CN1213962C - Low CTE cordierite bodies with narrow pore size distribution and mehtod of making same - Google Patents

Low CTE cordierite bodies with narrow pore size distribution and mehtod of making same Download PDF

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CN1213962C
CN1213962C CNB998167649A CN99816764A CN1213962C CN 1213962 C CN1213962 C CN 1213962C CN B998167649 A CNB998167649 A CN B998167649A CN 99816764 A CN99816764 A CN 99816764A CN 1213962 C CN1213962 C CN 1213962C
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CN1352625A (en
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G·A·默克尔
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Corning Inc
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Oxide Ceramics (AREA)
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Abstract

Cordierite body of CTE at 25-800 DEG C of <=4 x 10<-7>C<-1>, at least 85 % of porosity having pore diameter of 0.5-5.0 mu : or >4-6 x 10<-7>C<-1>, porosity at least 30 vol %, at least 85 % of porosity has pore diameter 0.5-5.0 mu . Raw materials talc, A12O3 source, and kaolin, calcined kaolin, and/or silica, and optionally spinel, particle diameter of talc <= 3.0 mu , of A12O3 source <= 2.0 mu , kaolin is < 35 wt % of raw materials when particle diameter is < 2.0 mu , are blended with vehicle and aids into plastic mixture. Green body is formed, dried, fired at 1370 DEG C-1435 DEG C. When particle diameter of talc is < 2.0 mu , and A12O3 source is < 20 wt % of raw materials, and dispersible high surface area A12O3 source having particle diameter of < 0.3 mu , is < 5.0 wt % of raw materials, and particle diameter of kaolin is < 2.0 mu , heating rate from 1150 DEG C-1275 DEG C is > 200 DEG C/hr. When particle diameter of talc is >= 2.0 mu , and A12O3 source is < 20 wt % of raw materials, and dispersible high surface area A12O3 source having particle diameter of < 0.3 mu , is < 5.0 wt % of raw materials, and particle diameter of kaolin is < 2.0 mu , heating rate from 1150 DEG C-1275 DEG C is > 50 DEG C/hr and < 6000 DEG C/hr. When A12O3 source is less than 20 wt % of raw materials, and dispersible A12O3 source having particle diameter < 0.3 mu is >/= 5.0 wt % of raw materials, and particle diameter of kaolin is < 2.0 mu , heating rate from 1150 DEG C-1275 DEG C is > 50 DEG C/hr. When particle diameter of kaolin is > 2.0 mu , heating rate from 1150 DEG C-1275 DEG C is < 600 DEG C/hr and > 30 DEG C/hr.

Description

Low heat expansion property cordierite bodies and manufacture method thereof that pore size distribution is narrow
The application is the U.S. Patent application of submitting on February 18th, 1,999 09/252,519 part continuation application, the exercise question that this U.S. Patent application requires G.A. Merkel to propose on February 25th, 1998 is the right of priority of the United States Patent (USP) provisional application 60/075,846 of " low heat expansion property cordierite bodies and manufacture method thereof that pore size distribution is narrow ".
Technical field
The cordierite bodies of unique over-all properties that the present invention relates to have low thermal coefficient of expansion (CTE) and pore size distribution is narrow.This cordierite bodies can make by using selected raw mix and sintering technology.More particularly, above-mentioned cordierite bodies is as catalyzed reaction carrier and the honeycomb structured body that is used for filtration applications.
Background technology
The cordierite honeycomb structure body is specially adapted to, but is not limited to carrier, diesel particulate filter or the regenerative heating combustion chamber etc. of automobile exhaust gas conversion catalyst.Trichroite is applicable to that these purposes are because it has good resistance to sudden heating.Resistance to sudden heating and thermal expansivity (CTE) are inversely proportional to.In other words, the honeycomb that thermal expansivity is low has good resistance to sudden heating, can stand the wide temperature fluctuation that runs in these purposes.
In some purposes,, preferably reduce overall porosity for improving intensity as the thin-walled honeycomb carrier.Yet the minimizing of porosity can cause comprising the reduction of the finish coat percentage heap(ed) capacity of catalyzer, thereby in some cases must be with support coating several for the finish coat that forms desired thickness.This multistep coating process can increase the cost of the finished product.Therefore, cordierite bodies preferably has the aperture less than about 10 microns narrow pore size distribution.The narrow advantage of pore size distribution is the adhesion amount that has improved finish coat, thereby only just can obtain the finish coat of desired thickness with an application step, and need not the multistep coating process.
Up to the present, it is low and at the cordierite bodies less than 10 micrometer range internal orifice dimension narrowly distributings also not make thermal expansivity.For above-mentioned reasons, press for the cordierite bodies that acquisition has these character in this area.The invention provides this cordierite bodies and preparation method thereof.
The content of invention
CTE when one aspect of the present invention provides 25-800 ℃≤4 * 10 -7℃ -1, at least 85% hole has the mean pore size of 0.5-5.0 micron in the overall porosity cordierite bodies.
CTE＞4-6 when another aspect of the present invention provides 25-800 ℃ * 10 -7℃ -1, overall porosity is at least the cordierite bodies that at least 85% hole has the 0.5-5.0 micron pore size in 30% volume, the overall porosity.
A third aspect of the present invention provides the manufacture method of above-mentioned cordierite bodies.This method comprises and will contain talcum powder; Al 2O 3Form raw material; The raw material of one or more in kaolin, calcined kaolin and the silicon-dioxide and optional spinel becomes plastic mixture with vehicle with the shaping additive intimate mixing.Talcous median size≤3.0 micron, Al 2O 3Form median size≤2.0 micron of raw material.If adding kaolin, then when its particle diameter＜2.0 micron, kaolinic add-on is less than 35% weight of raw material.Be made into green compact, drying then and fire at 1370-1435 ℃.When talcous median size＜2.0 micron, Al 2O 3Form 20% weight that raw material is less than the raw material total amount, particle diameter is less than 0.3 micron disperseed high surface area Al 2O 3Form 5.0% weight that raw material is less than the raw material total amount, kaolinic median size is during less than 2.0 microns, and the heating rate between 1150-1275 ℃ is greater than 200 ℃/hour.When talcous median size 〉=2.0 micron, Al 2O 3Form 20% weight that raw material is less than the raw material total amount, median size is less than 0.3 micron disperseed high surface area Al 2O 3Form 5.0% weight that raw material is less than the raw material total amount, kaolinic median size is during less than 2.0 microns, and the heating rate between 1150-1275 ℃ is greater than 50 ℃/hour but less than 600 ℃/hour.Work as Al 2O 3Form 20% weight that raw material is less than the raw material total amount, particle diameter is less than 0.3 micron disperseed high surface area Al 2O 3Form 5.0% weight of raw material more than or equal to the raw material total amount, kaolinic median size is during less than 2.0 microns, and 1150-1275 ℃ heating rate is greater than 50 ℃/hour.When kaolinic median size during greater than 2.0 microns, the heating rate between 1150-1275 ℃ is less than 600 ℃/hour but greater than 30 ℃/hour.
Embodiment
The present invention relates in 25-800 ℃ of temperature range, to have the cordierite bodies of the narrow unique over-all properties of low thermal coefficient of expansion and pore size distribution.This cordierite bodies is with selecting specified raw material mixture and the method for firing condition to make.Thermal expansivity among the present invention is the mean thermal expansion coefficients in the 25-800 ℃ of scope that records with dilatometry.In honeycomb, it is the mean thermal expansion coefficients on the open channel length parallel direction.
If do not explain in addition, particle diameter is expressed as median size.Particle diameter is measured with sedimentation techniques.
Porosity is the overall porosity that records with the mercury porosimetry, and is expressed as the % volume.
Raw material
The present invention can successfully obtain low thermal coefficient of expansion and very narrow pore size distribution (0.5-5.0 micron) is owing to use the mixture and the sintering technology of fine and smooth stone flour and some raw materials to keep low thermal expansivity.Use thin talcum powder to make to have very among the hole that height ratio is between the 0.5-5.0 micron.Yet owing to reduced minute crack, thinner talcum powder can produce the higher cordierite bodies of thermal expansivity.For thermal expansivity being returned to required low value, must select other raw material, and, must in sintering procedure, do some restrictions heating rate for some raw mix.
In order to obtain to contain about 49-53%SiO 2, about 12-16%MgO and about 33-38%Al 2O 3The low and narrow cordierite composition of pore size distribution of thermal expansivity, used raw material is talcum powder, Al 2O 3In formation raw material and kaolin component, calcined kaolin and the silicon-dioxide one or more.Randomly, spinel also can be used as raw material.
Talcous median size must be no more than 3.0 microns.
Al 2O 3Form raw material and refer to Al 2O 3Itself or other are transformed into Al when firing 2O 3The low water solubility raw material.Some typical A l 2O 3Form component and comprise aluminum oxide, Al (OH) 3(being also referred to as aluminum trihydrate or hydrargillite) or hydroxide aluminum oxide (being also referred to as a hydrated aluminum or boehmite or pseudobochmite ore deposit).
Dispersible high surface area Al 2O 3Forming component or raw material can be powder or colloidal sol." dispersible " is meant and very fine grainly granule can pulverizes and be dispersed into median size approximately less than 0.3 micron component particles.High surface area is meant that surface-area is greater than 10 meters 2/ gram is better greater than 40 meters 2/ gram.This powder can comprise boehmite, pseudobochmite, γ phase alumina, δ phase alumina or other so-called transitional alumina.
Al 2O 3The median size that forms raw material must be no more than 2.0 microns, and specific surface area is better greater than 5 meters 2/ gram.In order in the wideest heating rate scope, still to obtain the cordierite bodies of low thermal coefficient of expansion, Al 2O 3The consumption that forms raw material preferably at least about is 20% weight of raw material total amount.
If exist, kaolinic median size can be the 0.2-10 micron.Yet, if its median size less than about 2 microns, this kaolinic consumption must be less than 35% weight of raw material total amount.Form the required surplus Al of trichroite 2O 3By calcined kaolin or Al 2O 3The formation raw material provides.Surplus SiO 2Provide by calcined kaolin or SiO 2 powder.As disperseing high surface area Al 2O 3Form the Al of raw material 2O 3The consumption that forms raw material better is no less than 5% weight of raw material total amount.
Raw material and vehicle and shaping additive are kneaded.When being configured as green compact, these vehicles and shaping additive are given raw material PLASTIC SHAPING OF HIGH and green strength.When being shaped with extrusion molding, extrusion aid generally is the lubricant of ether of cellulose organic binder bond and ammonium stearate, sodium stearate (sodium ammonium) or diglycol stearate and so on, but the present invention is not limited to these extrusion aids.
Organic binder bond produces plasticity-when helping mixture and being configured as green compact.Plasticising organic binder bond of the present invention is meant cellulose ether binder.Typical organic binder bonds more of the present invention are methylcellulose gum, Type 3U, hydroxy butyl methyl cellulose, Walocel MT 20.000PV, Vltra tears, hydroxyethylmethyl-cellulose, hydroxybutyl cellulose, Natvosol, hydroxypropylcellulose, Xylo-Mucine and their mixture.Methylcellulose gum and/or methylcellulose gum derivative particularly suitable are made the organic binder bond among the present invention, and methylcellulose gum, Vltra tears or their mixture are preferred.Preferred ether of cellulose component is Methocel A4M, F4M, F240 and the K75M available from Dow Chemical Co..Methocel A4M is a methylcellulose gum, and Methocel F4M, F240 and K75M are Vltra tearss.
By raw material, the content of organic binder bond is generally about 3-6%.
Vehicle can be inorganic vehicle (mainly be made up of water, generally account for but definitely for 28-46%), also can be organic vehicle.Better make water, though can partly or entirely be replaced by transpirable organic liquid (as lower alcohol) as required.
The weight percentage of organic binder bond, vehicle and other additive is calculated with the additive of raw material.
Then mixture is configured as green compact.Preferred moulding method is to extrude by die head.Extrude and to carry out with hydraulic efficiency piston extrusion machine, two step degassing single screw extrusion machines or the twin screw mixing machine that the die head assembly that links to each other with discharge end is housed.Under latter event, force batch of material to pass through die head in order to produce enough pressure, should select suitable screw element according to raw material of the present invention and other processing condition.
Green compact of the present invention can have suitable size and shape.Yet method of the present invention is specially adapted to make porous integral, as honeycomb.Porous body can be used for many purposes, as support of the catalyst, strainer (as diesel particulate filter, filter for molten metal), regenerative heating combustion chamber etc.
The hole density of honeycomb (cell density) be generally 235 holes/centimetre 2(about 1500 hole/inches 2) to 15 holes/centimetre 2(about 100 hole/inches 2).Wall (film) thickness is generally 0.07-0.6 millimeter (about 3-25 mil).The outside dimension and the shape of honeycomb depend on purposes, for example depend on engine size and the space that is used for installing etc. in the automobile purposes.The present invention is particularly suitable for making the honeycomb of wall very thin (for example≤0.13 millimeter (5 mils)).With mixtures more of the present invention, particularly contain median size all less than 3 microns clay, aluminum oxide and steatitic mixture, can make the honeycomb of wall thinner (as 0.025-0.1 micron (1-4 mil)).
Use the dry trichroite green compact of the present invention of ordinary method then, as baking oven or radio-frequency drying.
Under 1370-1435 ℃ temperature, fire dried green compact then.The condition of firing should change according to the difference of raw mix.
For example, when talcous median size＜2.0 micron, Al 2O 3The consumption that forms raw material is less than 20% weight of raw material total amount, and median size is less than 0.3 micron disperseed high surface area Al 2O 3Form raw material (if any words) be less than 5.0% weight of raw material total amount, kaolinic median size is during less than 2.0 microns, the heating rate between 1150-1275 ℃ should be greater than 200 ℃/hour, to make the crack microstructure required with low thermal coefficient of expansion of splitting.
When talcous median size is not less than 2.0 microns, Al 2O 3The amount that forms raw material is less than 20% weight of raw material total amount, and median size is less than 0.3 micron disperseed high surface area Al 2O 3Form raw material (if any words) be less than 5.0% weight of raw material total amount, kaolinic median size is during less than 2.0 microns, the heating rate between 1150-1275 ℃ should be greater than 50 ℃/hour but less than 600 ℃/hour.
Work as Al 2O 3The amount that forms raw material is less than 20% weight of raw material total amount, and median size is less than 0.3 micron disperseed high surface area Al 2O 3The amount that forms raw material is not less than 5.0% weight of raw material total amount, and kaolinic median size is during less than 2.0 microns, and the heating rate between 1150-1275 ℃ should be greater than 50 ℃/hour.
When kaolinic median size during greater than 2.0 microns, the heating rate between 1150-1275 ℃ should be less than 600 ℃/hour but greater than 30 ℃/hour.
In the short as far as possible time, the fired cordierite body is cooled to room temperature then.
Cordierite bodies of the present invention has following characteristics: the mean thermal expansion coefficients that (1) is 25-800 ℃≤4 * 10 -7℃ -1Or (2) mean thermal expansion coefficients＞4 * 10 -7℃ -1But≤6 * 10 -7℃ -1Overall porosity is not less than about 30% volume.When thermal expansivity less than 4 * 10 -7℃ -1The time, overall porosity can be any value, but better greater than about 18%.In all cases, at least 85% overall porosity is between the 0.5-5.0 micron.
Porous fine fisssure body of the present invention can be used as catalytic carrier, adheres to and the fixed cover surface layer because its pore size distribution is favourable.Method of the present invention is specially adapted to make the honeycomb of the high density holes of thin-walled (0.152 millimeter, less than 0.006 inch) and ultra-thin-wall (0.102 millimeter, less than 0.004 inch).In addition, the porosity of the honeycomb that makes with the inventive method and pore size distribution are than much lower to the susceptibility of heating rate variation in the sintering procedure with the honeycomb that uses thicker talcous ordinary method to make.It is believed that these character make the finish coat heap(ed) capacity of the carrier that different sites is fired in kiln change less.Narrow pore size distribution also can be used for some filtration applications.
In order to illustrate in greater detail the present invention, provide following non-restrictive example.If do not explain in addition, all umbers, part and percentage ratio are all by weight.
In following all embodiments of the invention and Comparative Examples,, be placed on then in the stainless-steel grinding machine and mix about 20 minutes with the water of about 30-46% with raw material and about 3-6% methyl cellulose binder and 0.5-1.0% sodium stearate lubricant dry blending.Then the moldable mixture of gained is extruded pore-forming density be about 62 holes/centimetre 2(about 400 hole/inches 2) and wall thickness be about the honeycomb of 0.152 millimeter (0.006 inch).Extrudate wrapped up with aluminium foil, drying about 85 ℃ about 72 hours.It is long then this honeycomb to be cut into about 10.16 centimetres (4 inches), is placed on the thick aluminum oxide sand in aluminum oxide in the electric furnace or the trichroite pallet.
The raw material composition is listed in the table 1.Median size is measured with the Sedigraph analytical method.Sintering technology is listed in the table 2 with the physical properties of the honeycomb that burns till.
Embodiment 1-3 show when the mixture of 1.6 microns talcum powder, 0.4 micron Alpha-alumina and 4.5 microns crystalline silicas is fired in wide heating rate scope produce that thermal expansivity is low, overall porosity is high and overall porosity be the honeycomb of the present invention of 0.5-5.0 micron pore size more than 85%.
Comparative Examples 4-6 shows, when talcous median size is increased to 6.1 microns, when then mixing with 0.4 micron Alpha-alumina and 4.5 microns crystalline silicas, mean pore size increases, it is much wide that pore size distribution becomes, and like this, the porosity of 0.5-5.0 micron is lower than 85% of overall porosity.
Embodiments of the invention 7 and 8 show, when median size be the mixture of 1.6 microns fine and smooth stone flour and thin kaolin, thin aluminum oxide and calcined kaolin between 1150-1275 ℃ during with 250-600 ℃/hour speed heating, the thermal expansivity that obtains is 4-6 * 10 -7℃ -1, overall porosity is greater than 30%, and pore size distribution is very narrow, makes overall porosity more than 85% between the 0.5-5.0 micron.Embodiment 9-11 shows, when this raw mix between 1150-1275 ℃ with greater than 600 ℃/hour speed heating the time, the thermal expansivity that obtains is less than 4 * 10 -7℃ -1, the overall porosity more than 85% is between the 0.5-5.0 micron.Comparative Examples 12-14 shows, when with the green compact that are made of these raw materials less than 250 ℃/hour speed heating, the thermal expansivity of gained surpasses 6 * 10 -7℃ -1Therefore, this result is not included in the scope of the present invention.
The embodiment of the invention 15 and 16 shows, when the heating rate between 1150-1275 ℃ during greater than 50 ℃/hour but less than 600 ℃/hour, median size is about 2.2 microns fine and smooth stone flour can mix use with thin kaolin, calcined kaolin and thin aluminum oxide.Comparative Examples 17 shows that when the heating rate between 1150-1275 ℃ was lower than 50 ℃/hour, thermal expansivity was greater than 6 * 10 -7℃ -1Comparative Examples 18 and 19 shows, when the heating rate between 1150-1275 ℃ is higher than 500 ℃/hour, and the obvious chap of porosity, whole porosity percentage ratios of 0.5-5.0 micron are lower than 85%.
Comparative Examples 20 and 21 shows, when 3.4 microns talcum powder mix use with thin kaolin, thin aluminum oxide and calcined kaolin, and the mean pore size chap, the porosity of 0.5-5.0 micron is lower than 85% of overall porosity.
Comparative Examples 22 shows, when 4.2 microns talcum powder mix use with thin kaolin, thin aluminum oxide and calcined kaolin, and when between 1150-1275 ℃, firing, obtain narrow pore size distribution, but thermal expansivity is increased to 6 * 10 with the heating rate that is lower than 150 ℃/hour -7℃ -1More than.Comparative Examples 23 and 24 shows, when for thermal expansivity is remained on 6 * 10 -7℃ -1Below when between 1150-1275 ℃, firing this raw mix with the heating rate that is higher than 150 ℃/hour, the mean pore size chap, whole porositys of 0.5-5.0 micron are lower than 85% as a result.
Embodiment 25-30 shows, when between 1150-1275 ℃ with greater than 50 ℃/hour speed heating the time, be about 180 meters with at least 5% surface-area 2/ gram and finely divided particle diameter are about 0.125 micron boehmite and partly replace 0.4 micron Alpha-alumina, and mix use with 1.6 microns talcum powder, 0.9 micron kaolin and calcined kaolin, and the thermal expansivity of gained cordierite bodies is less than 4 * 10 -7℃ -1, the porosity of 0.5-5.0 micron is greater than 85% of overall porosity.Therefore, in the raw mix of fine and smooth stone flour, thin kaolin, calcined kaolin and Alpha-alumina, add this boehmite and can use slower heating rate, keep the required over-all properties of low thermal coefficient of expansion and narrow pore size distribution simultaneously.
Embodiments of the invention 31 and 32 show, when between 1150-1275 ℃ being higher than 30 ℃/hour but when firing less than 600 ℃/hour rate of heating, make with the raw mix of 1.6 microns talcum powder, thicker 7.4 microns kaolin and 0.4 micron Alpha-alumina that thermal expansivity is low, pore size distribution is very narrow and overall porosity is not less than 30% cordierite bodies.Using fine and smooth stone flour and thick kaolin still can obtain low thermal expansivity never expects.Comparative Examples 33 shows that when 1150-1275 ℃ heating rate was less than about 30 ℃/hour, thermal expansivity can surpass 6 * 10 -7℃ -1Comparative Examples 34 and 35 shows, when heating rate surpasses about 600 ℃/hour, and the mean pore size chap, the porosity between the 0.5-5.0 micron no longer surpasses 85% of overall porosity as a result.
Comparative Examples 36-38 shows that when 4.5 microns thick alpha-alumina powders were mixed use with fine and smooth stone flour, thin kaolin and calcined kaolin, no matter heating rate is fast or slow, the thermal expansivity of gained all surpassed 6 * 10 -7℃ -1
Be to be understood that, though describe the present invention in detail with reference to some illustratives and specific embodiment, but invention is not to be considered as being limited to these embodiment, and will be understood that and otherwise to use the present invention in the condition that does not depart from the present invention's spirit and claims scope.
Table 1
Use the weight percentage and the median size of raw material among the embodiment
Batch of material is by weight percentage formed
(in the bracket with micron be the median size of unit for what record with deposition technique)
Composition Talcum powder Kaolin The kaolin of calcination α-aluminum oxide Quartzy Dispersible AlOOH-xH 2O 180m 2/g
1 2 3 4 5 6 7 8 9 10 11 42.4(1.6) 42.4(6.1) 40.9(1.6) 40.9(2.2) 40.9(3.4) 40.9(4.2) 40.9(1.6) 40.6(1.6) 40.3(1.6) 39.6(1.6) 40.9(1.6) 12.8(0.9) 12.8(0.9) 12.8(0.9) 12.8(0.9) 14.3(0.9) 14.2(0.9) 14.1(0.9) 47.1(7.4) 12.8(0.9) 32.6(1.6) 32.6(1.6) 32.6(1.6) 32.6(1.6) 29.6(1.6) 29.4(1.6) 29.2(1.6) 32.6(1.6) 34.2(0.4) 34.2(0.4) 13.7(0.4) 13.7(0.4) 13.7(0.4) 13.7(0.4) 8.2(0.4) 5.5(0.4) 2.7(0.4) 13.3(0.4) 13.7(4.5) 23.5(4.5) 23.5(4.5) 7.0(0.125) 10.4(0.125) 13.7(0.125)
Table 2 sample sintering technology and character
Sample Composition The embodiment type 1150-1275 ℃ rate of heating (℃/hour) 1275-1400 ℃ rate of heating (℃/hour) Top temperature (℃) The soaking time of top temperature (hour) Average CTE (10 -7℃ -1) (25- 800℃) Voidage (volume %) Total pore volume (cm 3/g) Mean pore size (micron) 0.5-5.0 whole hole % of μ The whole hole % that surpass 10 μ
1 2 3 1 1 1 EXAMPLE Example embodiment 25 50 200 25 50 200 1410 1410 1410 8 8 12 3.3 2.8 1.9 34.8 35.3 31.2 0.2161 0.2205 0.1924 1.5 1.5 2.5 89.2 88.6 90.0 6.1 7.1 6.5
4 5 6 2 2 2 Comparative example comparative example comparative example 25 50 625 25 50 200 1410 1410 1410 8 8 12 2.9 5.1 6.2 31.4 30.8 24.8 0.1858 0.1793 0.1327 4.1 4.9 9.7 63.2 51.0 1.1 11.7 16.7 44.5
7 8 9 10 11 12 13 14 3 3 3 3 3 3 3 3 EXAMPLE Example EXAMPLE Example embodiment comparative example comparative example comparative example 500 600 625 1200 1200 25 50 200 200 200 625 50 200 25 50 200 1410 1410 1414 1410 1410 1410 1410 1410 1.7 1.7 5 2.5 1.7 8 8 12 5.6 5.9 3.6 2.8 3.9 8.0 6.3 6.3 30.1 31.8 29.6 26.1 22.8 32.0 32.7 33.6 0.1721 0.1885 0.1693 0.1447 0.1692 0.1932 0.1976 0.1993 2.0 3.1 2.8 2.7 1.7 1.7 1.9 2.3 96.8 90.8 89.5 87.6 92.1 95.8 89.9 96.7 2.2 2.1 6.8 9.5 2.5 3.5 6.2 2.2
15 16 17 18 19 4 4 4 4 4 EXAMPLE Example comparative example comparative example comparative example 200 500 25 625 1200 200 200 25 625 200 1410 1410 1410 1414 1410 12 1.7 8 5 1.7 5.8 5.6 8.0 4.5 4.8 32.1 30.6 30.9 30.2 23.5 0.1956 0.1756 0.1849 0.1734 0.1254 2.7 3.0 1.9 3.9 4.3 93.1 87.4 96.0 72.2 64.5 3.4 5.6 2.9 10.0 11.2
20 21 5 5 The comparative example comparative example 50 625 50 625 1414 1414 8 5 4.2 5.8 26.6 29.4 0.1478 0.1677 3.6 4.1 56.5 70.7 19.0 10.3
Table 2 (continuing) sample sintering technology and character
Sample Composition The embodiment type 1150-1275 ℃ rate of heating (℃/hour) 1275-1400 ℃ rate of heating (℃/hour) Top temperature (℃) The soaking time of top temperature (hour) Average CTE (10 7℃ -1) (25- 800℃) Voidage (volume %) Total pore volume (cm 3/g) Mean pore size (micron) 0.5-5.0 whole hole % of μ The whole hole % that surpass 10 μ
22 23 24 6 6 6 Comparative example comparative example comparative example 50 200 625 50 200 625 1414 1410 1414 8 12 5 7.3 5.8 5.3 34.2 25.2 24.6 0.2106 0.1404 0.1307 1.6 4.8 7.4 95.4 48.4 9.6 4.1 17.8 30.5
25 26 7 7 The embodiment comparative example 250 40 200 25 1410 1405 1.7 8 3.9 5.4 26.5 28.5 0.1465 0.1587 1.8 1.3 88.5 83.9 10.9 13.4
27 28 8 8 The embodiment comparative example 250 40 200 25 1410 1405 1.7 8 2.0 4.7 22.3 25.0 0.1138 0.1332 1.6 1.2 92.6 86.6 4.0 9.6
29 30 9 9 The embodiment comparative example 250 40 200 25 1410 1405 1.7 8 0.4 3.8 20.7 26.3 0.1037 0.1431 1.6 1.1 91.2 74.2 6.6 22.0
31 32 33 34 35 10 10 10 10 10 EXAMPLE Example comparative example comparative example comparative example 50 200 25 625 1200 50 200 25 625 200 1410 1410 1410 1410 1410 8 12 8 5 1.7 5.8 3.2 7.1 3.6 3.1 30.6 30.0 31.4 23.1 26.8 0.1794 0.1764 0.1849 0.1245 0.1425 1.8 3.2 1.8 4.6 4.0 96.7 88.5 94.6 61.0 66.7 1.7 6.2 4.1 5.1 6.1
36 37 38 11 11 11 Comparative example comparative example comparative example 25 50 625 25 50 200 1410 1410 1410 8 8 12 10.3 8.6 8.2 38.0 36.4 33.8 0.2481 0.2327 0.2081 2.3 2.4 4.3 91.5 92.0 70.8 7.5 6.6 6.0

Claims (7)

1. the manufacture method of a cordierite bodies, this method comprises the steps:
A) select to contain talcum powder, Al 2O 3The trichroite of one or more in formation raw material and kaolin, calcined kaolin and the silica component forms raw material, optionally adds spinel, and wherein talcous median size is not more than 3.0 microns, Al 2O 3The median size that forms raw material is not more than 2.0 microns, and when selecting kaolin and its median size less than 2.0 microns for use, kaolinic add-on is less than 35% weight of raw material,
B) with the vehicle and the shaping additive intimate mixing of described raw material and significant quantity, make described raw material have PLASTIC SHAPING OF HIGH and green strength, and form plastic mixture;
C) described raw material is configured as green compact;
D) dry described green compact;
E) under 1370-1435 ℃ temperature, fire described green compact,
When talcous median size less than 2.0 microns, Al 2O 3Form raw material and be less than 20% of raw material gross weight, median size is less than 0.3 micron disperseed high surface area Al 2O 3Form raw material and be less than 5.0% of raw material gross weight, kaolinic median size is during less than 2.0 microns, and the heating rate between 1150-1275 ℃ is greater than 200 ℃/hour,
When talcous median size is not less than 2.0 microns, Al 2O 3Form raw material and be less than 20% of raw material gross weight, median size is less than 0.3 micron disperseed high surface area Al 2O 3Form raw material and be less than 5.0% of raw material gross weight, kaolinic median size is during less than 2.0 microns, and the heating rate between 1150-1275 ℃ is greater than 50 ℃/hour but less than 600 ℃/hour,
Work as Al 2O 3Form raw material and be less than 20% of raw material gross weight, median size is less than 0.3 micron disperseed high surface area Al 2O 3Form raw material and be no less than 5.0% of raw material gross weight, kaolinic median size is during less than 2.0 microns, and 1150-1275 ℃ heating rate is greater than 50 ℃/hour,
When kaolinic median size during greater than 2.0 microns, the heating rate between 1150-1275 ℃ is less than 600 ℃/hour but greater than 30 ℃/hour,
To make substantially by 49-53 weight %SiO 2, 33-38 weight %Al 2O 3Form and the cordierite bodies that have one of following character with 12-16 weight %MgO: the mean thermal expansion coefficients in the time of 25-800 ℃ is smaller or equal to 4 * 10 7℃ -1, the mean pore size that is no less than 85% hole in the overall porosity is the 0.5-5.0 micron, or the mean thermal expansion coefficients 25-800 ℃ the time is greater than 4 * 10 -7℃ -1, but smaller or equal to 6 * 10 -7℃ -1, overall porosity is not less than 30% volume, and the hole that is no less than overall porosity 85% has the 0.5-5.0 micron pore size.
2. the method for claim 1 is characterized in that Al 2O 3The amount that forms raw material is at least 20% of raw material gross weight.
3. the method for claim 1 is characterized in that adding kaolin as raw material, and its median size is not more than 2.0 microns, Al 2O 3The amount that forms raw material is no more than 20% of raw material gross weight.
4. method as claimed in claim 3 is characterized in that disperseing the Al of high surface area 2O 3Form raw material and be no less than 5.0% of raw material gross weight.
5. method as claimed in claim 4 is characterized in that disperseing the Al of high surface area 2O 3Form raw material and be selected from boehmite, pseudobochmite or their mixture.
6. cordierite bodies, the mean thermal expansion coefficients in the time of its 25-800 ℃ is smaller or equal to 4 * 10 -7℃ -1, the mean pore size that is no less than 85% porosity in the overall porosity is the 0.5-5.0 micron.
7. cordierite bodies, at 25-800 ℃ of its mean thermal expansion coefficients greater than 4 * 10 -7℃ -1, but smaller or equal to 6 * 10 -7℃ -1, overall porosity is not less than 30% volume, is not less than 85% hole in the overall porosity and has the 0.5-5.0 micron pore size.
CNB998167649A 1999-07-07 1999-09-01 Low CTE cordierite bodies with narrow pore size distribution and mehtod of making same Expired - Fee Related CN1213962C (en)

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US8530368B2 (en) 2008-08-19 2013-09-10 Basf Corporation Blended hydrous kaolin clay product
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