CN102718541B - Porous material with whiskers or rod crystals in apertures and preparation method thereof - Google Patents

Porous material with whiskers or rod crystals in apertures and preparation method thereof Download PDF

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CN102718541B
CN102718541B CN 201210039197 CN201210039197A CN102718541B CN 102718541 B CN102718541 B CN 102718541B CN 201210039197 CN201210039197 CN 201210039197 CN 201210039197 A CN201210039197 A CN 201210039197A CN 102718541 B CN102718541 B CN 102718541B
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porous material
tio
whisker
rod
brilliant
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CN102718541A (en
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崔洪芝
徐国刚
吴杰
曹丽丽
姜琳
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Shandong University of Science and Technology
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Shandong University of Science and Technology
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Abstract

A porous material with whiskers or rod crystals in apertures. The preparation method of the porous material comprises steps of: taking TiO2 and Al2O3 as raw materials and urea as a pore-forming agent, and sintering to obtain a Ti2AlO5 porous material; then immersing the porous material into pure Al melt under high temperature; and eventually forming the porous material with Al2O3 and TiAl whiskers or rod crystals grown on walls of apertures. The porous material provided by the invention has low cost and simple process, and is favorable to improve dispersion and catalytic conversion efficiency of catalyst and endowed with large performance regulating range. The porous material can be used as a carrier and a filtering body in catalysis and environmental purification.

Description

In the hole with whisker or the brilliant porous material of rod and preparation method thereof
Technical field
The present invention relates to a kind of porous material and preparation technology thereof, in especially a kind of hole with whisker or the brilliant Ti of rod 2AlO 5Base porous compound material and preparation method thereof belongs to material and synthesizes and manufacture field.
Background technology
Now, reducing the motor vehicle exhaust protection of the environment is the focus of paying close attention in global range.At present, the catalyst support material of purifying vehicle exhaust being used mainly contains pottery and metal two classes.For stagnant catalyst, usually apply equably the γ-Al of one deck high-specific surface area at carrier surface 2O 3Coating, and then noble metal active catalyst component appendix in its surface.For metallic carrier, because γ-Al 2O 3The thermal expansivity of coating and metallic matrix has larger difference, coating and catalyzer is come off from carrier, thereby lose catalyticing purifying effect.And for ceramic monolith, what be used widely is trichroite and silicon carbide ceramics solid support material, and its structure is cellular, is called honeycomb ceramic carrier.Because the thermal conductivity of cordierite carrier material is low, undercapacity, when causing cold-starting automobile, the catalyzer ignition is slow, and running car is easily broken when jolting.Although Carboround material thermal conductivity is high, intensity is high, and high thermal resistance is good, and the line expansion factor is large, poor thermal shock resistance.The present preparation technology of support of the catalyst in addition makes the wall of support of the catalyst be smooth straight, is unfavorable for the load of catalyzer.Therefore, at present in the support of the catalyst of the use preparation technology from the performance of material self to carrier, all be difficult to satisfy day by day harsh motor vehicle exhaust technical requirements, the desirable preparation technology of the solid support material of exploitation excellent performance and pass is significant.
Aluminium titanates (Al 2TiO 5) material is the stupalith that integrates low-expansion coefficient and high-melting-point, and has anti-slag, anti-corrosion, alkaline-resisting and to nonwettable characteristics of various metals and glass, be widely used in the environment of the condition harshnesses such as anti-thermal shock, high temperature resistant, wear-resistant, anticorrosive, alkali resistant, particularly require the occasion of highly heatproof and shockproof.Chinese patent CN200780045679.4 has invented a kind of Al 2TiO 5The manufacture method of matter ceramic honeycomb, this method are with TiO 2And Al 2O 3Powder is to carry out sintering after raw material is made base substrate, obtains the Al of clear opening 2TiO 5The honeycomb ceramic carrier.Japanese Patent 2005-519834 and WO2005/018776 disclose by adjusting TiO 2And Al 2O 3The proportioning of powder, add additive etc., suppress Al 2TiO 5Thermolysis, improve the technology of ultimate compression strength.China Patent Publication No. CN101607830A discloses the preparation method of a kind of fiber reinforced aluminum titanate composite material and goods, and it is directly with α-Al 2O 3With titanium yellow powder be that raw material adopts the synthetic aluminium titanates of reaction sintering, and add the mullite fiber that prevents the stablizer that aluminium titanates decomposes and play enhancement in admixtion, improved the intensity of material.Chinese patent application numbers 200980115069.6 has been invented a kind of aluminium titanates from the novel porous matter aluminium titanates as Porous, and the method is by the sintering of porous aluminum titanate powder own, thereby forms the al titanate sintering body of Porous more.Chinese patent application numbers 200910180843.3 has been invented a kind of aluminium nitride/carborundum/aluminium titanate porous ceramics and preparation method thereof, adopting aluminium nitride, silicon carbide, aluminium titanates is raw material, by adding paraffin, prepared the porous ceramics of porosity 60-80%, improved the heat-insulating capability of material.Chinese patent application numbers 200810136970.9 has been announced a kind of aluminum oxide/aluminium titanate porous ceramic and preparation method thereof, and this method is by adopting alumina in Nano level, titanium oxide powder raw material sintering to obtain porous alumina/aluminium titanates composite porous ceramic material.
Although above-mentioned patent is synthesized Ti by different methods 2AlO 5Porous material, and made the porous material of different shaped jet holes.But pure Al 2TiO 5The stupalith wall is relatively smooth, is difficult to satisfy the requirement of automobile exhaust purifier carrier demanding specific surface area and good catalyzed conversion effect when supported catalyst.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide in a kind of hole with nano level whisker or the brilliant Al of rod 2TiO 5Base porous compound material and the composite manufacture method with this pore structure, long on the hole wall of this composite inner radial dimension is arranged is nano level TiAl and Al 2O 3Whisker or rod are brilliant, are conducive to the combination of catalyst coat and hole wall, more can improve the specific surface area of hole, catalysis and conversion when being conducive to for support of the catalyst.
Technical scheme of the present invention is: in a kind of hole, with whisker or the brilliant porous material of rod, described porous material is with TiO 2And Al 2O 3For raw material, take urea as pore-forming material sintering Ti 2AlO 5Porous material immerses under this porous material high temperature in pure Al melt subsequently, and what finally form has Al in hole wall length 2O 3With TiAl whisker or the brilliant porous material of rod.
Preferably, described whisker or the brilliant length of rod are 0.2～2.0mm, the aperture 2.2～3.3mm of porous material, and porosity is 53.3～75.8%, ultimate compression strength is 4.4～8.5MPa.
With the preparation method of whisker or the brilliant porous material of rod, comprise the following steps in described hole:
The first step: get commercially pure TiO ready 2, Al 2O 3Powder stock, pore-forming material urea granules and Al ingot, wherein TiO 2, Al 2O 3Powder size is 200 orders, urea particle diameter 2～3mm;
Second step: Al 2TiO 5The porous material sintering is synthetic
With TiO 2, Al 2O 3Powder is according to mol ratio TiO 2: Al 2O 3=1:1 (mol) weighing according to volume ratio 50～80%, measures urea granules, packs into after evenly mixing in mould, adopts compression-moulding methods, is pressed into cylindrical green compact under 200MPa pressure; Pressed compact is put in resistance furnace again, be heated to 300 ℃ of insulations 1.5 hours, urea granules volatilizees fully; Pressed compact is put into resistance furnace, 1400～1500 ℃ of sintering 3 hours, take out the sample air cooling after sintering, obtain wide aperture Al 2TiO 5Porous material;
The 3rd step: hot dip aluminum plating
The industrial pure Al ingot is put into Al 2O 3In crucible, be heated to 800 ℃ under argon shield, the Al ingot all melts, with wide-aperture porous Al 2TiO 5Material immerses in pure Al melt, keeps 5～10 minutes, and Al liquid infiltrates in porous material, after extracting porous material, drops to 650 ℃ with furnace temperature in stove, obtains the aluminium film of a layer thickness 20～30 μ m on hole wall;
The 4th step: Al in hole 2O 3With TiAl whisker or excellent crystals growth
Treat that furnace temperature is down to 650 ℃, stop logical argon gas and opened fire door 1 minute, air is entered in stove, then 650 ℃ of heating, be incubated 25～50 minutes, part Ti 2AlO 5Decompose and generate TiO 2And Al 2O 3, Al film autoxidation simultaneously again with TiO 2Reaction generates Al 2O 3, Ti and Al react the TiAl phase that generates the pyro-oxidation resistance excellence, generate Al in hole wall original position 2O 3Brilliant with whisker or the rod of TiAl.
The TiAl of hole wall and Al 2O 3Bar-shaped and reaction generating principle whisker is as follows:
Al 2TiO 5+Al+O 2→Al 2TiO 5+TiAl+Al 2O 3
Beneficial effect of the present invention is: 1. with TiO 2And Al 2O 3Powder is raw material, take urea as pore-forming material, take pure Al ingot as the hot dip process raw material, by sintering reaction, hot dip process technology are combined, at first obtains the porous Al with the Al coating 2TiO 5Matrix composite, then become the hole wall with Al through high temperature oxidation 2O 3With TiAl whisker or the brilliant porous material of rod, with low cost, technique is simple; 2. porous Al of the present invention 2TiO 5Matrix composite, the generated in-situ Al of hole wall 2O 3Brilliant with TiAl whisker or rod, radial dimension is 50～100nm, and length is 0.2～2.0 μ m, has greatly improved specific surface area, when being used for support of the catalyst, is conducive to improve dispersion and the catalyzed conversion effect of catalyzer; 3. porous Al 2TiO 5The matrix material of matrix is by Al 2TiO 5With a small amount of Al 2O 3, TiO 2Form, hole is the open-celled structure of three-dimensional communication, aperture 2.2～3.3mm, and by adjusting Content of Pore-forming Agents, can obtain porosity is 53.3～75.8%, ultimate compression strength is the porous material of 4.4～8.5MPa, and the property regulation scope is large, and this porous material can be used as carrier and the filtering bodies in catalysis, environmental purification.
Embodiment
Embodiment 1
Composite porous preparation method of the present invention is as follows:
The first step: get commercially pure TiO ready 2, Al 2O 3Powder stock, pore-forming material urea granules and Al ingot, wherein TiO 2, Al 2O 3Powder size is 200 orders, urea particle diameter 2～3mm.
Second step: Al 2TiO 5The porous material sintering is synthetic
With TiO 2, Al 2O 3Powder is according to mol ratio TiO 2: Al 2O 3=1:1 (mol) weighing according to volume ratio 50%, measures urea granules, packs into after evenly mixing in mould, adopts compression-moulding methods, is pressed into cylindrical green compact under 200MPa pressure; Pressed compact is put in resistance furnace again, be heated to 300 ℃ of insulations 1.5 hours, urea granules volatilizees fully; Pressed compact is put into resistance furnace, 1400 ℃ of sintering 3 hours, take out the sample air cooling after sintering, obtain wide aperture Al 2TiO 5Porous material.
The 3rd step: hot dip aluminum plating
The industrial pure Al ingot is put into Al 2O 3In crucible, be heated to 800 ℃ under argon shield, the Al ingot all melts.With wide-aperture porous Al 2TiO 5Material immerses in pure Al melt, keeps 10 minutes, and Al liquid infiltrates in porous material.After extracting porous material, drop to 650 ℃ with furnace temperature in stove, obtain the aluminium film of a layer thickness 30 μ m on hole wall.
The 4th step: Al in hole 2O 3With TiAl whisker or excellent crystals growth
Treat that furnace temperature is down to 650 ℃, stop logical argon gas and opened fire door 1 minute, air is entered in stove.Then 650 ℃ of heated oxides, insulation are 50 minutes, part Al 2TiO 5Decompose and generate TiO 2And Al 2O 3, Al film autoxidation simultaneously again with TiO 2Reaction generates Al 2O 3, Ti and Al react the TiAl phase that generates the pyro-oxidation resistance excellence.At the generated in-situ Al of hole wall 2O 3Be about 100nm with the TiAl radial dimension, length is that the rod of 2.0 μ m is brilliant, the aperture 2.2～3.3mm of porous material, and porosity is 53.3%, ultimate compression strength is 8.5MPa.
Embodiment 2:
With the difference of embodiment 1 be that pore-forming material urea volume ratio is 60%, porous Al 2TiO 5Material immerses in pure Al melt, keeps 8 minutes, and the aluminium film thickness is 25 μ m approximately, heated oxide insulation 40 minutes, Al in hole 2O 3Be about 80nm with the brilliant radial dimension of TiAl rod, be about 1.5 μ m, the aperture of porous material is 2.2～3.3mm, and porosity is 68.7%, and ultimate compression strength is 6.2MPa.
Embodiment 3:
With the difference of embodiment 1 be that pore-forming material urea volume ratio is 70%, pressed compact is in 1500 ℃ of sintering 3 hours, porous Al 2TiO 5Material immerses in pure Al melt, keeps 8 minutes, and the aluminium film thickness is 25 μ m approximately, heated oxide insulation 25 minutes, Al in hole 2O 3Be about 70nm with TiAl whisker radial dimension, be about 0.8 μ m, the aperture of porous material is 2.2～3.3mm, and porosity is 71.4%, and ultimate compression strength is 5.3MPa.
Embodiment 4:
With the difference of embodiment 3 be that pore-forming material urea volume ratio is 80%, porous Al 2TiO 5Material immerses in pure Al melt, keeps 5 minutes, and the aluminium film thickness is 20 μ m approximately, heated oxide insulation 25 minutes, Al in hole 2O 3Be about 50nm with TiAl whisker radial dimension, be about 0.2 μ m, the aperture of porous material is 2.2～3.3mm, and porosity is 75.8%, and ultimate compression strength is 4.4MPa.

Claims (3)

  1. In a hole with whisker or the brilliant porous material of rod, described porous material is with TiO 2And Al 2O 3For raw material, take urea as pore-forming material sintering Ti 2AlO 5Porous material is characterized in that: immerse under this porous material high temperature in pure Al melt subsequently, what finally form has Al in hole wall length 2O 3With TiAl whisker or the brilliant porous material of rod.
  2. In hole as claimed in claim 1 with whisker or the brilliant porous material of rod, it is characterized in that: described whisker or the brilliant length of rod are 0.2～2.0mm, aperture 2.2～the 3.3mm of porous material, porosity is 53.3～75.8%, ultimate compression strength is 4.4～8.5MPa.
  3. In hole as claimed in claim 1 with the preparation method of whisker or the brilliant porous material of rod, it is characterized in that comprising the following steps:
    The first step: get commercially pure TiO ready 2, Al 2O 3Powder stock, pore-forming material urea granules and Al ingot, wherein TiO 2, Al 2O 3Powder size is 200 orders, urea particle diameter 2～3mm;
    Second step: Al 2TiO 5The porous material sintering is synthetic
    With TiO 2, Al 2O 3Powder is according to mol ratio TiO 2: Al 2O 3=1:1 (mol) weighing according to volume ratio 50～80%, measures urea granules, packs into after evenly mixing in mould, adopts compression-moulding methods, is pressed into cylindrical green compact under 200MPa pressure; Pressed compact is put in resistance furnace again, be heated to 300 ℃ of insulations 1.5 hours, urea granules volatilizees fully; Pressed compact is put into resistance furnace, 1400～1500 ℃ of sintering 3 hours, take out the sample air cooling after sintering, obtain wide aperture Al 2TiO 5Porous material;
    The 3rd step: hot dip aluminum plating
    The industrial pure Al ingot is put into Al 2O 3In crucible, be heated to 800 ℃ under argon shield, the Al ingot all melts, with wide-aperture porous Al 2TiO 5Material immerses in pure Al melt, keeps 5～10 minutes, and Al liquid infiltrates in porous material, after extracting porous material, drops to 650 ℃ with furnace temperature in stove, obtains the aluminium film of a layer thickness 20～30 μ m on hole wall;
    The 4th step: Al in hole 2O 3With TiAl whisker or excellent crystals growth
    Treat that furnace temperature is down to 650 ℃, stop logical argon gas and opened fire door 1 minute, air is entered in stove, then 650 ℃ of heating, be incubated 25～50 minutes, part Ti 2AlO 5Decompose and generate TiO 2And Al 2O 3, Al film autoxidation simultaneously again with TiO 2Reaction generates Al 2O 3, Ti and Al react the TiAl phase that generates the pyro-oxidation resistance excellence, generate Al in hole wall original position 2O 3Brilliant with whisker or the rod of TiAl.
CN 201210039197 2012-02-21 2012-02-21 Porous material with whiskers or rod crystals in apertures and preparation method thereof Active CN102718541B (en)

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CN110777275A (en) * 2019-10-10 2020-02-11 太原理工大学 Titanium-aluminum three-dimensional through hole structure material and preparation method thereof
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