CN108858681A - Mass prepares the equipment of bead biscuit and the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead - Google Patents
Mass prepares the equipment of bead biscuit and the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead Download PDFInfo
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- CN108858681A CN108858681A CN201810590004.8A CN201810590004A CN108858681A CN 108858681 A CN108858681 A CN 108858681A CN 201810590004 A CN201810590004 A CN 201810590004A CN 108858681 A CN108858681 A CN 108858681A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
- B28B3/20—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein the material is extruded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
- B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
- B28B3/20—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein the material is extruded
- B28B3/205—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein the material is extruded using vibrations
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- C—CHEMISTRY; METALLURGY
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6264—Mixing media, e.g. organic solvents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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Abstract
The invention discloses a kind of mass to prepare bead biscuit equipment, and based on provides the apparatus a kind of preparation methods of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead.The present invention first synthesizes the presoma powder of good dispersion, presoma powder is configured to slurry again, it is then based on the pneumatic wet process of high-pressure injection-, mass lithium titanate ceramic bead biscuit is obtained using the equipment that mass prepares bead biscuit, nanostructure metatitanic acid lithium ceramic bead is obtained finally by sintering processing, the yield for effectively increasing nanostructure metatitanic acid lithium ceramic bead realizes the mass production of nanostructure metatitanic acid lithium ceramic bead；And the preparation method also has many advantages, such as simple process, at low cost, is suitable for promoting the use of in this field.
Description
Technical field
The invention belongs to nuclear energy technology fields, are related to the preparation of tritium multiplication agent, and in particular to a kind of tritium multiplication agent tritium proliferation
The mass technology of preparing of agent nanostructure metatitanic acid lithium ceramic bead.
Background technique
Realize fusion energy controllably and civil nature be mankind's pursuit one of target, International Thermal-Nuclear Experimental Reactor (ITER)
(be commonly called as " artificial sun " plan, be one of maximum big science engineering International Sci & Tech Cooperation plan in the world today, and so far I
The largest International Sci & Tech Cooperation plan that state participates in；It is intended to realize that fusion energy is controllable by the cooperation made the country prosperous with world technology
Change, commercialization, target is the Science and Technology feasibility of verifying peaceful use fusion energy.It most possibly realizes at present controllable
Fusion reaction first is that magnetic confinement nuclear fusion, magnetic confinement nuclear fusion be with the magnetic field of specific form the light atoms such as deuterium, tritium core and
Free electron the forms, ultra-high temperature plasma in thermonuclear reaction state constrains in limited volume, controls it
A large amount of atom nuclear fusion reaction occurs for ground, releases heat.Reaction raw materials deuterium can largely be extracted from seawater, and tritium conduct
The isotope of non-natural existing hydrogen must react obtained with tritium multiplication agent (lithium-containing materials) by neutron and yield is lower.At present
Tritium multiplication agent mainly based on lithium ceramic bead, solid lithium ceramic bead as the tritium multiplication agent in deuterium tritium fusion reaction compared to
Liquid tritium multiplication agent overcomes MHD effect, while having many advantages, such as that chemical stability is good, high safety, in recent years
By the favor of domestic and international experts and scholars.In numerous lithium-based ceramics, people pass through steady to lithium content, chemical stability, heat
The composite factors such as qualitative, production tritium rate are considered, it is believed that lithium titanate is one of most promising solid tritium proliferation agent material.Lithium pottery
The shape of porcelain tritium multiplication agent has cyclic annular, column and spherical, wherein spherical tritium multiplication agent large specific surface area (is suitable for complicated shape ball bed
Handling), good permeability, bulk density it is high (helping to obtain high lithium density), and thermal stress and irradiation rupture can be reduced
Deng, therefore, tritium proliferation ceramics generally use spherical shape.ITER member state in 2007, which combines, proposes the items of tritium proliferation ceramic bead
Reference index：(1) crystallite dimension less than 5 μm (according to the literature, in order to obtain it is good release tritium performance, the crystalline substance of tritium proliferation ceramics
Particle size is more preferably less than 1 μm)；(2) microballoon consistency is more than 80~85%T.D.；(3) 0.25~2mm of bead size；(4) ball
Shape degree is greater than 0.7.
The Flouride-resistani acid phesphatase that the nanostructure tritium multiplication agent ceramic bead of little crystal grain can effectively improve and release tritium rate, improve material
Performance and mechanical property.However since nano-powder is easy to reunite, precursor pulp poor fluidity leads to the bead being prepared
Sphericity is low and crystal grain such as is easy to grow up the reasons during the sintering process, does not find to prepare nanometer tritium multiplication agent about mass at present
The report of bead.Existing ceramic bead preparation method includes capillary microfluidic technology, graphite nodule bed process, extrusion-round as a ball-sintering process
With molten atomizing method etc.；Capillary microfluidic technology is to be expressed into precursor pulp in silicone oil phase by surface by capillary
Power molding；Graphite nodule bed process is that by syringe needle extrusion, to be dropped in graphite bed spherical groove under the effect of gravity fast by precursor pulp
Speed is adsorbed by drying molding；Extrusion-round as a ball-sintering process is precursor pulp to be squeezed out to bar shaped, then be cut into blocky drying, rolling ball milling
Molding, obtains ceramic bead finally by calcining；Molten atomizing method is to melt ceramic powder at high temperature, by spray-on process at
Type, then ceramic bead is obtained through drying, sintering.These methods are lower to the extrusion process requirement of slurry, only to few dispersion of reuniting
Property good non-nano tritium multiplication agent slurry be more suitable for.Crystallite dimension is needed in nanoscale ceramic bead with grain in order to obtain
For diameter size in nanoscale nano-powder as presoma powder, nano-powder would generally reduce own face energy by reuniting
To reach the state of being stabilized, and reunite and often lead to slurry fluidity variation, is not easy extrusion molding.Furthermore existing ceramic bead
Preparation method is influenced more by extraneous factor (silicone oil, graphite, high temperature etc.), it is easy to lead to ceramic crystalline grain in later period sintering process
It grows up, mechanical properties decrease is unfavorable for the preparation of nanostructure tritium proliferation ceramics；And above-mentioned preparation method cannot achieve daily output
Feather weight ceramic bead, it is difficult to reach the target of lithium titanate ceramic bead mass production.
Therefore the equipment for researching and developing a kind of mass production nanometer tritium multiplication agent lithium titanate bead biscuit, for realizing tritium
High-volume control oneself, promote " tritium factory " plan implementation it is most important.
Summary of the invention
The purpose of the present invention is intended in view of the deficiency of the prior art, provide a kind of mass and prepare bead biscuit
Equipment, and be used for preparing lithium titanate ceramic bead, to improve lithium titanate ceramic bead yield, realize its batch metaplasia
It produces.
Another object of the present invention is intended to that it is small to provide a kind of tritium multiplication agent nanostructure metatitanic acid lithium ceramics based on above equipment
The preparation method of ball further increases the spherical shape of ceramic bead while improving lithium titanate tritium multiplication agent ceramic bead yield
Degree, and by the control of ceramic bead crystallite dimension in nanometer range.
Thinking of the invention is the presoma powder for first synthesizing good dispersion, then presoma powder is configured to slurry, is led to
It crosses wet forming and obtains lithium titanate ceramic bead biscuit, obtain lithium titanate ceramic bead finally by sintering processing.Wherein, it influences
The key of lithium titanate ceramic bead volume production is the preparation of lithium titanate ceramic bead biscuit, for this purpose, the present invention is based on current wet processes
Moulding process provides a kind of equipment that the pneumatic wet process mass of high-pressure injection-prepares bead biscuit.
The equipment that mass provided by the invention prepares bead biscuit, including for loading slurry the first container, be used for
Load second container, vibrator, slip casting machine and the air compressor machine of liquid nitrogen；The first container is fixed on pillar, and first holds
Device is container closed at both ends, and end face is provided with grouting port (A) and air inlet (B) thereon, and lower end surface is evenly distributed with several
The syringe needle communicated with container intracavity, Needle outlet position are provided with drainage silk；The second container be located at the first container just under
Side, second container are the container of lower end closed, and intracavity bottom is stacked with several layers sieve；The vibrator is mounted on the first appearance
On the outside of device lower edge；The slurry outlet of the slip casting machine is connected to by pipe fitting with the first container upper surface grouting port (A)；It is described
Air compressor machine output end is connected to by pipe fitting with the first container upper surface air inlet (B).
The equipment that above-mentioned mass prepares bead biscuit, the slurry in the first container is under air pressure and gravity from needle point
Place squeezes out, and and then bestirs oneself in the guidance of drainage silk and the micro- of vibrator and drips under, on second container liquid nitrogen surface by gravity
And surface tension effects forming, through on the cooling sieve being deposited in second container of liquid nitrogen.It is arranged on syringe needle through the invention
Drainage silk and be mounted on the vibrator of the first container lower edge so that the sphericity of bead biscuit has obtained greatly changing
It is kind.
The equipment that above-mentioned mass prepares bead biscuit, in order to obtain diameter in the bead of 0.25~2mm, the syringe needle
Hole aperture is about 0.2~2.5mm, the spacing at least 40mm between adjacent two syringe needle, to prevent the bead liquid squeezed out from syringe needle
It is drained silk and drops onto mutually viscous glutinous influence yield when liquid nitrogen surface.
The equipment that above-mentioned mass prepares bead biscuit, the drainage silk are copper wire, nylon yarn etc..In order to obtain sphericity
Preferable bead, and the drainage silk in needle adjacent is avoided to wind, the drainage silk diameter are not more than 0.1mm, and length is 10~
15mm。
The equipment that above-mentioned mass prepares bead biscuit, several layers sieve, which is stacked together, is placed in second container bottom, when
It is just pulled out (such as every the one layer of sieve of taking-up in 1 hour) after the sieve a certain number of beads of deposited thereon, makes subsequent to fall into liquid
Bead in nitrogen deposits on next layer of sieve, excessively squeezes viscous stick to avoid accumulating because of bead.In order to keep bead biscuit heavy
For product on sieve, the aperture of the sieve is less than the diameter of obtained bead biscuit, and in preferred embodiment, mesh size is about
For 0.50~0.83mm.For the ease of taking out sieve from second container, the screen periphery is at least equipped with a stretching
The handle of second container open end, handle tail end are in hook formation.
The equipment that above-mentioned mass prepares bead biscuit, the quantity of vibrator can be it is multiple, in order to make to squeeze out from syringe needle
Slurry receive uniform micro- use of bestirring oneself even number vibrator be evenly arranged in the first container in a preferred embodiment
Lower edge.
The equipment that above-mentioned mass prepares bead biscuit, when the spacing between the first container and second container is improper,
The second container can be placed on lifting platform；For ease of operation, the slurry machine and air compressor machine are placed in and are equipped with electricity
On the workbench in source.
Based on the equipment that above-mentioned mass prepares bead biscuit, invention further provides a kind of tritium multiplication agent nanometers
The preparation method of structural lithium titanate ceramic bead, steps are as follows：
(1) presoma powder is prepared
Lithium hydroxide is added to ethyl alcohol and deionized water according to volume ratio 1:First in the mixed solvent of 2 compositions, and in
40~60 DEG C of heating stirring to lithium hydroxides are completely dissolved, and obtain the solution that lithium concentration is 0.5~2.0mol/L；Then it presses
It is 2 according to lithium ion, titanium ion, cetyl trimethylammonium bromide molar ratio:1:0.06 metering nano-titanium dioxide and hexadecane
Base trimethylammonium bromide, and nano-titanium dioxide, cetyl trimethylammonium bromide be added sequentially to described dissolved with hydroxide
The first mixed liquor is obtained in the solution of lithium, the first mixed liquor of gained is transferred in reaction kettle, is warming up to 180~200 DEG C of reactions extremely
Few 20h；After reaction, isolate product and product is dry, be ground up, sieved to get to presoma powder；
(2) lithium titanate ceramic bead biscuit is prepared
The equipment for preparing bead biscuit using the mass operates as follows：By step (1) obtain presoma powder with
By polyacrylic acid and deionized water according to volume ratio 1:(4~5) it is 1.0 that the second mixed solvent formed, which is uniformly mixed and obtains concentration,
The slurry of~1.1g/mL then injects slurry in slip casting machine, starts slip casting machine, slurry is injected into first by slip casting machine
In container, start vibrator and air compressor machine, slurry squeezes out under air pressure and gravity from Needle outlet, under drainage silk guidance
It instills in liquid nitrogen and forms bead, bead is removed from liquid nitrogen to using sieve freeze-dried to obtain lithium titanate ceramics small after rear
Ball biscuit；
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 4~5h of sintering in 775~800 DEG C of sintering furnace, is burnt
It cools to room temperature after knot with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
The preparation method of above-mentioned tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead, the purpose of step (1) is to prepare powder
The nanometer presoma powder that uniform particle diameter, diameter are about 30~40nm, using mixed solvent thermal method, the first mixing used is molten
Agent is according to volume ratio 1:2 mixed ethyl alcohol and deionized water.Lithium hydroxide is first dissolved into the first in the mixed solvent, then will
Titanium dioxide and cetyl trimethylammonium bromide (CTAB) are added in the solution dissolved with lithium hydroxide and carry out solvent thermal reaction,
The addition of CTAB facilitates the dispersion of powder, inhibits the generation of aggregate.Being to the mode that gained reaction solution is dried will be anti-
It answers liquid to be placed in 12~15h of heat preservation in 70~80 DEG C of constant temperature blast drying ovens, dry obtained material is then ground up, sieved (sieve
Aperture be 250 mesh) to get to i.e. presoma powder.
The preparation method of above-mentioned tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead, the purpose of step (2) is mass system
The precursor powder that step (1) obtains first is configured to slurry, and slurry is ground uniformly by standby lithium titanate ceramic bead biscuit,
Specific implementation is that prepared slurry is placed in 1000ml nylon ball grinder, using 3mm zirconia ball as ball milling
Ball, 6~8h of ball milling in planetary ball mill.Then the good slurry of ball milling is poured into the preparation of lithium titanate ceramic bead biscuit mass
In the slip casting machine of equipment, by adjusting atmospheric pressure value, vibrator rate, the drainage filament length degree of air engine, liquid nitrogen surface and drainage silk
The lithium titanate ceramic bead biscuit of composite demand is prepared in four parameters of distance.In order to control in the first container slurry from syringe needle
The air pressure of the rate of extrusion, the air compressor machine is set as 20~25kgf/cm2.Slurry in the first container is made in high pressure and gravity
It under, exports and squeezes out from the needle point of syringe needle, then deposited in liquid nitrogen shaping surface through cooling under gravity and surface tension effects
In second container on the sieve of bottom.
The preparation method of above-mentioned tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead, the purpose of step (3) are sintering preparations
Nanostructure metatitanic acid lithium ceramic bead, to temperature extreme sensitivity, crystal grain is difficult to be sintered lithium titanate ceramic bead under low temperature environment, close
It is poor to spend low-intensity.Hot environment crystal grain is easily grown up, so selecting suitable sintering temperature and sintering time most important.Pass through
Test of many times analysis finally prepares crystallite dimension in 775~800 DEG C of temperature sections and is about 70~100nm and has certain fine and close
The nanostructure metatitanic acid lithium ceramic bead of degree and intensity.
Compared with prior art, the invention has the advantages that：
1, the equipment that mass of the present invention prepares bead biscuit, based on the pneumatic wet process principle of high-pressure injection-, in the first container
Slurry continuously squeezed out from several syringe needles that bottom is evenly arranged under air pressure and gravity, fall into liquid nitrogen formed it is small
Ball, it can be achieved that bead biscuit mass production, have the characteristics that structure is simple, at low cost, work efficiency is high, be suitable in ability
It is promoted the use of in domain；
2, the equipment that mass of the present invention prepares bead biscuit is provided with drainage silk on the syringe needle for squeezing out slurry,
The water conservancy diversion and the micro- of vibrator for draining silk are bestirred oneself under use, and the sphericity of bead biscuit can be greatly improved；
3, the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead of the present invention first synthesizes the forerunner of good dispersion
Body powder, then presoma powder is configured to slurry, it is then based on the pneumatic wet process of high-pressure injection-, prepares bead using mass
The equipment of biscuit obtains mass lithium titanate ceramic bead biscuit, obtains nanostructure metatitanic acid lithium ceramics finally by sintering processing
Bead effectively increases the yield of lithium titanate ceramic bead, realizes the mass production of lithium titanate ceramic bead；And the preparation
Method also has many advantages, such as simple process, at low cost, is suitable for promoting the use of in this field；
4, the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead of the present invention, by lithium titanate ceramic bead biscuit
It is sintered at (775~800 DEG C) of suitable hot conditions, the final crystallite dimension that obtains is in nanometer scale and the preferable titanium of mechanical property
Sour lithium ceramic bead；
5, the nanostructure metatitanic acid lithium ceramic bead crystallite dimension that preparation method of the present invention obtains is in nanometer scale, sphericity
Good, bead surface has certain porous structure, and be conducive to tritium is taken away by carrier gas, releases tritium efficiency with certain rush for raising
Into effect.
Detailed description of the invention
Fig. 1 is the device structure schematic diagram that mass of the present invention prepares nanostructure metatitanic acid lithium ceramic bead biscuit.1-
One container, 2- second container, 3- vibrator, 4- slip casting machine, 5- air compressor machine, 6- syringe needle, 7- sieve, 8- handle, 9- lifting platform,
10- workbench, 11- pillar, 12- clip.
Fig. 2 is 2 gained presoma powder Microstructure characterization picture of the embodiment of the present invention, wherein (a) is SEM picture,
It (b) is TEM picture.
Fig. 3 is lithium titanate ceramic bead biscuit picture obtained by the embodiment of the present invention, wherein (a) corresponding embodiment 2, (b)
Corresponding embodiment 3, (c) corresponding embodiment 4, (d) corresponding embodiment 5, (e) corresponding embodiment 6.
Fig. 4 is the XRD of nanostructure metatitanic acid lithium ceramic bead obtained by the embodiment of the present invention is prepared under different sintering conditions
Map, wherein the nanostructure metatitanic acid that 2 lithium titanate ceramic bead biscuit of (a) corresponding embodiment is sintered under the conditions of 775 DEG C
The characteristic peak of lithium ceramic bead, (b) 7 lithium titanate ceramic bead biscuit of corresponding embodiment is sintered receiving of obtaining under the conditions of 800 DEG C
The characteristic peak of rice structural lithium titanate ceramic bead.
Fig. 5 is the XRD of nanostructure metatitanic acid lithium ceramic bead obtained by the embodiment of the present invention is prepared under different sintering conditions
Map, wherein the nanostructure metatitanic acid that 2 lithium titanate ceramic bead biscuit of (a) corresponding embodiment is sintered under the conditions of 775 DEG C
The SEM picture under 10000 times is amplified in lithium ceramic bead cross section, and (b) 1 lithium titanate ceramic bead biscuit of corresponding embodiment is 775
The SEM picture under 50000 times is amplified in the nanostructure metatitanic acid lithium ceramic bead cross section being sintered under the conditions of DEG C, (c) corresponding
The nanostructure metatitanic acid lithium ceramic bead cross section that 7 lithium titanate ceramic bead biscuit of embodiment is sintered under the conditions of 800 DEG C
SEM picture under 10000 times of amplification, (d) 6 lithium titanate ceramic bead biscuit of corresponding embodiment is sintered under the conditions of 800 DEG C and obtains
Nanostructure metatitanic acid lithium ceramic bead cross section amplify 50000 times under SEM picture.
Specific embodiment
Clear, complete description is carried out below with reference to technical solution of the attached drawing to various embodiments of the present invention, it is clear that is retouched
Stating embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill obtained all other embodiment without making creative work, belongs to this hair
Bright protected range.
Embodiment 1
A kind of equipment that mass prepares bead biscuit is present embodiments provided, as shown in Figure 1 comprising for loading slurry
The first container 1 of material, the second container 2 for loading liquid nitrogen, vibrator 3, slip casting machine 4 and air compressor machine 5.The first container 1 passes through
Clip 12 is fixed on plumb post 11, the first container be container closed at both ends, the upper end be provided with grouting port A and into
Port B, lower end surface are evenly distributed with 15 syringe needles communicated with container intracavity 6 (inner hole aperture is 0.7mm), Needle outlet position
It is provided with drainage copper wire, drainage brass wire diameter is not more than 0.1mm, and length is 10~15mm, and drainage copper wire distance from bottom second holds
The height of liquid nitrogen liquid level is 300~500mm in device.Second container 2 is placed on the lifting platform 9 immediately below the first container 1, and second
Container is the container of lower end closed, and inner cavity stacks 7,8 layers of sieve 7 of sieve that 8 layers of aperture are 0.5mm and is stacked together and is placed in
Second container bottom, screen periphery are equipped with the handle 8 of a stretching second container open end, and handle tail end is in hook formation.
The quantity of the first container lower edge vibrator 3 is four, and four vibrators 3 are evenly arranged in outside the first container lower edge
Side.Slurry machine and air compressor machine are placed on the workbench 10 for being equipped with power supply, and the slurry outlet of slip casting machine 4 passes through pipe fitting and first
6 upper surface grouting port A of container connection, 5 output end of air compressor machine are connected to by pipe fitting with 6 upper surface air inlet B of the first container.
Above-mentioned drainage copper wire is welded to the needle point periphery of syringe needle by soldering iron.
Woods motor USB-3 vibrating motor in the model of vibrator 3, all slip casting machine DF-999 of the model base of a fruit of slip casting machine 4,
The cruel czk3603 of model vehicle will of air compressor machine 5.
The equipment application method that above-mentioned mass prepares bead biscuit is：The slurry of bead biscuit will be prepared first from pan feeding
In mouth injection slip casting machine, start slip casting machine 4, is injected the slurry in slip casting machine along the first container 1 along pipe fitting by high pressure, immediately
Starting air compressor machine 5 and vibrator 3, and adjust air compressor machine air pressure be 20~25kgf/cm2, the slurry in the first container 1 exists
It is squeezed out from needle point under air pressure and gravity, and then bestirs oneself in the guidance of drainage silk and the micro- of vibrator and dripped under,
Second container liquid nitrogen surface is shaped by gravity and surface tension effects, through the cooling sieve 7 being deposited in second container 2 of liquid nitrogen
On.The one layer of sieve for being deposited with bead biscuit taking-up was taken out every 1 hour to be freeze-dried, make it is subsequent fall into it is small in liquid nitrogen
Ball deposits on next layer of sieve, until the slurry in the first container is finished, completes the preparation of bead biscuit.Out of second container
The bead biscuit pulled out enters next step sintering process after drying.
Yield using above equipment preparation nanostructure metatitanic acid lithium ceramic bead biscuit is about 250~300g/h, significantly
The yield of lithium titanate tritium ceramic bead biscuit is improved, and then helps to realize the mass of lithium titanate tritium multiplication agent ceramic bead
Production.
The equipment that step (2) uses mass described in embodiment 1 to prepare bead biscuit in following example 2-11.
Embodiment 2
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen；It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 3
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 20kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen；It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 4
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 4500rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen.It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 5
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 10mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen.It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 6
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 300mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen.It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 7
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen.It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.(3) nanostructure metatitanic acid is prepared
Lithium ceramic bead
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 800 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 8
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 12.72g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is 0.5mol/L's
Solution；Then 12.01g particle size 5~10nm anatase nano-titanium dioxide and 3.32gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 180
DEG C reaction 22h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 91ml polyacrylic acid and 409ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator (its
Revolving speed is 3000rpm), slurry is squeezed out, is being drained from syringe needle (inner hole aperture is 0.70mm) outlet under air pressure and gravity
Copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm) guidance
In lower instillation liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen；One layer, which was taken out, every 1 hour is deposited with bead
Sieve takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is finished, from
The bead taken out in liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 9
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 80 DEG C of dry 12h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 550g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 550g step (1) obtains be made of 83ml polyacrylic acid and 417ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1.1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine,
Slurry is injected into the first container by high pressure, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen；It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 10
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 50.86g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is the molten of 2mol/L
Liquid；Then 48.02g particle size 5~10nm anatase nano-titanium dioxide and 13.26gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 200
DEG C reaction 20h；After reaction, it isolates product and grinds product in 70 DEG C of dry 15h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived.
It repeats step (1) to the precursor weight obtained and is greater than 500g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 500g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 8h obtains the slurry that concentration is 1g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting machine, leads to
It crosses high pressure slurry is injected into the first container, and then starting air compressor machine, (air pressure is set as 25kgf/cm2) and vibrator
(its revolving speed is 3000rpm), slurry squeeze out under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet,
Drain copper wire (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container is 500mm)
Guidance is lower to be instilled in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen；It is deposited with every one layer of taking-up in 1 hour small
The sieve of ball takes out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until the slurry in the first container is used
Complete, the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 5h, after sintering
It cools to room temperature with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
Embodiment 11
(1) presoma powder is prepared
By mono- hydronium(ion) lithia of 38.15g be added to 200ml ethyl alcohol with 400ml deionized water forms first mix it is molten
In agent, and heating stirring 30min is completely dissolved to lithium hydroxide in 50 DEG C of oil baths, and obtaining lithium concentration is 1.5mol/L's
Solution；Then 36.02g particle size 5~10nm anatase nano-titanium dioxide and 9.95gCTAB are added sequentially to described molten
Have and obtain the first mixed liquor in the solution of lithium hydroxide, the first mixed liquor of gained is transferred in 1000ml reaction kettle, is warming up to 190
DEG C reaction 21h；After reaction, it isolates product and grinds product in 75 DEG C of dry 13h, then by the product after drying
Mill crosses 250 meshes to get presoma powder is arrived；
It repeats step (1) to the precursor weight obtained and is greater than 525g.
(2) lithium titanate ceramic bead biscuit is prepared
By presoma powder that 525g step (1) obtains be made of 100ml polyacrylic acid and 400ml deionized water the
The mixing of two mixed solvents is placed in 1000ml nylon ball grinder (using 600 3mm zirconium oxides as ball milling ball), in planetary ball mill
Middle ball milling 6h obtains the slurry that concentration is 1.05g/mL, then injects in slip casting machine slurry by feeding inlet, starts slip casting
Slurry is injected into the first container by machine by high pressure, is and then started air compressor machine (air pressure is set as 25kgf/cm2) and is shaken
Dynamic device (its revolving speed is 3000rpm), slurry squeeze under air pressure and gravity from syringe needle (inner hole aperture is 0.70mm) outlet
Out, in drainage copper wire, (diameter 0.1mm, length 15mm, the height for draining liquid nitrogen liquid level in copper wire distance from bottom second container are
500mm) guidance is lower instills in liquid nitrogen, through on the cooling sieve being deposited in second container of liquid nitrogen；One layer was taken out every 1 hour to sink
Product has the sieve of bead to take out, make it is subsequent fall into the bead in liquid nitrogen and deposit on next layer of sieve, until in the first container
Slurry is finished, and the bead being removed from liquid nitrogen is freeze-dried to obtain lithium titanate ceramic bead biscuit.
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 775 DEG C of sintering furnace and is sintered 4.5h, sintering terminates
After cool to room temperature with the furnace and obtain nanostructured titanium acid lithium ceramic bead.
To above-mentioned section Example preparation presoma powder, lithium titanate ceramic bead biscuit and lithium titanate ceramic bead into
Row pattern, structure and performance evaluation：
1, presoma powder
The presoma powder obtained to 2 step of embodiment (1) carries out SEM and TEM morphology analysis, as a result as shown in Fig. 2, from
It is uniform to can be seen that the presoma powder structure that the solvent-thermal method provided through the invention is prepared in figure, dispersibility is preferable,
No big aggregate exists.
2, lithium titanate ceramic bead biscuit
It is taken pictures to the lithium titanate ceramic bead biscuit that 6 step of embodiment (2) obtains by camera to embodiment 2 and carries out pattern
Analysis, analysis result in embodiment 2 by the equipment that embodiment 1 provides as shown in figure 3, it can be seen from the figure that be prepared
Mass lithium titanate ceramic bead preform structure it is uniform, bead biscuit sphere diameter is between 0.8~1.2mm, sphericity 1.03；
The mass lithium titanate ceramic bead preform structure being prepared in embodiment 3 by the equipment that embodiment 1 provides is uniform, bead
Biscuit sphere diameter is between 0.9~1.3mm, sphericity 1.06；It is prepared in embodiment 4 by the equipment that embodiment 1 provides
Mass lithium titanate ceramic bead preform structure it is uniform, between 1.0~1.3mm, sphericity is bead biscuit sphere diameter
1.03；The mass lithium titanate ceramic bead preform structure being prepared in embodiment 5 by the equipment that embodiment 1 provides is equal
Even, bead biscuit sphere diameter is between 0.9~1.1mm, sphericity 1.04；The equipment system provided in embodiment 6 by embodiment 1
Standby obtained mass lithium titanate ceramic bead preform structure is uniform, and bead biscuit sphere diameter is between 0.8~1.0mm, sphericity
It is 1.07.
As can be seen from the above analysis, the equipment provided through the invention is realizing lithium titanate ceramic bead biscuit batch
While metaplasia produces, phase purity, the structural homogeneity of lithium titanate ceramic bead biscuit ensure that.
3, nanostructure metatitanic acid lithium ceramic bead
XRD analysis, analysis knot are carried out to the nanostructure metatitanic acid lithium ceramic bead that embodiment 2 and embodiment 7 are prepared
Fruit is as shown in figure 4, the nanostructure metatitanic acid lithium ceramic bead that as can be seen from the figure preparation method obtains through the invention is free of
Other miscellaneous phases, purity is high, meet operating condition requirement.
Sem analysis, analysis knot are carried out to the nanostructure metatitanic acid lithium ceramic bead that embodiment 2 and embodiment 7 are prepared
Fruit as shown in figure 5, as can be seen from the figure nanostructure metatitanic acid lithium ceramic bead crystallite dimension nanometer scale (71.36~
99.21nm), its surface has certain porous structure, this is conducive to tritium and is taken out of by carrier gas, releases tritium efficiency with one for raising
Fixed facilitation.
The nanostructure metatitanic acid lithium ceramic bead mechanical property characterization that 1 embodiment 2 of table and embodiment 7 are prepared
The mechanical property for the nanostructure metatitanic acid lithium ceramic bead that embodiment 2 and embodiment 7 are prepared is characterized,
Characterization parameter is shown in Table 1.It is obtained from table, with the raising of sintering temperature, crystallite dimension, relative density and crushing load are equal
It increases, but still meets requirement, temperature may cause that the bead density being prepared is low, crushing is strong lower than 775 DEG C
Spend it is small cause that lithium content is small, cracky under operating condition, it is difficult to load and unload.Temperature may cause crystal grain higher than 800 DEG C and grow up, according to fine grain
Strengthening mechanism, crushing strength can also reduce, and furthermore anti-radiation performance and release tritium performance and can also decline.Therefore it is considered herein that lithium titanate
The optimal calcination temperature of nano ceramics is 775 DEG C to 800 DEG C.
Claims (10)
1. the equipment that a kind of mass prepares bead biscuit, it is characterised in that including the first container (1), the use for loading slurry
In the second container (2), vibrator (3), slip casting machine (4) and the air compressor machine (5) that load liquid nitrogen；The first container (1) installation is solid
It being scheduled on pillar (11), the first container is container closed at both ends, and end face is provided with grouting port (A) and air inlet (B) thereon,
Lower end surface is evenly distributed with several syringe needles (6) communicated with container intracavity, and Needle outlet position is provided with drainage silk；Described second
Container is located at the underface of the first container, and second container is the container of lower end closed, and intracavity bottom is stacked with several layers sieve
(7)；The vibrator (3) is mounted on the outside of the first container lower edge；The slurry outlet of the slip casting machine (4) by pipe fitting with
The first container (6) upper surface grouting port (A) connection；Air compressor machine (5) output end passes through pipe fitting and the first container (6) upper surface
Air inlet (B) connection.
2. the equipment that mass prepares bead biscuit according to claim 1, it is characterised in that the syringe needle inner hole hole
Diameter is 0.2~2.5mm.
3. the equipment that mass prepares bead biscuit according to claim 2, it is characterised in that the drainage silk diameter is little
In 0.1mm, length is 10~15mm.
4. according to claim 1 to the equipment that mass described in 3 any claims prepares bead biscuit, it is characterised in that described
The aperture of sieve is less than the diameter of bead biscuit.
5. the equipment that mass prepares bead biscuit according to claim 4, it is characterised in that the screen periphery is at least pacified
The handle (8) of second container open end is stretched out equipped with one.
6. the equipment that mass prepares bead biscuit according to claim 4, it is characterised in that the second container (2) is placed
In on lifting platform (9)；The slurry machine (4) and air compressor machine (5) are placed on the workbench (10) for being equipped with power supply.
7. a kind of preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead, it is characterised in that steps are as follows：
(1) presoma powder is prepared
Lithium hydroxide is added to ethyl alcohol and deionized water according to volume ratio 1:First in the mixed solvents of 2 compositions, and in 40~
60 DEG C of heating stirring to lithium hydroxides are completely dissolved, and obtain the solution that lithium concentration is 0.5~2.0mol/L；Then according to lithium
Ion, titanium ion, cetyl trimethylammonium bromide molar ratio be 2:1:0.06 metering nano-titanium dioxide and cetyl
Trimethylammonium bromide, and nano-titanium dioxide, cetyl trimethylammonium bromide be added sequentially to described dissolved with lithium hydroxide
Solution in obtain the first mixed liquor, the first mixed liquor of gained is transferred in reaction kettle, be warming up to 180~200 DEG C reaction at least
20h；After reaction, isolate product and product is dry, be ground up, sieved to get to presoma powder；
(2) lithium titanate ceramic bead biscuit is prepared
The equipment for preparing bead biscuit using mass described in any claim in claim 1 to 6 operates as follows：It will step
Suddenly (1) obtain presoma powder with by polyacrylic acid and deionized water according to volume ratio 1:(4~5) the second mixing of composition is molten
Agent, which is uniformly mixed, obtains the slurry that concentration is 1.0~1.1g/mL, then injects in slip casting machine slurry, starts slip casting machine, pass through
Slurry is injected into the first container by slip casting machine, starts vibrator and air compressor machine, slurry is under air pressure and gravity from syringe needle
Outlet squeezes out, and instills in liquid nitrogen under drainage silk guidance and forms bead, bead is removed from liquid nitrogen through cold using sieve after rear
Freeze drying to obtain lithium titanate ceramic bead biscuit；
(3) nanostructure metatitanic acid lithium ceramic bead is prepared
The lithium titanate ceramic bead biscuit that step (2) obtain is put into 4~5h of sintering in 775~800 DEG C of sintering furnace, sintering knot
It cools to room temperature after beam with the furnace and obtains nanostructured titanium acid lithium ceramic bead.
8. the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead according to claim 7, it is characterised in that institute
It states in step (2), the air pressure of the air compressor machine is set as 20~25kgf/cm2。
9. claim 7 or the tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead of 8 the methods preparation.
10. tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead according to claim 9, it is characterised in that the lithium titanate pottery
The crystallite dimension of porcelain bead is 70~100nm.
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