CN102718541A - 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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CN102718541A
CN102718541A CN2012100391970A CN201210039197A CN102718541A CN 102718541 A CN102718541 A CN 102718541A CN 2012100391970 A CN2012100391970 A CN 2012100391970A CN 201210039197 A CN201210039197 A CN 201210039197A CN 102718541 A CN102718541 A CN 102718541A
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porous material
tio
whisker
rod
brilliant
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CN102718541B (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

Have brilliant porous material of whisker or rod and preparation method thereof in the hole
Technical field
The present invention relates to a kind of porous material and preparation technology thereof, have whisker or the brilliant Ti of rod in especially a kind of hole 2AlO 5Base porous compound material and preparation method thereof belongs to the synthetic and manufacture field of material.
Background technology
Now, reducing motor vehicle exhaust protection environment is the focus of paying close attention in the global range.At present, the catalyst support material of purifying vehicle exhaust being used mainly contains pottery and two types on metal.For stagnant catalyst, apply the γ-Al of one deck high-specific surface area usually equably 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 bigger difference, is prone to make coating and catalyzer to come off from carrier, thereby loses 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 low, the undercapacity of the thermal conductivity of cordierite carrier material, the catalyzer ignition is slow when causing cold-starting automobile, and running car is broken easily when jolting.Although Carboround material thermal conductivity is high, intensity is high, and high thermal resistance is good, and the line expansion factor is big, poor thermal shock resistance.The present preparation technology of support of the catalyst in addition, it is smooth straight to make that the wall of support of the catalyst is, and is unfavorable for the load of catalyzer.Therefore, at present in the support of the catalyst of the usefulness preparation technology from the performance of material self to carrier, all be difficult to satisfy harsh day by day motor vehicle exhaust technical requirements, the solid support material and the pass ideal preparation technology of exploitation excellent performance are significant.
Aluminium titanates (Al 2TiO 5) material is that collection low-expansion coefficient and HMP are the stupalith of one; And has anti-slag, anti-corrosion, alkaline-resisting and to nonwettable characteristics of multiple metal and glass; Be widely used in condition rigorous environment 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 method of manufacture of matter ceramic honeycomb, this method are with TiO 2And Al 2O 3Powder is to carry out sintering after raw material is processed base substrate, obtains the Al of clear opening 2TiO 5The honeycomb ceramic carrier.Japanese Patent 2005-519834 and WO2005/018776 disclose through adjustment TiO 2And Al 2O 3The proportioning of powder, adding additive etc. suppress Al 2TiO 5Thermolysis, improve the technology of ultimate compression strength.Chinese patent publication number 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 in admixtion, add and prevent aluminium titanates stablizer that decomposes and the mullite fiber that plays enhancement, improved the intensity of material.One Chinese patent application numbers 200980115069.6 has been invented a kind of aluminium titanates from the novel porous matter aluminium titanates as porous matter, and this method is through the sintering of porous matter aluminium titanates powder own, thereby forms the al titanate sintering body of porous matter more.One Chinese patent application numbers 200910180843.3 has been invented a kind of aluminium nitride AlN/silit/aluminium titanates ceramic foam and preparation method thereof; Adopting aluminium nitride AlN, silit, aluminium titanates is raw material; Through adding paraffin, prepared the ceramic foam of porosity 60-80%, improved the heat-insulating capability of material.One 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 obtains porous alumina/aluminium titanates composite porous ceramic material through adopting alumina in Nano level, titanium oxide powder raw material sintering.
Though above-mentioned patent is through the synthetic Ti of different methods 2AlO 5Porous material, and processed the porous material of different passes.But pure Al 2TiO 5The stupalith wall is smooth relatively, is difficult to satisfy automobile exhaust purifier carrier demanding specific surface area and good catalytic conversion effect of requirement when supported catalyst.
Summary of the invention
The objective of the invention is to deficiency, provide to have nano level whisker or the brilliant Al of rod in a kind of hole to prior art 2TiO 5Base porous compound material and the preparation method with matrix material of 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, help combining of catalyst coat and hole wall, more can improve the specific surface area of hole, catalysis when helping being used for support of the catalyst and conversion.
Technical scheme of the present invention is: have whisker or the brilliant porous material of rod in a kind of hole, described porous material is with TiO 2And Al 2O 3For raw material, with urea is pore-forming material sintering Ti 2AlO 5Porous material, this porous material high temperature immerses down in the 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.Have the preparation method of the brilliant porous material of whisker or rod in the described hole, may further comprise the 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: the 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%, is measured urea granules, in the mould of packing into behind the uniform mixing, adopts compression-moulding methods, presses down at 200Mpa pressure and processes cylindrical green compact; Pressed compact is put in the resistance furnace again, be heated to 300 ℃ of insulations 1.5 hours, urea granules volatilizees fully; Pressed compact is put into resistance furnace,, take out the sample air cooling behind the sintering, obtain wide aperture Al 1400～1500 ℃ of sintering 3 hours 2TiO 5Porous material;
The 3rd step: hot dip aluminum plating
The industrial pure Al ingot is put into Al 2O 3In the crucible, under argon shield, be heated to 800 ℃, the Al ingot all melts, with wide-aperture porous Al 2TiO 5Material immerses in the pure Al melt, keeps 5～10 minutes, and Al liquid infiltrates in the porous material, behind the extraction porous material, in stove, drops to 650 ℃ with furnace temperature, on hole wall, obtains the aluminium film of a layer thickness 20～30 μ m;
The 4th step: Al in the hole 2O 3Treat that with TiAl whisker or excellent crystals growth furnace temperature reduces to 650 ℃, stop logical argon gas and opened fire door 1 minute, make in the air admission stove, 650 ℃ of heating then, 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 generates the excellent TiAl of pyro-oxidation resistance mutually with the Al reaction, generates Al in hole wall original position 2O 3Brilliant with whisker or the rod of TiAl.
The TiAl of hole wall and Al 2O 3Reaction generating principle bar-shaped and whisker following:
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 a raw material, is pore-forming material with urea, is the hot dip process raw material with pure Al ingot, through sintering reaction, hot dip process technology are combined, at first obtains to have the porous Al of Al coating 2TiO 5Matrix composite becomes the hole wall through high temperature oxidation again and has Al 2O 3With TiAl whisker or the brilliant porous material of rod, with low cost, technology 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, helps improving the 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 through adjustment pore-forming material content; 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 big, and this porous material can be used as carrier and the filtering bodies in catalysis, the environmental purification.
Embodiment
Embodiment 1
Composite porous preparation method of the present invention is following:
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: the 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%, is measured urea granules, in the mould of packing into behind the uniform mixing, adopts compression-moulding methods, presses down at 200Mpa pressure and processes cylindrical green compact; Pressed compact is put in the resistance furnace again, be heated to 300 ℃ of insulations 1.5 hours, urea granules volatilizees fully; Pressed compact is put into resistance furnace,, take out the sample air cooling behind the sintering, obtain wide aperture Al 1400 ℃ of sintering 3 hours 2TiO 5Porous material.
The 3rd step: hot dip aluminum plating
The industrial pure Al ingot is put into Al 2O 3In the crucible, under argon shield, be heated to 800 ℃, the Al ingot all melts.With wide-aperture porous Al 2TiO 5Material immerses in the pure Al melt, keeps 10 minutes, and Al liquid infiltrates in the porous material.After extracting porous material, in stove, drop to 650 ℃, on hole wall, obtain the aluminium film of a layer thickness 30 μ m with furnace temperature.
The 4th step: Al in the hole 2O 3With TiAl whisker or excellent crystals growth
Treat that furnace temperature reduces to 650 ℃, stop logical argon gas and opened fire door 1 minute, make in the air admission stove.650 ℃ of heated oxides, insulation are 50 minutes then, part A l 2TiO 5Decompose and generate TiO 2And Al 2O 3, Al film autoxidation simultaneously again with TiO 2Reaction generates Al 2O 3, Ti generates the excellent TiAl of pyro-oxidation resistance mutually with the Al reaction.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 the pure Al melt, keeps the about 25 μ m of aluminium film thickness, heated oxide insulation 40 minutes, Al in the hole 8 minutes 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 the pure Al melt, keeps the about 25 μ m of aluminium film thickness, heated oxide insulation 25 minutes, Al in the hole 8 minutes 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 the pure Al melt, keeps the about 20 μ m of aluminium film thickness, heated oxide insulation 25 minutes, Al in the hole 5 minutes 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. have whisker or the brilliant porous material of rod in a hole, described porous material is with TiO 2And Al 2O 3For raw material, with urea is pore-forming material sintering Ti 2AlO 5Porous material is characterized in that: this porous material high temperature immerses down in the 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.
2. have whisker or the brilliant porous material of rod in the hole as claimed in claim 1; 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. have the preparation method of the brilliant porous material of whisker or rod in the hole as claimed in claim 1, it is characterized in that may further comprise the 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: the 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%, is measured urea granules, in the mould of packing into behind the uniform mixing, adopts compression-moulding methods, presses down at 200Mpa pressure and processes cylindrical green compact; Pressed compact is put in the resistance furnace again, be heated to 300 ℃ of insulations 1.5 hours, urea granules volatilizees fully; Pressed compact is put into resistance furnace,, take out the sample air cooling behind the sintering, obtain wide aperture Al 1400～1500 ℃ of sintering 3 hours 2TiO 5Porous material;
The 3rd step: hot dip aluminum plating
The industrial pure Al ingot is put into Al 2O 3In the crucible, under argon shield, be heated to 800 ℃, the Al ingot all melts, with wide-aperture porous Al 2TiO 5Material immerses in the pure Al melt, keeps 5～10 minutes, and Al liquid infiltrates in the porous material, behind the extraction porous material, in stove, drops to 650 ℃ with furnace temperature, on hole wall, obtains the aluminium film of a layer thickness 20～30 μ m;
The 4th step: Al in the hole 2O 3With TiAl whisker or excellent crystals growth
Treat that furnace temperature reduces to 650 ℃, stop logical argon gas and opened fire door 1 minute, make in the air admission stove, 650 ℃ of heating then, 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 generates the excellent TiAl of pyro-oxidation resistance mutually with the Al reaction, generates 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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113200761A (en) * 2021-06-17 2021-08-03 西南交通大学 Preparation method of alumina porous ceramic with similar ceramic fiber net structure inside

Citations (3)

* Cited by examiner, † Cited by third party
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CN101343175A (en) * 2008-08-20 2009-01-14 哈尔滨工业大学 Aluminum oxide/aluminium titanate porous ceramic and preparation thereof
CN102015539A (en) * 2008-04-28 2011-04-13 大塚化学株式会社 Porous aluminum titanate, sintered body of the same, and method for producing the same
CN102131747A (en) * 2008-08-28 2011-07-20 京瓷株式会社 Porous ceramic member, method for producing same and filter

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CN102131747A (en) * 2008-08-28 2011-07-20 京瓷株式会社 Porous ceramic member, method for producing same and filter

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113200761A (en) * 2021-06-17 2021-08-03 西南交通大学 Preparation method of alumina porous ceramic with similar ceramic fiber net structure inside
CN113200761B (en) * 2021-06-17 2022-08-09 西南交通大学 Preparation method of alumina porous ceramic with similar ceramic fiber net structure inside

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