CN114292088A - Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof - Google Patents
Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof Download PDFInfo
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Abstract
A tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and a preparation method thereof comprise the preparation and characterization of lithium lead-acid eutectic ceramic powder, the preparation of the lead-acid lithium eutectic ceramic spherulite with the diameter of about 1mm and the performance detection. Preparing gel with different element ratios by a sol-gel method, drying, sintering in air to obtain lead-acid lithium eutectic ceramic powder, preparing the lead-acid lithium eutectic ceramic powder and a polyvinyl alcohol aqueous solution into slurry, dripping liquid nitrogen into the slurry for quick freezing, and drying by utilizing an acetone evaporation principle. The invention enables the neutron multiplication reaction of lead element and the tritium breeding reaction of lithium element to be carried out in one material, and can simplify the design of the cladding while improving the tritium breeding rate; the similarity of Pb and Si (or Ti) in chemical bonding is utilized to form a eutectic structure, so that the eutectic structure has good mechanical-physical properties; the freeze drying process is improved, a special low-temperature vacuum dryer is not needed in the drying process, and the drying efficiency is greatly improved.
Description
Technical Field
The invention relates to a tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and a preparation method thereof, and belongs to the field of advanced nuclear reactor fuel research.
Background
The realization of controlled deuterium-tritium fusion is of great significance to meet the main energy requirements of human society in a long period of time. Because tritium as fusion fuel almost does not exist in nature, tritium (namely tritium breeding reaction) is obtained by nuclear reaction of high-energy neutrons generated by fusion and isotopes of lithium in a fusion reactor cladding, so that tritium breeding and recycling are realized. The design and construction of the international thermonuclear fusion experimental reactor (ITER) and the Chinese fusion engineering experimental reactor (CFETR) can verify and solve the specific engineering problem of controlled deuterium-tritium fusion, wherein tritium self-sustaining is one of the core engineering problems. ITER and CFETR are mainly designed by adopting a solid multiplication cladding, the main alternative neutron multiplier is beryllium or beryllium titanium pellets, and the tritium multiplier is lithium orthosilicate (Li)4SiO4) Or lithium metatitanate (Li)2TiO3) Ceramic pellets.
Because 1mol of neutrons are consumed to generate at most 1mol of tritium in the tritium breeding reaction, the tritium consumed in the deuterium-tritium fusion reaction cannot be compensated, namely tritium self-sustaining cannot be realized. Therefore, in the cladding structure of the fusion reactor, a neutron multiplication material, usually beryllium or lead, is further arranged, and the high-energy neutrons react with beryllium or lead nuclei to generate more neutrons (i.e. neutron multiplication reaction) so as to improve the tritium breeding rate and further realize tritium self-sustaining. In existing fusion reactor cladding designs, tritium breeder materials are typically placed in alternating zones with neutron multiplier materials to maximize the reaction of neutrons with lithium nuclei. This makes the fusion reactor blanket structure complex, which not only increases the construction, operation and maintenance costs, but also is not conducive to further improvement of the tritium breeding reaction. In addition, since beryllium has a great threat to human health and environmental safety, reducing the use of beryllium is also a major development requirement of advanced nuclear fuels.
The tritium-proliferated ceramic pellets are usually formed by adopting a freeze-drying process, and the obtained pellets have the advantages of narrow particle size distribution, good sphericity and good mechanical properties. The existing process flow is that slurry containing ceramic powder is dropped into liquid nitrogen to be frozen and formed, and then a low-temperature vacuum dryer is used for drying frozen pellets through the sublimation process of water molecules, wherein the drying time is usually more than 24 hours.
Disclosure of Invention
The eutectic ceramic simultaneously contains Pb with neutron multiplication function and Li with tritium multiplication function, so that the neutron multiplication reaction and the tritium multiplication reaction are carried out in one material
The technical problem solved by the invention is as follows: overcomes the defects of the prior art and provides a tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and a preparation method thereof. The fusion reactor cladding neutron-tritium composite breeder lead-acid lithium eutectic ceramic spherulite and the preparation method integrate the functions of a tritium breeder material and a neutron multiplier material in the existing cladding design, and enable the tritium breeder reaction and the neutron multiplier reaction to be realized in one material. The cladding structure is simplified, the problem that when lithium orthosilicate spherulites are used as breeding materials, multiple layers of beryllium or lead neutron multiplication materials need to be arranged in the cladding is solved, the tritium breeding efficiency is improved, and the problem of fusion reactor tritium self-sustaining can be effectively solved. In addition, the similarity of Pb and Si (or Ti) in chemical bonding is utilized to form a eutectic structure, and Li is kept4PbO4、Li4TiO4Original excellent mechanical-physical properties.
The technical scheme adopted by the invention is as follows:
a tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and a preparation method thereof, wherein the chemical formula of the lead-acid lithium eutectic ceramic is Li4PbxMO4M ═ Si or Ti, x ═ 0.1 &0.5, the lead-acid lithium eutectic ceramic structurally comprises Li4PbO4And Li4MO4A eutectic phase; the average diameter of the lithium plumbate eutectic ceramic spherulites is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 20-50N.
A tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and a preparation method thereof comprise the following steps:
(1) preparation of lead-acid lithium eutectic ceramic material
According to x (Li)4PbO4)-(1-x)(Li4MO4) Adding a lithium source and a lead source into deionized water according to the proportion of Li, Pb and Si or Ti elements, wherein M is Si or Ti, and x is 0.1-0.5; stirring and dissolving for 20-30 min, adding an alcohol solution dissolved with a silicon source or a titanium source, adjusting the pH value to 5.5-6.0, and continuously stirring for 20-30 min to prepare sol; heating the sol 333-353K in a water bath for 20-40 min to obtain gel, and drying the gel in a vacuum drying oven for 6-8h at 333-353K to obtain dry gel; heating the xerogel to 873-1073K in the air atmosphere, and sintering for 6-8h to obtain a lead-acid lithium eutectic ceramic material;
(2) preparation of frozen lithium plumbate eutectic ceramic spherulite by freezing method
Preparing the lead-acid lithium eutectic ceramic material into slurry; enabling the slurry to form liquid drops, enabling the liquid drops to enter liquid nitrogen, and enabling the liquid drops to contract and freeze into spherulites to obtain the frozen lead-acid lithium eutectic ceramic spherulites;
(3) drying of eutectic ceramic spherulites of frozen lithium plumbate
Soaking the frozen lithium plumbate eutectic ceramic spherulites in liquid nitrogen, taking out the spherulites, soaking the spherulites into an organic solvent at room temperature, and performing vacuum drying to obtain a lead-acid lithium eutectic ceramic spherulites blank;
(4) sintering of lithium plumbate eutectic ceramic spherulite blank
Heating the lead-acid lithium eutectic ceramic ball blank to 873-1073K in the air atmosphere, and sintering for 6-8h to obtain the lithium lead eutectic ceramic ball.
Further, the lithium source is lithium acetate. The lead source is lead acetate. The silicon source is tetraethyl silicate. The titanium source is tetrabutyl titanate
Further, in the step (1), the weight loss of the sintered xerogel is 40-60 wt%, and the temperature rise rate during sintering is 5-6 ℃/min.
Further, the method further comprises the step of carrying out sample analysis on the eutectic lead-acid lithium ceramic material obtained in the step (1), wherein the sample analysis comprises the following steps: grinding the sintered lead-acid lithium eutectic ceramic, adding a mixed solution of hydrochloric acid and hydrofluoric acid (the volume ratio is 1:1), and heating to 353K to fully dissolve the lead-acid lithium eutectic ceramic to obtain a sample solution. The sample solution was used to determine the atomic molar ratio of Li, Pb, and Si or Ti.
Further, the sample analysis further comprises: the composition of the lithium plumbate eutectic ceramic is scanned by an X-ray diffractometer.
Further, the step (2) specifically comprises the steps of grinding the lead-acid lithium eutectic ceramic material to obtain uniform powder, and fully mixing the powder with 1 wt% of polyvinyl alcohol aqueous solution according to the mass ratio of the powder to the solution of 1:1 to obtain slurry; the slurry flows out of the nozzle as droplets into 77K liquid nitrogen, which, under surface tension and low temperature, shrink and freeze into pellets.
Further, the step (3) specifically comprises the steps of soaking the frozen lithium plumbate eutectic ceramic spherulites prepared in the step (2) in liquid nitrogen, standing for 1-2 hours, taking out the spherulites, soaking the spherulites into acetone at room temperature, and drying for 0.5-1 hour in a vacuum drying oven at 323-333K until the acetone is completely evaporated to obtain a lead-acid lithium eutectic ceramic spherulites blank.
Further, when the lithium plumbate eutectic ceramic pellet is prepared by adopting a freezing method in the step (2), the adopted system comprises: the device comprises a slurry tank (1), a PVC pipeline (2), a peristaltic pump (3), a vibrator (4), a dropping nozzle (5), a heat insulation tank (6), a metal net bag, liquid nitrogen (8) and a liquid nitrogen storage and circulation device (9); the slurry tank (1) is sequentially connected with a peristaltic pump (3) and a vibrator (4) through a PVC pipeline (2); the vibrator (4) is provided with a drip nozzle (5); the heat insulation tank (6) is arranged below the dropping nozzle (5) of the vibrator; liquid nitrogen (8) is stored in the heat insulation tank (6); the upper end of the metal net bag is fixed at the opening of the heat insulation tank (6), and the lower end is immersed in liquid nitrogen (8); the upper end opening of the metal net bag faces the drip nozzle (5); the upper part of the heat insulation tank (6) is provided with a pipeline, and the lower part of the heat insulation tank (6) is provided with a pipeline; the upper side of the liquid nitrogen storage and circulation device (9) is connected with a pipeline at the upper part of the heat insulation tank (6) through a pipeline; the lower side of the liquid nitrogen storage and circulation device (9) is connected with a pipeline at the lower part of the heat insulation tank (6) through a pipeline.
Further, slurry obtained by mixing lithium plumbate eutectic ceramic powder and a polyvinyl alcohol aqueous solution is stored in the slurry tank (1), one end of the PVC pipeline (2) is immersed into the slurry in the slurry tank (1), the peristaltic pump (3) is started, the slurry enters the PVC pipeline (2), the speed of extracting the slurry is adjusted, and the slurry is dropwise dropped into liquid nitrogen (8) in the heat insulation tank (6) through the dropping nozzle (5) under the action of the vibrator (4); the liquid nitrogen storage and circulation device (9) is used for monitoring the liquid level height of liquid nitrogen in the heat insulation tank (6), supplementing the liquid nitrogen through a pipeline at the upper part of the heat insulation tank (6) when the evaporation liquid level of the liquid nitrogen descends, and extracting and storing the liquid nitrogen from the pipeline at the lower part of the heat insulation tank (6) after production is finished; the extraction of the frozen pellets was performed by directly pulling up the metal string bag.
Further, in the step (2), when the frozen lithium plumbate eutectic ceramic spherulites are prepared by a freezing method, the size of the lithium plumbate eutectic ceramic spherulites is in direct proportion to the diameter of the liquid drops. Preferably, the liquid drops are formed through the dropping nozzle, and the vibration frequency f of the dropping nozzle is 80-250 Hz. Preferably, the diameter of the liquid drop is 1.2-1.8 mm. The viscosity of the slurry is 0.8 to 2 pas. The diameter of the drip nozzle is 0.1-0.6 mm. Preferably, the slurry is prepared by: grinding a lead-acid lithium eutectic ceramic material to obtain uniform powder, and fully mixing the powder with a polyvinyl alcohol (PVA) aqueous solution to obtain slurry, wherein the content of the powder in the slurry is 50 wt%. The concentration of the PVA aqueous solution is 1-3 wt%. The average diameter of the prepared lead-acid lithium eutectic ceramic spherulites is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 20-50N.
The invention also provides a lead-acid lithium eutectic ceramic pellet prepared according to the method in any one of the above items, wherein the chemical formula of the lithium lead eutectic ceramic is Li4PbxMO4M is Si or Ti, x is 0.1-0.5, and the lead-acid lithium eutectic ceramic structure is Li4PbO4And Li4MO4A eutectic phase. The mean diameter of the lithium plumbate eutectic ceramic spherulites is 08mm to 1.2mm, the sphericity of 0.95 to 1.00, and the crushing load of 20 to 50N.
Specifically, the preparation method of the lead-acid lithium eutectic ceramic pellet comprises the following steps:
s1 preparation of lead-acid lithium eutectic ceramic material
Preparative analytically pure (AR) lithium acetate (CH)3COOLi), lead acetate ((CH)3COO)2Pb) and tetraethyl silicate/tetrabutyl titanate. At room temperature according to x (Li)4PbO4)-(1-x)(Li4MO4) Adding lithium acetate and lead acetate into deionized water according to the proportion of Li, Pb and Si/Ti elements (M is Si or Ti, x is 0.1-0.5), fully stirring and dissolving for 20-30 min, gradually adding an anhydrous ethanol solution in which 50 wt% of tetraethyl silicate/tetrabutyl titanate is dissolved, then gradually adding anhydrous ethanol, fully stirring until the solution is uniform, clear and transparent, adjusting the pH value to 5.5-6.0 by using ammonia water, and continuously stirring for 20-30 min to obtain the sol. And heating the sol 333-353K in a water bath for 20-40 min to obtain white elastic gel, and drying the gel in a vacuum drying oven for 6-8h at 333-353K to obtain dry gel. Heating the xerogel in a muffle furnace (box furnace) to 873-1073K in the air atmosphere, sintering for 6-8h, naturally cooling to room temperature along with the furnace after sintering, and taking out for analysis;
s2 sample analysis of lead-acid lithium eutectic ceramic material
Fully grinding a lead-acid lithium eutectic ceramic sample into particles of 2-3 mu m, analyzing the crystal grain components of the lead-acid lithium eutectic ceramic sample by XRD (X-ray diffraction), and analyzing the chemical composition of the lead-acid lithium eutectic ceramic sample by ICP-AES (inductively coupled plasma emission Spectroscopy), wherein the atomic molar ratio of Li, Pb and Si/Ti in the particles is basically consistent with the atomic molar ratio of Li, Pb and Si/Ti gelled in the step S1;
s3 preparation of lithium plumbate eutectic ceramic ball grain by freezing method
When the lithium plumbate eutectic ceramic spherulite is prepared by adopting a freeze drying method, the lithium plumbate eutectic ceramic material is fully ground to obtain uniform powder, and the powder and 1 wt% of polyvinyl-alcohol (PVA) aqueous solution are fully mixed according to the mass ratio of 1:1 of the powder to the solution to obtain slurry. The slurry flows out of the dropping nozzle to form liquid drops, the liquid drops enter liquid nitrogen with low temperature of 77K, and the liquid drops shrink and are frozen into spherulites under the action of surface tension and low temperature;
s4 drying of eutectic ceramic pellets of frozen lithium plumbate
Soaking and standing the lithium plumbate eutectic ceramic spherical particle in liquid nitrogen for 1-2 h, taking out the spherical particle, soaking the spherical particle into acetone at room temperature, and drying the spherical particle in a vacuum drying oven at 323-333K for 0.5-1 h until the acetone is completely evaporated to obtain a lead-acid lithium eutectic ceramic spherical particle blank.
S5 sintering of eutectic lead-acid lithium ceramic pellets
Heating the lithium plumbate eutectic ceramic ball blank in a muffle furnace to 873-1073K in the air atmosphere, sintering for 6-8h, naturally cooling to room temperature along with the furnace after sintering, and taking out to perform performance detection;
s6 detection of performance of lead-acid lithium eutectic ceramic spherulites
Taking a lead-acid lithium eutectic ceramic spherulite sample, analyzing microstructures on the surface and in the crushed interior of the sample by using a Scanning Electron Microscope (SEM), analyzing crystal grain components of the sample by using an XRD (X-ray diffraction), measuring the density of the sample by using a drainage method, analyzing the sphericity of the spherulite by using a digital image, and testing the size of the crushing load of the spherulite by using a static pressure method.
In the step S1, with the increase of the sintering temperature, moisture in the sample is continuously evaporated, the weight of the sample is continuously reduced, the change of the weight of the sample with the temperature during the heating period and the pyrolysis pattern of the weight change process are monitored by using thermogravimetric/differential thermal analysis (TG-DTA), and the heating rate during sintering is 5-6 ℃/min.
In the step S2, the sintered lead-acid lithium eutectic ceramic is ground, mixed solution of hydrochloric acid and hydrofluoric acid (volume ratio 1:1) is added, and the mixture is heated to 353K to fully dissolve the lead-acid lithium eutectic ceramic. A certain amount of the solution was taken out, and the atomic molar ratio of Li, Pb and Si was measured by using an ICP-AES Model Optima2100DV (Perkinelmer Co.).
In the step S2, the components of the lead-acid lithium eutectic ceramic are scanned by an X-ray diffractometerScanning conditions are Cu-KαRadiation (λ):
the voltage is 40kV, the current is 100mA, the 2 theta range is 20-80 degrees, the scanning speed is 1.5 degrees/minute, and the gap width is 0.01 degrees.
When the lithium plumbate eutectic ceramic pellet is prepared by adopting a freezing method in the step S3, the adopted system comprises: the device comprises a slurry tank (1), a PVC (polyvinyl chloride) pipeline (2), a peristaltic pump (3), a vibrator (4), a dropping nozzle (5), a heat insulation tank (6), a metal net bag, liquid nitrogen (8) and a liquid nitrogen storage and circulation device (9);
the slurry tank (1) is stored with slurry obtained by mixing lithium plumbate eutectic ceramics and 1 wt% of polyvinyl alcohol aqueous solution, one end of a PVC pipeline (2) is immersed into the slurry in the slurry tank (1), a peristaltic pump (3) is started, the slurry enters the PVC pipeline (2), the speed of extracting the slurry is adjusted to be 0.1ml/min, and under the action of a vibrator (4), the slurry is dropwise dripped into low-temperature 77K liquid nitrogen in an insulation tank (6) through a dripping nozzle (5); the liquid nitrogen storage and circulation device (9) is used for monitoring the liquid level height of liquid nitrogen in the heat insulation tank (6), supplementing the liquid nitrogen through a pipeline at the upper part of the heat insulation tank (6) in time when the liquid level of liquid nitrogen evaporation descends, and extracting and storing the liquid nitrogen from the pipeline at the lower part of the heat insulation tank (6) after production is finished; the mesh number of the metal net bag is 30 meshes, and the extraction of the frozen spherulites is carried out by directly lifting the metal net bag.
In the step S3, when the experiment for preparing the lithium plumbate eutectic ceramic pellet by the freezing method is adopted, the size of the lithium plumbate eutectic ceramic pellet is in direct proportion to the diameter of the liquid drop. According to experimental experience, when the vibration frequency f of the dropping nozzle is within the range of 80-250 Hz, the sphericity of the spherical particle is good; in addition, the diameter of the liquid drop is also related to the viscosity of the solution, the diameter of the drop nozzle and the wettability between the mixed solution and the material of the drop nozzle; according to the experiment, the solution ratio, the diameter of a dripping nozzle and the vibration frequency parameters are optimized, so that the average diameter of the prepared lead-acid lithium eutectic ceramic spherulite is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 20-50N.
Compared with the prior art, the invention has the advantages that: in the prior art, a fusion reactor usually carries out tritium multiplication reaction and neutron multiplication reaction respectively through two different materialsThe seed materials are alternately arranged in multiple layers, so that the complexity of the fusion reactor cladding structure is increased, and the tritium breeding efficiency is not further improved. According to the invention, by utilizing the characteristic that the lithium plumbate eutectic ceramic simultaneously contains lead element with neutron multiplication function and lithium element with tritium multiplication function, the neutron multiplication reaction and the tritium multiplication reaction are carried out in one material, the tritium multiplication rate can be improved, and the design of a cladding can be simplified; utilizes the similarity of Pb and Si (or Ti) in chemical bonding to form eutectic structure and maintain Li4PbO4、Li4TiO4Original excellent mechanical-physical properties; the drying process of the frozen spherulites is improved, a special low-temperature vacuum dryer is not needed in the drying process, and the drying efficiency is greatly improved.
Drawings
FIG. 1 is a schematic diagram of a system for preparing lithium plumbate eutectic ceramic pellets by a sol-gel method.
In the figure, a slurry tank 1, a PVC pipeline 2, a peristaltic pump 3, a vibrator 4, a dropping nozzle 5, a heat insulation tank 6, a soft metal net bag 7, liquid nitrogen 8 and liquid nitrogen 9 are stored and circulated.
Detailed Description
And S1, preparing the lead-acid lithium eutectic ceramic material. Preparative analytically pure (AR) lithium acetate (CH)3COOLi), lead acetate ((CH)3COO)2Pb) and tetraethyl silicate/tetrabutyl titanate. At room temperature according to (Li)4PbxMO4Adding lithium acetate and lead acetate into deionized water according to the proportion of Li, Pb and Si/Ti elements, wherein M is Si or Ti, and x is 0.1-0.5), fully stirring and dissolving for 20-30 min, gradually adding an anhydrous ethanol solution in which 50 wt% of tetraethyl silicate/tetrabutyl titanate is dissolved, then gradually adding anhydrous ethanol, fully stirring until the solution is uniform, clear and transparent, adjusting the pH value to 5.5-6.0 by using ammonia water, and continuously stirring for 20-30 min to obtain the sol. And heating the sol 333-353K in a water bath for 20-40 min to obtain white elastic gel, and drying the gel in a vacuum drying oven for 6-8h at 333-353K to obtain dry gel. Under the air atmosphere, heating the xerogel to 873-1073K in a muffle furnace (box furnace), sintering for 6-8h, naturally cooling to room temperature along with the furnace after sintering, taking out and analyzing；
And S2, analyzing the lead-acid lithium eutectic ceramic material sample. And taking a proper amount of lithium plumbate eutectic ceramic sample, and fully grinding into particles of 2-3 mu m. Analyzing the grain components of the lead-acid lithium eutectic ceramic sample by adopting XRD (X-ray diffraction), and analyzing the chemical composition of the lead-acid lithium eutectic ceramic sample by adopting an inductively coupled plasma atomic emission spectrometry (ICP-AES), wherein the atomic molar ratio of Li, Pb and Si/Ti in the particles is basically consistent with the atomic molar ratio of Li, Pb and Si/Ti gelled in the step S1;
s3, preparing the lithium plumbate eutectic ceramic ball by a freezing method. The following provides a specific implementation mode and a technical scheme for preparing the lithium plumbate spheres by adopting a sol-gel method in the invention by combining with the accompanying drawings.
As shown in fig. 1, the system for preparing lithium plumbate eutectic ceramic pellets by using a sol-gel method in the invention comprises a slurry tank 1, a PVC (polyethylene) pipeline 2, a peristaltic pump 3, a vibrator 4, a dropping nozzle 5, a heat insulation tank 6, a soft metal string bag 7, liquid nitrogen 8 and a liquid nitrogen storage and circulation device 9. The slurry tank 1 is used for storing slurry. The slurry tank 1 is sequentially connected with a peristaltic pump 3 and a vibrator 4 through a PVC (polyethylene) pipeline 2. The vibrator 4 has a drip nozzle 5. An insulated tank 6 is placed below the shaker spout 5. Liquid nitrogen 8 is stored in the heat-insulating tank 6. The upper end of the soft metal net bag 7 is fixed at the opening of the heat insulation tank 6, and the lower end is immersed in liquid nitrogen 8. The upper end opening of the soft metal net bag 7 is opposite to the drip nozzle 5. The upper part of the heat insulation tank 6 is provided with a pipeline, and the lower part of the heat insulation tank 6 is provided with a pipeline. The upper side of the liquid nitrogen storage and circulation device 9 is connected with a pipeline at the upper part of the heat insulation tank 6 through a pipeline; the lower side of the liquid nitrogen storage and circulation device 9 is connected with a pipeline at the lower part of the heat insulation tank 6 through a pipeline.
Fully grinding a lead-acid lithium eutectic ceramic sample into particles of 2-3 mu m to obtain lead-acid lithium eutectic ceramic powder. The working process of the system is as follows: the slurry tank 1 is stored with slurry formed by fully mixing the lithium plumbate eutectic ceramic powder and 1 wt% of polyvinyl alcohol aqueous solution, one end of the PVC pipeline 2 is immersed in the slurry tank 1, the peristaltic pump 3 is started, the slurry enters the PVC pipeline 2, the speed of extracting the slurry is adjusted to be 0.1ml/min, and the slurry is dropwise dripped into low-temperature 77K liquid nitrogen 8 in the heat insulation tank 6 through the dripping nozzle 5 under the action of the vibrator 4; the liquid nitrogen storage and circulation device 9 is used for monitoring the liquid level height of liquid nitrogen in the heat insulation tank 6, supplementing the liquid nitrogen through a pipeline at the upper part of the heat insulation tank 6 in time when the liquid level of the liquid nitrogen evaporation descends, and extracting and storing the liquid nitrogen from a pipeline at the lower part of the heat insulation tank 6 after production is finished; the soft metal net bag 7 has 30 meshes, and the extraction of the frozen small balls is carried out by directly lifting the soft metal net bag 7.
S4 drying of frozen lead-acid lithium eutectic ceramic pellets
Soaking and standing the lead-acid lithium eutectic ceramic pellet in liquid nitrogen for 1-2 h, taking out the pellet, soaking the pellet into acetone at room temperature, and drying the pellet in a vacuum drying oven at 323-333K for 0.5-1 h until the acetone is completely evaporated to obtain a lead-acid lithium eutectic ceramic pellet blank with certain strength.
S5 sintering of lead-acid lithium eutectic ceramic pellets
Heating the lithium plumbate eutectic ceramic pellet blank in a muffle furnace to 873-1073K in the air atmosphere, sintering for 6-8h, naturally cooling to room temperature along with the furnace after sintering, and taking out to perform performance detection;
s6 detection of lead-acid lithium eutectic ceramic pellet performance
Taking a lead-acid lithium eutectic ceramic pellet sample, analyzing microstructures on the surface and in the crushed pellet sample by using a Scanning Electron Microscope (SEM), analyzing crystal grain components of the sample by using an XRD (X-ray diffraction), measuring the density of the sample by using a drainage method, analyzing the sphericity of the pellet by using a digital image, and testing the crushing load of the pellet by using a static pressure method.
In the step S1, thermogravimetric/differential scanning calorimetry (TG-DTA) is used to monitor the weight change of the sample with temperature and the pyrolysis pattern of the weight change process during the heating, and the heating rate during sintering is 5-6 ℃/min.
In the step S2, the sintered lead-acid lithium eutectic ceramic is ground, mixed solution of hydrochloric acid and hydrofluoric acid (volume ratio 1:1) is added, and the mixture is heated to 353K to fully dissolve the lead-acid lithium eutectic ceramic. A certain amount of the solution was taken out and the Li/Pb ratio was measured by using an ICP-AES Model Optima2100DV (Perkinelmer Co.).
In the step S2, the lead-acid lithium eutectic ceramic is scanned by an X-ray diffractometer under the scanning condition of Cu-KαRadiation (λ):
the voltage is 40kV, the current is 100mA, the 2 theta range is 10-70 degrees, the scanning speed is 2 degrees/minute, and the gap width is 0.01 degrees.
In the step S3, when the lithium plumbate eutectic ceramic pellet is prepared by a freezing method, the size of the lithium plumbate eutectic ceramic pellet is in direct proportion to the diameter of the liquid drop, and according to the experimental experience, when the vibration frequency f of the drop nozzle is within the range of 80-250 Hz, the sphericity of the pellet is good. In addition, the droplet diameter is also related to the viscosity of the solution, the diameter of the nozzle, and the wettability between the solution and the nozzle material. According to the parameters such as solution proportion, diameter of a dripping nozzle, vibration frequency and the like optimized through experiments, the average diameter of the prepared lead-acid lithium eutectic ceramic pellet is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 20-50N.
Example 1
And S1, preparing the lead-acid lithium eutectic ceramic material. Preparative analytically pure (AR) lithium acetate (CH)3COOLi), lead acetate ((CH)3COO)2Pb) and tetraethyl silicate. At room temperature, according to Li4PbxMO4Adding lithium acetate and lead acetate into deionized water according to the proportion of Li, Pb and Si elements with M being equal to Si and x being equal to 0.2, fully stirring and dissolving for 30min, gradually adding an absolute ethyl alcohol solution in which 50 wt% of tetraethyl silicate is dissolved, gradually adding absolute ethyl alcohol, fully stirring until the solution is uniform, clear and transparent, adjusting the pH value to 5.5 by using ammonia water, and continuously stirring for 30min to prepare the sol. And heating the sol 333K in a water bath for 30min to obtain white elastic gel, and drying the gel in a vacuum drying oven 343K for 6h to obtain dry gel. Heating the xerogel in a muffle furnace (box furnace) to 873K in the air atmosphere, sintering for 8h, wherein the temperature rise rate during sintering is 5/min, naturally cooling the xerogel to room temperature along with the furnace after sintering, and taking out the xerogel for analysis;
and S2, analyzing the lead-acid lithium eutectic ceramic material sample. Taking a proper amount of lithium lead eutectic ceramic material sample, fully grinding into particles of 2-3 mu m, analyzing the crystal grain components of the lithium lead eutectic ceramic sample by XRD (X-ray diffraction), analyzing the chemical composition of the lithium lead eutectic ceramic sample by ICP-AES (inductively coupled plasma emission spectroscopy), wherein the atomic molar ratio of Li, Pb and Si in the particles is basically consistent with the atomic molar ratio of Li, Pb and Si in gel in the step S1;
s3, preparing the lithium plumbate eutectic ceramic ball by a freezing method. The following provides a specific implementation mode and a technical scheme for preparing the lithium plumbate spheres by adopting a sol-gel method in the invention by combining with the accompanying drawings.
The present embodiment employs a system as shown in fig. 1. As shown in fig. 1, the sol-gel method employed in the present invention for preparing lithium plumbate eutectic ceramic bead system has been described in detail in the detailed description section.
Fully grinding a lead-acid lithium eutectic ceramic sample into particles of 2-3 mu m to obtain lead-acid lithium eutectic ceramic powder. The working process of the system is as follows: the slurry tank 1 is stored with slurry formed by fully mixing the lithium plumbate eutectic ceramic powder and 1 wt% of polyvinyl alcohol water solution, and the ceramic powder content in the slurry is 50 wt%. One end of a PVC pipeline 2 is immersed into the slurry in the slurry tank 1, a peristaltic pump 3 is started, the slurry enters the PVC pipeline 2, the speed of extracting the slurry is adjusted to be 0.1ml/min, and the slurry is dropwise added into low-temperature (77K) liquid nitrogen in an insulation tank 6 through a dropping nozzle 5 under the action of a vibrator 4; the droplets shrink and freeze into pellets. The liquid nitrogen storage and circulation device 9 is used for monitoring the liquid level height of liquid nitrogen in the heat insulation tank 6, supplementing the liquid nitrogen through a pipeline at the upper part of the heat insulation tank 6 in time when the liquid level of the liquid nitrogen evaporation descends, and extracting and storing the liquid nitrogen from a pipeline at the lower part of the heat insulation tank 6 after production is finished; the soft metal net bag 7 has 30 meshes, and the extraction of the frozen small balls is carried out by directly lifting the soft metal net bag 7.
S4 drying of frozen lead-acid lithium eutectic ceramic pellets
Soaking the lead-acid lithium eutectic ceramic pellet in liquid nitrogen, standing for 1h, taking out the pellet, soaking the pellet into acetone at room temperature, and drying in a vacuum drying oven 323K for 0.5h until the acetone is completely evaporated to obtain a lead-acid lithium eutectic ceramic pellet blank with certain strength.
S5 sintering of lead-acid lithium eutectic ceramic pellets
Heating the lithium plumbate eutectic ceramic pellet blank in a muffle furnace to 873K in the air atmosphere, sintering for 6h, naturally cooling to room temperature along with the furnace after sintering, and taking out to perform performance detection;
s6 detection of lead-acid lithium eutectic ceramic pellet performance
Taking a lead-acid lithium eutectic ceramic pellet sample, analyzing microstructures on the surface and in the crushed pellet sample by using a Scanning Electron Microscope (SEM), analyzing crystal grain components of the sample by using an XRD (X-ray diffraction), measuring the density of the sample by using a drainage method, analyzing the sphericity of the pellet by using a digital image, and testing the crushing load of the pellet by using a static pressure method. The average diameter of the prepared lead-acid lithium eutectic ceramic pellet is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 20-30N.
Meanwhile, in this example, the change of the sample weight with temperature and the weight change process in the step S1 were measured. Thermogravimetric-differential scanning calorimetry (TG-DTA) was used to monitor the weight of the sample as a function of temperature during warming and the thermogram of the weight change with a heating rate of 5 ℃/min during sintering.
In the step S2, the sintered lead-acid lithium eutectic ceramic is ground, mixed solution of hydrochloric acid and hydrofluoric acid (volume ratio 1:1) is added, and the mixture is heated to 353K to fully dissolve the lead-acid lithium eutectic ceramic. A certain amount of the solution was taken out and the Li/Pb ratio was measured by using an ICP-AES Model Optima2100DV (Perkinelmer Co.).
In the step S2, the lead-acid lithium eutectic ceramic is scanned by an X-ray diffractometer under the scanning condition of Cu-KαRadiation (λ):
the voltage is 40kV, the current is 100mA, the 2 theta range is 10-70 degrees, the scanning speed is 2 degrees/minute, and the gap width is 0.01 degrees.
In the step S3, when the experiment for preparing the lithium plumbate eutectic ceramic pellet is performed by using the freezing method, the size of the lithium plumbate eutectic ceramic pellet is in direct proportion to the diameter of the liquid drop, and the diameter of the liquid drop is related to the viscosity of the solution, the diameter of the liquid drop nozzle, and the wettability between the solution and the polypropylene liquid drop nozzle material. In this example, a 1 wt% PVA solution was used, the content of ceramic powder in the slurry was 50 wt%, the viscosity of the slurry was 1 pas, the diameter of the nozzle was 0.5mm, and the vibration frequency of the nozzle was 100 Hz.
Example 2
And S1, preparing the lead-acid lithium eutectic ceramic material. Preparative analytically pure (AR) lithium acetate (CH)3COOLi), lead acetate ((CH)3COO)2Pb) and tetrabutyl titanate. At room temperature, according to Li4PbxMO4Adding lithium acetate and lead acetate into deionized water according to the proportion of Li, Pb and Ti elements with M being Ti and x being 0.2, fully stirring and dissolving for 30min, gradually adding an absolute ethanol solution in which 50 wt% of tetrabutyl titanate is dissolved, gradually adding absolute ethanol, fully stirring until the solution is uniform, clear and transparent, adjusting the pH value to 6.0 by using ammonia water, and continuously stirring for 30min to obtain the sol. Heating the sol 343K in a water bath for 30min to obtain white elastic gel, and drying the gel 343K in a vacuum drying oven for 8h to obtain dry gel. Heating the xerogel to 1073K in a muffle furnace (box furnace) in an air atmosphere, sintering for 8 hours at the temperature rise rate of 5 ℃/min, naturally cooling the xerogel to room temperature along with the furnace after sintering, and taking out the xerogel for analysis;
and S2, analyzing the lead-acid lithium eutectic ceramic material sample. Taking a proper amount of lithium lead eutectic ceramic material sample, fully grinding into particles of 2-3 mu m, analyzing the crystal grain components of the lithium lead eutectic ceramic sample by XRD (X-ray diffraction), analyzing the chemical composition of the lithium lead eutectic ceramic sample by ICP-AES (inductively coupled plasma emission spectroscopy), wherein the atomic molar ratio of Li, Pb and Ti in the particles is basically consistent with the atomic molar ratio of Li, Pb and Ti in gel in the step S1;
s3, preparing the lithium plumbate eutectic ceramic ball by a freezing method. The following provides a specific implementation mode and a technical scheme for preparing the lithium plumbate spheres by adopting a sol-gel method in the invention by combining with the accompanying drawings.
The present embodiment employs a system as shown in fig. 1. As shown in fig. 1, the sol-gel method employed in the present invention for preparing lithium plumbate eutectic ceramic bead system has been described in detail in the detailed description section.
Fully grinding a lead-acid lithium eutectic ceramic sample into particles of 2-3 mu m to obtain lead-acid lithium eutectic ceramic powder. The working process of the system is as follows: the slurry tank 1 is stored with slurry formed by mixing the lithium plumbate eutectic ceramic powder and 1 wt% of polyvinyl alcohol aqueous solution, the content of the ceramic powder in the slurry is 50 wt%, one end of the PVC pipeline 2 is immersed in the slurry tank 1, the peristaltic pump 3 is started, the slurry enters the PVC pipeline 2, the speed of extracting the slurry is adjusted to be 0.1ml/min, and under the action of the vibrator 4, the slurry is dropwise dripped into low-temperature (the temperature is 77K) liquid nitrogen in the heat insulation tank 6 through the dripping nozzle 5; the droplets shrink and freeze into pellets. The liquid nitrogen storage and circulation device 9 is used for monitoring the liquid level height of liquid nitrogen in the heat insulation tank 6, supplementing the liquid nitrogen through a pipeline at the upper part of the heat insulation tank 6 in time when the liquid level of the liquid nitrogen evaporation descends, and extracting and storing the liquid nitrogen from a pipeline at the lower part of the heat insulation tank 6 after production is finished; the soft metal net bag 7 has 30 meshes, and the extraction of the frozen small balls is carried out by directly lifting the soft metal net bag 7.
S4 drying of frozen lead-acid lithium eutectic ceramic pellets
Soaking the lead-acid lithium eutectic ceramic pellet in liquid nitrogen, standing for 1h, taking out the pellet, soaking the pellet into acetone at room temperature, and drying in a vacuum drying oven 323K for 0.5h until the acetone is completely evaporated to obtain a lead-acid lithium eutectic ceramic pellet blank with certain strength.
S5 sintering of lead-acid lithium eutectic ceramic pellets
Heating the lithium plumbate eutectic ceramic pellet blank in a muffle furnace to 1073K in the air atmosphere, sintering for 8 hours, naturally cooling to room temperature along with the furnace after sintering, and taking out for performance detection;
s6 detection of lead-acid lithium eutectic ceramic pellet performance
Taking a lead-acid lithium eutectic ceramic pellet sample, analyzing microstructures on the surface and in the crushed pellet sample by using a Scanning Electron Microscope (SEM), analyzing crystal grain components of the sample by using an XRD (X-ray diffraction), measuring the density of the sample by using a drainage method, analyzing the sphericity of the pellet by using a digital image, and testing the crushing load of the pellet by using a static pressure method. The average diameter of the prepared lead-acid lithium eutectic ceramic pellet is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 30-50N.
Meanwhile, in this example, the change of the sample weight with temperature and the weight change process in the step S1 were measured. Thermogravimetric-differential scanning calorimetry (TG-DTA) was used to monitor the weight of the sample as a function of temperature during warming and the thermogram of the weight change with a heating rate of 5 ℃/min during sintering.
In the step S2, the sintered lead-acid lithium eutectic ceramic is ground, mixed solution (volume ratio is 1:1) of hydrochloric acid and hydrofluoric acid is added, the mixture is heated to 353K to fully dissolve the lead-acid lithium eutectic ceramic, a certain amount of solution is taken out, and the Li/Pb ratio is measured by adopting ICP-AES Model Optima2100DV (Perkinelmer company).
In the step S2, the lead-acid lithium eutectic ceramic is scanned by an X-ray diffractometer under the scanning condition of Cu-KαRadiation (λ):
the voltage is 40kV, the current is 100mA, the 2 theta range is 10-70 degrees, the scanning speed is 2 degrees/minute, and the gap width is 0.01 degrees.
In the step S3, when the experiment for preparing the lithium plumbate eutectic ceramic pellet is performed by using the freezing method, the size of the lithium plumbate eutectic ceramic pellet is in direct proportion to the diameter of the liquid drop, and the diameter of the liquid drop is related to the viscosity of the solution, the diameter of the liquid drop nozzle, and the wettability between the solution and the polypropylene liquid drop nozzle material. In this example, a 1 wt% PVA solution was used, the content of the ceramic powder in the slurry was 50 wt%, the viscosity of the slurry was 1 pas, the diameter of the nozzle was 0.5mm, and the vibration frequency of the nozzle was 100 Hz.
Although particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to these embodiments without departing from the principles and implementations of the invention, the scope of which is therefore defined by the appended claims.
Claims (10)
1. A tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and a preparation method thereof are characterized by comprising the following steps:
(1) preparation of lead-acid lithium eutectic ceramic material
According to x (Li)4PbO4)-(1-x)(Li4MO4) Adding a lithium source and a lead source into deionized water according to the proportion of Li, Pb and Si or Ti elements, wherein M is Si or Ti, and x is 0.1-0.5; stirring and dissolving for 20-30 min, adding an alcohol solution dissolved with a silicon source or a titanium source, adjusting the pH value to 5.5-6.0, and continuously stirring for 20-30 min to prepare sol; heating the sol 333-353K in a water bath for 20-40 min to obtain gel, and drying the gel in a vacuum drying oven for 6-8h at 333-353K to obtain dry gel; heating the xerogel to 873-1073K in the air atmosphere, and sintering for 6-8h to obtain a lead-acid lithium eutectic ceramic material;
(2) preparation of frozen lithium plumbate eutectic ceramic spherulite by freezing method
Preparing the lead-acid lithium eutectic ceramic material into slurry; enabling the slurry to form liquid drops, enabling the liquid drops to enter liquid nitrogen, and enabling the liquid drops to contract and freeze into spherulites to obtain the frozen lead-acid lithium eutectic ceramic spherulites;
(3) drying of eutectic ceramic spherulites of frozen lithium plumbate
Soaking the frozen lithium plumbate eutectic ceramic spherulites in liquid nitrogen, taking out the spherulites, soaking the spherulites into an organic solvent at room temperature, and performing vacuum drying to obtain a lead-acid lithium eutectic ceramic spherulites blank;
(4) sintering of lithium plumbate eutectic ceramic spherulite blank
Heating the lead-acid lithium eutectic ceramic ball blank to 873-1073K in the air atmosphere, and sintering for 6-8h to obtain the lithium lead eutectic ceramic ball.
2. The method of claim 1, wherein: in the step (1), the temperature rise rate during sintering is 5-6 ℃/min.
3. The method of claim 1, wherein: the method further comprises the step of carrying out sample analysis on the lead-acid lithium eutectic ceramic material obtained in the step (1), wherein the sample analysis comprises the following steps: grinding the sintered lead-acid lithium eutectic ceramic, adding a mixed solution of hydrochloric acid and hydrofluoric acid, and heating to fully dissolve the lead-acid lithium eutectic ceramic to obtain a sample solution; the sample solution was used to determine the atomic molar ratio of Li, Pb, and Si or Ti.
4. The method of claim 3, wherein: the sample analysis further comprises: the composition of the lithium plumbate eutectic ceramic is scanned by an X-ray diffractometer.
5. The method of claim 1, wherein: in the step (2), grinding the lead-acid lithium eutectic ceramic material to obtain uniform powder, and mixing the powder with 1 wt% of polyvinyl alcohol aqueous solution according to the mass ratio of the powder to the solution of 1:1 to obtain slurry; the slurry flows out of the drop nozzle as droplets into liquid nitrogen, which shrink and freeze into pellets.
6. The method of claim 1, wherein: in the step (3), the frozen lithium plumbate eutectic ceramic spherulites prepared in the step (2) are soaked in liquid nitrogen and stand still for 1-2 hours, the spherulites are taken out and immersed into acetone at room temperature, and the mixture is dried in a vacuum drying oven at 323-333K for 0.5-1 hours until the acetone is completely evaporated, so that a lead-acid lithium eutectic ceramic spherulites blank is obtained.
7. The method of claim 1, wherein: when the lithium plumbate eutectic ceramic spherical particle is prepared by adopting a freezing method in the step (2), the adopted system comprises: the device comprises a slurry tank (1), a PVC pipeline (2), a peristaltic pump (3), a vibrator (4), a dropping nozzle (5), a heat insulation tank (6), a metal net bag, liquid nitrogen (8) and a liquid nitrogen storage and circulation device (9); the slurry tank (1) is sequentially connected with a peristaltic pump (3) and a vibrator (4) through a PVC pipeline (2); the vibrator (4) is provided with a drip nozzle (5); the heat insulation tank (6) is arranged below the dropping nozzle (5) of the vibrator; liquid nitrogen (8) is stored in the heat insulation tank (6); the upper end of the metal net bag is fixed at the opening of the heat insulation tank (6), and the lower end is immersed in liquid nitrogen (8); the upper end opening of the metal net bag faces the drip nozzle (5); the upper part of the heat insulation tank (6) is provided with a pipeline, and the lower part of the heat insulation tank (6) is provided with a pipeline; the upper side of the liquid nitrogen storage and circulation device (9) is connected with a pipeline at the upper part of the heat insulation tank (6) through a pipeline; the lower side of the liquid nitrogen storage and circulation device (9) is connected with a pipeline at the lower part of the heat insulation tank (6) through a pipeline.
8. The method of claim 7, wherein: the slurry tank (1) is stored with slurry obtained by mixing lithium plumbate eutectic ceramic powder and polyvinyl alcohol aqueous solution, one end of a PVC pipeline (2) is immersed into the slurry in the slurry tank (1), a peristaltic pump (3) is started, the slurry enters the PVC pipeline (2), the speed of extracting the slurry is adjusted, and the slurry is dripped into liquid nitrogen (8) in an insulating tank (6) through a dripping nozzle (5) under the action of a vibrator (4); the liquid nitrogen storage and circulation device (9) is used for monitoring the liquid level height of liquid nitrogen in the heat insulation tank (6), supplementing the liquid nitrogen through a pipeline at the upper part of the heat insulation tank (6) when the evaporation liquid level of the liquid nitrogen descends, and extracting and storing the liquid nitrogen from the pipeline at the lower part of the heat insulation tank (6) after production is finished; the extraction of the frozen pellets was performed by directly pulling up the metal string bag.
9. The method of claim 1, wherein: in the step (2), when the frozen lithium plumbate eutectic ceramic spherulites are prepared by a freezing method, the size of the lithium plumbate eutectic ceramic spherulites is in direct proportion to the diameter of liquid drops;
preferably, liquid drops are formed through the dripping nozzle, and the vibration frequency f of the dripping nozzle is 80-250 Hz;
preferably, the diameter of the liquid drop is 1.2-1.8 mm, and the viscosity of the slurry is 0.8-2 Pa.s;
preferably, the diameter of the drip nozzle is 0.1-0.6 mm;
preferably, the slurry is prepared by: grinding the lead-acid lithium eutectic ceramic material to obtain uniform powder, and fully mixing the powder with a polyvinyl alcohol aqueous solution to obtain slurry, wherein the content of the powder in the slurry is 50 wt%.
10. A tritium-neutron composite breeder lead-acid lithium eutectic ceramic pellet prepared according to any of claims 1-9, characterized in that the lithium lead eutectic ceramic has a chemical formula of Li4PbxMO4, M ═ Si or Ti, x ═ 0.1 to 0.5, and is structurally a eutectic phase of Li4PbO4 and Li4MO 4; the average diameter of the lithium plumbate eutectic ceramic spherulites is 0.8-1.2 mm, the sphericity is 0.95-1.00, and the crushing load is 20-50N.
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