CN102471170A - Aluminium magnesium titanate composite ceramics - Google Patents

Aluminium magnesium titanate composite ceramics Download PDF

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CN102471170A
CN102471170A CN2010800322274A CN201080032227A CN102471170A CN 102471170 A CN102471170 A CN 102471170A CN 2010800322274 A CN2010800322274 A CN 2010800322274A CN 201080032227 A CN201080032227 A CN 201080032227A CN 102471170 A CN102471170 A CN 102471170A
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pottery
mixture
roasting
mgo
tio
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S·伊瓦托
R·亚马纳卡
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • C04B35/46—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 titanium oxides or titanates
    • C04B35/462—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 titanium oxides or titanates based on titanates
    • C04B35/478—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 titanium oxides or titanates based on titanates based on aluminium titanates
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    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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Abstract

An aluminium magnesium titanate composite ceramic which comprising the firing raw materials, as expressed on a weight percent oxide basis, 36.0-57.0 % of TiO2; 41.5-62.0 % of Al2O3; and 0-2.2 % of MgO, with the sum total of the three components adding up to 100 %, and 0-10 % of SiO2, for forming particulate filters, with a relatively high porosity, low thermal expansion efficiency (CTE), and high mechanical strength.

Description

The aluminum magnesium titanate composite ceramics
Invention field
The present invention relates to be used to form the aluminum magnesium titanate composite ceramics and the working method thereof of particulate filter, said composite ceramics be characterised in that higher porosity, low-thermal-expansion efficient (CTE), with and measure high mechanical strength as flexural strength.
Background technology
Particulate filter is used to remove particulate matter (PM), for example oil smoke and the ash content in the waste gas of compression-ignition internal combustion engine (that is oil motor) generation.In general; With granule capturing in its hole with its wall on the exemplary honeycomb structure strainer on the particle collected can remove by strainer through regeneration, said regeneration is carried out (through measuring the different pressures between the strainer upstream and downstream and determining whether that the particulate matter that surpasses predetermined amount accumulates on the strainer) through heating or the scorching hot particulate matter that has been collected in the strainer basically.
Expectation always for a long time obtains diesel particulate filter (DPF) with following performance: have enough anti-decomposabilities, high thermal-shock resistance and high porosity being higher than under 1,300 ℃ the temperature.
Following discloses can relate to many aspects of the present invention, and can summarize as follows:
WO2004/039747 discloses the physical strength with excellence of representing with flexural strength and has had the aluminum magnesium titanate of the elementary composition ratio of aluminium, magnesium and the titanium represented with formula (1 '):
Al 2(1-x)Mg xTi (1+x)O 5 (1’)
Wherein coefficient x satisfies 0.1≤x＜1.
Add alkali feldspar ((Na yK 1-y) AlSi 3O 8, wherein y satisfies 0≤y＜1) and to strengthen the coking property of aluminum magnesium titanate owing to its lower melting point.
The more excellent physical strength that this type of pottery is described to have low thermal coefficient of expansion and representes with flexural strength.
USP 5,153,153 disclose the doped titanic acid aluminium that has following composition as comprising of the particulate filter in the oil motor and the Al of the sintered ceramic material of mullite: 50-61.5% 2O 3, the titanate oxide of 36-47.5%, the SiO of 2.5-5% 2, the summation of these three kinds of components adds up at the most 100%, and said sintered ceramic material also comprises red stone and 1% the impurity at the most of MgO, the 0.015%-0.5% of 0.3-1%.Yet the production of this type of stupalith is consuming time and expensive, and during the whole particle strainer forms, can not obtain the required characteristic such as porosity and thermal-shock resistance.This is because iron oxide component at high temperature influences the intensity of aluminum magnesium titanate pottery.In addition; Expectation provides a kind of aluminum magnesium titanate pottery; Said pottery passes through 1; 400-1; 700 ℃ roasting temperature comprises the mixture of raw material of aluminum contained compound, titanium-containing compound and magnesium-containing compound and subsequently said mixture of raw material ground into fine powder (it is more little good more to be generally understood as mean particle size) and prepare, said pottery realized being used for diesel particulate filter at least 30% expectation voidage and thermal-shock resistance (its be calculated as R (thermal-shock resistance)=σ (ceramics strength) (1-V)/E α-be proportional to ceramics strength and be inversely proportional to thermal expansivity; Wherein V is a PR, and E is a Young's modulus, the thermal linear expansion coefficient of α for providing with (1/ ℃)) avoided the routine of known aluminum magnesium titanate pottery to limit simultaneously.
Summary of the invention
In the first embodiment, the present invention relates to its main ingredient with empirical formula Mg xAl 2 (1-x)Ti (1+x)O 5The aluminum magnesium titanate composite ceramics of (wherein coefficient x satisfies 0≤x＜0.1) expression comprises the following roasting starting material of representing based on the weight percent of oxide compound: the TiO of 36.0-57.0% 2The Al of 41.5-62.0% 2O 3With the MgO of 0-2.2%, wherein the summation of these three kinds of components adds up at the most 100%, and the SiO of 0-10% 2
Second embodiment of the present invention relates to the method for preparing the aluminum magnesium titanate composite ceramics, and the main ingredient of said pottery is with empirical formula Mg xAl 2 (1-x)Ti (1+x)O 5(wherein coefficient x satisfies 0＜x≤1) expression comprises the following starting material of representing based on the weight percent of oxide compound: the TiO of 36.0-57.0% 2The Al of 41.5-62.0% 2O 3With the MgO of 0-2.2%, wherein the summation of these three kinds of components adds up at the most 100%, and the SiO of 0-10% 2, said method is included in the said starting material of the roasting temperature that is not less than 1,300 ℃.
Another embodiment of the invention be comprise first component comprise TiO by roasting 2, Al 2O 3, MgO and SiO 2The pottery that obtains of mixture, said first component is used empirical formula Mg xAl 2 (1-x)Ti (1+x)O 5(wherein coefficient x satisfies 0≤x＜0.1) expression, said mixture is represented as the TiO based on the weight percent 36.0-57.0% of oxide compound 2The Al of 41.5-62.0% 2O 3With the MgO of 0-2.2%, wherein TiO 2, Al 2O 3, MgO summation add up at the most 100%, and add the SiO of 0-10% 2This pottery has shown to have less than 3 * 10 -6Thermal expansivity (1/K) (30-1000 ℃) and the porosity of pressing the hole spatial volumeter at least 28% of ceramic main body.In addition, the applicant also illustrates pottery of the present invention according to JIS R1601 and has the flexural strength greater than about 8MPa.The roasting temperature of preferred pottery of the present invention in 1200 ℃ of-1700 ℃ of scopes.
Another embodiment of the invention said method comprising the steps of for producing the method for pottery: a) combination TiO 2, Al 2O 3, MgO and SiO 2To form mixture, said mixture is represented as the TiO based on the weight percent 36.0-57.0% of oxide compound 2The Al of 41.5-62.0% 2O 3With the MgO of 0-2.2%, wherein TiO 2, Al 2O 3, the MgO summation adds up at the most 100%, and adds the SiO of 0-10% 2B) mix said mixture; B) dry said mixture; C) the said mixture of roasting temperature in 1200 ℃ of-1700 ℃ of scopes.Preferably, drying step is under 110 ℃-130 ℃ temperature, and is blended in and carries out with wet method in the ball mill.In addition, said mixture can comprise one or more combination of the auxiliary agent of milling, dispersion agent, skimmer or they.Method of the present invention also can may further comprise the steps: the pottery of milling after the roasting, said pottery of milling is placed mould, and subsequently in mould the said pottery of milling of roasting to produce forming ceramic.
Detailed Description Of The Invention
Form:
Aluminum magnesium titanate composite ceramics of the present invention mainly comprises the titanium-containing compound based on oxide compound 36-57.0%, the aluminum contained compound of 41.5-62.0%, the magnesium-containing compound of 0-2.2%; Wherein the summation of these three kinds of components adds up at the most 100%; And the silicon-containing compound of 0-10%, the mixture of the said compound of roasting forms said composite ceramics through mixing also.
Aluminum magnesium titanate composite ceramics of the present invention can randomly comprise other additives, for example titanate oxide; Aluminum oxide; Natural manganese dioxide; Silicon oxide; MgAl 2O 4Mullite etc., precondition be their existence can not perceive ground or increase the thermal expansivity of composite ceramics nocuously.
Work as TiO 2When content was lower than 36.0 weight %, thermal expansivity was because excessive Al 2O 3And uprise.Work as TiO 2When content surpassed 57.0 weight %, thermal expansivity was because excessive TiO 2And uprise.In a similar fashion, work as Al 2O 3When content was lower than 41.5 weight %, thermal expansivity was because excessive TiO 2And uprise, and work as Al 2O 3When content surpassed 62.0 weight %, thermal expansivity was because excessive Al 2O 3And uprise.As for MgO, when the content of MgO surpasses 2.2 weight %, can not obtain sufficiently high porosity.In addition, as for SiO 2, work as SiO 2When content surpassed 10 weight %, thermal expansivity uprised.
More preferably; Aluminum magnesium titanate composite ceramics of the present invention mainly comprises the titanium-containing compound based on oxide compound 37.5-49.0%, the aluminum contained compound of 50.0-61.5%, the magnesium-containing compound of 0-2.2%; Wherein the summation of these three kinds of components adds up at the most 100%, and the silicon-containing compound of 0-10%.
So that when paying close attention to thermal-shock resistance, the aluminum magnesium titanate composite ceramics does not also comprise other components, for example titanium oxide as much as possible except comprising aluminum magnesium titanate itself when the lower thermal expansivity of needs; Aluminum oxide; Natural manganese dioxide; Silicon oxide; MgAl 2O 4Mullites etc., said aluminum magnesium titanate is with empirical formula Mg xAl 2 (1-x)Ti (1+x)O 5(wherein coefficient x satisfies 0＜x＜0.1) expression.
The content of silicon-containing compound is preferably in the scope based on oxide compound 0-7% in the stupalith.
And so that when paying close attention to lower pressure loss, aluminum magnesium titanate composite ceramics of the present invention mainly comprises the TiO based on oxide compound 38.3-43.9% when the needs high porosity 2, 55.5-61.5% Al 2O 3, 0-1.0% MgO, wherein the summation of these three kinds of components adds up at the most 100%, and the SiO of 0-10% 2
The titanium source is as the compound of the titanium composition of forming aluminum magnesium titanate, for example, comprises titanium oxide.Titanium oxide comprises for example titanium oxide (IV), titanium oxide (III), titanium oxide (II) etc.Preferred titanium oxide (IV).The crystal formation of titanium oxide (IV) comprises Detitanium-ore-type, rutile-type, brookite type etc., and can be amorphous.More preferably Detitanium-ore-type and rutile-type.
The titanium source comprises the compound powder that generates titanium oxide (titanium oxide) through independent roasting in air.Said compound comprises for example titanium salt, pure titanium, titanium hydroxide, titanium nitride, titanium sulfide, metal titanium etc.
Titanium salt comprises titanous chloride, titanium tetrachloride, titanium sulfide (IV), titanium sulfide (VI), titanium sulfate (IV) etc. particularly.The alcohol titanium comprises titanium ethanolate (IV), methyl alcohol titanium (IV), trimethyl carbinol titanium (IV), titanium isobutoxide (IV), n-propyl alcohol titanium (IV), titanium tetraisopropylate (IV) and their chelate compound etc. particularly.
The titanium source is preferably titanium oxide.
Aluminium source in the mixture is as the compound of the aluminium component of forming aluminum magnesium titanate, for example comprises alumina (aluminum oxide) powder.The crystal formation of aluminum oxide comprises γ-type, δ-type, θ-type, α-type and other, and can be amorphous.As aluminum oxide, preferred α-type aluminum oxide.
The aluminium source also comprise can be in air separately roasting generate the compound of aluminum oxide.Said compound comprises for example aluminium salt, aluminium alcoholates, white lake, metallic aluminium etc.
Aluminium salt can be the inorganic salt with mineral acid, perhaps has organic acid organic salt.Specifically, al inorganic salt comprises for example aluminum nitrate salt, such as aluminum nitrate, an ammonium nitrate aluminium etc.; Aluminium carbonate salt is such as volatile salt aluminium etc.Aluminium organic salt comprises for example oxalic acid aluminium, aluminum acetate, StAl, Aluctyl, Aluminum trilaurate etc.
Specifically, aluminium alcoholates comprises for example aluminum isopropylate, aluminum ethylate, ASBD, trimethyl carbinol aluminium etc.
The crystal formation of white lake comprises for example gibbsite type, bayerite type, promise gibbsite type, boehmite-type, pseudo-boehmite type etc., and can be amorphous.Amorphous aluminum hydroxide comprises the aluminium hydrolysate of the aqueous hydrolysis acquisition of for example passing through water soluble aluminum compound, and said aluminum compound is aluminium salt, aluminium alcoholates etc. for example.
The aluminium source is preferably alumina.
The magnesium source is as the compound of the magnesium component of forming aluminum magnesium titanate, for example comprises Natural manganese dioxide (magnesium oxide) powder.
The magnesium source also comprises and can in air, independent roasting generate magnesian compound.Said compound comprises for example magnesium salts, magnesium alkoxide, Marinco H, magnesium nitride, MAGNESIUM METAL 99 etc.
Magnesium salts comprises magnesium chloride, magnesium perchlorate, trimagnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesiumcarbonate, magnesium acetate, sal epsom, magnesium citrate, magnesium lactate, Magnesium Stearate, magnesium salicylate, magnesium myristate, Menesia, magnesium dimethacrylate, magnesium benzoate etc. particularly.
Magnesium alkoxide comprises magnesium methylate, magnesium ethylate etc. particularly.
As the magnesium source, available is the compound that is used as magnesium source and aluminium source simultaneously.Said compound comprises for example magnesia spinel (MgAl 2O 4).
The silicon source for example, comprises Si oxide (silicon oxide), for example silicon-dioxide, silicon monoxide etc. for the compound of silicon composition is provided in the aluminum magnesium titanate composite ceramics.
The silicon source also comprises the compound that can generate silicon through independent roasting in air.Said compound comprises for example silicic acid, silit, silicon nitride, silicon sulfide, silicon tetrachloride, acetate silicon, water glass, sodium orthosilicate, frit etc.Consider preferred glass material etc. from commercial availability.
As the silicon source, also available is the compound that is used as the aluminium source in addition.For example, said compound comprises and comprises at least a element that is selected from sodium, potassium and calcium and comprise silicon and the silico-aluminate of aluminium.Elementary composition when said compound with composition formula (2):
(c 1Na 2O，d 1K 2O，e 1CaO)·y’Al 2O 3·zSiO 4 (2)，
During expression, coefficient c wherein 1, d 1And e 1Satisfy c 1+ d 1+ e 1=1, coefficient y ' satisfies 0.4≤y '≤1.2 (preferably 0.6≤y '≤1.1), and coefficient z satisfies 6≤z≤12, preferably 7≤z≤11.Alumino-silicate is called feldspar, and feldspar can be natural materials or synthetic product, and synthetic product is industrial can the acquisition easily.
In addition, as the silicon source, also available is the compound that is used as titanium source, aluminium source and magnesium source in addition.This type of examples for compounds comprises any in titanium source, aluminium source and/or the magnesium source that is coated with the silicon source in its surface.
Working method
Generally use as powder in aluminium source, magnesium source and titanium source.
For example, said mixture can pass through aluminum mixture source, magnesium source and the acquisition of titanium source.Said mixing can or obtain by wet method by dry method.
For example, in mixing, aluminium source, magnesium source and titanium source can preferably utilize the stirring and the mixing of milling with the medium of milling in milling container, have the aluminum magnesium titanate composite ceramics of even composition with preparation.
When mixing raw material, can additive be added wherein said additive such as the auxiliary agent of milling, defloculating agent or dispersion agent, skimmer (will be interpreted as and be meant the skimmer that is used to reduce blistered material) etc.As used herein, term " dispersion agent " or " dispersion reagent " mean and join in the suspension medium to promote superfine short grained homodisperse or isolating tensio-active agent usually.The dispersion agent that is applicable to purposes of the present invention can be selected from any anionic dispersing agents, cation dispersing agent or non-ionic dispersing agent, or their combination.The instance of suitable dispersion agent is an iso-butylene maleic acid sodium salt, with trade(brand)name Orotan TM731 are sold by Rohm and Haas.The instance of conventional " skimmer " will be interpreted as by those skilled in the art and belong to the present invention.Suitable skimmer is the blend of modified fatty alcohol and ZGK 5, and said blend is with trade(brand)name Dehydran TM1620 are sold by Cognis Corp..
The auxiliary agent of milling comprises for example alcohol, such as methyl alcohol, ethanol, propyl alcohol etc.; Divalent alcohol is such as Ucar 35, W 166, terepthaloyl moietie etc.; Amine is such as trolamine etc.; Higher fatty acid is such as palmitinic acid, Triple Pressed Stearic Acid, oleic acid etc.; Carbon material is such as carbon black, graphite etc.In these one or more can use or make up use separately.
Through the said mixture of roasting, can obtain aluminum magnesium titanate composite ceramics of the present invention.
With regard to roasting, said mixture can roasting when Powdered, perhaps can roasting after moulding.Powder mixture can be according to moulding such as for example drawing methods.
The production that is easy to from aluminum magnesium titanate considers that maturing temperature can be generally 1200 ℃-1700 ℃, and from feasibility, is preferably 1400 ℃-1600 ℃.The heating rate that reaches maturing temperature can be generally 10 ℃/hr-500 ℃/hr.
Roasting generally can be accomplished in air; But the type and the blend ratio that depend on the raw material (aluminium source, magnesium source, titanium source reach randomly silicon source) that will utilize; Roasting can be accomplished in the rare gas element such as nitrogen, argon gas etc., perhaps can in the reducing gas such as CO gas, hydrogen etc., accomplish.During the roasting, the water vapor pressure in the atmosphere can reduce.
In general, roasting utilizes common stoving oven to accomplish, stove etc. at the bottom of said stoving oven such as electric tube furnace, cabinet-type electric furnace, continuous tunnel furnace, far-infrared oven, microwave oven, shaft furnace, reverberatory furnace, rotary oven, the roller.Roasting can be accomplished through batch methods or continuation method, and can static schema or the completion of fluidization pattern.
The required time of roasting can be the time that is enough to prepared by mixture aluminum magnesium titanate, and can still generally can be 10 minutes to 24 hours according to the amount of used mixture, type, maturing temperature, calcination atmosphere and other changes of stoving oven.In general, maturing temperature is at least 1,200 ℃.
Mill and classify and can carry out through domestic method, for example ball mill, medium grinding machine, roller mill, hammer mill, pin card grinding, aeropulverizer, planetary mill, vibration mill, mill with hand or with mortar.The aluminum magnesium titanate powder that gained is milled can be classified through general sorting technique.
The mean particle size of aluminum magnesium titanate composite ceramic powder (D50) is about 10-60 micron.15-45 micron more preferably.
Composite ceramics can have less than 3 * 10 -6Thermal expansivity (1/K) (RT30-1000 ℃).CTE (30-1000 ℃) can be-3 * 10 -6-3 * 10 -6In the scope (1/K).
As measuring of the hole spatial volume percent of roasting pottery, composite ceramics can have by volume at least 28%, specifically at least 30% porosity.Volume percent can be in the scope of 25%-60% by volume.
Composite ceramics can have the flexural strength greater than about 8MPa according to JIS R1601.Flexural strength can be in the scope of 6MPa-40MPa.
Testing method
The testing method and the standard that are used for acquisition table 1-3 result comprise as follows:
Porosity: the following calculating of porosity (per-cent by volume) that is directed against the rectangle sample of the 3mm * 4mm * 40mm that cuts by the second agglomerating forming ceramic:
(sample volume-(example weight/absolute specific gravity=3.8g/cm 3)/sample volume) * 100%.
Thermal expansivity (CTE): the thermal expansivity that is directed against the rectangle sample of the 3mm * 4mm * about 20mm that is cut by the agglomerating forming ceramic utilizes hot analysis measuring device to measure, and said measuring apparatus is such as the Thermo Plus Evo that can be purchased acquisition from Rigaku Corporation.Under air conditions, sample is heated to 1300 ℃ at the most by room temperature (22-25 ℃) with 20 ℃/min.Thermal expansion slope of a curve by between 30 and 1000 ℃ calculates thermal expansivity.
Flexural strength: utilize JIS R1601 that the 3mm * 4mm * 40mm sample of the second agglomerating ceramic main body processed by material according to the invention is carried out three point method and measure.
Mean particle size (the D of every kind of material 50): D 50Utilization is such as the laser diffraction technology measurement that can be purchased the LA-920 of acquisition from Horiba Ltd.; Utilize JIS R16222 and 1629 to calculate.
Embodiment
Describe the present invention in detail with reference to following examples.Yet the present invention is not limited to these embodiment.
Application implementation example 1,2 and comparing embodiment 1 and 2:
Put into following component in the milling container that has aluminium ball (diameter 15mm) and in ball mill, mixed 5 hours with wet stirring; The titanium oxide powder that said component is shown in Table 1 for its composition, alpha-aluminium oxide powder and Natural manganese dioxide; The summation of these three kinds of components adds up at the most 100%; SiO 2 powder by 5 parts of quality; By the iso-butylene maleic acid sodium salt as Orotan 731 (selling) (10% aqueous solution) dispersion agent of 1.5 parts of quality by Rohm & Haas, by 0.2 part of quality as the modified fatty alcohol of skimmer and the blend of ZGK 5, by Cognis Corp with trade(brand)name Dehydran TMSell (10% aqueous solution), and by the water of 100 parts of quality.Subsequently with mixture about 12 hours of 120 ℃ of dryings to obtain mixture of raw material.
Alpha-aluminium oxide powder: Al 2O 3, Sumitomo Chemical, " AES-12 "
Titanium oxide powder: TiO 2, DuPont, " R-900 ".
Natural manganese dioxide: MgO, Konoshima Kagaku K.K., trade(brand)name " StarMagL ".
SiO 2 powder: Fukushima feldspar
Dispersion agent: Orotan (trade mark) 731 (10% aqueous solution), iso-butylene maleic acid sodium salt can be purchased acquisition from Rohm & Hass.
Skimmer: Dehydran TM 1620, the Fatty Alcohol(C12-C14 and C12-C18) of modification and the blend of ZGK 5 derive from Cognis Corp., Ambler, PA.
The gained mixture of raw material is put into the aluminium case, and in cabinet-type electric furnace with the roasting in air of following operating characteristics.The agglomerating material cooled to room temperature, is obtained the aluminum magnesium titanate composite ceramics.
Room temperature (RT)-1450 ℃, wherein RT is that room temperature (about 20-25 ℃) continues 30 hours
Remain on 1450 ℃ 4 hours
1450 ℃-room temperature keeps cooling
Gained agglomerating material is milled and classified to obtain having the powder of milling of about 24 microns average grain size.Take out the 10g gained powder of milling, and put into and have 10mm * 10mm * rectangular mould of 50mm size, at 120kgf/cm 2The forming pressure pressed, thereby forming ceramic is provided.With forming ceramic once more in cabinet-type electric furnace with the maturing temperature shown in the table 1 and time roasting in air, thereby the second agglomerating forming ceramic is provided.
Through utilizing the second agglomerating forming ceramic of above acquisition, the rectangle sample of cutting 3mm * 4mm * 40mm and 3mm * 4mm * 20mm.Carry out porosity, thermal expansivity and flexible measurement as stated.The result is summarized in the table 1.
As shown in table 1, the application implementation example 1 and 2 of the MgO content of 0-2 weight % has realized being lower than 2 * 10 -The low thermal coefficient of expansion of 6/K and about by volume 30% high porosity.On the other hand, the comparing embodiment 1 of the MgO content of about 5 weight % shows about 4 * 10 -6The high thermal expansion coefficient of/K keeps 30% porosity simultaneously.In addition, comparing embodiment 2 shows about by volume 19% low porosity, and it shows low thermal coefficient of expansion simultaneously, and comparing embodiment 2 has the composition identical with comparing embodiment 1, and different is that roasting time is 10 hours.
Therefore, when MgO content was higher, high porosity and low thermal coefficient of expansion were incompatible.Therefore, preferred 0 MgO content to about 2 weight %.
Table 1
Figure BPA00001497893400101
Application implementation example 3-5 and comparing embodiment 3:
Application implementation example 3-5 carries out with the mode identical with embodiment 1-2 with comparing embodiment 3, and the composition and the maturing temperature of different is forming ceramic are as shown in table 2.
As shown in table 2, have the Al that is lower than 62 weight % 2O 3The application implementation of content example 3,4 and 5 realized by volume greater than 28% high porosity, be lower than 2 * 10 -6The low thermal coefficient of expansion of/K and be higher than 8MPa simultaneously.On the other hand, has the Al that is higher than 62 weight % 2O 3The comparing embodiment 3 of content causes 3.5 * 10 -6The high thermal expansion coefficient of/K.
Therefore, the Al of preferred 41.5-62.0 weight % 2O 3TiO with 36.0-57.0 weight % 2Compositing range.Especially when low thermal coefficient of expansion was important, advantageous applications embodiment 3.
Table 2
Application implementation example 6-8 and comparing embodiment 4:
Application implementation example 6 with 7 with comparing embodiment 4 carrying out with embodiment 1 and 2 identical modes, the composition and the maturing temperature of different is forming ceramic are as shown in table 3.Application implementation example 8 is carried out with the mode identical with embodiment 1 and 2, and different is utilizes the composition and the maturing temperature of TiO2 powder replacement SiO 2 powder with SiO2 coating (about 5 weight %) and forming ceramic as shown in table 3.
Consist of TiO based on oxide compound 36.0-57.0 weight % 2, 41.5-62.0 weight % Al 2O 3, 0-2.2 weight % MgO and by the SiO of quality 0-10 part 2Application implementation example 7 show high porosity.In addition, do not utilize SiO 2 powder and utilize TiO with silica dioxide coating 2The application implementation example 8 of powder shows 1.3 * 10 -6The very low thermal expansivity of/K is kept above 8MPa simultaneously.
Table 3
Figure BPA00001497893400121

Claims (10)

1. what comprise first component comprises TiO by roasting 2, Al 2O 3, MgO and SiO 2The pottery that obtains of mixture, said first component is used empirical formula Mg xAl 2 (1-x)Ti (1+x)O 5(wherein coefficient x satisfies 0≤x＜0.1) expression, said mixture is represented as the TiO based on the weight percent 36.0-57.0% of oxide compound 2The Al of 41.5-62.0% 2O 3And the MgO of 0-2.2%, wherein said TiO 2, Al 2O 3, MgO summation add up at the most 100%, and add the SiO of 0-10% 2
2. the pottery of claim 1, said pottery has less than 3 * 10 -6Thermal expansivity (1/K) (30-1000 ℃).
3. according to the pottery of claim 1, said pottery has the porosity by the hole spatial volumeter at least 28% of said ceramic main body.
4. according to the pottery of claim 1, said pottery has the flexural strength greater than about 8MPa according to JIS R1601.
5. according to the pottery of claim 1, wherein said roasting is under the temperature in 1200 ℃ of-1700 ℃ of scopes.
6. be used to produce the method for pottery, said method comprising the steps of:
A) mix TiO 2, Al 2O 3, MgO and SiO 2To form mixture, said mixture is represented as the TiO based on the weight percent 36.0-57.0% of oxide compound 2The Al of 41.5-62.0% 2O 3And the Natural manganese dioxide of 0-2.2%, wherein said TiO 2, Al 2O 3, MgO summation add up at the most 100%, and add the SiO of 0-10% 2
B) mix said mixture;
B) dry said mixture;
C) the said mixture of roasting temperature in 1200 ℃ of-1700 ℃ of scopes.
7. the method for claim 6, wherein said drying takes place under 110 ℃-130 ℃ temperature.
8. the method for claim 6, wherein said being blended in the ball mill carried out with wet method.
9. the method for claim 6, wherein said mixture also comprise one or more combination of the auxiliary agent of milling, dispersion agent, skimmer or they.
10. the method for claim 6, the pottery that wherein said pottery is milled after roasting and milled with preparation places mould with said pottery of milling, and subsequently in said mould the said pottery of milling of roasting to produce forming ceramic.
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