CN1962547A - Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process - Google Patents
Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process Download PDFInfo
- Publication number
- CN1962547A CN1962547A CN 200610119248 CN200610119248A CN1962547A CN 1962547 A CN1962547 A CN 1962547A CN 200610119248 CN200610119248 CN 200610119248 CN 200610119248 A CN200610119248 A CN 200610119248A CN 1962547 A CN1962547 A CN 1962547A
- Authority
- CN
- China
- Prior art keywords
- solid content
- colloidal sol
- porous ceramic
- gel
- drying process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a preparing method of porous alumina ceramic through sol-gel freezing drying technique, which comprises the following steps: adopting aluminium isopropoxide as former; hydrolyzing under high temperature to obtain alumina sol; controlling the solid content of sol; adding moulding agent; blending evenly; casting; moulding; removing air to form vacuum; freezing at low temperature; drying and moulding the frozen sample; detackifying moulded sample under low temperature; placing in the high-temperature furnace; sintering; obtaining the porous alumina ceramic with bending-proof strength reaching 65Mpa and bulk density at 0.14-2.4g/cm3. The adjustable aperture is 1-100um, which can be filter, catalyst carrier and heat insulating material.
Description
Technical field
The present invention relates to a kind of method of preparing alumina porous ceramic using gelatin wrapping-freeze drying process, relate to or rather with collosol and gel powder synthetic method and prepare the method for high porosity, low density alumina porous ceramic, belong to the porous ceramics field in conjunction with the method for freeze drying example moulding process.
Background technology
Alumina porous ceramic is owing to have resistance to chemical attack, wear-resisting, advantages such as lightweight, high permeability, low-expansion coefficient and good high-temperature stability, and show wide application prospect in fields such as strainer, support of the catalyst, thermal insulating material and refractory materialss.For satisfying the application in different field, about the preparation method of alumina porous ceramic so that many reports to be arranged, for example, people such as Cheng Changrui (Chinese patent, the patent No. 96105627) adopting aluminum salt solution or acid solution and alkaline solution or alkali metal aluminate solution is basic raw material, regulate pH value, make solution become glue, prepared specific surface and reached 250～350m
2/ g, γ-Al of aperture 40～100A
2O
3Porous insert, the support of the catalyst when can be used as the hydrotreatment of heavy crude fraction oil; People such as Yang Qinghe (Chinese patent, the patent No. 01134279) are with γ-Al
2O
3Forming composition finish drying fast at 90～300 ℃, and roasting more than 0.5 hour in 600～800 ℃ moisture vapor atmosphere, thus obtain having the aluminum oxide porous body of concentrated pore distribution, be especially suitable for use as the carrier of Hydrodemetalation catalyst; People such as Fang Xudong (Chinese patent, the patent No. 200410041065) adopt α-Al
2O
3Be main raw material, with calcium oxide and rare earth oxide is additive, form structural opening micropore, the even and high alumina porous ceramic of physical strength of micropore size by the sintering reaction under the high temperature, as support of the catalyst the time, can support more catalyzer, and catalyzed reaction rate height; The little firm people (Cao Xiaogang that waits of Cao, Tian Jiemo, the gel casting forming of porous alumina ceramic, functional materials, 32 (5) (2001) 523-528) select for use Graphite Powder 99 as pore-forming material, and join in the finely disseminated alumina slurry, make slurry pass through the gel moldings formed therefrom then, base substrate after the moulding is 1520 ℃ of heat preservation sinterings 2 hours, obtained to be evenly distributed, the aperture is the alumina porous ceramic of 15～30 μ m.
Because colloidal sol has lower solid content, and connect into bigger reticulated structure between the sol particle, so sol-gel method is convenient to be used for preparing high porosity, low density, wide-aperture porous ceramics, flow-like colloidal sol also is used in coating on the carrier, in colloidal sol, add different second solid content and the sintering character that can change colloidal sol after mutually, thus the various performances of regulating porous ceramic sinter.People such as Xue Mingjun (Xue Mingjun, Sun Chengxu, Li Yan, be equipped with the research of alumina porous ceramic with the Sol-Gel legal system, Chinese pottery, 35 (3) (1999) 5-8) add the organic pore-forming agents polyvinyl alcohol in aluminium colloidal sol, colloidal sol is dried aftershaping, sintering, obtains the alumina porous ceramic of porosity 34～54% and aperture 6～12 μ m.
Lyophilize is a dewatered method commonly used during food-processing is handled, cryodesiccated principle is at first to make the moisture in the sample be frozen into ice, vacuumize reduction pressure then rapidly, under low-temp low-pressure, make ice be directly sublimed into steam, thereby realize the removal of moisture.At present, the application of freeze-drying in ceramic material mainly is the drying of nano-powder; Compare with traditional air oven dry, lyophilize can effectively reduce the reunion of nanoparticle, keeps the chemically reactive of nanoparticle.People such as Liu Jun (Liu Jun, Xu Chenghai, Dou new life, vacuum freeze-drying method prepares the experimental study of nano aluminium oxide ceramics powder, vacuum, 41 (4) (2004) 80-83) Tai-Ace S 150 with cheapness is raw material, and choosing aluminum subacetate is presoma, prepares the aluminium oxide nano micro mist that median size is 10～20nm with vacuum freeze-drying method.People such as Gu Yanfang (Gu Yanfang, Hu Liming, look after one's family and build, Chen Minheng, freeze-drying prepare highly active aluminum oxide ultrafine particle, the silicate circular, 1 (1994) 21-25) be raw material with aluminum nitrate and volatile salt, hydrolysis prepares aluminum hydroxide sol, and the colloidal sol of preparation is carried out lyophilize, has obtained good dispersity, that specific surface is big, reactive behavior is high is alumina powder jointed.
At present, use freeze-drying to the ceramic powder straight forming then rarely have report, the lyophilize moulding can reduce the contraction that common drying and moulding causes base substrate, simultaneously, after the slurry casting, is convenient to obtain the ceramics sample of complicated shape by the lyophilize moulding.The direct lyophilize moulding of alumina sol will reduce many technologies such as powder drying, powder moulding, base substrate oven dry, base substrate processing, utilize in the vesicular structure of colloidal sol itself and the colloid ice pellets to remove unique hole that the back forms simultaneously, obtain having low density, the alumina porous ceramic of high hole, different pore size distributions.
The present invention plans collosol and gel and two kinds of methods of lyophilize combine, and brings into play advantage separately, with the preparation alumina porous ceramic.
Summary of the invention
At the above-mentioned state of the art, the objective of the invention is to utilize the simple collosol and gel of technology to prepare high porosity, low density and wide-aperture alumina porous ceramic, to satisfy the application in fields such as strainer, support of the catalyst, thermal insulating material and refractory materials in conjunction with cryodesiccated forming method.The present invention prepares the method for alumina porous ceramic, comprises the sintering of base substrate after the lyophilize moulding of control, colloidal sol slurry of preparation, the colloidal sol solid content of alumina sol and the moulding.Core of the present invention is to regulate the solid content of alumina sol by means of different, utilizes freeze-drying to make the colloidal sol slurry directly-forming then, thereby obtains the alumina porous ceramic of different porosities, pore size and mechanical property.The present invention is with aluminum isopropylate, Virahol, acetic acid and the water raw material as the preparation alumina sol, and PVA (polyvinyl alcohol) is as the binding agent of moulding, γ-Al
2O
3(50-200nm) and α-Al
2O
3(the meta particle diameter is 0.6 μ m) is as the additive of regulating the alumina sol solid content.Add binding agent and alumina powder and obtain the alumina sol slurry of different solid contents in alumina sol, freezing after the cast molding, the strip after freezing is put into the vacuum freeze drier lyophilize, and unsticking, sintering obtain alumina porous ceramic then.
Concrete processing step: 1. be presoma with the aluminum isopropylate, the Virahol that adds 2～30wt% is a solvent, and the water of 40～80wt% is hydrolysis reactant, and the acetic acid of 1～30wt% is peptizing agent, 70～100 ℃ of hydrolysis, obtains the Al that solid content is 2-20wt%
2O
3Colloidal sol.Because the aluminum oxide solid content in the colloidal sol has material impact to porosity, pore size and the mechanical property of preparation porous ceramics, therefore need the solid content of controlled oxidation aluminium colloidal sol.2. the present invention adopts three kinds of methods to regulate the solid content of alumina sol:
Heating evaporation, this method can only obtain the lower alumina sol of solid content, and after the colloidal sol solid content surpassed 15wt%, the formation gel will lump:
Add nano level γ-Al
2O
3Powder (50-200nm) is because γ-Al
2O
3Powder has higher specific surface, thereby the high solids content of the colloidal sol slurry that obtains can not surpass 20wt%;
Add nanometer alpha-Al
2O
3Powder (the meta particle diameter is 0.6 μ m), the colloidal sol slurry that this method obtains also keeps certain fluidity when solid content 70wt%.3. in order to keep the base substrate after the lyophilize not cave under the high porosity situation keeping, need in the colloidal sol slurry, add the binding agent (PVA, polyvinyl alcohol) of 0～20wt%.The colloidal sol slurry for preparing is poured into cast molding in the mould of desired shape rapidly, and put into the vacuum drying oven vacuum outgas, remove the bubble in the slurry, then sample place cryogenic refrigerator (＜-20 ℃=, sample is freezed fully, freeze good sample and be transferred to fast in the freeze drier, lyophilize under the environment of-10～80 ℃ and 5～100Pa distils ice crystal in the sample and removes.4. the sample after the freeze-drying slowly is warming up to 400～800 ℃ with the speed less than 3 ℃/min under air atmosphere, is incubated 1～8 hour, and unsticking is removed organism volatile matter wherein.5. the sample after the unsticking is put into High Temperature Furnaces Heating Apparatus, rises to 2 hours sintering of 1400～1700 ℃ of insulations with 5 ℃/min, and furnace cooling obtains alumina porous ceramic then.Concrete technical process as shown in Figure 1.
The typical microstructure of the alumina porous ceramic of use the present invention preparation is shown in Fig. 2,3 and 4, Fig. 2 is the typical microstructure of the porous ceramics (embodiment 2) for preparing when not adding aluminum oxide and solid content for 10wt%, porous ceramics has very high porosity, and connect mutually between the hole, hole shape is rectangular dendroid, ice pellets when these holes derive from lyophilize in the sample, crystal form decision by ice pellets, and some circular ports in the dendritic hole of bar shaped intermediate distribution, these holes are formed by the alumina sol network.Fig. 3 adds γ-Al
2O
3And the section SEM pattern of porous ceramics when solid content is 20wt% (embodiment 6), because γ-Al
2O
3Powder has vesicular structure and very high specific surface, and therefore the porous ceramics that obtains still has higher porosity, because the increase of solid content, the porosity of porous ceramics and aperture size all have a spot of minimizing.Fig. 4 adds α-Al
2O
3And the section SEM pattern of porous ceramics when solid content is 50wt% (embodiment 8), the increase of solid content sharply reduces the porosity of porous ceramics and aperture, because α-Al
2O
3Have bigger particle diameter, thereby changed the direction of growth of ice pellets in the slurry, make the duct shape that change take place, the α-Al of simultaneously big particle diameter
2O
3In particles filled and the alumina sol network, reduced the aperture of colloidal sol pore-forming.Fig. 5 adds γ-Al
2O
3And as can be seen, only there is α-Al in the XRD figure of porous ceramics when solid content is 20wt% (embodiment 6) spectrum in the porous ceramics
2O
3Phase, this is because the unformed Al in the colloidal sol
2O
3With the γ-Al that adds
2O
3At high temperature all change high-temperature stable phase α-Al for aluminum oxide
2O
3
By heating evaporation alumina sol, interpolation γ-Al
2O
3Powder or interpolation α-Al
2O
3Powder is adjusted the colloidal sol solid content of slurry all has significant effects to volume density, porosity and the mechanical property that makes porous ceramics.Fig. 6 and 7 shows, during by evaporation oxidation aluminium colloidal sol control solid content, the porous ceramics that obtains has extremely low volume density and high porosity, and the overall porosity of porous ceramics and open porosity are more or less the same, along with the increase of solid content, the volume density of porous ceramics increases, porosity reduces.Fig. 8 and 9 shows, adds γ-Al
2O
3The time, the increase of solid content improved porous ceramics volume density, reduced porosity, but during identical solid content, the porous ceramics that obtains by evaporation colloidal sol control solid content has lower volume density and the porosity of Geng Gao.Figure 10,11 and 12 shows, adds α-Al
2O
3When regulating slurry, the increase of solid content increases the volume density of porous ceramics, porosity reduces, bending strength increases, and compares with preceding two kinds of methods of regulating solid content, adds α-Al
2O
3The easier acquisition high-density of method, low porosity and high-intensity alumina porous ceramic.
The characteristics of this technology are that moulding is simple, are easy to obtain complicated shape, and the performance adjustability is good, can obtain high porosity, low-density alumina porous ceramic, the volume density 0.14-2.4g/cm of the alumina porous ceramic of preparation
3, porosity 30-97%, pore size 1-100 micron, high-flexural strength reaches 65MPa.
In sum, utilizing the present invention to prepare alumina porous ceramic has the following advantages:
(1) the lyophilize pore-forming of collosol and gel pore-forming and ice pellets is combined, guaranteed the high porosity of alumina porous ceramic;
(2) adding of binding agent makes the sample after the lyophilize keep certain intensity, and unlikely caving in;
(3) the colloidal sol slurry has flowability, makes things convenient for cast molding, is easy to obtain the sample of complicated shape;
(4) the performance controllability of porous ceramics is good.
Description of drawings
The technical process of Fig. 1 preparing alumina porous ceramic using gelatin wrapping-freeze drying process.
Fig. 2 obtains the typical microstructure of porous ceramics when not adding aluminum oxide and solid content for 10wt%.
Fig. 3 adds γ-Al
2O
3And the section SEM pattern of porous ceramics when solid content is 20wt%.
Fig. 4 adds α-Al
2O
3And the section SEM pattern of porous ceramics when solid content is 50wt%.
Fig. 5 adds γ-Al
2O
3And the XRD figure of porous ceramics spectrum when solid content is 20wt%, X-coordinate is 2 times of diffraction angle, and unit is degree, and ordinate zou is the relative value of diffracted intensity.
When Fig. 6 did not add aluminum oxide, solid content was to the influence of porous ceramics volume density, and X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a volume density, the g/cm of unit
3
When Fig. 7 did not add aluminum oxide, solid content was to the influence of porous ceramics overall porosity and open porosity, and X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a porosity, the % of unit.
Fig. 8 adds γ-Al
2O
3The time, solid content is to the influence of porous ceramics volume density, and X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a volume density, the g/cm of unit
3
Fig. 9 adds γ-Al
2O
3The time, solid content is to the influence of porous ceramics overall porosity and open porosity, and X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a porosity, the % of unit.
Figure 10 adds α-Al
2O
3When regulating slurry, the influence of solid content porous ceramics volume density, X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a volume density, the g/cm of unit
3
Figure 11 adds α-Al
2O
3When regulating slurry, solid content is to the influence of porous ceramics overall porosity and open porosity, and X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a porosity, the % of unit.
Figure 12 adds α-Al
2O
3When regulating slurry, solid content is to the influence of porous ceramics bending strength, and X-coordinate is the colloidal sol solid content of slurry, and unit is wt%, and ordinate zou is a bending strength, and unit is MPa.
Embodiment
Below by concrete enforcement the present invention is described further, but the present invention is confined to embodiment absolutely not, process implementing is for example shown in the following table:
| Embodiment | The solid content regulative mode | The colloidal sol solid content | Binder content (wt%) | Sublimation drying (hour) | Lyophilize pressure (Pa) | The lyophilize temperature (℃) |
| 1 | Heating evaporation | 5 | 3 | 48 | 20 | 60 |
| 2 | |
10 | 3 | 48 | 20 | 60 |
| 3 | Heating evaporation | 15 | 3 | 48 | 20 | 60 |
| 4 | Add γ-Al 2O 3 | 10 | 3 | 48 | 20 | 60 |
| 5 | Add γ-Al 2O 3 | 15 | 3 | 48 | 20 | 60 |
| 6 | Add γ-Al 2O 3 | 20 | 3 | 48 | 20 | 60 |
| 7 | Add α-Al 2O 3 | 30 | 3 | 48 | 20 | 60 |
| 8 | Add α-Al
2 |
50 | 3 | 48 | 20 | 60 |
| 9 | Add α-Al
2 |
70 | 3 | 48 | 20 | 60 |
The performance of the alumina porous ceramic for preparing in the foregoing description is as shown in the table:
| Embodiment | The solid content regulative mode | Volume density (g/cm 3) | Overall porosity (%) | Open porosity (%) | The porosity of remaining silent (%) | Bending strength (MPa) |
| 1 | Heating evaporation | 0.14 | 96.6 | 96.5 | 0.1 | ＜1.0 |
| 2 | Heating evaporation | 0.20 | 94.9 | 94.7 | 0.2 | ＜1.0 |
| 3 | Heating evaporation | 0.25 | 93.8 | 93.4 | 0.4 | ＜1.0 |
| 4 | Add γ-Al 2O 3 | 0.50 | 87.6 | 87.3 | 0.3 | ＜1.0 |
| 5 | Add γ-Al 2O 3 | 0.55 | 86.3 | 85.7 | 0.6 | ＜1.0 |
| 6 | Add γ-Al 2O 3 | 0.70 | 82.6 | 74.8 | 7.8 | ＜1.0 |
| 7 | Add α-Al 2O 3 | 1.26 | 72.4 | 63.2 | 9.2 | 8.9±1.2 |
| 8 | Add α-Al 2O 3 | 1.76 | 56.2 | 49.3 | 6.9 | 29.7±3.5 |
| 9 | Add α-Al 2O 3 | 2.28 | 43.3 | 38.0 | 5.3 | 53.2±4.1 |
Shown in embodiment 1,100g is heated to 80 ℃ the alumina sol for preparing (solid content 3.5%), constantly stir, make colloidal sol be evaporated to 70g, stop heated and stirred, cover the beaker lid, be cooled to normal temperature, add 2.1g binding agent (PVA), stir, then the colloidal sol slurry for preparing is poured into cast molding in the mould of definite shape rapidly, and put into the vacuum drying oven vacuum outgas, remove the bubble in the slurry, then sample is placed cryogenic refrigerator (25 ℃), kept 12 hours, sample is freezed fully, freeze good sample and be transferred to fast in the freeze drier, moisture in the sample is gone out in lyophilize under the environment of 80 ℃ and 10Pa.Sample after the freeze-drying is taken off mould, speed with 0.5 ℃/min under air atmosphere slowly is warming up to 600 ℃, be incubated 8 hours, unsticking is removed organism volatile matter wherein, sample after the unsticking is put into High Temperature Furnaces Heating Apparatus, rise to 2 hours sintering of 1600 ℃ of insulations with 5 ℃/min, furnace cooling obtains volume density 0.14g/cm then
3Alumina porous ceramic with overall porosity 96.6%.
Shown in embodiment 4, in the 100g alumina sol for preparing (solid content 3.5%), add γ-Al of 7.2g
2O
3Binding agent with 3.2g, stir and form uniform sizing material, then the colloidal sol slurry for preparing is poured into cast molding in the mould of definite shape rapidly, and put into the vacuum drying oven vacuum outgas, go out bubble in the slurry, then sample is placed cryogenic refrigerator (25 ℃), kept 12 hours, sample is freezed fully, freeze good sample and be transferred in the freeze drier fast, the moisture in the sample is removed in lyophilize under the environment of 80 ℃ and 10Pa.Sample after the freeze-drying is taken off mould, speed with 0.5 ℃/min under air atmosphere slowly is warming up to 600 ℃, be incubated 8 hours, unsticking is removed organism volatile matter wherein, sample after the unsticking is put into High Temperature Furnaces Heating Apparatus, rise to 2 hours sintering of 1600 ℃ of insulations with 5 ℃/min, furnace cooling obtains volume density 0.50g/cm then
3Alumina porous ceramic with overall porosity 87.6%.
Shown in embodiment 7, in the 100g alumina sol for preparing (solid content 3.5%), add α-Al of 37.9g
2O
3Binding agent with 4.1g, stir and form uniform sizing material, then the colloidal sol slurry for preparing is poured into cast molding in the mould of definite shape rapidly, and put into the vacuum drying oven vacuum outgas, remove the bubble in the slurry, then sample is placed cryogenic refrigerator (25 ℃), kept 12 hours, sample is freezed fully, freeze good sample and be transferred in the freeze drier fast, moisture in the sample is gone out in lyophilize under the environment of 80 ℃ and 10Pa.Sample after the freeze-drying is taken off mould, speed with 0.5 ℃/min under air atmosphere slowly is warming up to 600 ℃, be incubated 8 hours, unsticking is removed organism volatile matter wherein, sample after the unsticking is put into High Temperature Furnaces Heating Apparatus, rise to 2 hours sintering of 1600 ℃ of insulations with 5 ℃/min, furnace cooling obtains volume density 1.26g/cm then
3Alumina porous ceramic with overall porosity 72.4%.
Claims (9)
1, a kind of collosol and gel-freeze drying process prepares the method for alumina porous ceramic, it is characterized in that described preparation method comprises the unsticking and the sintering of bad body after the lyophilize moulding of adjusting, colloidal sol slurry of preparation, the colloidal sol solid content of alumina sol and the moulding;
Concrete processing step is:
1. the preparation of alumina sol
With the aluminum isopropylate is presoma, and the Virahol that adds 2～30wt% is a solvent, and the water of 40～80wt% is hydrolysis reactant, and the acetic acid of 1～30wt% is peptizing agent, 70～100 ℃ of hydrolysis, obtains the Al that solid content is 2-20wt%
2O
3Colloidal sol
2. the adjusting of colloidal sol solid content
Adopt three kinds of methods to regulate the solid content of alumina sol:
Heating evaporation can only obtain the lower alumina sol of solid content, and after the colloidal sol solid content surpassed 15wt%, the formation gel will lump;
Add nanometer γ-Al
2O
3Powder, the high solids content of the colloidal sol slurry that obtains can not surpass 20wt%;
Add micro/nano level α-Al
2O
3It is mobile that the colloidal sol slurry that powder obtains also keeps when solid content 70wt%;
3. the lyophilize moulding of colloidal sol slurry
The mixed colloidal sol slurry of binding agent that adds 0～20wt% in 2. step regulates the colloidal sol slurry of solid content is poured cast molding in the mould of desired shape into, and put into the vacuum drying oven vacuum outgas, remove the bubble in the slurry, then sample is placed the refrigerator of low temperature-20 ℃, sample is freezed fully, freeze good sample and be transferred to fast in the freeze drier, lyophilize under the environment of-10～80 ℃ and 5～100Pa distils ice crystal in the sample and removes;
4. base substrate unsticking and sintering after the moulding
Under air atmosphere, slowly be warming up to 400～800 ℃ after the freeze-drying with speed less than 3 ℃/min, unsticking is removed organism volatile matter wherein, and puts into High Temperature Furnaces Heating Apparatus after the unsticking, rises to 1400～1700 ℃ of sintering with 5 ℃/min, furnace cooling obtains alumina porous ceramic then.
2, the method for preparing alumina porous ceramic by the described collosol and gel-freeze drying process of claim 1 is added nanometer γ-Al when it is characterized in that the 2. described adjusting colloidal sol of step solid content
2O
3Powder diameter is 50-200nm.
3, the method for preparing alumina porous ceramic by the described collosol and gel-freeze drying process of claim 1 is characterized in that adding micron order γ-Al during the regulator solution solid content during step 2.
2O
3The meta particle diameter be 0.6 μ m.
4, the method for preparing alumina porous ceramic by the described collosol and gel-freeze drying process of claim 1 is characterized in that the binding agent that uses during step 3. is polyvinyl alcohol.
5, the method for preparing alumina porous ceramic by the described collosol and gel-freeze drying process of claim 1, soaking time is 1-8 hour when it is characterized in that during step 4. 400-800 ℃ of following unsticking.
6, the method for preparing alumina porous ceramic by the described collosol and gel-freeze drying process of claim 1 is characterized in that during step 4. that soaking time is 2 hours during 1400-1700 ℃ of sintering.
7, prepare the method for alumina porous ceramic by any described collosol and gel-freeze drying process among the claim 1-6, it is characterized in that the Al for preparing
2O
3Many porositys 30-97%, pore size are the 1-100 micron.
8, prepare the method for alumina porous ceramic by any described collosol and gel-freeze drying process among the claim 1-6, it is characterized in that prepared Al
2O
3Connect mutually between the porous crack, hole shape is rectangular dendroid.
9, the method for preparing alumina porous ceramic by the described collosol and gel-freeze drying process of claim 8 is characterized in that rectangular dendritic hole intermediate section is furnished with circular port.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101192485A CN100408512C (en) | 2006-12-06 | 2006-12-06 | Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101192485A CN100408512C (en) | 2006-12-06 | 2006-12-06 | Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962547A true CN1962547A (en) | 2007-05-16 |
| CN100408512C CN100408512C (en) | 2008-08-06 |
Family
ID=38081800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101192485A Expired - Fee Related CN100408512C (en) | 2006-12-06 | 2006-12-06 | Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100408512C (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429050B (en) * | 2008-12-04 | 2011-04-13 | 北京航空航天大学 | Method for producing porous ceramic with oriented structure by employing freeze dehydration |
| CN102584329A (en) * | 2012-01-20 | 2012-07-18 | 安徽理工大学 | High-porosity porous ceramic and preparation method thereof |
| CN103878372A (en) * | 2013-12-25 | 2014-06-25 | 华侨大学 | Method of manufacturing metal parts having geometric structures such as thin wall or thin groove |
| CN104108131A (en) * | 2014-07-04 | 2014-10-22 | 航天特种材料及工艺技术研究所 | 3D printing forming method for ceramic materials |
| CN104385154A (en) * | 2014-09-12 | 2015-03-04 | 陕西德赛新材料科技有限公司 | Preparation method of low-temperature ceramic bond for grinding tool |
| CN104451235A (en) * | 2014-12-15 | 2015-03-25 | 中国矿业大学 | Method for preparing porous copper of complicated shape by utilizing copper oxide powder |
| CN105289461A (en) * | 2015-10-22 | 2016-02-03 | 苏州莲池环保科技发展有限公司 | Formula and preparing method of automobile three-way catalyst |
| CN105402010A (en) * | 2015-10-22 | 2016-03-16 | 苏州莲池环保科技发展有限公司 | Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter |
| CN107180963A (en) * | 2017-06-21 | 2017-09-19 | 四川科能锂电有限公司 | A kind of nickel-cobalt lithium manganate material and preparation method thereof |
| CN107973592A (en) * | 2016-10-24 | 2018-05-01 | 天津工业大学 | A kind of γ-Al of even aperture distribution2O3Ceramic micro filter film and preparation method thereof |
| CN108455978A (en) * | 2016-09-14 | 2018-08-28 | 航天特种材料及工艺技术研究所 | The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications |
| CN108892423A (en) * | 2018-07-17 | 2018-11-27 | 哈尔滨工业大学 | A kind of inorganic aerogels fill the preparation method of the composite heat-insulated material of orderly porous aluminum oxide template |
| CN109437959A (en) * | 2018-12-20 | 2019-03-08 | 东北大学 | A kind of method that environment-friendly type gel injection-moulding prepares mullite fiber base porous ceramics |
| CN110937882A (en) * | 2019-12-17 | 2020-03-31 | 中国铝业股份有限公司 | Alumina light heat-insulating material and preparation method thereof |
| CN111207564A (en) * | 2019-09-30 | 2020-05-29 | 中国科学院上海硅酸盐研究所 | Freeze drying system and method |
| CN111229155A (en) * | 2020-01-13 | 2020-06-05 | 东北师范大学 | Alumina layer-level porous carrier, level porous composite nano material, preparation method and application |
| CN114196448A (en) * | 2022-02-16 | 2022-03-18 | 北京中航天业科技有限公司 | Full-flow dry type blast furnace gas fine desulfurization system and method |
| CN116673017A (en) * | 2023-04-25 | 2023-09-01 | 中南大学 | Hierarchical porous piezoelectric ceramic catalyst and preparation method and application thereof |
| CN117004119A (en) * | 2023-07-30 | 2023-11-07 | 福建鑫邦新材料科技有限公司 | Environment-friendly wear-resistant EVA color master batch and preparation process thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6236083A (en) * | 1985-08-09 | 1987-02-17 | 日本特殊陶業株式会社 | Manufacture of porous ceramics |
| CN1686949A (en) * | 2005-04-11 | 2005-10-26 | 曾宇平 | Method for preparing poruos material in micro-nano magnitude |
-
2006
- 2006-12-06 CN CNB2006101192485A patent/CN100408512C/en not_active Expired - Fee Related
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429050B (en) * | 2008-12-04 | 2011-04-13 | 北京航空航天大学 | Method for producing porous ceramic with oriented structure by employing freeze dehydration |
| CN102584329A (en) * | 2012-01-20 | 2012-07-18 | 安徽理工大学 | High-porosity porous ceramic and preparation method thereof |
| CN102584329B (en) * | 2012-01-20 | 2013-06-05 | 安徽理工大学 | Preparation method of high-porosity porous ceramic |
| CN103878372A (en) * | 2013-12-25 | 2014-06-25 | 华侨大学 | Method of manufacturing metal parts having geometric structures such as thin wall or thin groove |
| CN104108131B (en) * | 2014-07-04 | 2017-02-22 | 航天特种材料及工艺技术研究所 | 3D printing forming method for ceramic materials |
| CN104108131A (en) * | 2014-07-04 | 2014-10-22 | 航天特种材料及工艺技术研究所 | 3D printing forming method for ceramic materials |
| CN104385154A (en) * | 2014-09-12 | 2015-03-04 | 陕西德赛新材料科技有限公司 | Preparation method of low-temperature ceramic bond for grinding tool |
| CN104451235A (en) * | 2014-12-15 | 2015-03-25 | 中国矿业大学 | Method for preparing porous copper of complicated shape by utilizing copper oxide powder |
| CN104451235B (en) * | 2014-12-15 | 2016-11-02 | 中国矿业大学 | A kind of method utilizing cupric oxide powder to prepare complicated shape Porous Cu |
| CN105402010A (en) * | 2015-10-22 | 2016-03-16 | 苏州莲池环保科技发展有限公司 | Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter |
| CN105289461A (en) * | 2015-10-22 | 2016-02-03 | 苏州莲池环保科技发展有限公司 | Formula and preparing method of automobile three-way catalyst |
| CN108455978B (en) * | 2016-09-14 | 2021-01-22 | 航天特种材料及工艺技术研究所 | Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof |
| CN108455978A (en) * | 2016-09-14 | 2018-08-28 | 航天特种材料及工艺技术研究所 | The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications |
| CN107973592A (en) * | 2016-10-24 | 2018-05-01 | 天津工业大学 | A kind of γ-Al of even aperture distribution2O3Ceramic micro filter film and preparation method thereof |
| CN107973592B (en) * | 2016-10-24 | 2021-01-26 | 天津工业大学 | Gamma-Al with evenly distributed aperture2O3Ceramic microfiltration membrane and preparation method thereof |
| CN107180963A (en) * | 2017-06-21 | 2017-09-19 | 四川科能锂电有限公司 | A kind of nickel-cobalt lithium manganate material and preparation method thereof |
| CN108892423A (en) * | 2018-07-17 | 2018-11-27 | 哈尔滨工业大学 | A kind of inorganic aerogels fill the preparation method of the composite heat-insulated material of orderly porous aluminum oxide template |
| CN109437959A (en) * | 2018-12-20 | 2019-03-08 | 东北大学 | A kind of method that environment-friendly type gel injection-moulding prepares mullite fiber base porous ceramics |
| CN111207564A (en) * | 2019-09-30 | 2020-05-29 | 中国科学院上海硅酸盐研究所 | Freeze drying system and method |
| CN111207564B (en) * | 2019-09-30 | 2022-01-04 | 中国科学院上海硅酸盐研究所 | Freeze drying system and method |
| CN110937882A (en) * | 2019-12-17 | 2020-03-31 | 中国铝业股份有限公司 | Alumina light heat-insulating material and preparation method thereof |
| CN111229155A (en) * | 2020-01-13 | 2020-06-05 | 东北师范大学 | Alumina layer-level porous carrier, level porous composite nano material, preparation method and application |
| CN111229155B (en) * | 2020-01-13 | 2022-05-31 | 东北师范大学 | Alumina layer-level porous carrier, level porous composite nano material, preparation method and application |
| CN114196448A (en) * | 2022-02-16 | 2022-03-18 | 北京中航天业科技有限公司 | Full-flow dry type blast furnace gas fine desulfurization system and method |
| CN116673017A (en) * | 2023-04-25 | 2023-09-01 | 中南大学 | Hierarchical porous piezoelectric ceramic catalyst and preparation method and application thereof |
| CN116673017B (en) * | 2023-04-25 | 2024-02-13 | 中南大学 | Hierarchical porous piezoelectric ceramic catalyst and preparation method and application thereof |
| CN117004119A (en) * | 2023-07-30 | 2023-11-07 | 福建鑫邦新材料科技有限公司 | Environment-friendly wear-resistant EVA color master batch and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100408512C (en) | 2008-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100408512C (en) | Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process | |
| Chen et al. | Porous ceramics: Light in weight but heavy in energy and environment technologies | |
| CN101037345B (en) | Method for preparing mullite porous ceramic by gel refrigeration drying process | |
| US8262957B2 (en) | Ceramic porous body with communication macropores and process for producing the ceramic porous body | |
| CN100384781C (en) | Method for preparing silicon carbide porous ceramic using gelatin wrapping-freeze drying process | |
| CN106588074B (en) | Method for preparing gradient porous ceramic by slip casting combined with vacuum foaming process | |
| CN101182233A (en) | Gradient porous ceramics film and method for preparing the same | |
| CN101429050B (en) | Method for producing porous ceramic with oriented structure by employing freeze dehydration | |
| CN105669174A (en) | Porous mullite material with high porosity and oriented pore structure and preparation method thereof | |
| CN109627011B (en) | Preparation method of porous ceramic with concentric holes and porous ceramic | |
| CN105084878A (en) | Preparation method of acicular mullite porous ceramic block material with superhigh amount of porosity | |
| CN113277859B (en) | Nano-coated alumina particles and high-purity thermal shock resistant alumina ceramic material prepared from same | |
| CN102372499A (en) | Method for preparing porous Ti2AlN ceramic by organic foam impregnation process | |
| Ren et al. | Preparation of porous TiO2 by a novel freeze casting | |
| CN103274704A (en) | Micron-order honeycomb ceramic and method for adjusting and controlling pore diameter and size of pore wall of micron-order honeycomb ceramic | |
| CN104671826A (en) | Porous alumina ceramic, and preparation method and application thereof | |
| CN103467072A (en) | Preparation method for light microporous corundum ceramic | |
| CN111410523A (en) | Ultra-light porous fused quartz foam and preparation method thereof | |
| JP2011195437A (en) | Ceramic porous heat-insulating material and method for forming the same | |
| JP2018140905A (en) | Method for producing ceramic porous body, and ceramic porous body | |
| CN109320257B (en) | Preparation method of high-strength high-porosity porous silicon nitride ceramic | |
| CN109485420B (en) | Method for improving wet-process formability and sinterability of ceramic nano powder | |
| CN108083811B (en) | Double-gradient porous ceramic material and preparation method thereof | |
| CN111056846B (en) | Directional porous aluminum nitride honeycomb ceramic rapidly prepared by adopting freeze drying and combustion synthesis method and method thereof | |
| CN104311109A (en) | Method for preparing foamed ceramic through foaming, injection molding and cementing of aluminum dihydrogen phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080806 Termination date: 20111206 |