Patent Application
20050118097
1. Field of the Invention
The present invention relates to a gas permeable (hereinafter sometimes referred to as “porous”) alumina sintered body having communicating pores, and a method for producing the same. More particularly, it relates to a porous alumina sintered body in which characteristics of the communicating pores, such as pore diameter and porosity, are accurately controlled to desired ranges and which is suitably usable as various gas permeable industrial materials, e.g., electrode protective layers for measurement electrodes of gas sensors, filters of dust collectors, etc., and a method for efficient production of the alumina sintered body.
2. Description of the Prior Art
Porous alumina sintered bodies are suitably used as various gas permeable industrial materials, e.g., electrode protective layers for measurement electrodes of gas sensors, filters of dust collectors, etc. The gas sensors include, for example, oxygen sensors used for measuring oxygen concentration in exhaust gases of automobiles to detect the combustion state in the engines (JP-A-9-68515).
Recently, for the improvement of performance of automobiles, it is attempted not only to enhance performance of engines, but also to add various additives such as phosphorus, zinc, magnesium and calcium to engine oil or gasoline. However, if these additives mingle into exhaust gases, they stick to the surface of oxygen sensor to clog the communicating pores of the diffusion resistant layer or stick to the measuring electrode in a measuring chamber to deteriorate the electrode, resulting in reduction of output of the sensor or reduction of responsiveness. Moreover, the porous alumina sintered body is produced, for example, by coating and drying a slurry having a proper viscosity and thereafter sintering the coat, and there are caused considerable variations in pore diameter and porosity of the resulting alumina sintered body (electrode protective layer), and the gas output yield is not stabilized. Furthermore, since the gas to be measured must permeate the electrode protective layer and reach the electrode to output an electrical signal, the layer is required to have uniform porosity higher than a specific value, and, besides, in order to inhibit deterioration of the measuring electrode caused by the effect of the additives in the gas, the layer is required to have a uniform pore diameter smaller than a specific value. In other words, the electrode protective layer is required to have intermediate physical properties between those of porous body and dense body.
At present, there have not yet been obtained porous alumina bodies in which pore characteristics of the communicating pores, such as pore diameter and porosity, are accurately controlled to desired ranges.
The present invention has been accomplished in an attempt to solve the above problems, and the object of the present invention is to provide a porous alumina sintered body in which characteristics of the communicating pores, such as pore diameter and porosity, are accurately controlled to desired ranges and which are usable suitably as various gas permeable industrial materials, e.g., electrode protective layers for measuring electrodes of gas sensors, filters of dust collectors, etc., and a method for efficiently producing the alumina sintered body.
In the drawings, the reference numerals have the following meanings:
1 - - - The first alumina particles, 2 - - - The second alumina particles, 3 - - - Communicating pores, 4 - - - The third alumina particles, 5 - - - Composite material, 6 - - - Composite material bonding layer, 7 - - - Communicating pores, 8 - - - The fourth alumina particles, 9 - - - The fifth alumina particles, 10 - - - Alumina sintered body obtained by the first production method, 11 - - - Communicating pores, 20 - - - 30 Alumina sintered body obtained by the second production method, - - - Alumina sintered body obtained by the third production method.
As a result of an intensive research conducted by the inventors for attaining the above object, it has been found that variations in pore diameter and porosity are caused by instability of dispersion due to cohesion of aggregate and pore forming material during mixing, and adjustment and control of the degree of sintering properties (e.g., densification) at sintering are essential for accurate control of the characteristics such as pore diameter and porosity, and the above object can be attained by using in combination aggregate and pore forming material having uniform particle diameter and uniform shape, and furthermore by combining the aggregate and the pore forming material differing in degree of sintering properties. Thus, the present invention has been accomplished. That is, the present invention provides the following alumina sintered body and the following method for producing the same.
(1) A gas permeable alumina sintered body having a plurality of communicating pores which is obtained by sintering alumina particles as an aggregate in the presence of a pore forming material, said communicating pores having an average pore diameter of 400-1100 Å and a porosity of 4-16%.
(2) An alumina sintered body described in the above (1), wherein the pore distribution (distribution width of pore diameter) of the communicating pores is 300-1100 Å.
(3) A method for producing a gas permeable alumina sintered body having a plurality of communicating pores which comprises mixing first alumina particles having a particle diameter of 0.2-0.7 μm and a sphericity of 0.7-1.0 as an aggregate and second alumina particles having a particle diameter of 0.01-0.1 μm as a pore forming material to embed a plurality of the second alumina particles in the spaces between the first alumina particles, and sintering the mixture at a temperature of 1200-1400° C., thereby obtaining an alumina sintered body having the communicating pores of 400-1100 Å in average pore diameter and 4-16% in porosity.
(4) A method for producing an alumina sintered body as described in the above (3), wherein the pore distribution (distribution width of pore diameter) of the alumina sintered body obtained is 300-1100 Å.
(5) A method for producing an alumina sintered body as described in the above (4), wherein the second alumina particles are mixed in an amount of 0.2-1.5% by mass based on the first alumina particles.
(6) A method for producing a gas permeable alumina sintered body having a plurality of communicating pores which comprises sintering third alumina particles having a particle diameter of 0.2-0.7 μm and a sphericity of 0.7-1.0 as an aggregate at a temperature of 1200-1400° C. in the presence of a composite material containing silicon dioxide (SiO2) and magnesium oxide (MgO) as a pore forming material to bond the third alumina particles to each other through a layer of the composite material, thereby obtaining an alumina sintered body having the communicating pores of 400-1100 Å in average pore diameter and 4-16% in porosity.
(7) A method for producing an alumina sintered body as described in the above (6), wherein the composite material is mixed in an amount of 0.02-2% by mass based on the third alumina particles.
(8) A method for producing an alumina sintered body as described in the above (6) or (7), wherein the pore distribution (distribution width of pore diameter) of the alumina sintered body obtained is 300-1100 Å.
(9) A method for producing a gas permeable alumina sintered body having a plurality of communicating pores which comprises mixing fourth alumina particles having a particle diameter of 0.3-1.0 μm and a sphericity of 0.7-1.0 as an aggregate and fifth alumina particles having a particle diameter of 0.2-0.8 μm as a pore forming material to insert the fifth alumina particles into the spaces between the fourth alumina particles and sintering the mixture at a temperature of 1200-1400° C., thereby obtaining an alumina sintered body having the communicating pores of 400-1100 Å in average pore diameter and 4-16% in porosity.
(10) A method for producing an alumina sintered body as described in the above (9), wherein the pore distribution (distribution width of pore diameter) of the alumina sintered body obtained is 300-1100 Å.
(11) A method for producing an alumina sintered body as described in the above (9) or (10), wherein the fifth alumina particles are mixed in an amount of 50-95% by mass based on the fourth alumina particles.
According to the present invention, there are provided a porous alumina sintered body in which characteristics of the communicating pores, such as pore diameter and porosity, are accurately controlled to desired ranges and which is suitably usable as various gas permeable industrial materials, e.g., electrode protective layers for measurement electrodes of gas sensors, filters of dust collectors, etc., and a method for efficient production of the said alumina sintered body.
Embodiments of the alumina sintered body and the method for producing the same according to the present invention will be explained in detail below referring to the drawings.
The embodiment of the alumina sintered body of the present invention is a gas permeable alumina sintered body having a plurality of communicating pores which is obtained by sintering alumina particles as an aggregate in the presence of a pore forming material, characterized in that the average particle diameter of the communicating pores is 400-1100 Å, preferably 500-900 Å, and the porosity thereof is 4-16%, preferably 9-14%. If the pore diameter is outside the range of 400-1100 Å, when the alumina sintered body is used, for example, as an electrode protective layer for a measurement electrode of a gas sensor, endurance of the layer is deteriorated due to the influence of gasoline additives mingled into exhaust gas and gas output reduction rate (%) increases. If the porosity is outside the range of 4-16%, when the alumina sintered body is used, for example, as an electrode protective layer, inflow rate of the gas into the measurement electrode varies to result in unstable yield of gas output.
In this embodiment, the pore distribution (distribution width of pore diameter) of the communicating pores is preferably 300-1100 Å, more preferably 500-900 Å. If the pore distribution is more than 1100 Å, the gas output reduction rate (%) increases and, furthermore, the yield of gas output sometimes becomes unstable.
The alumina particles, pore forming material and sintering method will be explained with reference to the method for production of alumina sintered body stated hereinafter.
The shape of the alumina sintered body of this embodiment is not particularly limited, and it may be in the form of, for example, a film or layer of 15-100 μm in thickness, a block, or the like.
Next, the method for producing the alumina sintered body according to the present invention (the first to third production methods) will be explained. The term “sphericity” is shown by r1/r2 in which r1 is a minor diameter of an ellipse and r2 is a major diameter of an ellipse. When “r1/r2” is 1, it means the true sphere. This definition will be applied hereinafter.
As shown in
If the particle diameter of the first alumina particles 1 is outside the range of 0.2-0.7 μm, and the sphericity is outside the range of 0.7-1.0, cohesiveness of the first alumina particles 1 increases or the sintering becomes insufficient, resulting in variation in pore diameter and porosity of the alumina sintered body 10 obtained by the sintering.
If the particle diameter of the second alumina particles 2 is outside the range of 0.01-0.1 μm, the sintering degree of the second alumina particles 2 at the time of sintering is outside the preferred range, resulting in variation in pore diameter and porosity of the alumina sintered body 10 obtained by the sintering. In this sense, the sphericity of the second alumina particles 2 is also preferably 0.7-1.0, more preferably 0.8-1.0. Furthermore, if the sintering temperature is outside the range of 1200-1400° C., the sintering becomes insufficient or excessive, and the necessary pore characteristics cannot be obtained.
In the present invention, the pore distribution (distribution width of pore diameter) is preferably 300-1100 Å, more preferably 500-1100 Å. If the pore distribution is outside this range, there occur deterioration in function to trap contaminants (gasoline additives, etc.) and reduction in gas permeability.
The first alumina particles 1 and the second alumina particles 2 are not particularly limited so long as they have the particle diameter and sphericity in the above ranges and have uniform particle diameter and uniform shape, and examples of the alumina particles are α-alumina, γ-alumina, and the like.
As a specific method for mixing the first alumina particles 1 and the second alumina particles 2 to embed a plurality of the second alumina particles 2 in the spaces between the first alumina particles 1, mention may be made of, for example, a method of coating a slurry prepared by dispersing the mixed alumina in an organic binder solution or a method of compacting the mixed alumina. In this case, the mixing ratio of the first alumina particles 1 and the second alumina particles is such that the second alumina particles 2 are mixed in an amount of preferably 0.2-1.5% by mass, more preferably 0.3-1.0% by mass based on the first alumina particles 1.
The sintering method is not particularly limited, and there is a method of, for example, heating the formed film or particle compact in an atmosphere.
In the present invention, the particle diameter, sphericity, pore diameter, porosity and pore distribution (distribution width of pore diameter) can be measured as mentioned below.
Particle diameter (by using a laser diffraction type particle size distribution measuring apparatus).
Sphericity (by measuring major diameter and minor diameter of particles by SEM).
Average particle diameter (by using a mercury penetration type pore distribution measuring apparatus).
Porosity (by using a mercury penetration type pore distribution measuring apparatus).
Pore distribution (distribution width of particle diameter) (by using a mercury penetration type pore distribution measuring apparatus).
As shown in
If the particle diameter of the third alumina particles 4 is outside the range of 0.2-0.7 μm, and the sphericity is outside the range of 0.7-1.0, cohesiveness of the third alumina particles 4 increases or the sintering degree becomes insufficient, resulting in variation in pore diameter and porosity of the alumina sintered body 20 obtained by the sintering.
The composite material 5 is not particularly limited so long as it contains silicon dioxide (SiO2) and magnesium oxide (MgO), and as examples, mention may be made of SiO2+MgO+CaO and SiO2+MgO+BaO. The composite material 5 is mixed in an amount of preferably 0.02-2% by mass, more preferably 0.05-1% by mass based on the third alumina particles 4.
In the second invention, the pore distribution (distribution width of pore diameter) of the alumina sintered body 20 obtained is preferably 400-1100 Å, more preferably 500-900 Å. If the pore distribution is outside this range, there occur deterioration in function to trap contaminants (gasoline additives, etc.) and reduction in gas permeability.
The third alumina particles 4 are not particularly limited so long as they have the particle diameter and sphericity in the above ranges and have uniform particle diameter and uniform shape, and examples of the alumina particles are α-alumina, γ-alumina, and the like.
As a specific method for mixing the third alumina particles 4 with the composite material 5 and bonding the third alumina particles 4 to each other through a layer of the composite material 5 (composite material bonding layer 6), mention may be made of, for example, a method of coating a slurry prepared by dispersing the mixture of the alumina and the composite material component in an organic binder solution or a method of compacting the mixture of the alumina and the composite material component.
The sintering method is not particularly limited, and there is a method of, for example, heating the coated film or particle compact in the atmosphere.
In the second production method, the particle diameter, sphericity, pore diameter, porosity and pore distribution (distribution width of pore diameter) can be measured in the same manner as in the first production method (interparticle embedding method).
As shown in
If the particle diameter of the fourth alumina particles 8 is outside the range of 0.3-1.0 μm, and the sphericity is outside the range of 0.7-1.0, cohesiveness of the fourth alumina particles 8 increases or the sintering degree becomes insufficient, resulting in variation in pore diameter and porosity of the alumina sintered body 30 obtained by the sintering.
If the particle diameter of the fifth alumina particles 9 is outside the range of 0.2-0.8 μm, the sintering degree of the fifth alumina particles 9 at the time of sintering is outside the preferred range, resulting in variation in pore diameter and porosity of the alumina sintered body 30 obtained by the sintering. In this sense, the sphericity of the fifth alumina particles 9 is also preferably 0.7-1.0, more preferably 0.8-1.0. Furthermore, if the sintering temperature is outside the range of 1200-1400° C., the sintering becomes insufficient or excessive, and the necessary pore characteristics cannot be obtained.
In the third invention, the pore distribution (distribution width of pore diameter) of the alumina sintered body 30 obtained is preferably 400-1100 Å, more preferably 500-900 Å. If the pore distribution is outside this range, there occur deterioration in function to trap contaminants (gasoline additives, etc.) and reduction in gas permeability.
The fourth alumina particles 8 and the fifth alumina particles 9 are not particularly limited so long as they have the particle diameter and sphericity in the above ranges and have uniform particle diameter and uniform shape, and examples of the alumina particles are α-alumina, γ-alumina, and the like.
As a specific method for mixing the fourth alumina particles 8 and the fifth alumina particles 9 to insert the fifth alumina particles 9 in the spaces between the fourth alumina particles 8, mention may be made of, for example, a method of coating a slurry prepared by dispersing the mixed alumina in an organic binder solution or a method of compacting the mixed alumina. In this case, the mixing ratio of the fourth alumina particles 8 and the fifth alumina particles 9 is such that the fifth alumina particles 9 are mixed in an amount of preferably 50-95% by mass, more preferably 50-90% by mass based on the fourth alumina particles 8.
The sintering method is not particularly limited, and there is a method of, for example, heating the coated film or particle compact in the atmosphere.
In the third production method, the particle diameter, sphericity, pore diameter, porosity and pore distribution (distribution width of pore diameter) can be measured in the same manner as in the first production method (interparticle embedding method).
The difference between the first production method (interparticle embedding method) and the third production method (aggregate blending method) resides in the size of the alumina particles 2 and that of the alumina particles 9.
The present invention will be explained specifically in the following examples, which should not be construed as limiting the invention in any manner.
Example of the first production method:
To a raw material powder comprising the first alumina particles 1 was added a slurry containing a dispersion medium (e.g., ethanol), a dispersant and the second alumina particles 2, followed by premixing them. Then, to the mixture was added a solution (hereinafter referred to as “organic binder solution”) prepared by previously dissolving an organic binder (e.g., ethyl cellulose) and a plasticizer in a solvent (e.g., terpineol), followed by further mixing them, and a paste obtained by adjusting the viscosity of the mixture by removing the dispersion medium and further adding the solvent was formed into a film by coating or printing, followed by sintering the film.
Example of the second production method:
To a raw material powder comprising the third alumina particles 4 were added a dispersion medium (e.g., ethanol), a dispersant, a source of SiO2 (e.g., silica sol) and a source of MgO (e.g., magnesium acetate), and thereafter the same subsequent procedures as in the above first production method were carried out to obtain a sintered body.
Example of the third production method:
To a mixture of a raw material powder comprising the fourth alumina particles 8 and a raw material powder comprising the fifth alumina particles 9 were added a dispersion medium (e.g., ethanol) and a dispersant, and thereafter the same subsequent procedures as in the above first production method were carried out to obtain a sintered body.
Comparative example of a conventional production method:
To a mixture of a raw material powder comprising conventional alumina particles and an aluminum salt (e.g., aluminum hydroxide) were added a dispersion medium (e.g., ethanol) and a dispersant, and thereafter the same subsequent procedures as in the above first production method were carried out to obtain a sintered body.
(Evaluation)
Table 1 shows particle diameter, shape, mixing ratio and sintering temperature of the materials (aggregate and pore forming material) used in Examples 1-3 and Comparative Example 1, and pore diameter, porosity and pore distribution (distribution width of pore diameter) of the alumina sintered bodies obtained in Examples 1-3 and Comparative Example 1. As shown in Table 1, the pore diameter, porosity and pore distribution (distribution width of pore diameter) of the alumina sintered bodies obtained in Examples 1-3 were more accurately controlled than those of the alumina sintered body obtained in Comparative Example 1.
A paste which forms a pump electrode was printed on the upper surface of a zirconia (solid electrolyte) sheet S1, and a paste which forms a pump electrode and an auxiliary pump electrode was printed on the under surface of the sheet S1.
Furthermore, a paste which forms a measurement electrode was printed on the upper surface of a zirconia (solid electrolyte) sheet S3, followed by printing the pastes obtained in Example 1 and Comparative Example 1.
Then, a punched zirconia (solid electrolyte) sheet S2 interposed between the zirconia (solid electrolyte) sheet S1 and the zirconia (solid electrolyte) sheet S3 which were subjected to the printing to form a space between the sheets S1 and S3, and the resulting laminate was subjected to cutting and sintering. In this case, an organic paste (binder solution) was coated on a part of the sheet S2 and dried, and thereafter the organic paste was removed at the sintering step, thereby to form gas passages between the sheet S1 and the sheet S2 and between the sheet S2 and the sheet S3.
The alumina sintered body of the present invention can be suitably utilized as various gas permeable industrial materials, e.g., electrode protective layers for measurement electrodes of gas sensors, filters of dust collectors, etc.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-398206 | Nov 2003 | JP | national |
