WO2011111666A1 - グリーン成形体、及び、チタン酸アルミニウム焼成体の製造方法 - Google Patents
グリーン成形体、及び、チタン酸アルミニウム焼成体の製造方法 Download PDFInfo
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- WO2011111666A1 WO2011111666A1 PCT/JP2011/055272 JP2011055272W WO2011111666A1 WO 2011111666 A1 WO2011111666 A1 WO 2011111666A1 JP 2011055272 W JP2011055272 W JP 2011055272W WO 2011111666 A1 WO2011111666 A1 WO 2011111666A1
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- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
- B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
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Definitions
- the present invention relates to a green molded body and a method for producing an aluminum titanate fired body.
- Aluminum titanate ceramics are ceramics that contain titanium and aluminum as constituent elements and have an aluminum titanate crystal pattern in the X-ray diffraction spectrum, and are known as ceramics having excellent heat resistance.
- Aluminum titanate ceramics have been conventionally used as a sintering jig such as a crucible, but in recent years, fine carbon particles contained in exhaust gas discharged from an internal combustion engine such as a diesel engine are collected. As a material constituting the ceramic filter, industrial utility value is increasing.
- Patent Document 1 As a method for producing aluminum titanate ceramics, a method is known in which a raw material mixture containing an aluminum source powder and a titanium source powder is formed and fired (Patent Document 1).
- the raw material mixture further contains organic additives such as an organic binder and pore former, and the green additive of this raw material mixture is heated to 150 to 900 ° C. in an oxygen-containing atmosphere to remove the organic additives.
- a method of firing at 1300 ° C. or higher is also known (paragraphs 0031 to 0032 of Patent Document 1).
- the strength (shape retention) of the green molded body is not sufficient, and the green molded body may not be able to maintain its shape when it is put into a firing furnace. As a result, the dimensional accuracy of the obtained aluminum titanate fired body was not sufficient.
- An object of the present invention is to provide a green molded body that can maintain its shape and a method for producing an aluminum titanate fired body using the green molded body.
- An inorganic compound source powder containing an aluminum source powder and a titanium source powder, and an organic binder, wherein the organic binder has a viscosity of 20 m ° C. of a 2 wt% aqueous solution of the organic binder of 5000 mPa ⁇ s or more.
- a green molded body containing an aluminum source powder and a titanium source powder, and an organic binder, wherein the organic binder has a viscosity of 20 m ° C. of a 2 wt% aqueous solution of the organic binder of 5000 mPa ⁇ s or more.
- An organic binder is a manufacturing method of the aluminum titanate sintered body whose viscosity in 20 degreeC of the 2 weight% aqueous solution of an organic binder becomes 5000 mPa * s or more.
- the amount of the organic binder is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the green molded body.
- the inorganic compound source powder preferably further contains a silicon source powder.
- the inorganic compound source powder preferably further contains a magnesium source powder.
- the molar ratio of the aluminum source powder in terms of Al 2 O 3 and the titanium source powder in terms of TiO 2 is preferably in the range of 35:65 to 45:55.
- the green molded body has a honeycomb shape.
- the green molded body of the present invention is excellent in shape retention by including an organic binder having a viscosity of 5000 mPa ⁇ s or more when a 2% by weight aqueous solution is formed.
- a molded body having excellent shape retention can be obtained by using an organic binder having a viscosity of 5000 mPa ⁇ s or more when a 2% by weight aqueous solution is used as a raw material.
- the obtained aluminum titanate fired body with high dimensional accuracy can be efficiently produced.
- FIG. 1 are schematic views showing how to examine shape retention in the embodiment.
- the green molded body of the present invention includes an inorganic compound source powder and an organic binder.
- the inorganic compound source powder includes an aluminum source powder and a titanium source powder.
- the inorganic compound source powder can further include a magnesium source powder and / or a silicon source powder.
- the aluminum source is a compound that becomes an aluminum component constituting the aluminum titanate fired body.
- the aluminum source include alumina (aluminum oxide).
- the crystal type of alumina include ⁇ -type, ⁇ -type, ⁇ -type, and ⁇ -type, and may be indefinite (amorphous). Of these, ⁇ -type alumina is preferably used.
- the aluminum source may be a compound that is led to alumina by firing alone in air.
- Examples of such a compound include an aluminum salt, aluminum alkoxide, aluminum hydroxide, and metal aluminum.
- the aluminum salt may be an inorganic salt with an inorganic acid or an organic salt with an organic acid.
- aluminum inorganic salts include aluminum nitrates such as aluminum nitrate and ammonium aluminum nitrate; and aluminum carbonates such as ammonium aluminum carbonate.
- aluminum organic salt include aluminum oxalate, aluminum acetate, aluminum stearate, aluminum lactate, and aluminum laurate.
- aluminum alkoxide examples include aluminum isopropoxide, aluminum ethoxide, aluminum sec-butoxide, aluminum tert-butoxide, and the like.
- Examples of the aluminum hydroxide crystal type include a gibbsite type, bayerite type, norosotrandite type, boehmite type, and pseudo-boehmite type, and may be amorphous (amorphous).
- Examples of the amorphous aluminum hydroxide include an aluminum hydrolyzate obtained by hydrolyzing an aqueous solution of a water-soluble aluminum compound such as an aluminum salt or an aluminum alkoxide.
- an aluminum source only 1 type may be used and 2 or more types may be used together.
- alumina is preferably used as the aluminum source, more preferably ⁇ -type alumina.
- the aluminum source may contain trace components derived from the raw materials or inevitably contained in the production process.
- the particle size of the aluminum source powder is not particularly limited. Usually, the particle size corresponding to a volume-based cumulative percentage of 50% (sometimes referred to as D50 or average particle size) measured by a laser diffraction method is in the range of 20 to 60 ⁇ m. Is within. From the viewpoint of reducing shrinkage during firing, it is preferable to use an aluminum source powder having a D50 in the range of 30 to 60 ⁇ m.
- an alumina sol or a silica sol described later can be added to the green molded body.
- alumina sol, silica sol or the like fine particles are adsorbed to each other, and the amount of particles having a particle diameter of 0.1 ⁇ m or less in the molded body is set to 100 parts by weight of the inorganic compound source powder (solid content). 1 to 5 parts by weight based on the above, whereby the strength of the molded body after degreasing at 500 ° C. can be set to 0.2 kgf or more, for example.
- the alumina sol is a colloid using fine particle alumina as a dispersoid and a liquid as a dispersion medium.
- Alumina sol can be used alone as an aluminum source, but is preferably used in combination with other aluminum sources.
- the dispersion medium of alumina sol is removed by evaporation or the like at the time of mixing or calcination, for example.
- the dispersion medium for the alumina sol examples include aqueous solutions and various organic solvents such as aqueous hydrochloric acid, aqueous acetic acid, aqueous nitric acid, alcohol, xylene, toluene, and methyl isobutyl ketone.
- a colloidal alumina sol having an average particle diameter of 1 to 100 nm is preferably used.
- Examples of commercially available products of alumina sol include “Alumina sol 100”, “Alumina sol 200”, “Alumina sol 520” manufactured by Nissan Chemical Industries, Ltd., and “NanoTekAl 2 O 3 ” manufactured by CI Kasei. Among these, it is preferable to use “Alumina sol 200" manufactured by Nissan Chemical Industries.
- the alumina sol can be used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the inorganic compound source powder (solid content). Two or more kinds of alumina sols may be mixed and used.
- titanium source powder The titanium source is a compound that becomes a titanium component constituting the aluminum titanate fired body, and examples of such a compound include titanium oxide.
- examples of titanium oxide include titanium (IV) oxide, titanium (III) oxide, and titanium (II) oxide.
- titanium (IV) oxide is preferably used.
- Examples of the crystal form of titanium (IV) oxide include anatase type, rutile type, brookite type and the like, and may be indefinite (amorphous). More preferred is anatase type or rutile type titanium (IV) oxide.
- the titanium source may be a compound that is led to titania (titanium oxide) by firing alone in air.
- titania titanium oxide
- examples of such compounds include titanium salts, titanium alkoxides, titanium hydroxide, titanium nitride, titanium sulfide, and titanium metal.
- titanium salt examples include titanium trichloride, titanium tetrachloride, titanium sulfide (IV), titanium sulfide (VI), and titanium sulfate (IV).
- titanium alkoxide examples include titanium (IV) ethoxide, titanium (IV) methoxide, titanium (IV) t-butoxide, titanium (IV) isobutoxide, titanium (IV) n-propoxide, titanium (IV) tetraiso Examples thereof include propoxide and chelates thereof.
- titanium source only 1 type may be used and 2 or more types may be used together.
- titanium oxide is preferably used, and titanium oxide (IV) is more preferable.
- the titanium source may contain a trace component derived from the raw material or inevitably contained in the production process.
- the particle size of the titanium source powder is not particularly limited, but those having a particle size (D50) equivalent to a volume-based cumulative percentage of 50% as measured by a laser diffraction method in the range of 0.5 to 25 ⁇ m are usually used. In order to achieve a sufficiently low firing shrinkage ratio, it is preferable to use a titanium source powder having a D50 in the range of 1 to 20 ⁇ m.
- the titanium source powder may show a bimodal particle size distribution. When using a titanium source powder showing such a bimodal particle size distribution, the particle size distribution measured by the laser diffraction method is used.
- the particle diameter of the peak having the larger particle diameter is preferably in the range of 20 to 50 ⁇ m.
- the mode diameter of the titanium source powder measured by the laser diffraction method is not particularly limited, but a mode diameter in the range of 0.3 to 60 ⁇ m can be used.
- the molar ratio of the aluminum source in terms of Al 2 O 3 (alumina) and the titanium source in terms of TiO 2 (titania) in the molded body is preferably in the range of 35:65 to 45:55, more Preferably it is within the range of 40:60 to 45:55. Within such a range, it becomes possible to reduce the shrinkage rate during firing by using the titanium source excessively relative to the aluminum source.
- the green molded body may contain a magnesium source powder.
- the obtained aluminum titanate fired body is a fired body made of aluminum magnesium titanate crystals.
- magnesium source examples include magnesia (magnesium oxide) and a compound that is led to magnesia by firing alone in air.
- magnesia magnesium oxide
- a compound that is led to magnesia by firing alone in air examples include magnesium salt, magnesium alkoxide, magnesium hydroxide, magnesium nitride, metal magnesium and the like.
- magnesium salts include magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium sulfate, magnesium citrate, magnesium lactate, magnesium stearate, Examples include magnesium salicylate, magnesium myristate, magnesium gluconate, magnesium dimethacrylate, and magnesium benzoate.
- magnesium alkoxide examples include magnesium methoxide and magnesium ethoxide.
- a magnesium source can contain the trace component contained unavoidable in the raw material origin or manufacturing process.
- a compound serving both as a magnesium source and an aluminum source can also be used.
- An example of such a compound is magnesia spinel (MgAl 2 O 4 ).
- MgAl 2 O 4 magnesia spinel
- As magnesium source when using a compound serving both as a magnesium source and an aluminum source, Al 2 O 3 (alumina) equivalent amount of the aluminum source, and, Al component contained in the compound serving both as a magnesium source and an aluminum source.
- the molar ratio of the total amount of Al 2 O 3 (alumina) converted to the TiO 2 (titania) converted amount of the titanium source is adjusted to be within the above range in the raw material mixture.
- magnesium source only 1 type may be used and 2 or more types may be used together.
- the particle size of the magnesium source powder is not particularly limited, but those having a volume-based cumulative particle size equivalent to 50% on a volume basis (D50) in the range of 0.5 to 30 ⁇ m are usually used. From the viewpoint of reducing the shrinkage during firing, it is preferable to use a magnesium source having a D50 in the range of 3 to 20 ⁇ m.
- the content of the magnesium source in terms of MgO (magnesia) in the green molded body is relative to the total amount of the aluminum source in terms of Al 2 O 3 (alumina) and the titanium source in terms of TiO 2 (titania),
- the molar ratio is preferably 0.03 to 0.15, more preferably 0.03 to 0.12.
- the green molded body may further contain a silicon source powder.
- the silicon source is a compound that becomes a silicon component and is contained in the aluminum titanate fired body. By using the silicon source in combination, it is possible to obtain an aluminum titanate fired body with improved heat resistance.
- Examples of the silicon source include silicon oxides (silica) such as silicon dioxide and silicon monoxide.
- the silicon source may be a compound that is led to silica by firing alone in air.
- examples of such compounds include silicic acid, silicon carbide, silicon nitride, silicon sulfide, silicon tetrachloride, silicon acetate, sodium silicate, sodium orthosilicate, feldspar, glass frit and the like.
- feldspar, glass frit and the like are preferably used, and glass frit and the like are more preferably used because they are easily available industrially and have a stable composition.
- Glass frit means flakes or powdery glass obtained by pulverizing glass.
- As the silicon source a powder made of a mixture of feldspar and glass frit can also be used.
- the silicon source is glass frit
- the yield point of the glass frit is defined as a temperature (° C.) at which the expansion of the glass frit is measured from a low temperature by using a thermomechanical analyzer (TMA: Thermo Mechanical Analysis), the expansion stops and then the contraction starts.
- a general silicate glass containing silicate [SiO 2 ] as a main component (0% by weight or more in all components) can be used.
- the glass constituting the glass frit includes, as other components, alumina [Al 2 O 3 ], sodium oxide [Na 2 O], potassium oxide [K 2 O], calcium oxide [ CaO], magnesia [MgO] and the like may be included.
- the glass constituting the glass frit may contain ZrO 2 in order to improve the hot water resistance of the glass itself.
- silicon source only 1 type may be used and 2 or more types may be used together.
- the particle size of the silicon source is not particularly limited, but those having a volume-based cumulative particle size equivalent to 50% by volume (D50) in the range of 0.5 to 30 ⁇ m, usually measured by a laser diffraction method, are used. In order to further improve the filling ratio of the molded body of the raw material mixture and obtain a fired body having higher mechanical strength, it is preferable to use a silicon source having a D50 in the range of 1 to 20 ⁇ m.
- the content of the silicon source in the green molded body is 100 weights of the total amount of the aluminum source in terms of Al 2 O 3 (alumina) and the titanium source in terms of TiO 2 (titania).
- the amount is usually 0.1 to 10 parts by weight, preferably 5 parts by weight or less, based on parts by weight in terms of SiO 2 (silica).
- the content of the silicon source in the green molded body is more preferably 2 wt% or more and 5 wt% or less in the inorganic compound source contained in the green molded body.
- the silicon source may contain trace components that are derived from the raw materials or inevitably contained in the production process.
- a compound containing two or more metal elements among titanium, aluminum, silicon and magnesium can be used as a raw material.
- such a compound can be considered to be the same as a mixture of the respective metal source compounds, and based on such an idea, an aluminum source, a titanium source, a magnesium source and silicon in the green molded body The amount of source is adjusted within the above range.
- silica sol is a colloid using fine particle silica as a dispersoid and liquid as a dispersion medium.
- the silica sol can be used alone as a silicon source, but is preferably used in combination with other silica sources.
- the dispersion medium of silica nasol is removed by evaporation or the like during mixing or calcination, for example.
- silica sol dispersion medium examples include aqueous solutions and various organic solvents such as an aqueous ammonia solution, alcohol, xylene, toluene, and triglyceride.
- a colloidal silica sol having an average particle diameter of 1 to 100 nm is preferably used.
- silica sol examples include “Snowtex 20, 30, 40, 50, N, O, S, C, 20L, OL, XS, XL, YL, ZL, QAS-40, LSS manufactured by Nissan Chemical Industries, Ltd. -35, LSS-45 "," Adelite AT-20, AT-30, AT-40, AT-50, AT-20N, AT-20A, AT-30A, AT-20Q, AT-300, manufactured by Asahi Denka Co., Ltd. “AT-300Q”, “Cataloid S-20L, S-20H, S-30L, S-30H, SI-30, SI-40, SI-50, SI-350, SI-500, SI-manufactured by Catalyst Kasei Kogyo Co., Ltd.
- the silica sol is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the inorganic compound source powder (solid content). Two or more kinds of silica sols may be mixed and used.
- the green molded body can contain aluminum titanate or aluminum magnesium titanate.
- the aluminum magnesium titanate when aluminum magnesium titanate is used as a constituent of the molded body, the aluminum magnesium titanate contains a titanium source, an aluminum source, and a magnesium source. It corresponds to the raw material which combines.
- the green molded body contains a water-soluble organic binder.
- This organic binder is an organic binder in which the viscosity of a 2% by weight aqueous solution of the organic binder is 5000 mPa ⁇ s or more, preferably 10,000 mPa ⁇ s or more at 20 ° C.
- the viscosity of the aqueous solution can be measured by, for example, a BrookField viscometer.
- the viscosity of a 2% by weight aqueous solution of the organic binder is preferably 50000 mPa ⁇ s or less at 20 ° C.
- organic binder examples include celluloses such as methyl cellulose, carboxymethyl cellulose, and sodium carboxymethyl cellulose; alcohols such as polyvinyl alcohol; salts such as lignin sulfonate.
- the amount of the organic binder is usually 20 parts by weight or less, preferably 15 parts by weight or less, based on the total amount of the aluminum source, titanium source, magnesium source and silicon source, that is, 100 parts by weight of the inorganic compound source powder. More preferably, it is 6 parts by weight.
- the lower limit amount of the organic binder is usually 0.1 parts by weight, preferably 3 parts by weight.
- the green molded body can contain an organic additive other than the organic binder.
- organic additives are, for example, pore formers, lubricants and plasticizers, dispersants, and solvents.
- Examples of the pore former include carbon materials such as graphite; resins such as polyethylene, polypropylene, and polymethyl methacrylate; plant materials such as starch, nut shells, walnut shells, and corn; ice; and dry ice.
- the amount of pore-forming agent added is generally 0 to 40 parts by weight, preferably 0 to 100 parts by weight of the total amount of the aluminum source, titanium source, magnesium source and silicon source, that is, 100 parts by weight of the inorganic compound source powder. ⁇ 25 parts by weight.
- Lubricants and plasticizers include alcohols such as glycerin; higher fatty acids such as caprylic acid, lauric acid, palmitic acid, alginic acid, oleic acid and stearic acid; stearic acid metal salts such as Al stearate, polyoxyalkylene alkyl Examples include ether.
- the addition amount of the lubricant and the plasticizer is generally 0 to 10 parts by weight, preferably 100 parts by weight of the total amount of the aluminum source, the titanium source, the magnesium source and the silicon source, that is, 100 parts by weight of the inorganic compound source powder. Is 1 to 5 parts by weight.
- the dispersant examples include inorganic acids such as nitric acid, hydrochloric acid and sulfuric acid; organic acids such as oxalic acid, citric acid, acetic acid, malic acid and lactic acid; alcohols such as methanol, ethanol and propanol; ammonium polycarboxylate Surfactant etc. are mentioned.
- the addition amount of the dispersing agent is usually 0 to 20 parts by weight, preferably 2 to 20 parts by weight based on the total amount of the aluminum source, the titanium source, the magnesium source and the silicon source, that is, 100 parts by weight of the inorganic compound source powder. 8 parts by weight.
- the solvent for example, alcohols such as methanol, ethanol, butanol and propanol; glycols such as propylene glycol, polypropylene glycol and ethylene glycol; and water can be used. Of these, water is preferable, and ion-exchanged water is more preferably used from the viewpoint of few impurities.
- the amount of the solvent used is generally 10 parts by weight to 100 parts by weight, preferably 20 parts by weight with respect to the total amount of the aluminum source, the titanium source, the magnesium source and the silicon source, ie, 100 parts by weight of the inorganic compound source powder. ⁇ 80 parts by weight.
- the shape of the green molded body is not particularly limited, and can take any shape depending on the application.
- a so-called honeycomb shape that is, a shape having a large number of through holes extending in the same direction and a large number of flow paths formed by the large number of through holes separated by partition walls.
- a so-called honeycomb shape that is, a shape having a large number of through holes extending in the same direction and a large number of flow paths formed by the large number of through holes separated by partition walls.
- rod shape, tube shape, plate shape, crucible shape, etc. can be mentioned.
- a green molded object can be manufactured as follows, for example. First, an aluminum source powder, a titanium source powder, an inorganic compound source powder containing a magnesium source powder and a silicon source powder blended as necessary, an organic binder, a solvent, and an additive added as necessary Prepare. And these are mixed with a kneader etc. by the above-mentioned ratio, a raw material mixture is obtained, and the green molded object of a desired shape can be obtained by shape
- molding method is not specifically limited, For example, a uniaxial press machine, an extrusion molding machine, a tableting machine, a granulator etc. are mentioned.
- An aluminum titanate fired body can be obtained by calcining (degreasing) and firing the green molded body described above.
- the obtained aluminum titanate fired body is a fired body made of aluminum titanate crystals.
- Calcination is a process for removing the organic binder in the green molded body and the organic additive blended as necessary by burning, decomposition, etc., and typically reaches the firing temperature. Up to a temperature rising stage (for example, a temperature range of 150 to 900 ° C.). In the calcination (degreasing) step, it is preferable to suppress the temperature increase rate as much as possible.
- the firing temperature in firing the green molded body is usually 1300 ° C. or higher, preferably 1400 ° C. or higher.
- the firing temperature is usually 1650 ° C. or lower, preferably 1550 ° C. or lower.
- the rate of temperature increase up to the firing temperature is not particularly limited, but is usually 1 ° C./hour to 500 ° C./hour.
- Firing is usually performed in the atmosphere, but depending on the type and usage ratio of the raw material powder used, that is, aluminum source powder, titanium source powder, magnesium source powder and silicon source powder, an inert gas such as nitrogen gas or argon gas.
- the firing may be performed in a reducing gas such as carbon monoxide gas or hydrogen gas. Further, the firing may be performed in an atmosphere in which the water vapor partial pressure is lowered.
- Calcination is usually performed using a normal firing furnace such as a tubular electric furnace, a box-type electric furnace, a tunnel furnace, a far-infrared furnace, a microwave heating furnace, a shaft furnace, a reflection furnace, a rotary furnace, or a roller hearth furnace. Firing may be performed batchwise or continuously. Moreover, you may carry out by a stationary type and may carry out by a fluid type.
- a normal firing furnace such as a tubular electric furnace, a box-type electric furnace, a tunnel furnace, a far-infrared furnace, a microwave heating furnace, a shaft furnace, a reflection furnace, a rotary furnace, or a roller hearth furnace.
- Firing may be performed batchwise or continuously.
- you may carry out by a stationary type and may carry out by a fluid type.
- the time required for firing may be sufficient time for the green molded body to transition to the aluminum titanate crystal, and varies depending on the amount of the green molded body, the type of firing furnace, firing temperature, firing atmosphere, etc. 10 minutes to 24 hours.
- a desired aluminum titanate fired body can be obtained.
- Such an aluminum titanate fired body has a shape that substantially maintains the shape of the green molded body immediately after molding.
- the obtained aluminum titanate fired body can be processed into a desired shape by grinding or the like.
- the calcined aluminum titanate obtained by the above-mentioned method is, for example, a firing furnace jig such as a crucible, a setter, a bowl, a furnace material; an exhaust gas filter used for exhaust gas purification of an internal combustion engine such as a diesel engine or a gasoline engine; Ceramic filters such as selective permeation filters for selectively permeating gas components generated during petroleum refining, such as carbon monoxide, carbon dioxide, nitrogen, oxygen, etc. It can be suitably applied to electronic parts such as substrates and capacitors.
- the aluminum titanate fired body has a high pore volume and an open porosity, so that good filter performance can be maintained over a long period of time.
- the aluminum titanate fired body may contain a crystal pattern of alumina, titania or the like in addition to the crystal pattern of aluminum titanate or aluminum magnesium titanate.
- the aluminum titanate fired body is composed of aluminum magnesium titanate crystals, it can be represented by the composition formula: Al 2 (1-x) Mg x Ti (1 + x) O 5 , and the value of x is 0.03 or more Preferably, it is 0.03 or more and 0.15 or less, More preferably, it is 0.03 or more and 0.12 or less.
- the aluminum titanate fired body obtained by the present invention can contain trace components that are derived from the raw materials or are unavoidably included in the production process.
- (1) Shape retention of green molded body As shown to (a) of FIG. 1, the test piece 10 of the magnitude
- the vertical displacement X of the lower surface of the portion 10b on the other end side of the test piece 10 60 seconds after removing the support was measured.
- the vertical displacement X was measured at a position 25 mm away from the end surface 5 b of the horizontal surface 5 a of the pedestal 5.
- the displacement was measured for a total of three test pieces, and the average value was obtained.
- Viscosity of 2% by weight aqueous solution of organic binder The organic binder was dissolved in pure water so as to be 2% by weight, and the viscosity was measured under a condition of 20 ° C. using a B-type viscometer.
- Example 1 A green molded body was obtained using the following as the inorganic compound source powder.
- the charged composition of the inorganic compound source powder is the molar percentage in terms of alumina [Al 2 O 3 ], titania [TiO 2 ], magnesia [MgO] and silica [SiO 2 ], [Al 2 O 3 ] / [TiO 2 ].
- / [MgO] / [SiO 2 ] 35.1% / 51.3% / 9.6% / 4.0%.
- the content of the silicon source powder in the total amount of the aluminum source powder, the titanium source powder, the magnesium source powder and the silicon source powder was 4.0% by weight.
- Aluminum source powder ⁇ -alumina powder having an average particle diameter shown in Table 1 24.6 parts by weight
- Magnesium source powder 15.7 parts by weight of magnesia spinel powder having an average particle size shown in Table 1 (4) Silicon source powder Glass frit having an average particle size shown in Table 1 (“CK0832” manufactured by Takara Standard) 3.4 parts by weight
- the green molded body After the green molded body is quickly heated in a microwave dryer, it is dried by holding at 100 ° C. for 5 hours, and then subjected to firing including a calcination (degreasing) step of removing the binder in an air atmosphere. A porous sintered body of aluminum magnesium titanate was obtained. The maximum temperature during firing was 1450 ° C., and the holding time at the maximum temperature was 5 hours. The shrinkage rate at this time was 8.9%.
- Example 2 A green molded body and a porous fired body were obtained by performing the same operation as in Example 1 except that the amount of methyl cellulose (trade name: Metroles 90SH-30000) was changed from 3.9 parts by weight to 4.9 parts by weight. Obtained. The green molded body had a shape retention of 8.2 mm. Shrinkage during firing was 9.1%
- Example 3 A green molded body and a porous fired body were obtained in the same manner as in Example 1 except that the amount of methylcellulose (trade name: Metrolose 90SH-30000) was changed from 3.9 parts by weight to 5.9 parts by weight. Obtained. The green molded body had a shape retention of 8.7 mm. The shrinkage during firing was 9.6%.
- methylcellulose trade name: Metrolose 90SH-30000
- Example 4> Instead of 3.9 parts by weight of methylcellulose (trade name: Metrolose 90SH-30000) as the organic binder, methylcellulose (trade name: Meserose PMB-15UFF, the viscosity of a 2% by weight aqueous solution is 15000 mPa ⁇ s at 20 ° C.) Except for changing the amount of methylcellulose to 6.0 parts by weight, the same operation as in Example 1 was performed to obtain a green molded body and a porous fired body. The green molded body had a shape retention of 10.0 mm. The shrinkage rate during firing was 9.4%.
- methylcellulose trade name: Metrolose 90SH-30000
- Meserose PMB-15UFF the viscosity of a 2% by weight aqueous solution is 15000 mPa ⁇ s at 20 ° C.
- methylcellulose (trade name: Metrolose 90SH-30000) as an organic binder
- methylcellulose (trade name: Metrolose 60SH-4000, viscosity of 2% by weight aqueous solution is 4000 mPa ⁇ s at 20 ° C.) 7.8
- a green molded body and a porous fired body were obtained in the same manner as in Example 1 except that parts by weight were used.
- the green molded body had a shape retention of 18.7 mm.
- the shrinkage during firing was 12.0%.
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Abstract
Description
得られたグリーン成形体を150~900℃に加熱して有機バインダを除去する工程、及び
有機バインダが除去されたグリーン成形体を1300℃以上で焼成する工程を備え、
有機バインダは、有機バインダの2重量%水溶液の20℃での粘度が5000mPa・s以上となるものである、チタン酸アルミニウム焼成体の製造方法。
また、本発明のチタン酸アルミニウム焼成体の製造方法によれば、原料として2重量%水溶液とした時の粘度が5000mPa・s以上となる有機バインダを使用することにより保形性に優れる成形体が得られ、また寸法精度の高いチタン酸アルミニウム焼成体を効率的に製造することができる。
本発明のグリーン成形体は、無機化合物源粉末、及び、有機バインダを含む。
無機化合物源粉末は、アルミニウム源粉末、及び、チタニウム源粉末を含む。無機化合物源粉末は、さらに、マグネシウム源粉末及び/又はケイ素源粉末を含むことができる。
アルミニウム源は、チタン酸アルミニウム焼成体を構成するアルミニウム成分となる化合物である。アルミニウム源としては、たとえば、アルミナ(酸化アルミニウム)が挙げられる。アルミナの結晶型としては、γ型、δ型、θ型、α型などが挙げられ、不定形(アモルファス)であってもよい。なかでも、α型のアルミナが好ましく用いられる。
チタニウム源は、チタン酸アルミニウム焼成体を構成するチタン成分となる化合物であり、かかる化合物としては、たとえば酸化チタンが挙げられる。酸化チタンとしては、たとえば、酸化チタン(IV)、酸化チタン(III)、酸化チタン(II)などが挙げられ、なかでも酸化チタン(IV)が好ましく用いられる。酸化チタン(IV)の結晶型としては、アナターゼ型、ルチル型、ブルッカイト型などが挙げられ、不定形(アモルファス)であってもよい。より好ましくは、アナターゼ型、ルチル型の酸化チタン(IV)である。
グリーン成形体は、マグネシウム源粉末を含有していてもよい。グリーン成形体がマグネシウム源粉末を含む場合、得られるチタン酸アルミニウム焼成体は、チタン酸アルミニウムマグネシウム結晶からなる焼成体である。
グリーン成形体は、ケイ素源粉末をさらに含有していてもよい。ケイ素源は、シリコン成分となってチタン酸アルミニウム焼成体に含まれる化合物であり、ケイ素源の併用により、耐熱性がより向上されたチタン酸アルミニウム焼成体を得ることが可能となる。ケイ素源としては、たとえば、二酸化ケイ素、一酸化ケイ素などの酸化ケイ素(シリカ)が挙げられる。
グリーン成形体は、水溶性の有機バインダを含む。この有機バインダは、この有機バインダの2重量%水溶液の粘度が20℃で5000mPa・s以上、好ましくは10000mPa・s以上となる有機バインダである。水溶液の粘度は、例えば、BrookField型粘度計により測定することができる。この有機バインダは、この有機バインダの2重量%水溶液の粘度が20℃で50000mPa・s以下であることが好ましい。
グリーン成形体は、有機バインダ以外の有機添加物を含むことができる。その他の有機添加物は、例えば、造孔剤、潤滑剤および可塑剤、分散剤、溶媒である。
グリーン成形体の形状は特に限定されず、用途に応じて任意の形状を取ることができる。例えば、DPFフィルタ用のグリーン成形体の場合、いわゆるハニカム形状、すなわち、同一方向に延びる多数の貫通孔を有し、多数の貫通孔により形成される多数の流路が隔壁によって分離された形状であることが好ましい。また、棒状、チューブ状、板状、るつぼ形状等も挙げることができる。
グリーン成形体は例えば以下のようにして製造することができる。
まず、アルミニウム源粉末、チタニウム源粉末、及び、必要に応じて配合されるマグネシウム源粉末およびケイ素源粉末を含む無機化合物源粉末と、有機バインダと、溶媒と、必要に応じて添加される添加物を用意する。
そして、これらを上述の比率で混練機等により混合して原料混合物を得、得られた原料混合物を成形することにより、所望の形状のグリーン成形体を得ることができる。ここで、成形法は特に限定されず、例えば、一軸プレス機、押出成形機、打錠機、造粒機などが挙げられる。
上述のグリーン成形体を仮焼(脱脂)および焼成することにより、チタン酸アルミニウム焼成体を得ることができる。得られるチタン酸アルミニウム焼成体は、チタン酸アルミニウム結晶からなる焼成体である。成形してから焼成を行なうことにより、原料混合物を直接焼成する場合と比較して、焼成中の収縮を抑えることができ、得られるチタン酸アルミニウム焼成体の割れを効果的に抑制でき、また、焼成により生成した多孔質性のチタン酸アルミニウム結晶の細孔形状が維持されたチタン酸アルミニウム焼成体を得ることができる。
保形性、収縮率、及び粘度は下記方法により測定した。
脱脂および焼成前(押し出し成形後)のグリーン成形体と、脱脂および焼成後の焼成品の押し出し断面方向(成形体における押し出し方向とは垂直な方向の断面)の長さを、それぞれ2点測定し、それらの値を平均することに得られる焼成前の平均長さおよび焼成後の平均長さから、下記式に基づき収縮率を算出した。
収縮率(%)={1-(焼成後の平均長さ)/(焼成前の平均長さ)}×100
有機バインダを2重量%となるように純水に溶解し、その粘度をB型粘度計を用い、20℃の条件下で測定した。
無機化合物源粉末として以下のものを用いて、グリーン成形体を得た。無機化合物源粉末の仕込み組成は、アルミナ〔Al2O3〕、チタニア〔TiO2〕、マグネシア〔MgO〕およびシリカ〔SiO2〕換算のモル百分率で、〔Al2O3〕/〔TiO2〕/〔MgO〕/〔SiO2〕=35.1%/51.3%/9.6%/4.0%であった。アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末およびケイ素源粉末の合計量中のケイ素源粉末の含有率は、4.0重量%であった。(1)アルミニウム源粉末
表1に示される平均粒子径を有するα-アルミナ粉末 24.6重量部(2)チタニウム源粉末
表1に示される平均粒子径を有するルチル型チタニア粉末 42.0重量部(3)マグネシウム源粉末
表1に示される平均粒子径を有するマグネシアスピネル粉末 15.7重量部(4)ケイ素源粉末
表1に示される平均粒子径を有するガラスフリット(タカラスタンダード社製「CK0832」) 3.4重量部
メチルセルロース(商品名:メトローズ 90SH-30000)の量を3.9重量部から4.9重量部に変更した以外、実施例1と同様な操作を行って、グリーン成形体および多孔質な焼成体を得た。グリーン成形体は、保形性が8.2mmであった。焼成時の収縮率は9.1%であった
メチルセルロース(商品名:メトローズ 90SH-30000)の量を3.9重量部から5.9重量部に変更した以外、実施例1と同様な操作を行って、グリーン成形体および多孔質な焼成体を得た。グリーン成形体は、保形性が8.7mmであった。焼成時の収縮率は9.6%であった。
<実施例4>
有機バインダとして、メチルセルロース(商品名:メトローズ 90SH-30000)3.9重量部に代えて、メチルセルロース(商品名:メセロース PMB-15UFF、2重量%の水溶液の粘度が20℃で15000mPa・s)に代え、メチルセルロースの量を6.0重量部に変更した以外、実施例1と同様な操作を行って、グリーン成形体および多孔質な焼成体を得た。グリーン成形体は、保形性が10.0mmであった。焼成時の収縮率は9.4%であった。
有機バインダとしてメチルセルロース(商品名:メトローズ 90SH-30000)3.9重量部に代えて、メチルセルロース(商品名:メトローズ 60SH-4000、2重量%の水溶液の粘度が20℃で4000mPa・s)7.8重量部を使用した以外、実施例1と同様な操作を行って、グリーン成形体および多孔質焼成体を得た。グリーン成形体は、保形性が18.7mmであった。焼成時の収縮率は12.0%であった。
Claims (12)
- アルミニウム源粉末およびチタニウム源粉末を含む無機化合物源粉末と、有機バインダと、を含み、
前記有機バインダは、前記有機バインダの2重量%水溶液の20℃での粘度が5000mPa・s以上となるものであるグリーン成形体。 - 前記有機バインダの量は、無機化合物源粉末100重量部に対し0.1~20重量部である請求項1記載のグリーン成形体。
- 前記無機化合物源粉末は、さらにケイ素源粉末を含む請求項1又は2記載のグリーン成形体。
- 前記無機化合物源粉末は、さらにマグネシウム源粉末を含む請求項1~3のいずれか一項記載のグリーン成形体。
- Al2O3換算での前記アルミニウム源粉末とTiO2換算での前記チタニウム源粉末とのモル比は、35:65~45:55の範囲内である請求項1~4いずれか一項記載のグリーン成形体。
- ハニカム形状を有する請求項1~5のいずれか一項記載のグリーン成形体。
- アルミニウム源粉末およびチタニウム源粉末を含む無機化合物源粉末と、有機バインダと、を含む原料混合物を成形してグリーン成形体を得る工程、
前記グリーン成形体を150~900℃に加熱して前記有機バインダを除去する工程、及び
前記有機バインダが除去された前記グリーン成形体を1300℃以上で焼成する工程を備え、
前記有機バインダは、前記有機バインダの2重量%水溶液の20℃での粘度が5000mPa・s以上となるものである、チタン酸アルミニウム焼成体の製造方法。 - 前記有機バインダの量は、前記無機化合物源粉末100重量部に対し0.1~20重量部である請求項7記載の方法。
- 前記無機化合物源粉末は、さらにケイ素源粉末を含む請求項7又は8記載の方法。
- 前記無機化合物源粉末は、さらにマグネシウム源粉末を含む請求項7~9の何れか一項記載の方法。
- 前記原料混合物中における、Al2O3換算でのアルミニウム源粉末とTiO2換算でのチタニウム源粉末とのモル比は、35:65~45:55の範囲内である請求項7~10いずれか一項記載の方法。
- 前記成形体は、ハニカム形状を有する請求項7~11いずれか一項記載の方法。
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