CN103360047A - TiO2 ceramic and preparation method thereof - Google Patents

TiO2 ceramic and preparation method thereof Download PDF

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Publication number
CN103360047A
CN103360047A CN2013103171619A CN201310317161A CN103360047A CN 103360047 A CN103360047 A CN 103360047A CN 2013103171619 A CN2013103171619 A CN 2013103171619A CN 201310317161 A CN201310317161 A CN 201310317161A CN 103360047 A CN103360047 A CN 103360047A
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tio
whisker
contact
ball milling
pore
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CN103360047B (en
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许建文
王继元
堵文斌
卞伯同
陈韶辉
杨爱武
柏基业
庞焱
朱庆奋
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention provides a preparation method of a TiO2 porous ceramic. The method comprises the following steps: contacting Al2O3 whisker, nanometer ZrO2, a pore forming agent, a sintering aid and TiO2 powder with water to obtain a contact product A; after drying, contacting the contact product A with a nitric acid solution to obtain a contact product B; and performing extrusion moulding on the contact product B, and drying to obtain the low-stress TiO2 porous ceramic. The prepared porous ceramic is good in toughness, high in strength, simple in preparation technology, low in cost and suitable for industrialized production.

Description

A kind of TiO 2Pottery and preparation method thereof
Technical field
The present invention relates to a kind of TiO 2Pottery and preparation method thereof relates in particular to a kind of low-stress TiO 2Porous ceramics and preparation method thereof.
Background technology
Porous ceramics refers to have the new ceramic material of the pore texture of certain size and quantity.Porous ceramics is at first to be succeeded in developing in 1978 by the U.S., and characteristic is widely used in the fields such as biomaterial, refractory materials, separation, filtration, catalyzed reaction, reaction electrode, engines tail gas disposal because having high-temperature stability, good thermal shock, thermal conductivity is low, chemical stability is good etc.
Porous ceramics can be according to the difference of ceramic matrix material kind, and it is divided into alumina base, zirconia base, silicon carbide-based and titania-based etc.Titania-based porous ceramics is a kind of in the stupalith, because it advantage that possesses the characteristics such as the titanium dioxide maturing temperature is low, erosion resistance is strong and porous ceramics has broad application prospects.The preparation method of a patent CN1793027(porous titanium dioxide ceramic) disclose a kind of preparation method of porous titanium dioxide ceramic, this invention utilizes the polymer suspension polymerization technique, with TiO 2Ceramic particle and spherical polymethylmethacrylate are made respectively suspension, with the pore-forming material polymethylmethacrylate of single dispersion as template, can prepare the controlled porous ceramics of even aperture distribution and aperture size, concentrate the defectives such as the poor toughness, the intensity that cause are low, preparation section is comparatively complicated and restrict its range of application but the stress that this porous ceramics exists distributes.
In order to reduce the stress of pottery, improve the toughness of stupalith, prior art occurs introducing some in stupalith can disperse the material of boundary stress, to absorb the energy of ceramic crack propagation.Introduce in the stupalith and strengthen body to form ceramic matric composite be one of main method (Mah T.I., Mendiratta M.G., Katz A.P., et al.Am.Ceram.Soc.Bull., 1987,66 (2): 304.) of improving stupalith toughness.
Such as US Patent No. 6361888(Toughening of ceramic composites by transformation weakening of interphases) a kind of ceramic toughening matrix material and preparation method thereof is provided.The ceramic toughening matrix material is comprised of ceramic substrate, second-phase and metastable crystal plane material.Ceramic substrate is one or more the combination in carbide, nitride, boride and the oxide compound; By the reactive force at the interface of having used a kind of metastable Material weakening that undergoes phase transition between ceramic substrate and the second-phase, obviously strengthened physical strength and the toughness of ceramic composite.Chinese patent ZL200610091975.5(fiber reinforced alumina ceramic-base composites and preparation method thereof) a kind of preparation method of mullite fiber reinforced alumina ceramic is disclosed, by in alumina-ceramic, adding mullite fiber and other auxiliary agent, effectively reduce the stress of alumina-ceramic, improved bending strength and the fracture toughness property of alumina ceramic material.But its range of application is improved not and limited to the defective such as poor toughness, the ultimate compression strength that prior art still exists stress concentration to cause is low.
Summary of the invention
For TiO in the prior art 2The defectives such as the stress height of porous ceramics, poor toughness, ultimate compression strength are low, the inventor finds by lucubrate, by introducing Al 2O 3Whisker, nanometer ZrO 2So that concentrated stress obtains disperseing, the porous ceramics of preparing is significantly improved at aspects such as toughness, intensity with sintering aid.
A kind of TiO 2Porous ceramics comprises Al 2O 30.1～5 part of whisker, nanometer ZrO 20.5～20 parts, 5～20 parts of pore-forming materials, 0.5～30 part of sintering aid, all the other are TiO 2Powder.
Above-mentioned porous ceramics, described TiO 2The ultimate compression strength of porous ceramics is 110～180N/cm, and fracture toughness property is 4.0～8.0MPa.
A kind of TiO 2The preparation method of porous ceramics is characterized in that: may further comprise the steps:
(1) with Al 2O 3Whisker, nanometer ZrO 2, pore-forming material, sintering aid, TiO 2Powder contacts to get product of contact A with deionized water;
(2) obtain product of contact B with contacting with 10% dilute nitric acid solution after the product of contact A drying;
(3) product of contact B extrusion moulding is got mold compound;
(4) the drying and roasting mold compound obtains low-stress TiO 2Porous ceramics.
Above-mentioned preparation method, described Al 2O 3The diameter of whisker is 0.3～1 μ m, and length is 30～100 μ m.
Above-mentioned preparation method, described nanometer ZrO 2Diameter be 3～50nm.
Above-mentioned preparation method, described pore-forming material is selected from any or its combination in polystyrene, carbon fiber, methylcellulose gum, polymethylmethacrylate, the starch.
Above-mentioned preparation method, described sintering aid is SiO 2, any or its combination among the MgO.
Above-mentioned preparation method, the described Al of getting 2O 30.1～5 part of whisker, nanometer ZrO 20.5～20 parts, 5～20 parts of pore-forming materials, 0.5～30 part of sintering aid, all the other are TiO 2Powder.
Above-mentioned preparation method, described TiO 2The ultimate compression strength of porous ceramics is 110～180N/cm, and fracture toughness property is 4.0～8.0MPa.
TiO of the present invention 2Cellular ceramic substrate, described ultimate compression strength are to measure according to chemical industry standard HG/T2782-1996.Described fracture toughness property test is tested according to USS ASTMC1421-2001 (advanced ceramic fracture toughness property testing standard under the room temperature).
The present invention is with Al 2O 3Whisker and nanometer ZrO 2Be incorporated into TiO 2The preparation process of porous ceramics.Under the effect of crack tip stress field, ZrO 2Particle has absorbed energy by the phase transformation that Tetragonal → monoclinic phase occurs, and external force has been done merit, thereby has improved fracture toughness property.And Al 2O 3Whisker then is combined with the weak interface of ceramic matrix and is brought up absorption system to external energy, thereby plays the purpose of improving stupalith fragility.Al 2O 3Crystal whisker toughened and nanometer ZrO 2Transformation toughening is coordinative role simultaneously, so that toughening effect is more obvious.On the other hand, sintering aid SiO 2, being added with to be beneficial to and reducing TiO of MgO 2The sintering temperature of porous ceramics has significantly improved TiO 2The ultimate compression strength of porous ceramics.With respect to prior art, advantage of the present invention is: one, TiO 2The stress of porous ceramics is little, good toughness, intensity high.Its two, TiO 2The preparation technology of porous ceramics is simple, and cost is lower, suitability for industrialized production.
Embodiment
The below further describes technical characterictic of the present invention.
The invention provides a kind of TiO 2Porous ceramics comprises Al 2O 30.1～5 part of whisker, nanometer ZrO 20.5～20 parts, 5～20 parts of pore-forming materials, 0.5～30 part of sintering aid, all the other are TiO 2Powder.
Above-mentioned porous ceramics, described TiO 2The ultimate compression strength of porous ceramics is 110～180N/cm, and fracture toughness property is 4.0～8.0MPa.
According to the present invention, provide a kind of TiO 2The preparation method of porous ceramics may further comprise the steps:
(1) with Al 2O 3Whisker, nanometer ZrO 2, pore-forming material, sintering aid, TiO 2Powder contacts to get product of contact A with deionized water;
(2) obtain product of contact B with contacting with 10% dilute nitric acid solution after the product of contact A drying;
(3) product of contact B extrusion moulding is got mold compound;
(4) the drying and roasting mold compound obtains low-stress TiO 2Porous ceramics.
According to the present invention, described contact is adopted any mode known in the art to form uniform product of contact such as mixing (in case of necessity auxiliary ball milling, stirring) to each feed composition and is got final product.
According to the present invention, described Al 2O 3Whisker, nanometer ZrO 2, pore-forming material, sintering aid the way of contact be selected from any of following several modes:
(1) incites somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material, 4. sintering aid and 5. TiO 2Powder contact contacts with 6. deionized water again;
(2) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Contact is again with 3. pore-forming material, 4. sintering aid and 5. TiO 2Powder contact contacts with 6. deionized water again;
(3) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 23. pore-forming material contact is again with 4. sintering aid and 5. TiO 2Powder contact contacts with 6. deionized water again;
(4) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid, again with 5. TiO 2Powder contact contacts with 6. deionized water again;
(5) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 2Powder contact contacts with 4. sintering aid with 3. pore-forming material again, contacts with 6. deionized water again;
(6) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material and 5. TiO 2Powder contact contacts with 4. sintering aid again, contacts with 6. deionized water again;
(7) incite somebody to action first 1. Al 2O 3Whisker and 5. TiO 2Powder contact is again with 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid, contact with 6. deionized water again;
(8) incite somebody to action first 2. nanometer ZrO 25. TiO 2Powder contact is again with 1. Al 2O 3Whisker, 3. pore-forming material contacts with 4. sintering aid, contacts with 6. deionized water again;
(9) incite somebody to action first 1. Al 2O 3Whisker and 5. TiO 26. powder contact adds that deionized water carries out ball milling, behind the ball milling with 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid;
(10) incite somebody to action first 2. nanometer ZrO 25. TiO 26. powder contact adds that deionized water carries out ball milling, ball milling after for some time with 1. Al 2O 3Whisker, 3. pore-forming material contacts with 4. sintering aid;
(11) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid, adds afterwards 6. that deionized water carries out ball milling, ball milling after for some time again with 5. TiO 2The powder contact;
(12) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 23. 6. pore-forming material contact adds afterwards that deionized water carries out ball milling, ball milling after for some time again with 4. sintering aid and 5. TiO 2The powder contact;
(13) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, ball milling after for some time again with 3. pore-forming material, 4. sintering aid and 5. TiO 2The powder contact;
(14) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 26. powder contact adds that deionized water carries out ball milling, and ball milling contacts with 4. sintering aid with 3. pore-forming material after for some time again;
(15) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, and ball milling adds 5. TiO again after for some time 2Powder contacts with 4. sintering aid with 3. pore-forming material after after a time again;
(16) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, and ball milling adds 5. TiO again after for some time 2Powder contacts with 3. pore-forming material after after a time again, contacts with 4. sintering aid after after a time again;
(17) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, and ball milling adds 3. pore-forming material again after for some time, contact with 4. sintering aid again after after a time, more after a time after and 5. TiO 2The powder contact;
(18) first will be 3. pore-forming material, 4. sintering aid and 5. TiO 2Powder contact is carried out ball milling with 6. deionized water, ball milling after for some time again with 1. Al 2O 3Whisker and 2. nanometer ZrO 2Contact;
(19) first will be 3. pore-forming material contact with 4. sintering aid, add 6. that deionized water carries out ball milling, ball milling after for some time again with 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 2The powder contact;
(20) first with 3. pore-forming material and 5. TiO 26. powder contact adds that deionized water carries out ball milling, ball milling after for some time again with 1. Al 2O 3Whisker, 2. nanometer ZrO 24. sintering aid contact;
(21) first with 4. sintering aid and 5. TiO 26. powder contact adds that deionized water carries out ball milling, ball milling after for some time again with 1. Al 2O 3Whisker, 2. nanometer ZrO 23. pore-forming material contact.
According to the present invention, described ball milling for some time refers to 2～6h, refers to after a time 3～5h, refers to after a time 3～5h again.
According to the present invention, the kneading time of dried A and rare nitric acid is 1～3h.
According to the present invention, described drying is to carry out at 100～150 ℃, dry 1～10h.
According to the present invention, described roasting is to carry out at 900～1450 ℃, insulation 1～10h.
According to the present invention, with Al 2O 3Whisker and nanometer ZrO 2Be incorporated into TiO 2The preparation process of porous ceramics, under the effect of crack tip stress field, ZrO 2Particle has absorbed energy by the phase transformation that Tetragonal → monoclinic phase occurs, and external force has been done merit, thereby has improved fracture toughness property, and Al 2O 3Whisker then is combined with the weak interface of ceramic matrix and is brought up absorption system to external energy, thereby plays the purpose of improving stupalith fragility, Al 2O 3Crystal whisker toughened and nanometer ZrO 2Transformation toughening is coordinative role simultaneously, so that toughening effect is more obvious.Such as according to technical scheme of the present invention, the TiO of preparation 2Porous ceramics toughness reaches 7.0MPa.
According to the present invention, sintering aid SiO 2, MgO interpolation, can in sintering process, form binary, ternary or polynary eutectic mixture with other composition, will form liquid phase when reaching certain limit, thereby by viscous flow mechanism domination sintering, and make its rapid densification, not only be conducive to reduce TiO 2The sintering temperature of porous ceramics, and significantly improved TiO 2The ultimate compression strength of porous ceramics, such as according to technical scheme of the present invention, the TiO of preparation 2Porous ceramics ultimate compression strength reaches 159N/cm.
Embodiment 1
(1) taking by weighing diameter is that 0.5 μ m, length are the Al of 50 μ m 2O 33 parts of whiskers, diameter are the nanometer ZrO of 10nm 210 parts, 10 parts of pore-forming material methylcellulose gum, sintering aid SiO 210 parts, all the other are TiO 2Powder obtains gross weight and is 100 parts mixture, does medium with 40 parts of deionized waters the material that weighs up is mixed into uniform sizing material A;
(2) slurry A is at 110 ℃ of lower dry 3h, adds afterwards 40 parts of concentration and be 10% dilute nitric acid solution, mixes 2h and forms compound B;
(3) the rectangular of 5～6mm is cut in the compound B extrusion moulding (extrudate diameter 2.0mm) after will mediating;
(4) rectangular through 120 ℃ of dryings, 1250 ℃ of roasting 4h obtain low-stress TiO 2Porous ceramics.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 2
(1) taking by weighing diameter is that 0.3 μ m, length are the Al of 30 μ m 2O 30.1 part of whisker, diameter are the nanometer ZrO of 3nm 20.5 part, 5 parts of pore-forming material polymethylmethacrylates, sintering aid SiO 20.5 part, all the other are TiO 2Powder obtains gross weight and is 100 parts mixture, does medium with 30 parts of deionized waters the material that weighs up is mixed into uniform sizing material A;
(2) slurry A is at 110 ℃ of lower dry 3h, adds afterwards 30 parts of concentration and be 10% dilute nitric acid solution, mixes 1h and forms compound B;
(3) the rectangular of 5～6mm is cut in the compound B extrusion moulding (extrudate diameter 0.5mm) after will mediating;
(4) rectangular through 120 ℃ of dryings, 900 ℃ of roasting 4h obtain low-stress TiO 2Porous ceramics.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 3
(1) taking by weighing diameter is that 1 μ m, length are the Al of 100 μ m 2O 35 parts of whiskers, diameter are the nanometer ZrO of 50nm 220 parts, 20 parts on pore-forming material carbon fiber, sintering aid SiO 230 parts, all the other are TiO 2Powder obtains gross weight and is 100 parts mixture, does medium with 50 parts of deionized waters the material that weighs up is mixed into uniform sizing material A;
(2) slurry A is at 110 ℃ of lower dry 3h, adds afterwards 50 parts of concentration and be 10% dilute nitric acid solution, mixes 3h and forms compound B;
(3) the rectangular of 5～6mm is cut in the compound B extrusion moulding (extrudate diameter 3.0mm) after will mediating;
(4) rectangular through 120 ℃ of dryings, 1450 ℃ of roasting 4h obtain low-stress TiO 2Porous ceramics.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 4
(1) taking by weighing diameter is that 0.4 μ m, length are the Al of 40 μ m 2O 30.1 part of whisker, diameter are the nanometer ZrO of 20nm 220 parts, 20 parts of pore-forming material starch, sintering aid MgO30 part, all the other are TiO 2Powder obtains gross weight and is 100 parts mixture, does medium with 40 parts of deionized waters the material that weighs up is mixed into uniform sizing material A;
(2) slurry A is at 110 ℃ of lower dry 3h, adds afterwards 40 parts of concentration and be 10% dilute nitric acid solution, mixes 3h and forms compound B;
(3) the rectangular of 5～6mm is cut in the compound B extrusion moulding (extrudate diameter 2.0mm) after will mediating;
(4) rectangular through 120 ℃ of dryings, 1250 ℃ of roasting 4h obtain low-stress TiO 2Porous ceramics.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 5
(1) taking by weighing diameter is that 0.8 μ m, length are the Al of 90 μ m 2O 35 parts of whiskers, diameter are the nanometer ZrO of 40nm 20.5 part, 20 parts of pore-forming material polystyrene, sintering aid MgO30 part, all the other are TiO 2Powder obtains gross weight and is 100 parts mixture, does medium with 40 parts of deionized waters the material that weighs up is mixed into uniform sizing material A;
(2) slurry A is at 110 ℃ of lower dry 3h, adds afterwards 40 parts of concentration and be 10% dilute nitric acid solution, mixes 3h and forms compound B;
(3) the rectangular of 5～6mm is cut in the compound B extrusion moulding (extrudate diameter 2.0mm) after will mediating;
(4) rectangular through 120 ℃ of dryings, 1250 ℃ of roasting 4h obtain low-stress TiO 2Porous ceramics.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 6
(1) taking by weighing diameter is that 0.5 μ m, length are the Al of 60 μ m 2O 33 parts of whiskers, diameter are the nanometer ZrO of 10nm 215 parts, 5 parts of pore-forming material polystyrene, 10 parts of methylcellulose gum, sintering aid SiO 210 parts, MgO10 part, all the other are TiO 2Powder obtains gross weight and is 100 parts mixture, does medium with 40 parts of deionized waters the material that weighs up is mixed into uniform sizing material A;
(2) slurry A is at 110 ℃ of lower dry 3h, adds afterwards 40 parts of concentration and be 10% dilute nitric acid solution, mixes 3h and forms compound B;
(3) the rectangular of 5～6mm is cut in the compound B extrusion moulding (extrudate diameter 2.0mm) after will mediating;
(4) rectangular through 120 ℃ of dryings, 1250 ℃ of roasting 4h obtain low-stress TiO 2Porous ceramics.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 7
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Mix, again with 3. pore-forming material methylcellulose gum, 4. sintering aid SiO 25. TiO 2Powder mixes, and puts into ball mill, and adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 8
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker, 2. nanometer ZrO 23. the pore-forming material methylcellulose gum mixes, again with 4. sintering aid SiO 25. TiO 2Powder mixes, and puts into ball mill, and adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 9
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix, again with 5. TiO 2Powder mixes, and puts into ball mill, and adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 10
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 2Powder mixes, again with 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix, put into ball mill, adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 11
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material methylcellulose gum and 5. TiO 2Powder mixes, again with 4. sintering aid SiO 2Mix, put into ball mill, adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 12
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 5. TiO 2Powder mixes, again with 2. nanometer ZrO 2, 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix, put into ball mill, adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 13
Substantially the same manner as Example 1, but following change is arranged:
To first 2. nanometer ZrO 25. TiO 2Powder mixes, again with 1. Al 2O 3Whisker, 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix, put into ball mill, adding 6., deionized water carries out the ball milling mixing again.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 14
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 5. TiO 2Powder mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 2. nanometer ZrO again after for some time 2, 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 15
Substantially the same manner as Example 1, but following change is arranged:
To first 2. nanometer ZrO 25. TiO 2Powder mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 1. Al again after for some time 2O 3Whisker, 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 16
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 2, 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix, put into afterwards ball mill, add 6. that deionized water carries out ball milling, ball milling adds 5. TiO again after for some time 2Powder mixes.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 17
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 23. the pore-forming material methylcellulose gum mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 4. sintering aid SiO again after for some time 25. TiO 2Powder mixes.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 18
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Mix, put into afterwards ball mill, add 6. that deionized water carries out ball milling, 3. ball milling adds pore-forming material methylcellulose gum, 4. sintering aid SiO again after for some time 25. TiO 2Powder mixes.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 19
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 2Powder mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 3. pore-forming material methylcellulose gum and 4. sintering aid SiO again after for some time 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 20
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Mix, put into afterwards ball mill, add 6. that deionized water carries out ball milling, ball milling adds 5. TiO again after for some time 2Powder adds 3. pore-forming material methylcellulose gum and 4. sintering aid SiO after after a time again 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 21
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Mix, put into afterwards ball mill, add 6. that deionized water carries out ball milling, ball milling adds 5. TiO again after for some time 23. powder adds that the pore-forming material methylcellulose gum mixes after after a time again, adds afterwards after a time more 4. sintering aid SiO 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 22
Substantially the same manner as Example 1, but following change is arranged:
To first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Mix, put into afterwards ball mill, add 6. that deionized water carries out ball milling, ball milling adds 3. pore-forming material methylcellulose gum again after for some time, adds 4. sintering aid SiO after after a time again 2Mix, add afterwards after a time more 5. TiO 2Powder mixes.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 23
Substantially the same manner as Example 1, but following change is arranged:
First will be 3. pore-forming material methylcellulose gum, 4. sintering aid SiO 25. TiO 2Powder mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 1. Al again after for some time 2O 3Whisker and 2. nanometer ZrO 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 24
Substantially the same manner as Example 1, but following change is arranged:
First with 3. pore-forming material methylcellulose gum and 4. sintering aid SiO 2Mix, put into afterwards ball mill, add 6. that deionized water carries out ball milling, ball milling adds 1. Al again after for some time 2O 3Whisker, 2. nanometer ZrO 25. TiO 2Powder mixes.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 25
Substantially the same manner as Example 1, but following change is arranged:
First with 3. pore-forming material methylcellulose gum and 5. TiO 2Powder mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 1. Al again after for some time 2O 3Whisker, 2. nanometer ZrO 24. sintering aid SiO 2Mix.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Embodiment 26
Substantially the same manner as Example 1, but following change is arranged:
To first 4. sintering aid SiO 25. TiO 2Powder mixes, and puts into afterwards ball mill, adds 6. that deionized water carries out ball milling, and ball milling adds 1. Al again after for some time 2O 3Whisker, 2. nanometer ZrO 23. the pore-forming material methylcellulose gum mixes.
The TiO that present embodiment obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Comparative example 1
Compare with embodiment 1, do not add Al 2O 3Whisker and nanometer ZrO 2, other material consumption is identical with embodiment 1 with operational condition.
The TiO that this comparative example obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Comparative example 2
Compare with embodiment 1, do not add sintering aid SiO 2, other material consumption is identical with embodiment 1 with operational condition.
The TiO that this comparative example obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Comparative example 3
This comparison example is compared with embodiment 1, and the method for describing according to patent CN101209925 (method of modifying of aluminum oxide titanium white multiple phase fine ceramics material) prepares stupalith.
(1) the binding agent polyvinyl alcohol of the deionized water of the mixed powder of 1 weight part, 0.5 weight part, 0.01 weight part being put into ball mill mixes.Mixed powder is comprised of 6 parts nano aluminium oxide, 4 parts nano-titanium oxide and 1.5 parts properties-correcting agent by weight, and described properties-correcting agent is comprised of 0.8 part cerium oxide and 0.7 part zirconium white by weight;
(2) gained slurry after mixing in the step (1) is carried out again granulation of spraying drying, obtain the powder that particle diameter is 20～80 μ m, inlet temperature is 230 ℃ during spray-drier work, and temperature out is 110 ℃, and the spraying rotating speed is 36000r/min;
(3) will be again the powder of the granulation fine alumina crucible of packing into, crucible is put into high temperature box type resistance furnace heat-treat, treating processes is as follows: temperature rise rate is 10 ℃/min in the heat treatment process, is warming up to first 600 ℃, then insulation 60min cools to room temperature with the furnace;
(4) powder after the thermal treatment is put into mould, under 75MPa pressure, carry out pre-molding, pressurize 3min;
(5) blocks behind the pre-molding is put into rubber mold, get rid of gas and encapsulate, put into again cold isostatic press, at the 260MPa forming under the pressure, pressurize 3min;
(6) gained blank after the isostatic cool pressing is put into resistance furnace, carry out pressureless sintering under 1450 ℃ temperature, sintering time is 60min, and temperature rise rate is 5 ℃/min, then cools to room temperature with the furnace.
The TiO that this comparative example obtains 2Ultimate compression strength and the fracture toughness property of porous ceramics see Table 1.
Table 1TiO 2The ultimate compression strength of porous ceramics and fracture toughness property
Figure 2013103171619100002DEST_PATH_IMAGE001
Comparative example 1～3 is compared with embodiment 1, can find out, the TiO of the inventive method preparation 2The stress of porous ceramics is little, good toughness, ultimate compression strength high, and preparation technology is simple, suitability for industrialized production.

Claims (7)

1. TiO 2The porous ceramics preparation method is characterized in that: may further comprise the steps: following all in mass:
(1) with Al 2O 3Whisker, nanometer ZrO 2, pore-forming material, sintering aid, TiO 2Powder contacts to get product of contact A with deionized water;
(2) obtain product of contact B with contacting with 10% dilute nitric acid solution after the product of contact A drying;
(3) product of contact B extrusion moulding is got mold compound;
(4) the drying and roasting mold compound obtains low-stress TiO 2Porous ceramics.
2. preparation method according to claim 1 is characterized in that: described Al 2O 3The diameter of whisker is 0.3～1 μ m, and length is 30～100 μ m.
3. preparation method according to claim 1 is characterized in that: described nanometer ZrO 2Diameter be 3～50nm.
4. preparation method according to claim 1 is characterized in that: described pore-forming material is selected from any or its combination in polystyrene, carbon fiber, methylcellulose gum, polymethylmethacrylate, the starch.
5. preparation method according to claim 1, it is characterized in that: described sintering aid is selected from SiO 2, any or its combination among the MgO.
6. preparation method according to claim 1 is characterized in that: described Al 2O 3Whisker, nanometer ZrO 2, pore-forming material, sintering aid the way of contact be selected from any of following several modes:
(1) incites somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material, 4. sintering aid and 5. TiO 2Powder contact contacts with 6. deionized water again;
(2) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 2Contact is again with 3. pore-forming material, 4. sintering aid and 5. TiO 2Powder contact contacts with 6. deionized water again;
(3) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 23. pore-forming material contact is again with 4. sintering aid and 5. TiO 2Powder contact contacts with 6. deionized water again;
(4) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid, again with 5. TiO 2Powder contact contacts with 6. deionized water again;
(5) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 2Powder contact contacts with 4. sintering aid with 3. pore-forming material again, contacts with 6. deionized water again;
(6) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 2, 3. pore-forming material and 5. TiO 2Powder contact contacts with 4. sintering aid again, contacts with 6. deionized water again;
(7) incite somebody to action first 1. Al 2O 3Whisker and 5. TiO 2Powder contact is again with 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid, contact with 6. deionized water again;
(8) incite somebody to action first 2. nanometer ZrO 25. TiO 2Powder contact is again with 1. Al 2O 3Whisker, 3. pore-forming material contacts with 4. sintering aid, contacts with 6. deionized water again;
(9) incite somebody to action first 1. Al 2O 3Whisker and 5. TiO 26. powder contact adds that deionized water carries out ball milling, behind the ball milling with 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid;
(10) incite somebody to action first 2. nanometer ZrO 25. TiO 26. powder contact adds that deionized water carries out ball milling, ball milling after for some time with 1. Al 2O 3Whisker, 3. pore-forming material contacts with 4. sintering aid;
(11) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 2, 3. pore-forming material contacts with 4. sintering aid, adds afterwards 6. that deionized water carries out ball milling, ball milling after for some time again with 5. TiO 2The powder contact;
(12) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 23. 6. pore-forming material contact adds afterwards that deionized water carries out ball milling, ball milling after for some time again with 4. sintering aid and 5. TiO 2The powder contact;
(13) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, ball milling after for some time again with 3. pore-forming material, 4. sintering aid and 5. TiO 2The powder contact;
(14) incite somebody to action first 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 26. powder contact adds that deionized water carries out ball milling, and ball milling contacts with 4. sintering aid with 3. pore-forming material after for some time again;
(15) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, and ball milling adds 5. TiO again after for some time 2Powder contacts with 4. sintering aid with 3. pore-forming material after after a time again;
(16) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, and ball milling adds 5. TiO again after for some time 2Powder contacts with 3. pore-forming material after after a time again, contacts with 4. sintering aid after after a time again;
(17) incite somebody to action first 1. Al 2O 3Whisker and 2. nanometer ZrO 26. contact adds that deionized water carries out ball milling, and ball milling adds 3. pore-forming material again after for some time, contact with 4. sintering aid again after after a time, more after a time after and 5. TiO 2The powder contact;
(18) first will be 3. pore-forming material, 4. sintering aid and 5. TiO 2Powder contact is carried out ball milling with 6. deionized water, ball milling after for some time again with 1. Al 2O 3Whisker and 2. nanometer ZrO 2Contact;
(19) first will be 3. pore-forming material contact with 4. sintering aid, add 6. that deionized water carries out ball milling, ball milling after for some time again with 1. Al 2O 3Whisker, 2. nanometer ZrO 25. TiO 2The powder contact;
(20) first with 3. pore-forming material and 5. TiO 26. powder contact adds that deionized water carries out ball milling, ball milling after for some time again with 1. Al 2O 3Whisker, 2. nanometer ZrO 24. sintering aid contact;
(21) first with 4. sintering aid and 5. TiO 26. powder contact adds that deionized water carries out ball milling, ball milling after for some time again with 1. Al 2O 3Whisker, 2. nanometer ZrO 23. pore-forming material contact.
7. preparation method according to claim 1 is characterized in that: prepared TiO 2The ultimate compression strength of porous ceramics is 110～180N/cm, and fracture toughness property is 4.0～8.0MPa.
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CN104163625A (en) * 2014-08-04 2014-11-26 余姚市巧迪电器厂 Scandium oxide and neodymium oxide composite stabilized titanium oxide-based multi-element nano-composite ceramic die
CN115353400A (en) * 2022-09-29 2022-11-18 四川交蓉思源科技有限公司 Toughened silicon nitride ceramic material and preparation method thereof

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CN101612097A (en) * 2009-07-16 2009-12-30 东南大学 Dental machinable diatomite full ceramic restoration material and preparation method thereof

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CN1793027A (en) * 2005-11-08 2006-06-28 桂林工学院 Process for preparing porous titanium dioxide ceramic
CN101612097A (en) * 2009-07-16 2009-12-30 东南大学 Dental machinable diatomite full ceramic restoration material and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN104163625A (en) * 2014-08-04 2014-11-26 余姚市巧迪电器厂 Scandium oxide and neodymium oxide composite stabilized titanium oxide-based multi-element nano-composite ceramic die
CN104163625B (en) * 2014-08-04 2016-02-17 余姚市巧迪电器厂 A kind of Scium trioxide and the titania based polynary nanometer composite ceramic die of Neodymium trioxide stable composition
CN115353400A (en) * 2022-09-29 2022-11-18 四川交蓉思源科技有限公司 Toughened silicon nitride ceramic material and preparation method thereof
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