CN101323528B - Preparation of continuous hole graded ceramic tube - Google Patents
Preparation of continuous hole graded ceramic tube Download PDFInfo
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- CN101323528B CN101323528B CN2008101230310A CN200810123031A CN101323528B CN 101323528 B CN101323528 B CN 101323528B CN 2008101230310 A CN2008101230310 A CN 2008101230310A CN 200810123031 A CN200810123031 A CN 200810123031A CN 101323528 B CN101323528 B CN 101323528B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
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Abstract
The invention relates to a preparation method of a gradient ceramic tube with continuous holes, which combines with the advantages of a centrifugal shaping method and gel-casting. Evenly distributed gel-casting suspension is poured into a pattern to carry out centrifugation and gelatinization occurs to the suspended slurry under the effect of centrifugal force and heating to realize solidification and shaping. A wet blank is demoulded, dried and sintered and the gradient ceramic tube with the continuous holes is prepared. The pore diameters of pattern tubes are distributed continuously along the radial direction of the pattern tubes, the pore diameter of an inner surface is the smallest while the bore diameter of an outer surface is the largest; in addition, the inner surface is quite flat and smooth without defect, therefore, the ceramic tube can be used both in the process of microfiltration and ultrafiltration and as a good support to further paint film on the inner surface. The preparation method is simple, thus saving the vacuum degassing procedure in traditional gel-casting; the gradient ceramic tube with the continuous holes can be shaped by one step; the pattern tubes with different pore diameters can be prepared by controlling the initial grain sizes of ceramic powders; the blank has high strength and is easy to operate with high efficiency and the yield of pattern tubes is high.
Description
Technical field
The present invention relates to a kind of preparation method of vitrified pipe, especially a kind of preparation method of continuous hole graded ceramic tube.
Background technology
Inorganic ceramic film is because its unique excellent properties has been widely used in various fields such as environmental protection, medicine, chemical industry and food.The hole gradient is meant the variation of aperture with thickness work rule, so just can finish the separation purpose, can reach the requirement of saving power consumption again.Be generally asymmetric membrane in the industrial application, i.e. shoulder hole graded ceramics, its structure is made of supporting layer and separating layer.Continuous hole graded being meant is continuous, non-stair-stepping variation in the thickness direction aperture, thereby is the minimum porous ceramics of a kind of pressure-losses.
At present, the shoulder hole graded ceramics adopts the slip casting dipping mostly, extrudes two kinds of methods of dipping.And the manufacturing process more complicated of continuous hole graded pottery and difficulty [Shen Junquan. hole graded ceramics, modern technologies pottery .1994,4,31～37].Usually tubular ceramic adopts the preparation of centrifugal grouting moulding process, and this method is quite paid close attention to a kind of in numerous colloidal formation technology in recent years.The ceramic size that uses in the centrifugal forming generally contains polyvinyl alcohol (PVA), ammonium polymethacrylate polymer organism such as (APMA) as cakingagent, thereby increased the viscosity of slurry, it is excessive to cause forming the required centrifugal force of gradient-structure, general rotating speed is all about 10000rpm, even up to 20000rpm[Steenkamp G.C et al.Centrifugal casting of ceramic membranetubes and the coating with chitosan.Separation and Purification Technology.2001,25,407-413].High rotating speed is all very high to the requirement of equipment and operation, has also therefore improved the manufacturing cost of graded ceramics.
In the centrifugal forming process, particles with different sizes is because the centrifugal reason that is subjected to is different, and the aperture distributes internal surface aperture minimum, outside surface aperture maximum by be continuous gradient in the pipe outside pipe; Minimum particle concentrates on the internal surface of film pipe, forms rete.Thereby centrifugal forming has natural potential advantages in the preparation of gradient material.
It is to be taught in a kind of novel forming technology [Omatete O O of earlier 1990s invention by U.S.'s Oak Ridge National Laboratory (Oak Ridge National Laboratory) Jenny and Omatete that gel is annotated film, Janney M A, Strehlow R A.Gelcasting--a new ceramic forming process.TheAmerican Ceramic Society Bulletin, 1991,70 (10): 1641-1647].The main thought of its technology is: under the effect of dispersion agent ceramic powder is disperseed in solvent, add organic monomer again and linking agent is made slurry, add initiator and catalyzer then, change envrionment conditions (referring generally to temperature condition), make organic monomer and linking agent polymerization reaction take place form macromolecular chain, the connection of not breaking off a friendship, thus form three-dimensional net structure, ceramic particle is wrapped in the ceramic body that wherein formation has certain intensity, obtains pottery by high temperature sintering then.
Gel injection has very strong suitability and practicality as a kind of novelty, advanced, technology of preparing flexibly, has following remarkable advantage:
(1) versatility is good, and the suitable ceramic powder is very wide;
(2) ceramic part of various complicated shapes of moulding and size;
(3) the molding blank component is even, uniform microstructure, and defective is few;
(4) gel casting forming slurry solid load height (solid volume fraction＞50%), body drying and sintering shrink little, can realize the dead size moulding;
(5) this technology does not have particular requirement to mould yet, and mould can be metal, glass and plastics etc.;
(6) the intensity height of molding blank, dried base substrate flexural strength generally reaches 20～40MPa, can directly carry out mechanical workout;
(7) organic content is lower in the base substrate, prevents that subsequent process from discharging too much organism and causing environmental pollution;
(8) simply to reach required equipment simple for forming operation, and cost is low, can produce in batches.
The preparation method and the centrifugal shaper of the disclosed thin-film ceramics pipe of Chinese patent ZL02144131.6.Its moulding is to be after the batching fine powder of Alpha-alumina grinds, to drop in the gel injection liquid with major ingredient, vacuumizes while stirring, obtains suspended nitride after treating evenly.The barrel that suspended nitride is injected centrifugal shaper carries out the gel centrifugal forming then, obtains needed ceramic thin-walled tubes behind the dry body drying sintering after the moulding.Adopt ball mill to carry out ball milling in the process of batching.The density of gained vitrified pipe is 3.89-3.92g/m
3The gel monomer acrylamide of using in the test is a kind of neurotoxin, and toxicity is bigger, may be subjected to restriction to a certain degree in industrial application.
World patent WO9821164 discloses the Functional Graded Ceramics film.The polydisperse slurry of this invention obtains the functionally gradient tissue by colloid unstability technology.Its key is to prepare controlled and unsettled or metastable soliquid that have wide particle diameter to distribute.So, when sedimentation, the different particle of size will take place poly-partially owing to the difference of gravity of self in sedimentation, thereby obtains porous Functional Graded Ceramics material.But this method can only obtain flat sheet membrane, can't make tubular film.
The disclosed gradient creamics with ceramic membrane fenestrata of Chinese patent ZL92105179.4, be to be major ingredient by aluminum oxide or silicon-dioxide or titanium dioxide, add clay and feldspar is formulated, through slip casting, heat perfusion, extruding forming method moulding, the mode of through the wet type drying, closely piling up crouch dress and lifting is adorned the cellar for storing things then, fires then to form under 1100-1550 ℃ of high temperature, gained ceramic membrane aperture is 0.1-15 μ m, void content 30-50%, thickness are 1-200 μ m, total 2-10 layer.The preparation method technology of this ceramic membrane is comparatively complicated, and the ceramic membrane that real income goes out is the shoulder hole gradient ceramic-film, but not continuous hole graded ceramic membrane.
The production method and the device thereof of Chinese patent ZL95102519.8 high purity ceramic-film tube adopt outer rigidity, the double-deck pipe die of internal layer fusile.Then slurry is added carry out in the pipe die centrifugal.And little by little improve rotating speed, the descending inwall moulding that is attached to pipe die of the alumina particle in the slurry.With the sintering at high temperature of the green tube after the moulding, obtain required asymmetric high purity aluminium oxide supporting tube then.This method need remove internal layer meltability mould at 50-100 ℃, has increased preparation cost.
Chinese patent ZL00117221.2 gradient ceramic-film tube and preparation method thereof is that base-material and water-soluble binder are made slurry through stirring in carrier; Start rotary casting ceramic-film tube machine, slurry is injected in the rigidity pipe die, make the gradient ceramic-film tube green compact; Green compact oven dry is after the demoulding, sintering, cooling obtain graded ceramic tube.The gravity coefficient is controlled between 20～500 during rotary casting, and used rotating speed is 5000～12000rpm among the embodiment.
Chinese patent ZL200610011551.3 method for preparing ceramic with pore gradient, be in ceramic powder, to add deionized water, utilize ball milling method to prepare slurry, in solidifying organism, add deionized water simultaneously, utilize ultra-sonic dispersion or ball milling method to prepare slurry; Slurry injects designed mould through the vacuum static mixer with the slurry short mix, through curing molding, drying, sintering, makes the ceramic with pore gradient material.The principle that forms pore gradient in the material is at first to introduce the Gradient distribution of starch content in base substrate, base substrate sample void content after high-temperature starch is got rid of has the distribution same with starch content.Dry back blank strength is between 2～4MPa.
Summary of the invention
The objective of the invention is difficulty for the complicate fabrication process that solves existing continuous hole graded pottery, and general centrifugal rotational speed problem of higher and a kind of preparation method of continuous hole graded ceramic tube is provided during the employing centrifugal formation method.
Technical scheme of the present invention is: a kind of preparation method of continuous hole graded ceramic tube, and its concrete steps are as follows:
(1) preparation of slurry
In deionized water, add ceramic powder, organic monomer, linking agent and dispersion agent, be made into homodisperse suspended nitride, in prepared slurry, add catalyzer and initiator then, stir by thorough mixing;
(2) centrifugal gel forming
The centrifuge tube that slurry is injected rotation carries out centrifugal, treats to heat after the centrifugal beginning again, makes the pulp gel curing molding, obtains the wet base of vitrified pipe;
(3) drying
The wet base of vitrified pipe is dry under heating, can from centrifuge tube, come off naturally after the wet base dehydration, obtain the vitrified pipe dry body;
(4) sintering
Dry body after the dehydration is warming up to the sintering temperature insulation, and cooling obtains continuous hole graded ceramic tube then.
Wherein above-mentioned ceramic powder is at least a kind of in aluminum oxide powder, silicon dioxide powder, zirconia powder, titanium dioxide powder or the carborundum powder; Organic monomer is a kind of in 2-hydroxyethyl methylacrylate (HEMA), N hydroxymethyl acrylamide (NMA) or the Methacrylamide (MAM); Linking agent is N, N '-methylene-bisacrylamide (MBAM); Dispersion agent is Triammonium citrate (TAC) or poly amic acid (PAA-NH
4) in a kind of.The quality proportioning of described slurry is: ceramic powder 50～95%, organic monomer 1～30%, linking agent 0.01～10%, deionized water 2～30%, dispersion agent 0.01～20%.Suspended nitride viscosity is 20～800mPas in the step (1).Above-mentioned aluminum oxide powder, silicon dioxide powder, zirconia powder, titanium dioxide powder or carborundum powder median size are 0.2～50 μ m.
Described catalyzer is Tetramethyl Ethylene Diamine (TEMED), and initiator is a kind of in ammonium persulphate (APS) or the Potassium Persulphate; The add-on of catalyzer account for the ceramic powder quality 0.001～4%, the add-on of initiator accounts for 0.0001～2% of ceramic powder quality.
In the above-mentioned steps (1), adding the time of stirring behind catalyzer and the initiator in prepared slurry is 1～20min.
The centrifuge tube that slurry is injected rotation carries out centrifugal, and gel solidification moulding simultaneously obtains the wet base of vitrified pipe; Centrifuge tube is a rigid die, makes as stainless steel or glass, its level is installed in the rotating speed with 100～9000rpm carries out centrifugal on the homemade centrifugal shaper.Heat behind centrifugal beginning 1～30min, Heating temperature is 30～90 ℃; Centrifugation time is that 1～100min makes the pulp gel curing molding, obtains the wet base of vitrified pipe.
Inject the size decision of the vitrified pipe that what of slurry of centrifuge tube are made by needs, required vitrified pipe size is bigger, and it is more then to inject slurry, otherwise it is less then to inject slurry.
After the centrifugal end with centrifuge tube at 30～90 ℃ of drying 1～200h, it is higher to have 1～3% linear shrinkage and intensity after the base substrate dehydration, can come off naturally from centrifuge tube.Obtain the vitrified pipe dry body.When drying temperature is low time of drying longer, when drying temperature is higher time of drying then slightly short, can not be too high but just begun drying temperature, with the too fast cracking that causes of damp proof base dehydration.
In the above-mentioned steps (4) base substrate is warming up to 600～1700 ℃ of insulation 0～10h with 1～10 ℃/min, organic removal and one step of sintering process are finished, obtain continuous hole graded alumina tube of the present invention.
Continuous hole graded ceramic tube of the present invention is cylinder-like structure.The aperture of film pipe is continuous distribution at the film caliber to direction, the internal surface minimum, and outside surface maximum, film pipe mean pore size are 0.05～3 μ m, and length is 5～2000mm, and diameter is 4～200mm, and wall thickness is 1～20mm.
Because slurry is mobile fine, solid content is higher, and viscosity is lower, and therefore in the process of centrifugal forming, particle can move under action of centrifugal force, and can carry out centrifugal under lower rotating speed.Behind centrifugal beginning 1～30min, particle size dispersion (little near the internal surface particle, big near the outside surface particle) basic forming is heated to 30～90 ℃ then, keeps centrifugal rotational speed 1～100min to make the pulp gel curing molding, obtains the wet base of vitrified pipe.The blank strength that obtains is higher.In centrifugal process, ceramic particle all is subjected to action of centrifugal force, and macrobead has different travelling speeies with small-particle in centrifugal process because the centrifugal force that is subjected to varies in size, thereby is depositing along the different place of caliber.And, therefore can avoid influence of air bubbles in the colloidizing process, thereby can save the vacuum stripping program in the conventional gel injection molding because particle has certain migration deposition in the process of moulding.Because internal surface particle diameter identical particle is subjected to identical centrifugal force in moulding process, therefore prepared film pipe internal surface is very smooth, smooth, zero defect, this can be applied in micro-filtration or the ultra-filtration process it, also can be used as the good supporting body and further films for internal surface.
Beneficial effect:
The preparation method of continuous gradient vitrified pipe of the present invention compared with prior art has following advantage:
(1) the present invention combines the advantage of gel injection and centrifugal forming, the blank strength height that obtains;
(2) centrifugal rotational speed of centrifugal requirement is lower, can reduce the manufacturing processed energy consumption;
(3) very smooth, smooth, the zero defect of the obtained film pipe internal surface of the present invention, this can be applied in micro-filtration or the ultra-filtration process it, also can be used as the good supporting body and further films for internal surface;
(4) preparation method of the present invention is simple, can save the vacuum stripping program of conventional gel injection molding;
(5) but preparation method's one-step moulding continuous hole graded ceramic tube of the present invention is easy to operate continuously;
(6) the prepared continuous hole graded ceramic tube of the present invention, the stress distribution that is subjected in the sintering is even, solved traditional shoulder hole graded ceramic tube and needed repeatedly sintering, because of layer with layer between the different rete rimose problems that easily cause of contraction;
(7) can by control ceramic powder initial particle to obtain the film pipe in different apertures; Have that pore structure is adjustable, blank strength is high, easy handling, efficient height, film pipe yield rate advantages of higher, be a kind of preparation method with practical value.
Description of drawings
Fig. 1 is the prepared continuous hole graded ceramic tube synoptic diagram of the present invention.
Fig. 2 is the schematic cross-section of continuous hole graded ceramic tube of the present invention.
Wherein 1 is the inwall of vitrified pipe, and 2 is the outer wall of vitrified pipe.
Embodiment
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further:
The present invention by controlling the particle diameter of initial ceramic powder, may be controlled to the aperture of type caudacoria pipe according to the design requirements of material.The slurry of preparing in following examples is 200g.
Material purity used in the test is:
Various ceramic powders are that particle diameter is the powder (commercially available) of 0.2～50 μ m, and purity is greater than 95%; Deionized water: specific conductivity＜7 μ s/cm; NMA: chemical pure; HEMA: chemical pure; MAM: chemical pure; MBAM: chemical pure; TAC: analytical pure; PAA-NH
4: solution (massfraction 1%～50%); TEMED: solution (massfraction＞98%); APS: analytical pure; Potassium Persulphate: analytical pure.
Embodiment 1:
The preparation method of continuous hole graded ceramic tube of the present invention comprises batching, centrifugal gel forming, drying and sintering.
The preparation of slurry: at first,, add TAC again, prepare the slurry that viscosity is 100mPas by stirring thorough mixing with alumina powder jointed, organic monomer HEMA and linking agent MBAM.
The stock quality proportioning is: alumina powder jointed 70%, organic monomer (HEMA) 2.5%, linking agent (MBAM) 0.1%, deionized water 27%, dispersion agent (TAC) 0.4%.
Centrifugal gel forming: take out the 20g slurry, to wherein adding catalyzer Tetramethyl Ethylene Diamine (TEMED) and initiator ammonium persulfate (APS) (be respectively ceramic powder quality 0.005% and 0.008%), inject the stainless steel centrifuge tube after stirring 5min, its level is installed in the rotating speed with 5000rpm carries out centrifugal forming on the homemade centrifugal shaper.After 5 minutes,, obtain the wet base of vitrified pipe keeping under the situation of centrifugal speed heating centrifuge tube to 70 ℃ and keeping 40min.
Dry: the base that will wet after the centrifugal end is at 80 ℃ of dry 50h, have certain linear shrinkage after the base substrate dehydration and intensity higher, can from centrifuge tube, come off naturally.
Sintering: base substrate is warming up to 1400 ℃ of insulation 2h with 2 ℃/min, organic removal and one step of sintering process are finished, obtain the continuous hole graded alumina tube of the present invention.
The gained ceramic-film tube increases from inside to outside gradually, internal surface aperture minimum, and outside surface aperture maximum, film pipe mean pore size are 0.1 μ m, and length is 110mm, and internal diameter is 8mm, and wall thickness is 1.5mm.
The prepared continuous hole graded ceramic tube of the present invention as shown in Figure 1, particle is ascending continuous gradient from inside to outside and distributes, round tube type vitrified pipe aperture is ascending continuous gradient from inside to outside and distributes.
Embodiment 2:
At first,, add TAC again, prepare the slurry that viscosity is 150mPas by stirring thorough mixing with silica powder, organic monomer NMA and linking agent MBAM.The stock quality proportioning is: silica powder 80%, organic monomer (NMA) 4%, linking agent (MBAM) 0.1%, deionized water 15.6%, dispersion agent (TAC) 0.3%.
Centrifugal gel forming: take out the 30g slurry, in slurry, add catalyzer TEMED and initiator A PS (be respectively ceramic powder quality 0.003% and 0.007%), inject the stainless steel centrifuge tube after stirring 2min, its level is installed in the rotating speed with 5000rpm carries out centrifugal forming on the homemade centrifugal shaper.After 5 minutes, keeping under the situation of centrifugal speed heating centrifuge tube to 80 ℃ and keeping 50min to make blank forming.
Dry: the base that will wet after the centrifugal end is at 50 ℃ of dry 30h, and it is higher to have 1～3% linear shrinkage and intensity after the base substrate dehydration, can come off naturally from centrifuge tube.
Sintering: base substrate is warming up to 1200 ℃ of insulation 2h with 2 ℃/min, organic removal and one step of sintering process are finished, obtain the continuous hole graded silica tube of the present invention.
Embodiment 3:
At first, with aluminum oxide, titanium oxide hybrid ceramic powder, organic monomer NMA and linking agent MBAM, add PAA-NH again
4: solution (massfraction 30%), prepare the slurry that viscosity is 85mPas by thorough mixing.
Aluminum oxide/titanium dioxide=90/10), organic monomer 10%, linking agent 1%, deionized water 29%, dispersion agent 5% the stock quality proportioning is: ceramic powder 55% (powder quality ratio:.
Centrifugal gel forming: take out the 40g slurry, in slurry, add catalyzer TEMED and initiator ammonium persulfate (be respectively ceramic powder quality 0.003% and 0.007%), inject the stainless steel centrifuge tube after stirring 2min, its level is installed in the rotating speed with 2000rpm carries out centrifugal forming on the homemade centrifugal shaper.After 10 minutes, keeping under the situation of centrifugal speed heating centrifuge tube to 80 ℃ and keeping 50min to make blank forming.
Dry: the base that will wet after the centrifugal end is at 40 ℃ of dry 180h, and it is higher to have 1～3% linear shrinkage and intensity after the base substrate dehydration, can come off naturally from centrifuge tube.
Sintering: base substrate is warming up to 1150 ℃ of insulation 2h with 2 ℃/min, organic removal and one step of sintering process are finished, obtain continuous hole graded aluminum oxide titanium white composite ceramic tube.
Embodiment 4:
At first,, add TAC again, prepare the slurry that viscosity is 80mPas by thorough mixing with alumina powder jointed, organic monomer NMA and linking agent MBAM.
The stock quality proportioning is: alumina powder jointed 60%, organic monomer 3.5%, linking agent 0.2%, deionized water 36%, dispersion agent 0.3%.
Centrifugal gel forming: take out the 20g slurry, in slurry, add catalyzer TEMED and initiator A PS (be respectively ceramic powder quality 0.003% and 0.007%), inject the stainless steel centrifuge tube after stirring 2min, its level is installed in the rotating speed with 3000rpm carries out centrifugal forming on the homemade centrifugal shaper.After 5 minutes, keeping under the situation of centrifugal speed heating centrifuge tube to 80 ℃ and keeping 30min to make blank forming.
Dry: the base that will wet after the centrifugal end is at 70 ℃ of dry 10h, have certain linear shrinkage after the base substrate dehydration and intensity higher, can from centrifuge tube, come off naturally.
Sintering: base substrate is warming up to 1300 ℃ of insulation 5h with 3 ℃/min, organic removal and one step of sintering process are finished, obtain continuous hole graded alumina tube.
Embodiment 5:
The parameter that the preparation method of this routine described continuous hole graded ceramic tube relates to is as follows, and other is with embodiment 2.
At first,, add TAC again, prepare the slurry that viscosity is 110mPas by thorough mixing with aluminum oxide, titanium dioxide, silicon carbide hybrid ceramic powder, organic monomer MAM and linking agent MBAM.
Aluminum oxide/titanium dioxide/silicon carbide=90/5/5), organic monomer 3%, linking agent 0.3%, deionized water 26.2%, dispersion agent 0.5% the stock quality proportioning is: ceramic powder 70% (powder quality ratio:.
Centrifugal gel forming: take out the 30g slurry, in slurry, add catalyzer TEMED and initiator A PS (be respectively ceramic powder quality 0.003% and 0.007%), inject the stainless steel centrifuge tube after stirring 2min, its level is installed in the rotating speed with 4000rpm carries out centrifugal forming on the homemade centrifugal shaper.After 10 minutes, keeping under the situation of centrifugal speed heating centrifuge tube to 80 ℃ and keeping 50min to make blank forming.
Dry: the base that will wet after the centrifugal end is at 40 ℃ of dry 180h, have certain linear shrinkage after the base substrate dehydration and intensity higher, can from centrifuge tube, come off naturally.
Sintering: base substrate is warming up to 900 ℃ of insulation 2h with 2 ℃/min, organic removal and one step of sintering process are finished, obtain continuous hole graded alumina-based ceramic pipe.
Embodiment 6:
The parameter that the preparation method of this routine described continuous hole graded ceramic tube relates to is as follows, and other is with embodiment 2.
At first,, add TAC again, prepare slurry by stirring thorough mixing with Zirconium powder, organic monomer MAM and linking agent MBAM.
The stock quality proportioning is: Zirconium powder 60%, organic monomer 2.5%, linking agent 0.1%, deionized water 37%, dispersion agent 0.4%.Sintering temperature is 1300 ℃.
Embodiment 7:
The parameter that the preparation method of this routine described continuous hole graded ceramic tube relates to is as follows, and other is with embodiment 2.
Used ceramic powder quality group becomes: alumina/silica=95/5.Sintering temperature is 1350 ℃.
Claims (6)
1. the preparation method of a continuous hole graded ceramic tube, its concrete steps are as follows:
(1) preparation of slurry
In deionized water, add ceramic powder, organic monomer, linking agent and dispersion agent and be made into homodisperse suspended nitride, in prepared slurry, add catalyzer and initiator then, stir by mixing; The quality proportioning of described slurry is: ceramic powder 50～95%, organic monomer 1～30%, linking agent 0.01～10%, deionized water 2～30%, dispersion agent 0.01～20%;
(2) centrifugal gel forming
The centrifuge tube that slurry is injected rotation carries out centrifugal, treats to heat after the centrifugal beginning again, makes the pulp gel curing molding, obtains the wet base of vitrified pipe; Wherein the centrifuge tube rotating speed is 100～9000rpm; Centrifugation time is 1～100min; Centrifugal beginning back 1～30min heats, and Heating temperature is 30～90 ℃;
(3) drying
The wet base of vitrified pipe is dry under heating, can from centrifuge tube, come off naturally after the wet base dehydration, obtain the vitrified pipe dry body;
(4) sintering
Dry body after the dehydration is warming up to the sintering temperature insulation, and cooling obtains continuous hole graded ceramic tube then.
2. according to the described preparation method of claim 1, it is characterized in that the described ceramic powder of step (1) is at least a kind of in aluminum oxide powder, silicon dioxide powder, zirconia powder, titanium dioxide powder or the carborundum powder; Organic monomer is a kind of in 2-hydroxyethyl methylacrylate, N hydroxymethyl acrylamide or the Methacrylamide; Linking agent is N, N '-methylene-bisacrylamide; Dispersion agent is a kind of in Triammonium citrate (TAC) or the poly amic acid.
3. according to the described preparation method of claim 1, it is characterized in that described catalyzer is a Tetramethyl Ethylene Diamine, initiator is a kind of in ammonium persulphate or the Potassium Persulphate; The add-on of catalyzer account for the ceramic powder quality 0.001～4%, the add-on of initiator accounts for 0.0001～2% of ceramic powder quality.
4. according to the described preparation method of claim 1, it is characterized in that described to add the time of stirring behind catalyzer and the initiator in prepared slurry be 1～20min to step (1).
5. according to the described preparation method of claim 1, it is characterized in that the described drying temperature of step (3) is 30～90 ℃, be 1～200h time of drying.
6. according to the described preparation method of claim 1, it is characterized in that the described temperature rise rate of step (4) is 1～10 ℃/min, sintering temperature is 600～1700 ℃, and soaking time is 0～10h.
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