CN103408319A - Method for preparing porous ceramic microspheres with different pore structures and spraying and freezing device - Google Patents
Method for preparing porous ceramic microspheres with different pore structures and spraying and freezing device Download PDFInfo
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Abstract
The invention discloses a method for preparing porous ceramic microspheres with different pore structures and a spraying and freezing device. The method comprises the following steps: preparing ceramic slurry at first; spraying the slurry in a controllable ring-shaped temperature field to be frozen, collecting the frozen particles to freeze and dry, rising the temperature to degrease, rising the temperature again to sinter to obtain a porous ceramic microsphere with a pore structure, and controlling the ring-shaped temperature field to obtain porous ceramic microspheres with different pore structures. The spraying and freezing device comprises a sprayer and a freezing device, wherein the freezing device takes a cylindrical liquid nitrogen container as the main body; the cylindrical liquid nitrogen container comprises a large-diameter cylinder and a small-diameter cylinder, which are concentric; the area between the large-diameter cylinder and the small-diameter cylinder is closed; a plurality of baffles are arranged in the area between the large-diameter cylinder and the small-diameter cylinder. The method is simple to operate, and the porous ceramic microspheres with uniform sizes, high degrees of sphericity and controllable pore structures can be prepared through the method, and the device has a simple structure, is strong in practicability, and can control the pore structures of the porous ceramic microspheres through controlling the temperature field.
Description
Technical field
The present invention relates to prepare method and the spray chilling device of the porous ceramics microballoon of Different Pore Structures, belong to the stupalith field.
Background technology
Porous microsphere has the characteristics such as specific surface area is large, density is low because its special structure makes it, has a wide range of applications in fields such as medical science, Materials science, can be used as catalyzer, pharmaceutical carrier etc.The size distribution of microballoon with and inner vesicular structure directly affect porosity and other performances of particle.Therefore, preparing required particle diameter microballoon and vesicular structure is one of gordian technique prepared porous microsphere.
At present, because the layered porous structure in microballoon can guide differentiation of stem cells or growth as the 3D support, caused that Chinese scholars is to its research boom in the application aspect biotechnology.Traditional spray-drying process for preparing porous microsphere (Spray Drying) method is atomized into small droplets by solution (or colloidal sol, slip), through solidify and drying after obtain spheroidal particle.Though this preparation method is simple and applied widely, but prepared porous particle distribution of sizes is inhomogeneous, and the vesicular structure controllability is poor.By the porous particle that will add the light-cured resin slurry to prepare after lyophilize, sphericity is better for novel FPC (Freeze Photocuring Casting), but particle size distribution is inhomogeneous, the vesicular structure poor controllability.For solving the inhomogeneous problem of particle size distribution, someone has proposed to adopt the inconsistent principle of water oil of O/W emulsion, wetting ability slurry and hydrophobic polymer are stirred to then freezing having prepared and have the microparticle that layered porous structure, particle size distribution evenly reach good sphericity, but particle size and pore texture are single, applicable material system narrow range.
Summary of the invention
The present invention is directed to spray-drying process in prior art exists the porous particle distribution of sizes of preparing inhomogeneous, and the poor defect of the controllability of vesicular structure, purpose be to provide a kind of simple to operate, can prepare size uniform, the method of the porous ceramics microballoon that sphericity is high and pore texture is controlled, the material system scope that the method is suitable for is wide, can suitability for industrialized production.
Another object of the present invention is to be to provide a kind of simple in structure but practical spray chilling device, but after this freezing plant freezing treatment preparation size size evenly and pore texture controlled, the much higher hole of sphericity ceramic microsphere.
The invention provides the method for the porous ceramics microballoon of preparation Different Pore Structures, the method is first ceramic powder and caking agent to be dispersed in solvent and to obtain slurry by dispersion agent; The slurry of gained is sprayed to and in regulatable annular temperature, carries out freezingly, and the particle of collecting freezing gained carries out lyophilize, obtains porous particle; The porous particle of gained is slowly intensification degreasing first, then is warmed up to the sintering temperature sintering, obtains a kind of porous ceramics microballoon of pore structure, and annular temperature field is regulated and controled to the porous ceramics microballoon that can make Different Pore Structures; Described regulation and control are to realize around the distribution of the amount of liquid nitrogen outside the venue of annular temperature by gate ring; The distribution of the amount of described liquid nitrogen is that liquid nitrogen is filled in the airtight annular region of round shape liquid nitrogen vessel, described annular region is to be formed by the zone between the concentrically ringed large radius cylinder of having of round shape liquid nitrogen vessel and minor radius cylinder and the baffle plate of interior setting thereof, the liquid nitrogen be filled with can be regulated it by the baffle plate arranged and distribute, and the zone in minor radius cylinder cylinder forms annular temperature; The described liquid nitrogen amount of being filled with is 100～7000mL can regulate and control annular temperature field between-170～20 ℃ temperature.
Described round shape liquid nitrogen vessel comprises having concentrically ringed large radius cylinder and minor radius cylinder, zone sealing between the two, and should in zone, be provided with some baffle plates; Sealing area between two concentric(al) circles cylinders has formed the round shape liquid nitrogen vessel of topping up nitrogen, realized that the liquid nitrogen be filled with is all formulas of ring and distributes, region division baffle plate between two concentric(al) circles cylinders again, should cut off into some minizones in zone, the liquid nitrogen be filled with is blocked in to the minizone that needs cooling, has realized the adjusting that liquid nitrogen is distributed.
Described round shape liquid nitrogen vessel top is provided with lid, in the middle of lid, is provided with a circular hole, and the slip drop after spraying enters annular temperature by circular hole; Lid seals liquid nitrogen, has guaranteed the stability of warm.
Described baffle plate is vertical shape baffle plate or horizontal shape baffle plate; Described horizontal shape baffle plate is circular baffle plate, and described vertical shape baffle plate is vertical rectangle baffle plate, vertical dentation baffle plate or vertical trilateral baffle plate; Selecting different baffle effect is that liquid nitrogen can be lowered the temperature in needed position, thereby can form different temperature according to the baffle plate of selecting is different, has also increased the stability of warm simultaneously.
Described spray height is 10cm～1000cm.
Described lyophilize is to be-20～-70 ℃ in temperature, and air pressure is to carry out under the condition of 8～40Pa.
Described sublimation drying is 17～28h.
Described concentric(al) circles cylinder heights is 30～300cm, and the radius of two concentric(al) circles cylinders is respectively 8～100cm and 16～200cm, and the two radius difference is 8～100cm.
Aforesaid method Small Radius bottom of cylinder is provided with movable screen cloth; The ceramic particle size that movable screen cloth can be selected as required and change the screen cloth of different mesh.
Described degreasing is with the temperature rise rate of 0.1～1 ℃/min, to be elevated to 550～650 ℃ from room temperature, then constant temperature 1.5～2.5h.
Described sintering is sintering under the corresponding sintering temperature of selection material.
The mass ratio of described ceramic powder and binding agent is 100:1～200:1, and the mass ratio of ceramic powder and dispersion agent is 70:1～150:1.
Described slurry solid load is 1～40vol.%.
In above-mentioned preparation method, ceramic powder is (as hydroxylapatite powder, aluminum oxide powder, zirconium white, titanium dioxide, the powder mix of Graphene and hydroxylapatite powder, the PZT powder, the powder mix of barium titanate and hydroxyapatite, barium titanate powder, the ferrous acid nickel powder, the powder mix of nickel ferrite based magnetic loaded and barium titanate, the titanium dioxide lead powder, the powder mix of KNN powder and hydroxylapatite powder etc.) with binding agent (as polyvinyl alcohol, polyvinyl butyral acetal etc.) pass through dispersion agent (as tricresyl phosphate second fat, cationic polyacrylamide, anionic polyacrylamide, non-ionic polyacrylamide etc.) be dispersed in water and/or short chain alcohol (comprises dehydrated alcohol, isopropylcarbinols etc.) in solvent, forming solid load is the slurry of 1～40vol.%.
The preparation method of porous ceramics microballoon of the present invention, concrete steps comprise:
Step 1:
The preparation slurry: ceramic powder and binding agent are mixed by dispersion agent and be dispersed in solvent and obtain the slurry that solid load is 1～40vol.%, by the slurry ball milling 18～26h prepared, standby; Wherein, the mass ratio of ceramic powder and binding agent is 100:1～200:1, and the mass ratio of ceramic powder and dispersion agent is 70～150:1;
Step 2:
Spray chilling is shaped: by the slurry of step 1 gained by atomizer spray in the regulatable annular temperature of freezing plant, drop moves downward in annular temperature field, freezing rear formation particle, the screen cloth of particle through having certain pore size, finally drop on collection container; Wherein, spray height is 10cm～1000cm; Freezing plant comprises atomizer and freezing plant, the freezing plant main body is the round shape liquid nitrogen vessel, the round shape liquid nitrogen vessel comprises the concentric(al) circles cylinder of two different radiis, the concentric(al) circles cylinder heights is 30～300cm, the radius of two concentric(al) circles cylinders is respectively 8～100cm and 16～200cm, and the radius difference is 8～100cm; Zone sealing between two concentric(al) circles cylinders; Between two cylinders, zone is provided with some baffle plates; Enclosed space between two concentric(al) circles cylinders is filled with the liquid nitrogen of 100～7000mL, and these liquid nitrogen form all formula isolation of ring and distribute between big or small cylinder by barrier partitions, can freely regulate and control a temperature temperature and maintain between-170～20 ℃; The amount of being filled with by regulating nitrogen and select different baffle plates, regulate and control annular temperature, prepares the particle of Different Pore Structures;
Step 3:
Lyophilize: at-20～-70 ℃, air pressure is to carry out lyophilize under the condition of 8～40Pa by the particle collected in step 2 collection container, makes the ice crystal as template in particle or the solid-state distillation mutually of other solvents, forms porous particle;
Step 4:
Degreasing sintered: the porous particle after step 3 lyophilize is being placed in to stove, with the temperature rise rate of 0.1～1 ℃/min, is being elevated to 550～650 ℃ from room temperature, then constant temperature 1.5～2.5h carries out binder removal, then at the sintering temperature sintering of selected stupalith; Obtain the porous ceramics microballoon.
The spray chilling device that the present invention also provides a kind of method for preparing the porous ceramics microballoon of Different Pore Structures to use, comprise atomizer and freezing plant, described freezing plant main body is the round shape liquid nitrogen vessel, the round shape liquid nitrogen vessel comprises having concentrically ringed large radius cylinder and minor radius cylinder, zone sealing between the two; Between described large radius cylinder and minor radius cylinder, be provided with some baffle plates in zone.
Described baffle plate is longitudinal baffle and horizontal shape baffle plate.
Described horizontal shape baffle plate is circular baffle plate, and described vertical shape baffle plate is vertical rectangle baffle plate, vertical dentation baffle plate or vertical trilateral baffle plate.
Round shape liquid nitrogen vessel top is provided with sealable lid.
In the middle of described lid, be provided with a circular hole.
Described round shape liquid nitrogen vessel Small Radius bottom of cylinder is provided with movable screen cloth.
The minor radius bottom of cylinder of described freezing plant is provided with collection container.
The method of the freezing slip of spray chilling device of the present invention: between two concentric(al) circles cylinders of the round shape liquid nitrogen vessel of freezing plant, baffle plate is installed, between two concentric(al) circles cylinders, be filled with again a certain amount of liquid nitrogen, liquid nitrogen is along distributing in cylinder ring week, and become several parts by barrier partitions, after covering the lid on the concentric(al) circles cylinder top, by required ceramic particle size, change screen cloth, the height that gets final product the adjustable spraying device carries out the slip spraying, the slip drop enters through the circular hole in the middle of lid the annular temperature field that in freezing plant, the round shape liquid nitrogen vessel provides and carries out freezing, obtain the bottom that particle drops to the minor radius cylinder, after screen cloth is selected, enter collection container.
Beneficial effect of the present invention: the present invention is directed to the porous ceramics particulate sphericity that method of the prior art makes bad, the microspherulite diameter skewness, the defect of pore texture poor controllability and existing preparation method's narrow application range, the present invention is in preparing the process of porous ceramics particulate by the ice template method in conjunction with spraying drying, designed a kind of novel spray chilling device, be arranged to the annular liquid nitrogen vessel in the spray chilling device cylindric, and the lid that is provided with middle with hole seals liquid nitrogen vessel, the liquid nitrogen be filled with distributes along cylinder Cheng Huanzhou formula, by the amount of being filled with of regulating liquid nitrogen, just can obtain temperature gradient stable orientation temperature, then thereby to be configured as sphericity better by freezing in the directed temperature of pulp jets, the more uniform microballoon of particle size, after lyophilize, obtain porous microsphere, further device has been done to improvement on this basis, zone adds some baffle plates between two concentric(al) circles cylinders of round shape liquid nitrogen vessel, the liquid nitrogen that baffle plate will be filled with is blocked in needs the cooling zone, the position cooling that liquid nitrogen is being set, further strengthened the controllability of warm, by the difference of the amount that different baffle plates is filled with in conjunction with liquid nitrogen and the position be filled with is set, can form different stable temperature, can be by a temperature furnishing along the upper and lower distribution gradient of cylinder as the transverse circular baffle plate, but each interval forms again a plurality of little temperature, make whole temperature field highly become along the longitudinal the wavy line formula to distribute, vertically the shape baffle plate can be radial temperature difference and the vertically combined type temperature difference distribution of the temperature difference of height by warm field control, the porous ceramics microballoon that can prepare multiple pore texture by regulating and controlling the temperature field, as transverse circular shape baffle plate, can prepare laminate structure porous ceramics microballoon in conjunction with the temperature of certain nitrogen amount regulation and control, vertically the rectangle baffle plate can be prepared dendritic structure porous ceramics microballoon in conjunction with the temperature of necessarily nitrogen amount regulation and control, thereby has realized preparing multiple pore structure material by the regulation and control to the temperature field, this preparation method has adopted usings ice crystal or other organic solid phases and as template and mist projection granulating preparation, has the microballoon of vesicular structure, and preparation process is simple, applied widely, and energy-conserving and environment-protective.
The accompanying drawing explanation
[Fig. 1] is spray chilling device sketch: 1 is lid, and 2 is collection container, and 3 is movable screen cloth, and 4 is shower nozzle, and 5 is pump, and 6 is slurry container.
[Fig. 2] is the transverse circular baffle plate for difform baffle plate figure: a, and b is vertical rectangle baffle plate, and c is vertical dentation baffle plate, and d is vertical trilateral baffle plate.
[Fig. 3] is the sectional view of liquid nitrogen vessel: 7 are the round shape liquid nitrogen vessel; 8 is the minor radius cylinder; 9 is large radius cylinder; Left figure is the round shape liquid nitrogen vessel that is provided with transverse baffle, and a is the transverse circular baffle plate; Right figure is the round shape liquid nitrogen vessel that is provided with longitudinal baffle, and b is vertical rectangle baffle plate.
[Fig. 4] is the scanning electron microscope (SEM) photograph of the layered porous structure aluminum oxide micro-sphere of embodiment 2.
[Fig. 5] is the scanning electron microscope (SEM) photograph of the HA porous microsphere of embodiment 3 layered porous structures.
[Fig. 6] is the scanning electron microscope (SEM) photograph of the aluminum oxide micro-sphere of embodiment 4 dendroid vesicular structures.
Embodiment
Following examples are intended to further illustrate the present invention, rather than limit the scope of the invention.
Embodiment 1
The method of the freezing slip of spray chilling device: at two concentric(al) circles cylinders (8 of the round shape liquid nitrogen vessel (7) of freezing plant, baffle plate (a is installed 9), b, c or d), again at two concentric(al) circles cylinders (8, 9) between, be filled with a certain amount of liquid nitrogen, make liquid nitrogen along distributing in cylinder ring week, and by barrier partitions (a, b, c or d) become some parts, cover concentric(al) circles cylinder (8, 9) after the lid on top (1), by required ceramic particle size, change screen cloth (3), the height that gets final product the adjustable spraying device carries out the slip spraying, the slip drop enters through the circular hole in the middle of lid (1) the annular temperature field that in freezing plant, the round shape liquid nitrogen vessel provides and carries out freezing, obtain the bottom that particle drops to minor radius cylinder (8), after screen cloth (3) is selected, enter collection container (2), for the needs of the porous microsphere for preparing Different Pore Structures, can regulate the amount of liquid nitrogen and the shape of baffle plate, to reach requirement.
1) ratio that is 1:15 by aluminum oxide powder (particle diameter is about 0.3 μ m) and deionized water according to mass ratio is mixed, ball milling 24h, then the PVA aqueous solution (1wt.% of slurry total mass) that adds 1wt.%, then ball milling 1h, be mixed with the slurries that solid load is 6.2wt.%.
2) slurry of the different solid loads of above preparation is ejected into through simple spraying plant in the temperature field with temperature and the distribution that vertically highly becomes the inside bottom of cylinder curve of wave to descend, carry out freezing, then collect microballoon, at-55 ℃, air pressure is to carry out lyophilize 24h under the condition of 10Pa, wherein, spray height is 160mm, and the amount of liquid nitrogen provided is 600mL, and what in liquid nitrogen vessel, adopt is some transverse circular baffle plates; Adopt 4 transverse baffles that inner cylindrical tube is separated to five volumes and equate and non-interfering zone, the 2nd, 4 zones that the inner core upper end is downward are filled with liquid nitrogen, thereby obtain needed temperature.
3) microballoon after lyophilize is placed in to sintering oven, first the temperature rise rate with 1 ℃/min is warmed up to 600 ℃, degreasing 2h, then be warmed up to 1550 ℃, sintering 2h.Obtain layered porous structure aluminum oxide micro-sphere shown in Figure 4.
1) ratio that is 1:20 by hydroxylapatite powder (particle diameter is about 0.3 μ m) and deionized water according to mass ratio is mixed, ball milling 24h, then the PVA aqueous solution (1wt.% of slurry total mass) that adds 1.5wt.%, then ball milling 1h, be mixed with the slurries that solid load is 5wt.%.
2) slurry of the different solid loads of above preparation is ejected into through simple spraying plant in the temperature field with temperature and the distribution that vertically highly becomes the inside bottom of cylinder curve of wave to descend, carry out freezing, then collect the microballoon after freezing, at-45 ℃, air pressure is to carry out lyophilize 24h under the condition of 10Pa, wherein, spray height is 270mm, and the amount of liquid nitrogen provided is 1120mL, and what in liquid nitrogen vessel, adopt is some transverse circular baffle plates.Adopt 4 transverse baffles that inner cylindrical tube is separated to 5 volumes and equate and non-interfering zone, the 2nd, 4 zones that the inner core upper end is downward are filled with liquid nitrogen, thereby obtain needed temperature.
3) microballoon after lyophilize is placed in to sintering oven, first the temperature rise rate with 0.2 ℃/min is warmed up to 600 ℃, degreasing 2h, then be warmed up to 1250 ℃, sintering 2h, obtain layered porous structural hydroxyl phosphatic rock microballoon shown in Figure 5.
1) ratio that is 1:12 by aluminum oxide powder (particle diameter is about 0.3 μ m) and deionized water according to mass ratio is mixed, ball milling 24h, then the PVA aqueous solution (1wt.% of slurry total mass) that adds 1wt.%, then ball milling 1h, the preparation solid load is at the slurry of 7.6wt.%.
2) by the slurry of above preparation through simple spraying plant be ejected into have temperature radially inwardly cylinder center raise with temperature longitudinally highly inwardly two of the distribution that descends of bottom of cylinder curve compound temperature fields carry out freezing, then collect the microballoon after freezing, at-40 ℃, air pressure is to carry out lyophilize 24h under the condition of 20Pa, wherein, spray height is 760mm, and the amount of liquid nitrogen provided is 3792mL, and what in liquid nitrogen vessel, adopt is some vertical rectangle baffle plates.Adopt 12 baffle plates to separate 12 volumes and equate and non-interfering zone, at interval of two zones, be filled with liquid nitrogen, having 4 zones has liquid nitrogen cooling, thereby reaches needed temperature field.
3) microballoon after lyophilize is placed in to sintering oven, first the temperature rise rate with 0.2 ℃/min is warmed up to 600 ℃, degreasing 2h, then be warmed up to 1250 ℃, sintering 2h, obtain dendroid vesicular structure aluminum oxide micro-sphere shown in Figure 6.
1) ratio that is 1:13 by zirconia powder (particle diameter is about 0.5 μ m) and deionized water according to mass ratio is mixed, ball milling 24h, then the PVA aqueous solution (1wt.% of slurry total mass) that adds 1wt.%, then ball milling 1h, be mixed with the slurries of solid load at 7.1wt.%.
2) slurry of the different solid loads of above preparation is ejected into through simple spraying plant in the temperature field with temperature and the distribution that vertically highly becomes the inside bottom of cylinder curve of wave to descend, carry out freezing, then collect the microballoon of freezing rear gained, at-30 ℃, air pressure is to carry out lyophilize 24h under the condition of 15Pa, wherein, spray height is 560mm, and the amount of liquid nitrogen provided is 1120mL, and what in liquid nitrogen vessel, adopt is some transverse circular baffle plates.Adopt 9 transverse baffles that inner cylindrical tube is separated to 10 volumes and equate and non-interfering zone, the 2nd, 4,6,8 zones that the inner core upper end is downward are filled with liquid nitrogen, thereby obtain needed temperature.
3) microballoon after lyophilize is placed in to sintering oven, first the temperature rise rate with 0.5 ℃/min is warmed up to 600 ℃, degreasing 2h, then be warmed up to 1500 ℃, sintering 2h, obtain layered porous structural zirconia microballoon.
1) ratio that is 1:5 by titanium dioxide powder (particle diameter is about 0.5 μ m) and deionized water according to mass ratio is mixed, ball milling 24h, then the PVA aqueous solution (1wt.% of slurry total mass) that adds 1wt.%, then ball milling 1h, be mixed with the slurries of solid load at 20wt.%.
2) slurry of the different solid loads of above preparation is ejected into through simple spraying plant in the temperature field with temperature and the distribution that vertically highly becomes the inside bottom of cylinder curve of wave to descend, carry out freezing, then collect the microballoon that freezes rear gained, at-55 ℃, air pressure is to carry out lyophilize 24h under the condition of 10Pa, wherein, spray height is 270mm, and the amount of liquid nitrogen provided is 1120mL, and what in liquid nitrogen vessel, adopt is some transverse circular baffle plates.Adopt 4 transverse baffles that inner cylindrical tube is separated to 5 volumes and equate and non-interfering zone, the 2nd, 4 zones that the inner core upper end is downward are filled with liquid nitrogen, thereby obtain needed temperature.
3) microballoon after lyophilize is placed in to sintering oven, first the temperature rise rate with 1 ℃/min is warmed up to 600 ℃, degreasing 2h, then be warmed up to 1350 ℃, sintering 2h, obtain layered porous titania microsphere.
Claims (10)
1. the method for the porous ceramics microballoon of preparation Different Pore Structures, is characterized in that, first ceramic powder and caking agent is dispersed in solvent and obtains slurry by dispersion agent; The slurry of gained is sprayed to and in regulatable annular temperature, carries out freezingly, and the particle of collecting freezing gained carries out lyophilize, obtains porous particle; The porous particle of gained is slowly intensification degreasing first, then is warmed up to the sintering temperature sintering, obtains a kind of porous ceramics microballoon of pore structure, and annular temperature field is regulated and controled to the porous ceramics microballoon that can make Different Pore Structures; Described regulation and control are to realize by the distribution of gate ring around the amount of annular temperature liquid nitrogen outside the venue; The distribution of the amount of described liquid nitrogen is that liquid nitrogen is filled in the airtight annular region of round shape liquid nitrogen vessel, described annular region is to be formed by the zone between the concentrically ringed large radius cylinder of having of round shape liquid nitrogen vessel and minor radius cylinder and the baffle plate of interior setting thereof, the liquid nitrogen be filled with can be regulated it by the baffle plate arranged and distribute, and the zone in minor radius cylinder cylinder forms annular temperature; The described liquid nitrogen amount of being filled with is 100～7000mL can regulate and control annular temperature field between-170～20 ℃ temperature.
2. the method for claim 1, is characterized in that, described round shape liquid nitrogen vessel comprises having concentrically ringed large radius cylinder and minor radius cylinder, zone sealing between the two, and should in zone, be provided with some baffle plates.
3. method as claimed in claim 2, is characterized in that, described baffle plate is vertical shape baffle plate or horizontal shape baffle plate.
4. method as claimed in claim 2, is characterized in that, described concentric(al) circles cylinder heights is 30～300cm, and the radius of two concentric(al) circles cylinders is respectively 8～100cm and 16～200cm, and the two radius difference is 8～100cm.
5. the method for claim 1, is characterized in that, described spray height is 10cm～1000cm.
6. the method for claim 1, is characterized in that, described lyophilize is to be-20～-70 ℃ in temperature, and air pressure is to carry out under the condition of 8～40Pa.
7. spray chilling device that the method for preparing the porous ceramics microballoon of Different Pore Structures is used, comprise atomizer and freezing plant, it is characterized in that, described freezing plant main body is round shape liquid nitrogen vessel (7), round shape liquid nitrogen vessel (7) comprises having concentrically ringed large radius cylinder (9) and minor radius cylinder (8), zone sealing between the two; Between described large radius cylinder (9) and minor radius cylinder (8), be provided with some baffle plates (a, b) in zone.
8. spray chilling device as claimed in claim 7, is characterized in that, described baffle plate is longitudinal baffle (b) and horizontal shape baffle plate (a).
9. spray chilling device as claimed in claim 7, is characterized in that, round shape liquid nitrogen vessel (7) top is provided with the lid (1) of salable round shape liquid nitrogen vessel (7).
10. spray chilling device as described as claim 7～9 any one, is characterized in that, minor radius cylinder (8) bottom is provided with movable screen cloth (3).
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| WO2015010473A1 (en) * | 2013-07-26 | 2015-01-29 | 中南大学 | Method and spraying and freezing device for preparing porous ceramic microspheres with different pore structures |
| CN105999292A (en) * | 2016-05-06 | 2016-10-12 | 中南大学 | Preparation method of porous hollow ceramic microspheres |
| 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 |
| CN106946586A (en) * | 2016-01-06 | 2017-07-14 | 深圳兰度生物材料有限公司 | Porous bioceramic scaffold and preparation method thereof |
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| CN103408319B (en) | 2015-01-14 |
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