CN113200681B - Preparation method of fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste - Google Patents
Preparation method of fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 47
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- 239000010436 fluorite Substances 0.000 title claims abstract description 41
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 22
- 239000011733 molybdenum Substances 0.000 title claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 18
- 239000002699 waste material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 239000011521 glass Substances 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
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Abstract
The invention discloses a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste, which comprises the following steps: taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3And MoO3Mixing uniformly to obtain a mixture; putting the mixture into an alumina crucible, putting the alumina crucible filled with the mixture into a high-temperature furnace, heating to 1400 ℃, preserving heat, and pouring the obtained melt into water to obtain primary glass; pulverizing the primary glass, and packagingAnd heating the new alumina crucible to 1450 ℃, preserving the heat, then immediately transferring the alumina crucible to another furnace which is heated to the crystallization temperature in advance, preserving the heat, finally directly taking out the alumina crucible, and cooling the alumina crucible in the air to obtain the fluorite-based glass ceramic substrate. The crystal phase of the glass ceramic substrate prepared by the invention is mainly fluorite phase, and the scanning electron microscope picture shows that the crystal is embedded in the glass substrate to form a compact glass ceramic substrate, so that the effective stable solidification of molybdenum can be realized.
Description
Technical Field
The invention relates to the technical field of high-level radioactive waste liquid treatment, in particular to a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high-level radioactive nuclear waste.
Background
With the rapid development of social science and technology, nuclear energy will gradually replace fossil energy, and the amount of flooding fuel discharged from nuclear reactors is gradually increased every year. However, the great advantages of nuclear energy are still not prevented from building and developing nuclear power projects. The disposal of radioactive waste is a crucial link in nuclear energy safety, and nuclear energy development can be developed to the best extent only if the radioactive waste is properly treated. Therefore, how to isolate radioactive waste from the biosphere where humans live has become a primary concern in the development of nuclear energy.
The high level effluent is raffinate produced by separating and recovering U, Pu from spent fuel in the post-treatment process. The high level radioactive waste liquid contains not only U and Pu but also minor actinide nuclides (Np, Am and Cm) and more than thirty isotopes of more than thirty elements including fission nuclides such as Sr, Cs and Mo. The high-level radioactive waste liquid not only has strong radioactive toxicity, but also has complex nuclide components, has the characteristic of multiple elements (fission and actinide nuclides with various valence states and ionic radii), and has large treatment and disposal difficulty. In the prior art, an economically feasible treatment method for high-level waste is to select a solidification substrate with high stability, to confine radioactive nuclides, and then to carry out deep geological treatment so as to isolate the radioactive nuclides from a biosphere to the maximum extent.
The glass ceramic is solidified by making the solidified body into good crystal phase/amorphous phase mutual inlaid multiphase material, and the mechanical stability of the solidified body is superior to that of the glass solidified body. The (glass ceramic) curing technology can effectively combine the advantages of ceramic and glass, the glass ceramic curing process is similar to the glass curing process, and the existing relatively mature glass curing process can be directly or improved to realize the glass ceramic curing. Therefore, the glass ceramic solidification is called as the 'next generation' radioactive waste solidification treatment technology, and is an important development direction for the treatment and disposal of the radioactive waste.
Mo is contained in the high radioactive waste liquid, the treatment of the Mo is relatively difficult, and no technical scheme for solidifying the molybdenum by adopting the glass ceramic is found in the prior art, particularly no technical scheme for solidifying the molybdenum-containing high radioactive nuclear waste by adopting a fluorite-based glass ceramic substrate is found.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a solidified molybdenum-containing high radioactive nuclear waste fluorite-based glass ceramic substrate, comprising the steps of:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Uniformly mixing the simulated radioactive waste with the simulated radioactive waste to obtain a mixture; the simulated radioactive waste is MoO3 ；
Step two, filling the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 1350-1400 ℃, preserving heat for 2-4 hours, and pouring the obtained melt into water to obtain primary glass;
and step three, crushing the primary glass, putting the crushed glass into a new alumina crucible, heating to 1450-1500 ℃, preserving heat for 2-4 hours, immediately transferring the alumina crucible into another furnace which is heated to 740-780 ℃ in advance, preserving heat for 1.5-2.5 hours, directly taking out the alumina crucible, and cooling in the air to obtain the fluorite-based glass ceramic substrate.
Preferably, in the step one, the dosage ratio of each raw material is as follows: SiO 22 28~31wt%、Al2O3 8~9.5wt%、CaO 15~16.5wt%、TiO2 12.5~14wt%、ZrO2 8.5~9.5wt%、CeO2 4.5~5.5wt%、Na2O 5~6wt%、B2O39-10 wt% and MoO3 0~6wt%。
Preferably, in the second step, the temperature raising process is: heating to 550-650 ℃ at the speed of 10 ℃/min, preserving heat for 10min, heating to 800-1000 ℃ at the speed of 5 ℃/min, preserving heat for 30min, heating to 1350-1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2-4 h.
Preferably, in the third step, the temperature raising process is as follows: heating to 800-1000 ℃ at the speed of 10 ℃/min, preserving heat for 30min, then heating to 1450-1500 ℃ at the speed of 1 ℃/min, and preserving heat for 2-4 h.
Preferably, in the third step, the obtained fluorite-based glass ceramic substrate is subjected to laser shock treatment, and the process comprises the following steps: an absorption layer is stuck on the surface of the fluorite-based glass ceramic substrate, and then impact treatment is performed by using a high-energy pulse laser.
Preferably, the laser energy of the high-energy pulse laser is 5-10J, the laser wavelength is 1064nm, the pulse width is 20-30 ns, the diameter of a circular light spot is 3-5 mm, and a flowing water film with the thickness of 2mm is used as a constraint layer during laser shock treatment; the absorption layer is a black polytetrafluoroethylene adhesive tape.
The invention at least comprises the following beneficial effects: the crystal phase of the glass ceramic substrate prepared by the invention is mainly fluorite phase which is fluorite-based glass ceramic substrate; as can be seen from the scanning electron microscope images, the crystals are embedded in the glass substrate, forming a dense glass-ceramic substrate that can achieve an effective stable solidification of molybdenum.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a comparison of the results of thermal analysis DSC of the primary glasses of examples 1 to 4 and example 7.
FIG. 2 is a graph showing the comparison results of Raman spectra of the primary glasses of examples 1 to 4 and example 7.
FIG. 3 is a graph showing the comparison result of XRD patterns of the primary glasses of examples 1 to 4 and 7 after being crystallized at the corresponding crystallization temperatures for 2 hours.
FIG. 4 is a comparison result of XRD patterns of the primary glasses of examples 1 to 4 and example 7 after the primary glasses are crystallized at a corresponding crystallization temperature for a prolonged crystallization time.
FIG. 5 is a back-scattered SEM photograph of the preliminary glass of example 7 after being crystallized at the corresponding crystallization temperature for 2 hours.
FIG. 6 is a back-scattered SEM photograph of the preliminary glass of example 1 after being crystallized at a corresponding crystallization temperature for 2 hours.
FIG. 7 is a back-scattered SEM photograph of the preliminary glass of example 2 after being crystallized at the corresponding crystallization temperature for 2 hours.
FIG. 8 is a back-scattered SEM photograph of the preliminary glass of example 3 after being crystallized at the corresponding crystallization temperature for 2 hours.
FIG. 9 is a back-scattered SEM photograph of the preliminary glass of example 4 after being crystallized at the corresponding crystallization temperature for 2 hours.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Examples 1 to 2:
a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear wastes comprises the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Uniformly mixing the simulated radioactive waste with the simulated radioactive waste to obtain a mixture; the simulated radioactive waste is MoO3 (ii) a The amount ratio of each raw material is shown in table 1;
step two, placing the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 550 ℃ at the speed of 10 ℃/min, preserving heat for 10min, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 3 h; pouring the obtained melt into water to obtain primary glass;
and step three, crushing the primary glass, putting the crushed primary glass into a new alumina crucible, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30min, heating to 1450 ℃ at the speed of 1 ℃/min, preserving heat for 3h, immediately transferring the alumina crucible into another furnace which is heated to 760 ℃ in advance, preserving heat for 2h, directly taking out the alumina crucible, and cooling in the air to obtain the fluorite-based glass ceramic substrate.
Example 3:
a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste comprises the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Uniformly mixing the simulated radioactive waste with the simulated radioactive waste to obtain a mixture; the simulated radioactive waste is MoO3 (ii) a The amount ratio of each raw material is shown in table 1;
step two, placing the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 550 ℃ at the speed of 10 ℃/min, preserving heat for 10min, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 3 h; pouring the obtained melt into water to obtain primary glass;
and step three, crushing the primary glass, putting the crushed primary glass into a new alumina crucible, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30min, heating to 1450 ℃ at the speed of 1 ℃/min, preserving heat for 3h, immediately transferring the alumina crucible into another furnace which is heated to 750 ℃ in advance, preserving heat for 2h, directly taking out the alumina crucible, and cooling in the air to obtain the fluorite-based glass ceramic substrate.
Example 4:
a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste comprises the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Uniformly mixing the simulated radioactive waste with the simulated radioactive waste to obtain a mixture; the simulated radioactive waste is MoO3 (ii) a The amount ratio of each raw material is shown in table 1, for example;
step two, placing the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 550 ℃ at the speed of 10 ℃/min, preserving heat for 10min, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 3 h; pouring the obtained melt into water to obtain primary glass;
and step three, crushing the primary glass, putting the crushed primary glass into a new alumina crucible, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30min, heating to 1450 ℃ at the speed of 1 ℃/min, preserving heat for 3h, immediately transferring the alumina crucible into another furnace which is heated to 745 ℃ in advance, preserving heat for 2h, directly taking out the alumina crucible, and cooling in the air to obtain the fluorite-based glass ceramic substrate.
Example 5:
a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste comprises the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3And simulatingUniformly mixing the radioactive wastes to obtain a mixture; the simulated radioactive waste is MoO3 (ii) a The amount ratio of each raw material is shown in table 1;
step two, placing the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 550 ℃ at the speed of 10 ℃/min, preserving heat for 10min, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 3 h; pouring the obtained melt into water to obtain primary glass;
step three, crushing the primary glass, putting the crushed primary glass into a new alumina crucible, heating the crushed primary glass to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the crushed primary glass to 1450 ℃ at the speed of 1 ℃/min, preserving the heat for 3h, immediately transferring the alumina crucible into another furnace which is heated to 760 ℃ in advance, preserving the heat for 2h, and finally directly taking out the alumina crucible, and cooling the alumina crucible in the air to obtain the fluorite-based glass ceramic substrate; the obtained fluorite-based glass ceramic substrate is subjected to laser shock treatment, and the process comprises the following steps: adhering an absorption layer on the surface of the fluorite-based glass ceramic substrate, and then carrying out impact treatment by using a high-energy pulse laser; the laser energy of the high-energy pulse laser is 7J, the laser wavelength is 1064nm, the pulse width is 30ns, the diameter of a circular light spot is 4mm, and a flowing water film with the thickness of 2mm is used as a constraint layer during laser shock treatment; the absorption layer is a black polytetrafluoroethylene adhesive tape.
Example 6:
a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste comprises the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Uniformly mixing the simulated radioactive waste with the simulated radioactive waste to obtain a mixture; the simulated radioactive waste is MoO3 (ii) a The amount ratio of each raw material is shown in table 1;
step two, placing the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 550 ℃ at the speed of 10 ℃/min, preserving heat for 10min, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 3 h; pouring the obtained melt into water to obtain primary glass;
step three, crushing the primary glass, putting the crushed primary glass into a new alumina crucible, heating the crushed primary glass to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the crushed primary glass to 1450 ℃ at the speed of 1 ℃/min, preserving the heat for 3h, immediately transferring the alumina crucible into another furnace which is heated to 750 ℃ in advance, preserving the heat for 2h, and finally directly taking out the alumina crucible, and cooling the alumina crucible in the air to obtain the fluorite-based glass ceramic substrate; the obtained fluorite-based glass ceramic substrate is subjected to laser shock treatment, and the process comprises the following steps: adhering an absorption layer on the surface of the fluorite-based glass ceramic substrate, and then carrying out impact treatment by using a high-energy pulse laser; the laser energy of the high-energy pulse laser is 7J, the laser wavelength is 1064nm, the pulse width is 30ns, the diameter of a circular light spot is 4mm, and a flowing water film with the thickness of 2mm is used as a constraint layer during laser shock treatment; the absorption layer is a black polytetrafluoroethylene adhesive tape.
Example 7:
a preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste comprises the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Obtaining a mixture; the amount ratio of each raw material is shown in table 1;
step two, placing the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 550 ℃ at the speed of 10 ℃/min, preserving heat for 10min, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 3 h; pouring the obtained melt into water to obtain primary glass;
and step three, crushing the primary glass, putting the crushed primary glass into a new alumina crucible, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30min, heating to 1450 ℃ at the speed of 1 ℃/min, preserving heat for 3h, immediately transferring the alumina crucible into another furnace which is heated to 765 ℃ in advance, preserving heat for 2h, directly taking out the alumina crucible, and cooling in the air to obtain the fluorite-based glass ceramic substrate.
TABLE 1
FIG. 1 is a comparison of the results of thermal analysis DSC of the primary glasses of examples 1 to 4 and example 7. As can be seen from the figure, all of the preliminary glass samples exhibited two crystallization peaks, and the crystallization temperature was dependent on MoO3 The content increases and decreases. Table 2 shows the glass transition temperatures (T) of the preliminary glasses obtained by thermal analysis of the DSC curvesg) And crystallization temperature (T)c). As can be seen from Table 2, the glass transition temperature T of the mother glassgWith MoO3The content is increased and reduced continuously, i.e. without MoO3674 ℃ reduction to 6wt.% MoO3649 ℃ in time. For the first crystallization peak, it corresponds to the crystallization of cubic-zirconia; while the second crystallization peak corresponds to the crystallization of zirconolite. Crystallization temperature for cubic-zirconia, which follows MoO3Decreased by increasing the content, i.e. by not containing MoO3766 ℃ to contain 6wt.% MoO3746 deg.c. For the crystallization temperature of zirconolite, it also follows MoO3Decreased by increasing the content, i.e. by not containing MoO3At 942 ℃ to contain 6wt.% MoO3895 ℃ when required.
TABLE 2
| Glass transition temperature (T)g，℃) | Crystallization temperature (T)c，℃） | Crystallization temperature (T)c，℃） | |
| Example 1 | 669 | 762 | 914 |
| Example 2 | 665 | 761 | 911 |
| Example 3 | 655 | 651 | 906 |
| Example 4 | 649 | 746 | 895 |
| Comparative example 1 | 674 | 766 | 942 |
FIG. 2 is a graph showing the comparison results of Raman spectra of the primary glasses of examples 1 to 4 and example 7. As can be seen, all the primary glasses are only 500 to 1000cm-1Raman vibrational spectral excitation occurs in the range. Wave numbers of 326 and 395cm-1Corresponds to the stretching of Si-O-Si. Wave number of 820 cm-1Corresponds to the peak of SiO4Stretching effect and MoO4Asymmetric stretching effect of (2), and a wave number of 930 cm-1Corresponds to MoO4The symmetric telescoping effect of (a).
FIG. 3 is a graph showing the comparison results of XRD patterns of examples 1 to 4 and example 7 after crystallization for 2 hours at the corresponding crystallization temperatures. As can be seen from the graph, the primary crystal phases of the glasses of example 7, example 1 and example 2 were cubic-zirconia after 2 hours of primary crystallization. For the samples of example 3 and example 4, each had a composition of three crystalline phases, cubic-zirconia, zirconia and CaMoO, respectively4. XRD of the obtained sample after prolonging the crystallization time is shown in FIG. 4. The crystallization time was extended to 4 hours and the crystalline phase of example 7, example 1 and example 2 remained cubic-zirconia. For the samples of examples 3 and 4, the crystalline phases cubic-zirconia and CaMoO were obtained after the crystallization time was extended to 8 hours4. The above results illustrate that MoO3The upper limit of solid solubility in this glass system is 2 wt.%. When MoO3When the content of (A) is more than this value, CaMoO will be present after crystallization4This is a crystal which is easily soluble in water and easily releases Mo atoms into the environment.
FIGS. 5 to 9 are back-scattered SEM images of examples 1 to 4 and 7 after crystallization at the corresponding crystallization temperatures for 2 hours. As can be seen, the grown crystals are distributed relatively uniformly throughout the matrix, indicating that the glass is highly uniform during the melting process. The grown crystal grows in a form of dendrite basically. After 2 hours of crystallization, the size of the crystal is between 1 and 3 microns. And no significant micropores were seen throughout the substrate.
Leaching experiment tests were performed on the fluorite-based glass ceramic substrates prepared in examples 1 to 6:
(1) the leaching test of the fluorite-based glass ceramic substrate is tested according to an international comparative approved ASTM-C1285-97 (MCC-1 block leaching method) leaching method, and the anti-leaching performance of the fluorite-based glass ceramic substrate is researched, wherein the steps are as follows:
1. cleaning the fluorite-based glass ceramic substrate by using ultrasound, deionized water and ethanol in sequence, and finally drying in a 75 ℃ oven for 2.5 h;
2. according to the mass ratio of the fluorite-based glass ceramic substrate to the liquid of 1:10, tying a sample by using a nylon rope, suspending the sample in a polytetrafluoroethylene bottle filled with deionized water, placing the polytetrafluoroethylene in a stainless steel reaction kettle, reacting for a certain number of days at the temperature of 90 +/-1 ℃, and taking out the liquid every certain number of days;
3. after the leaching solution is cooled, taking a proper amount of liquid to test the concentration of molybdenum ions in the liquid by using an inductively coupled plasma mass spectrometer;
4. the specific surface area of the sample was calculated.
(2) Calculating the leaching rate
Standard leaching rateLR i （g·m-2·d-1) Calculated using the formula given below:
in the formula (I), the compound is shown in the specification,C i is the mass concentration (g.L) of the elements in the leaching solution-1）；VIs the leachate volume (L);f i is the mass fraction of the elements in the solid solution;Sis the geometric surface area (m) of the sample surface2·g-1)；TIs the duration of the experiment (d).
(3) The leaching element concentrations of molybdenum in the fluorite-based glass-ceramic substrate samples are shown in table 3:
TABLE 3
| Examples | Leaching rate (g.m) of molybdenum in 7 days-2·d-1) |
| Example 1 | 6.3×10-4 |
| Example 2 | 6.5×10-4 |
| Example 3 | 6.1×10-4 |
| Example 4 | 6.8×10-4 |
| Example 5 | 1.5×10-5 |
| Example 6 | 1.4×10-5 |
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (3)
1. A preparation method of a fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear wastes is characterized by comprising the following steps:
step one, taking raw material SiO2、Al2O3、CaO、TiO2、ZrO2、CeO2、Na2O、B2O3Uniformly mixing the simulated radioactive waste with the simulated radioactive waste to obtain a mixture; the analog amplifierThe radioactive waste is MoO3 ；
Step two, filling the mixture into an alumina crucible, placing the alumina crucible filled with the mixture into a high-temperature furnace, heating to 1350-1400 ℃, preserving heat for 2-4 hours, and pouring the obtained melt into water to obtain primary glass;
step three, crushing the preliminary glass, putting the crushed preliminary glass into a new alumina crucible, heating the crushed preliminary glass to 1450-1500 ℃, preserving the heat for 2-4 hours, immediately transferring the alumina crucible into another furnace which is heated to 740-780 ℃ in advance, preserving the heat for 1.5-2.5 hours, directly taking out the alumina crucible, and cooling the alumina crucible in the air to obtain a fluorite-based glass ceramic substrate;
in the first step, the dosage proportion of each raw material is as follows: SiO 22 28~31wt%、Al2O3 8~9.5wt%、CaO 15~16.5wt%、TiO2 12.5~14wt%、ZrO2 8.5~9.5wt%、CeO2 4.5~5.5wt%、Na2O 5~6wt%、B2O39-10 wt% and MoO3 0~6wt%；
In the third step, the obtained fluorite-based glass ceramic substrate is subjected to laser shock treatment, and the process comprises the following steps: adhering an absorption layer on the surface of the fluorite-based glass ceramic substrate, and then carrying out impact treatment by using a high-energy pulse laser;
the laser energy of the high-energy pulse laser is 5-10J, the laser wavelength is 1064nm, the pulse width is 20-30 ns, the diameter of a circular light spot is 3-5 mm, and a flowing water film with the thickness of 2mm is used as a constraint layer during laser shock treatment; the absorption layer is a black polytetrafluoroethylene adhesive tape.
2. The method of preparing a solidified molybdenum-containing high radioactive nuclear waste fluorite-based glass ceramic substrate according to claim 1, wherein in the second step, the temperature is raised by: heating to 550-650 ℃ at the speed of 10 ℃/min, preserving heat for 10min, heating to 800-1000 ℃ at the speed of 5 ℃/min, preserving heat for 30min, heating to 1350-1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2-4 h.
3. The method for preparing a solidified molybdenum-containing high radioactive nuclear waste fluorite-based glass ceramic substrate according to claim 1, wherein in said third step, the temperature is raised by: heating to 800-1000 ℃ at a speed of 10 ℃/min, preserving heat for 30min, heating to 1450-1500 ℃ at a speed of 1 ℃/min, and preserving heat for 2-4 h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097401A (en) * | 1975-07-30 | 1978-06-27 | Gesellschaft Fur Kernforschung M.B.H. | Thermodynamically stable product for permanent storage and disposal of highly radioactive liquid wastes |
| GB2037059A (en) * | 1978-11-09 | 1980-07-02 | Litovitz T | Immobilisation of radwastes in glass containers and products formed thereby |
| US5340372A (en) * | 1991-08-07 | 1994-08-23 | Pedro Buarque de Macedo | Process for vitrifying asbestos containing waste, infectious waste, toxic materials and radioactive waste |
| CN101734857A (en) * | 2009-12-30 | 2010-06-16 | 陕西乾盛环保建材工程有限公司 | Method for manufacturing black microcrystalline glass plates from molybdenum tailings |
| CN110092588A (en) * | 2019-05-13 | 2019-08-06 | 中国建筑材料科学研究总院有限公司 | A kind of borosilicate glass ceramic solidification substrate and its preparation method and application |
| CN110335693A (en) * | 2019-05-27 | 2019-10-15 | 西南科技大学 | A kind of preparation method for radioactive waste glass solidification basic material and glass solidified body |
| CN110590161A (en) * | 2019-10-10 | 2019-12-20 | 西南科技大学 | Adding V2O5Method for improving solubility of molybdenum oxide in glass ceramic solidified body |
| CN110970146A (en) * | 2019-11-27 | 2020-04-07 | 中国建筑材料科学研究总院有限公司 | Borosilicate glass ceramic curing substrate and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1233839A (en) * | 1984-04-11 | 1988-03-08 | Lynn A. Boatner | Lead-iron phosphate glass as a containment medium for the disposal of high-level nuclear wastes |
| KR101390039B1 (en) * | 2006-05-18 | 2014-05-27 | 상뜨르 나쇼날 드 라 러쉐르쉬 샹띠피끄 | Process for preparing ceramics, ceramics thus obtained and uses thereof, especially as a sputtering target |
| CN101412576A (en) * | 2007-10-16 | 2009-04-22 | 秦皇岛玻璃工业研究设计院 | Technological process of thin type nucleated glass wall surface decorative plate |
| CN105060717B (en) * | 2015-08-10 | 2018-06-26 | 武汉理工大学 | It is a kind of using molybdic tailing as building decorative glass ceramics of main material and preparation method thereof |
| EP3409648B1 (en) * | 2017-06-01 | 2021-01-06 | Ivoclar Vivadent AG | Lithium silicate glass ceramic with scheelite or powellite crystal phase |
-
2021
- 2021-05-21 CN CN202110557857.3A patent/CN113200681B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097401A (en) * | 1975-07-30 | 1978-06-27 | Gesellschaft Fur Kernforschung M.B.H. | Thermodynamically stable product for permanent storage and disposal of highly radioactive liquid wastes |
| GB2037059A (en) * | 1978-11-09 | 1980-07-02 | Litovitz T | Immobilisation of radwastes in glass containers and products formed thereby |
| US5340372A (en) * | 1991-08-07 | 1994-08-23 | Pedro Buarque de Macedo | Process for vitrifying asbestos containing waste, infectious waste, toxic materials and radioactive waste |
| CN101734857A (en) * | 2009-12-30 | 2010-06-16 | 陕西乾盛环保建材工程有限公司 | Method for manufacturing black microcrystalline glass plates from molybdenum tailings |
| CN110092588A (en) * | 2019-05-13 | 2019-08-06 | 中国建筑材料科学研究总院有限公司 | A kind of borosilicate glass ceramic solidification substrate and its preparation method and application |
| CN110335693A (en) * | 2019-05-27 | 2019-10-15 | 西南科技大学 | A kind of preparation method for radioactive waste glass solidification basic material and glass solidified body |
| CN110590161A (en) * | 2019-10-10 | 2019-12-20 | 西南科技大学 | Adding V2O5Method for improving solubility of molybdenum oxide in glass ceramic solidified body |
| CN110970146A (en) * | 2019-11-27 | 2020-04-07 | 中国建筑材料科学研究总院有限公司 | Borosilicate glass ceramic curing substrate and preparation method and application thereof |
Non-Patent Citations (7)
| Title |
|---|
| Effect of Na2O and CaO on the solubility and crystallization of Mo in borosilicate glasses;Zhou Junjie等;《Journal of Non-Crystalline Solids》;20210401;第557卷;全文 * |
| 制备工艺对铀烧绿石基玻璃陶瓷固化体结构及性能的影响;冯志强等;《原子能科学技术》;20190831;第53卷(第8期);全文 * |
| 含Pu废物的玻璃和玻璃陶瓷固化基材研究进展;袁晓宁等;《原子能科学技术》;20150220(第02期);全文 * |
| 含钼硼硅酸盐玻璃陶瓷固化体成分、结构及化学稳定性研究;连启会;《中国优秀博硕士学位论文全文数据库（硕士）-工程科技I辑》;20200815;5.1-5.2部分，表5-1中N0 * |
| 复合晶核剂(MoO_3+CaF_2)对铝硅酸盐玻璃析晶行为的影响作用研究;滕立东;《硅酸盐通报》;19970630(第03期);全文 * |
| 日本高放废液玻璃固化技术;卢嘉炜等;《辐射防护》;20200120(第01期);全文 * |
| 玻璃固化过程中Mo的化学行为研究进展;王长福等;《核化学与放射化学》;20191231;第41卷(第6期);全文 * |
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