 4 (a) shows the surface morphology of the ceramic microspheres, the surface morphology is analyzed by energy spectrum, and the result is shown in fig. 4 (b), and the cesium nitrate loading amount on the surfaces of the ceramic microspheres is up to 87.26wt%; FIG. 4 (c) shows the cross-sectional morphology of the ceramic microspheres obtained at 400 ℃, and the energy spectrum analysis is carried out on the cross-sectional morphology, so that the loading amount of cesium nitrate on the cross-section of the ceramic microspheres is up to 14.34wt% as shown in FIG. 4 (d).
Cesium nitrate is diffused into the microspheres to cause the different contents of cesium nitrate on the surfaces of the ceramic microspheres and cesium nitrate in the microspheres, and the ceramic microspheres have high contents of cesium nitrate and low contents of cesium nitrate in the microspheres. The ceramic microspheres obtained at 400 ℃ are subjected to X-ray fluorescence spectrum analysis, and the result shows that the loading amount of cesium nitrate in the ceramic microspheres obtained at 400 ℃ is up to 17.82wt%, and the purpose of ceramic curing cesium nitrate is successfully achieved by the invention, so that the invention has important research value for observing the release behavior of fission products.
Example 2
The treatment method in this example is the same as that in example 1, except that in step (5), the gel microspheres are sufficiently dried in a far infrared box and then placed in a muffle furnace for heat treatment, and calcined at 600 ℃ for 2 hours in an air atmosphere, thereby finally obtaining the YSZ ceramic microspheres with high cesium nitrate load.
The cesium nitrate loading amount on the surface of the ceramic microspheres obtained in the embodiment is up to 60wt%, and the cesium nitrate loading amount on the section is up to 10.52wt%.
Comparative example 1
The treatment method in this comparative example was the same as in example 1 except that cesium nitrate was supported by ion implantation in the prior art in step (5), i.e., the ceramic microspheres were irradiated with an ion source of accelerated cesium atoms in a vacuum system.
In the comparative example, cesium elements are unevenly distributed on the surface of the ceramic microspheres and concentrated on the surface of the ceramic microspheres, and the cesium nitrate loading on the surface of the ceramic microspheres is less than 1.5wt% and is far less than that in the examples.
Comparative example 2
The treatment method in this comparative example was the same as in example 1 except that cesium nitrate was adsorbed by impregnation with the dried gel microspheres in step (5), and then dried in a far infrared drying oven at 80 ℃ for 24 hours, and the sufficiently dried gel microspheres were placed in a muffle furnace for heat treatment and calcined at 400 ℃ for 2 hours in an air atmosphere, to finally obtain cesium nitrate-loaded YSZ ceramic microspheres.
The loading amount of cesium nitrate on the surface of the YSZ ceramic microsphere obtained in the comparative example is 10wt percent, but the cracking rate of the ceramic microsphere reaches 100 percent.
Compared with example 1, the ceramic microspheres obtained by the treatment method adopted in the comparative example are basically completely cracked. This is because, in this comparative example, the dried gel microspheres were dried again after adsorbing cesium nitrate, the pores in the dried gel microspheres were mostly closed, the adsorption capacity for cesium nitrate was poor, and the gel microspheres received a relatively large capillary force during the secondary drying process, which resulted in the gel microspheres being liable to generate microcracks, and the microcracked gel microspheres easily cracked the ceramic microspheres produced during the subsequent sintering process, resulting in substantially complete cracking of the ceramic microspheres produced in comparative example 2.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (10)
1. The method for loading cesium nitrate on ceramic microspheres is characterized by comprising the following steps:
(1) Sequentially performing trichloroethylene washing and ammonia water washing treatment on the gel microspheres to obtain wet gel microspheres;
(2) Placing the wet gel microspheres obtained in the step (1) in cesium nitrate solution for soaking and adsorbing;
(3) And (3) soaking the gel microsphere adsorbed with cesium nitrate obtained in the step (2) in propylene glycol methyl ether, and then drying and calcining.
2. The method for loading cesium nitrate on ceramic microspheres according to claim 1, wherein in the step (1), the temperature of the trichloroethylene washing is 60-80 ℃ and the washing time is 80-120 min.
3. The method for supporting cesium nitrate on ceramic microspheres according to claim 1 or 2, wherein in the step (1), the temperature of the ammonia water washing is 60-80 ℃, and the concentration of the ammonia water is 0.5M.
4. The method for supporting cesium nitrate on ceramic microspheres according to claim 3, wherein the conductivity of the washing liquid is reduced to 700 μs/cm after the aqueous ammonia washing.
5. The method for supporting cesium nitrate on ceramic microspheres according to claim 1, wherein in the step (1), the gel microspheres are yttrium-stabilized zirconia gel microspheres.
6. The method for supporting cesium nitrate on ceramic microspheres according to claim 1, wherein in the step (2), the concentration of the cesium nitrate solution is 0.1-0.2M; and/or, the cesium nitrate solution is an aqueous solution of cesium nitrate.
7. The method for supporting cesium nitrate on ceramic microspheres according to claim 1 or 6, wherein in the step (2), the soaking adsorption temperature is 60-80 ℃ and the time is 3-12 h.
8. The method for supporting cesium nitrate on ceramic microspheres according to claim 1, wherein in the step (3), the soaking treatment in propylene glycol methyl ether is performed at a temperature of 60-80 ℃ for 10-20 min.
9. The method for supporting cesium nitrate on ceramic microspheres according to claim 1, wherein in the step (3), the drying treatment is performed at a temperature of 60 to 80 ℃ for a time of 10 to 30 hours.
10. The method for supporting cesium nitrate on ceramic microspheres according to claim 1 or 9, wherein in the step (3), the calcination treatment is performed at a temperature of 400 to 600 ℃ for a time of 2 to 4 hours.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6602919B1 (en) * | 1999-09-17 | 2003-08-05 | Ut-Battelle Llc | Method for preparing hydrous zirconium oxide gels and spherules |
| CN1558794A (en) * | 2001-09-25 | 2004-12-29 | PQ�عɹ�˾ | Method for making silica supported, crush-resistant catalysts |
| CN103212388A (en) * | 2013-04-23 | 2013-07-24 | 中国科学院青海盐湖研究所 | Gel ball type rubidium/caesium ion adsorbent, and preparation method and application thereof |
| CN103736472A (en) * | 2014-01-14 | 2014-04-23 | 中国科学院青海盐湖研究所 | Gel sphere-type cesium-ion adsorbing agent, preparation method and application thereof |
| CN104671797A (en) * | 2015-02-09 | 2015-06-03 | 清华大学 | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature |
| CN105013450A (en) * | 2015-08-04 | 2015-11-04 | 西南科技大学 | Double metal loaded sodium alginate/carboxymethylcellulose double-functional microballoon adsorbing material and preparation method thereof |
| CN105688853A (en) * | 2016-04-08 | 2016-06-22 | 中国人民解放军海军工程大学 | Selective adsorbent for caesium and preparation method of selective adsorbent |
| CN106040190A (en) * | 2016-06-21 | 2016-10-26 | 西南科技大学 | Preparation method of iron ion croscarmellose in-situ growing Prussian-blue microsphere adsorbing material |
| CN108840683A (en) * | 2018-07-05 | 2018-11-20 | 清华大学 | It is used to prepare the technique and zirconium nitride ceramic microsphere of zirconium nitride ceramic microsphere |
-
2023
- 2023-02-03 CN CN202310121444.XA patent/CN116283277A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6602919B1 (en) * | 1999-09-17 | 2003-08-05 | Ut-Battelle Llc | Method for preparing hydrous zirconium oxide gels and spherules |
| CN1558794A (en) * | 2001-09-25 | 2004-12-29 | PQ�عɹ�˾ | Method for making silica supported, crush-resistant catalysts |
| CN103212388A (en) * | 2013-04-23 | 2013-07-24 | 中国科学院青海盐湖研究所 | Gel ball type rubidium/caesium ion adsorbent, and preparation method and application thereof |
| CN103736472A (en) * | 2014-01-14 | 2014-04-23 | 中国科学院青海盐湖研究所 | Gel sphere-type cesium-ion adsorbing agent, preparation method and application thereof |
| CN104671797A (en) * | 2015-02-09 | 2015-06-03 | 清华大学 | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature |
| CN105013450A (en) * | 2015-08-04 | 2015-11-04 | 西南科技大学 | Double metal loaded sodium alginate/carboxymethylcellulose double-functional microballoon adsorbing material and preparation method thereof |
| CN105688853A (en) * | 2016-04-08 | 2016-06-22 | 中国人民解放军海军工程大学 | Selective adsorbent for caesium and preparation method of selective adsorbent |
| CN106040190A (en) * | 2016-06-21 | 2016-10-26 | 西南科技大学 | Preparation method of iron ion croscarmellose in-situ growing Prussian-blue microsphere adsorbing material |
| CN108840683A (en) * | 2018-07-05 | 2018-11-20 | 清华大学 | It is used to prepare the technique and zirconium nitride ceramic microsphere of zirconium nitride ceramic microsphere |
Non-Patent Citations (2)
| Title |
|---|
| TEL, H等: "Preparation of ZrO2 and ZrO2-TiO2 microspheres by the sol-gel method and an experimental design approach to their strontium adsorption behaviours", 《CHEMICAL ENGINEERING JOURNAL》, vol. 161, no. 1, pages 151 - 160, XP027075677, DOI: 10.1016/j.cej.2010.04.053 * |
| 聂磊等: "溶胶-凝胶法制备氮化硅陶瓷微球", 《陶瓷学报》, vol. 42, no. 5, pages 819 - 824 * |
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