CN101066883A - Freeze forming prepn process of ternary lithium ceramic microphere - Google Patents
Freeze forming prepn process of ternary lithium ceramic microphere Download PDFInfo
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- CN101066883A CN101066883A CN 200710048921 CN200710048921A CN101066883A CN 101066883 A CN101066883 A CN 101066883A CN 200710048921 CN200710048921 CN 200710048921 CN 200710048921 A CN200710048921 A CN 200710048921A CN 101066883 A CN101066883 A CN 101066883A
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Abstract
The freeze forming preparation process of ternary lithium ceramic microsphere includes the following steps: mixing the material for ternary lithium ceramic microsphere, high molecular adhesive and solvent, mixing in a ball mill to form suspension slurry and defoaming; dropping the slurry into cooling medium to form microsphere in a microsphere forming unit, and low temperature vacuum drying in a freezing drier to form ceramic microsphere precursor; roasting, calcining and sintering; and programmed heat treatment to obtain ternary lithium ceramic microsphere. The ternary lithium ceramic microsphere has high sphericity, controllable size, high size dispersivity, high apparent density, high phase purity, high strength and other features.
Description
Technical field
The invention belongs to porous ceramics microsphere preparation technology field, be specifically related to a kind of freeze forming preparation process of ternary lithium ceramic microphere.
Background technology
For solving the world energy sources shortage problem, various countries as tapping a new source of energy, solve one of effective way of energy dilemma to research.The fuel tritium that needs in the thermonuclear fusion heap generally be by
6(n, α) T reacts and realizes Li.In order to realize Fuel cycle. reactor must be accomplished " controlling oneself " of tritium, for this reason, need add the tritium multiplication agent that contains lithium in covering, and the neutron and the interior lithium-containing materials reaction of propagation covering that utilize pile core D-T reaction to produce produce tritium and realize tritium propagation.
The lithium pottery produces tritium stupalith (tritium multiplication agent) as a kind of solid, have easy to use, characteristics such as thermal characteristics and satisfactory mechanical property and structured material, neutron multiplication agent consistency are good, and anti-irradiation ability is strong.The shape of solid tritium multiplication agent can adopt column, ring-type or spherical etc., and wherein, spherical multiplication agent is easy to loading and unloading, has bigger specific surface area, have more passage between microballoon, be beneficial to the carrier band of tritium, so the spheric multiplication agent is nearly all adopted in the selection of multiplication agent in the present various countries fusion reactor.
For the preparation technology of lithium ceramic microphere, the preparation method of lithium ceramic microphere mainly contains molten atomizing method, wet method, sol-gel method, solid reaction process and extrude-film trap-ball milling spherical container shaping method etc.Wherein, the molten atomizing method can make highdensity lithium ceramic microphere, but the defective of this method has been to use expensive platinum rhodium burner hearth.When adopting conventional wet to prepare lithium ceramic microphere, be difficult to surpass 50% owing to prepare the gel solids content of microballoon presoma, so the density of the lithium ceramic microphere of final molding is difficult to be higher than 90%T.D. (theoretical density).
Existing ceramic microsphere preparation method need prepare the ceramic powder of ternary lithium compound mostly in advance, and then generates ceramic microsphere, and the sphericity of ceramic microsphere is bad, and inner pore passage structure is abundant inadequately, and microspherulite diameter is wayward, and particle size dispersion is poor.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of freeze forming preparation process of ternary lithium ceramic microphere.
The freeze forming preparation process of ternary lithium ceramic microphere of the present invention may further comprise the steps:
1.. required hydrophilic macromolecule binding agent is dissolved in the solvent, is mixed with stable macromolecular solution;
2.. the solid material that will prepare ternary lithium ceramic microphere joins in the macromolecular solution of above-mentioned steps in 1., and adds defoamer, grinds 2 hours～6 hours on planetary-type grinding machine, forms the suspension liquid slurry of stablizing, mixing;
3.. the suspension liquid slurry of above-mentioned steps in 2. gone to the container of nozzle and pressure adjustable size joint, and the suspension liquid slurry is sprayed onto by nozzle and is frozen into solid-state-microspherical in the low-temperature cooling media;
4.. the microballoon in the 3. middle low-temperature cooling media of above-mentioned steps is transferred to rapidly in the freeze drier, and vacuum-drying obtains having the microballoon presoma of certain intensity at low temperatures;
5.. the microballoon presoma that above-mentioned steps is had certain intensity in 4. is transferred in the high temperature sintering furnace, adopts temperature programming that the roasting of microballoon presoma is become green microspheres;
6.. the green microspheres of step in 5. calcined and sintering;
7.. step is calcined the microballoon of finishing with sintering in 6. under the certain temperature gradient, be cooled to room temperature, obtained ternary lithium ceramic microphere.
The main component of described ternary lithium ceramic microphere is a kind of in positive lithium silicate, lithium silicate, lithium titanate, lithium zirconate, lithium niobate, the lithium tantalate, and its general formula is Li
XM
YO
ZX, y, z are respectively the positive integer of 1-4, and M is a kind of among Ti, Si, Zr, Ta, the Al.
The high polymer binder of step in 1. is alginate or polyvinyl alcohol, and its concentration is 1%～15%, and solvent is a kind of in water, ethanol, the ethylene glycol.
The solid material of described step in 2. is the reacting material mixture of preparation ternary lithium compound.
The reacting material mixture of the preparation ternary lithium compound of described step in 2. is Li
2CO
3And SiO
2Powder, Li
2CO
3And TiO
2Powder, Li
2CO
3And Al
2O
3Powder, Li
2CO
3And ZrO
2Powder, LiNO
3And TiO
2Powder, LiNO
3And SiO
2Powder, Li
2CO
3And TaO
2A kind of in the powder combinations.
The solid material of described step in 2. is ternary lithium compound ceramic powder.
The defoamer of step in 2. is isooctyl alcohol or lipid acid.
The low-temperature cooling media of step in 4. can be one or more in liquid nitrogen, liquid helium, the ethylene glycol solvent, and system's gauge pressure scope that pressure control system is controlled is 0.2KPa～2MPa.
Described step is 5. middle to adopt temperature programming that the roasting of microballoon presoma is become green microspheres, and wherein maturing temperature is 400 ℃ to 800 ℃, and roasting time is 12 hours to 48 hours.
The green microspheres of described step in 6. calcined and sintering, and wherein calcining temperature is 600 ℃ to 800 ℃, and calcination time is 12 hours to 48 hours; Sintering temperature is 900 ℃ to 1300 ℃, and sintering time is 12 hours to 48 hours.
The present invention adopts freeze forming preparation process to prepare ternary lithium ceramic microphere, do not need to prepare in advance ceramic powder, do not adopt platinum rhodium burner hearth expensive in the molten atomizing method, adopt the method for freeze forming to make the solid material mould-free forming, then, the solid material microballoon that will contain solvent again carries out drying under low temperature, vacuum environment, slough solvent, obtain exsiccant solid material microballoon, transfer to temperature programming in the high temperature sintering furnace and carry out multistep roasting, calcining and sintering and realize the solid state reaction of solid material microballoon and further potteryization fully.
Solid phase raw material among the present invention mainly adopts the reactant feed mixture of preparation ternary lithium ceramic, but also can be the powder of ternary lithium ceramic.The mould-free forming technology balling-up of cryogenic freezing is adopted in the microballoon moulding, and removes solvent in the microballoon with freeze-drying method.By the ceramic microsphere good sphericity of this method preparation, the apparent density height can surpass 85%T.D., and it is mutually pure also can to reach more than 90%.Simultaneously, the ternary lithium ceramic microphere controllable size of preparation, the microballoon size can be diameter below 1.5mm, can require to regulate the microballoon size according to demand; The ternary lithium ceramic of preparation has higher strength at break, can be used as irradiation and produces tritium lithium ceramic microphere ideal preparation method.
Preparation method's moulding process of the present invention is simple, and cost is low, and the good sphericity of ceramic microsphere has good inside pore passage structure, and microspherulite diameter is controlled, and particle size dispersion is good, has characteristics such as high apparent density, Gao Xiangchun.
Description of drawings
The green microspheres shaped device synoptic diagram that Fig. 1 the present invention adopts
Among the figure, a. slurry container b. pressure control system c. nozzle d. refrigerant
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing
The green microspheres shaped device synoptic diagram that Fig. 1 adopts for the present invention, a is for storing the suspension liquid slurry container, be connected to pressure control system b, be provided with the nozzle c for the slurry ejection in the bottom that stores slurry container, slurry aloft directly enters behind the motion certain distance after by nozzle c and is cooled to the microballoon presoma among the refrigerant d rapidly.
Embodiment 1
(1) the 4g polyvinyl alcohol is dissolved fully set aside for use in 96g distilled water; (2) by metering than weighing 150g Quilonum Retard and silica mixture, join in the polyvinyl alcohol solution that (1) prepare, on planetary-type grinding machine, ground 3 hours, form stable suspension liquid slurry; (3) the suspension liquid slurry is gone in the container of band nozzle, open pressure control system, pressure-controlling is at 40kPa, and slurry sprays from nozzle, drops to the bottom ceramic microsphere presoma of formation is housed in the container of liquid nitrogen; (4) the ceramic microsphere presoma is transferred in the enamel tray, put into cooling driers lyophilize 12h, temperature is-30 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 120 ℃, handle 36h at 500 ℃ again, and then be warming up to 1000 ℃ and handle 20h, continue to be warming up to 1100 ℃ and handle 8h, be cooled to room temperature according to certain thermograde, screening obtains the positive lithium silicate ceramic microsphere of desired size.
Embodiment 2
(1) the 2g polyvinyl alcohol is dissolved in 98g distilled water transparent, stand-by; (2) by measuring, join in (1), on planetary-type grinding machine, ground 4 hours, obtain stable suspension liquid than weighing 150g lithium nitrate and silica mixture; (3) suspension liquid is poured in the container of band nozzle, opened pressure control system, pressure-controlling is at 40kPa, and droplet sprays from nozzle, drops to the bottom ceramic microsphere presoma of formation is housed in the container of liquid nitrogen; (4) the ceramic microsphere presoma is transferred in the enamel tray, put into cooling driers lyophilize 8h, temperature is-30 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 120 ℃, handle 48h at 400 ℃ again, and then be warming up to 1050 ℃ and handle 24h, continue to be warming up to 1150 ℃ and handle 4h, be cooled to room temperature according to certain thermograde, screening obtains the positive lithium silicate ceramic microsphere of desired size.
Embodiment 3
(1) the 5g polyvinyl alcohol is dissolved set aside for use in 95g ethanol; (2) by measuring, join in (1), on planetary-type grinding machine, ground 2 hours, obtain stable suspension liquid slurry than weighing 150g Quilonum Retard and titanium dioxide blends; (3) the suspension liquid slurry is gone in the container of band nozzle, open pressure control system, pressure-controlling is at 70kPa, and drop sprays from jet hole, because the surface tension effects globulate drops in the ethylene glycol liquid nitrogen mixed solution of bottom, forms the ceramic microsphere presoma; (4) the microballoon presoma is transferred in the enamel tray, put into cooling driers lyophilize 10h, freezing temp is-20 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 150 ℃, handle 18h for 700 ℃, and then be warming up to 1100 ℃ and handle 12h, continue to be warming up to 1150 and handle 4h, be cooled to room temperature according to certain thermograde, screening obtains the lithium titanate ceramic microsphere of desired size.
(1) the 2g polyvinyl alcohol is dissolved set aside for use in 98g ethanol; (2) weighing 120g lithium titanate ceramic powder joins in (1), grinds 3 hours on planetary-type grinding machine, obtains stable suspension liquid slurry; (3) the suspension liquid slurry is gone in the container of band nozzle, open pressure control system, pressure-controlling is at 30kPa, and drop sprays from jet hole, because the surface tension effects globulate drops in the ethylene glycol liquid nitrogen mixed solution of bottom, forms the ceramic microsphere presoma; (4) the microballoon presoma is transferred in the enamel tray, put into cooling driers lyophilize 8h, freezing temp is-15 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 150 ℃, and then be warming up to 1000 ℃ and handle 12h, continue to be warming up to 1150 and handle 4h, be cooled to room temperature according to certain thermograde, screening obtains the lithium titanate ceramic microsphere of desired size.
Embodiment 5
(1) the 2g polyvinyl alcohol is dissolved set aside for use in 98g ethanol; (2) weighing 150g Quilonum Retard and zirconium dioxide powder mixture join in (1), grind 3 hours on planetary-type grinding machine, obtain stable suspension liquid slurry; (3) the suspension liquid slurry is gone in the container of band nozzle, open pressure control system, pressure-controlling is at 30kPa, and drop sprays from jet hole, because the surface tension effects globulate drops in the ethylene glycol liquid nitrogen mixed solution of bottom, forms the ceramic microsphere presoma; (4) the microballoon presoma is transferred in the enamel tray, put into cooling driers lyophilize 8h, freezing temp is-15 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 150 ℃, and then be warming up to 1000 ℃ and handle 12h, continue to be warming up to 1150 and handle 4h, be cooled to room temperature according to certain thermograde, screening obtains the lithium zirconate ceramic microsphere of desired size.
Embodiment 6
(1) the 2g polyvinyl alcohol is dissolved set aside for use in 98g ethanol; (2) weighing 150g Quilonum Retard and aluminium sesquioxide powder mixture join in (1), grind 3 hours on planetary-type grinding machine, obtain stable suspension liquid slurry; (3) the suspension liquid slurry is gone in the container of band nozzle, open pressure control system, pressure-controlling is at 30kPa, and drop sprays from jet hole, because the surface tension effects globulate drops in the ethylene glycol liquid nitrogen mixed solution of bottom, forms the ceramic microsphere presoma; (4) the microballoon presoma is transferred in the enamel tray, put into cooling driers lyophilize 8h, freezing temp is-15 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 150 ℃, and then be warming up to 1000 ℃ and handle 12h, continue to be warming up to 1150 and handle 4h, be cooled to room temperature according to certain thermograde, screening obtains the lithium aluminate ceramic microsphere of desired size.
Embodiment 7
(1) the 4g polyvinyl alcohol is dissolved fully set aside for use in 96g distilled water; (2) by metering than weighing 150g Quilonum Retard and tantalum oxide mixture, join in the polyvinyl alcohol solution that (1) prepare, on planetary-type grinding machine, ground 3 hours, form stable suspension liquid slurry; (3) the suspension liquid slurry is gone in the container of band nozzle, open pressure control system, pressure-controlling is at 40kPa, and slurry sprays from nozzle, drops to the bottom ceramic microsphere presoma of formation is housed in the container of liquid nitrogen; (4) the ceramic microsphere presoma is transferred in the enamel tray, put into cooling driers lyophilize 12h, temperature is-30 ℃; (5) will obtain dry microspheres through (4) processing and put into high temperature sintering furnace, carry out the program processing of heating, handle 24h for 120 ℃, handle 36h at 500 ℃ again, and then be warming up to 1000 ℃ and handle 20h, continue to be warming up to 1100 ℃ and handle 8h, be cooled to room temperature according to certain thermograde, screening obtains the lithium tantalate ceramic microsphere of desired size.
Claims (10)
1. the freeze forming preparation process of a ternary lithium ceramic microphere may further comprise the steps:
1.. the hydrophilic macromolecule binding agent with required 2%～10% is dissolved in 90%～98% the solvent, is mixed with stable macromolecular solution;
2.. the solid material that will prepare ternary lithium ceramic microphere joins in the macromolecular solution among the above-mentioned steps a, and adds defoamer, grinds 2 hours～6 hours on planetary-type grinding machine, forms the suspension liquid slurry of stablizing, mixing;
3.. the suspension liquid slurry of above-mentioned steps in 2. gone to the container of nozzle and pressure adjustable size joint, and slurry is sprayed onto by nozzle and is frozen into solid-state-microspherical in the low-temperature cooling media;
4.. the microballoon in the 3. middle low-temperature cooling media of above-mentioned steps is transferred to rapidly in the freeze drier, and vacuum-drying obtains having the microballoon presoma of certain intensity at low temperatures;
5.. the microballoon presoma that above-mentioned steps is had certain intensity in 4. is transferred in the high temperature sintering furnace, adopts temperature programming that the roasting of microballoon presoma is become green microspheres;
6.. the green microspheres of step in 5. calcined and sintering;
7.. step is calcined the microballoon of finishing with sintering in 6. under the certain temperature gradient, be cooled to room temperature, obtained ternary lithium ceramic microphere.
2. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1, it is characterized in that: the main component of described ternary lithium ceramic microphere is a kind of in positive lithium silicate, lithium silicate, lithium titanate, lithium zirconate, lithium niobate, the lithium tantalate, and its general formula is Li
XM
YO
ZX, y, z are respectively the positive integer of 1-4, and M is a kind of among Ti, Si, Zr, Ta, the Al.
3. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1 is characterized in that: the high polymer binder of step in 1. is alginate or polyvinyl alcohol, and its concentration is 1%～15%, and solvent is a kind of in water, ethanol, the ethylene glycol.
4. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1 is characterized in that: the solid material of described step in 2. is the reacting material mixture of preparation ternary lithium compound.
5. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 4 is characterized in that: the reacting material mixture of the preparation ternary lithium compound of described step in 2. is Li
2CO3 and SiO
2Powder, Li
2CO
3And TiO
2Powder, Li
2CO
3And Al
2O
3Powder, Li
2CO
3And ZrO
2Powder, LiNO
3And TiO
2Powder, LiNO
3And SiO
2Powder, Li2CO
3And TaO
2A kind of in the powder combinations.
6. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1 is characterized in that: the solid material of described step in 2. is ternary lithium compound ceramic powder.
7. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1 is characterized in that: the defoamer of step in 2. is isooctyl alcohol or lipid acid.
8. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1, it is characterized in that: the low-temperature cooling media of step in 4. can be one or more in liquid nitrogen, liquid helium, the ethylene glycol solvent, the temperature of low-temperature cooling media is-193 ℃～-100 ℃, and system's gauge pressure scope that pressure control system is controlled is 0.2KPa～2MPa.
9. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1, it is characterized in that: described step is 5. middle to adopt temperature programming that the roasting of microballoon presoma is become green microspheres, wherein maturing temperature is 400 ℃ to 800 ℃, and roasting time is 12 hours to 48 hours.
10. the freeze forming preparation process of ternary lithium ceramic microphere according to claim 1 is characterized in that: the green microspheres of described step in 6. calcined and sintering, and wherein calcining temperature is 600 ℃ to 800 ℃, and calcination time is 12 hours to 48 hours; Sintering temperature is 900 ℃ to 1300 ℃, and sintering time is 12 hours to 48 hours.
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| CN101864620A (en) * | 2010-07-30 | 2010-10-20 | 哈尔滨工业大学 | Preparation method of silicon nitride whisker |
| CN102603305A (en) * | 2012-03-03 | 2012-07-25 | 赣州虔东稀土集团股份有限公司 | Forming method and device of ceramic micro-bead green body |
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| CN102603305A (en) * | 2012-03-03 | 2012-07-25 | 赣州虔东稀土集团股份有限公司 | Forming method and device of ceramic micro-bead green body |
| CN102603305B (en) * | 2012-03-03 | 2014-03-19 | 赣州虔东稀土集团股份有限公司 | Forming method and device of ceramic micro-bead green body |
| CN104200850A (en) * | 2014-08-22 | 2014-12-10 | 中国工程物理研究院核物理与化学研究所 | Lithium oxide centrifugal bead-making method and device |
| CN104200850B (en) * | 2014-08-22 | 2016-05-11 | 中国工程物理研究院核物理与化学研究所 | A kind of centrifugal ball making method and device of oxidate for lithium |
| CN106207150A (en) * | 2016-09-23 | 2016-12-07 | 湖南桑顿新能源有限公司 | A kind of atomizing freeze drying prepares the method for lithium cell negative pole material lithium titanate |
| CN107010955A (en) * | 2017-05-08 | 2017-08-04 | 中国科学院上海应用物理研究所 | A kind of preparation method of the ceramic microsphere of thorium oxide |
| CN107010955B (en) * | 2017-05-08 | 2019-08-06 | 中国科学院上海应用物理研究所 | A kind of preparation method of the ceramic microsphere of thorium oxide |
| CN108911736A (en) * | 2018-08-13 | 2018-11-30 | 四川大学 | Lithium titanate ceramic bead preparation method and product based on hydrolysis combined solvent-thermal method |
| CN108911736B (en) * | 2018-08-13 | 2020-09-11 | 四川大学 | Preparation method of lithium titanate ceramic pellets based on hydrolysis combined solvothermal method and product |
| CN109454752A (en) * | 2018-10-31 | 2019-03-12 | 华中科技大学 | A kind of ceramic microsphere preparation method and its device |
| CN111217592A (en) * | 2020-01-13 | 2020-06-02 | 西安理工大学 | Preparation method of tritium-proliferated ceramic pellets with high lithium content based on molten salt growth method |
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| CN112125313A (en) * | 2020-09-30 | 2020-12-25 | 华中科技大学 | Spherical lithium-based CO2Method for preparing adsorbent |
| CN113927702A (en) * | 2021-11-30 | 2022-01-14 | 中国工程物理研究院核物理与化学研究所 | Preparation device and method of lithium ceramic microspheres |
| CN114292088A (en) * | 2021-12-30 | 2022-04-08 | 安徽大学 | Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof |
| CN114292088B (en) * | 2021-12-30 | 2022-10-11 | 安徽大学 | Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof |
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|---|---|
| CN100551877C (en) | 2009-10-21 |
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