In the accompanying drawings:
With reference to the accompanying drawings, a method for manufacturing a ceramic stack according to an embodiment of the present invention will now be described.
The present embodiment is an example where the method for manufacturing a ceramic stack has been applied to a method for manufacturing a gas sensing element which is incorporated into an air-fuel ratio sensor used for controlling air-fuel ratio of an engine of a vehicle, for example.
A brief explanation is provided first on a gas sensing element (ceramic stack) 1 fabricated in the present embodiment.
As shown in
As shown in
Also, as shown in
The heater layer 15 is provided, on its surface facing the duct layer 14, with a heater element 19 that generates heat with a supply of electric power, and a lead portion 191 for supplying electric power to the heater element 19. Further, a terminal portion 192 is provided to a surface, which is a rear face of the surface provided with the heater element 19 and the lead portion 191. The terminal portion 192 and the lead portion 191 are electrically conductive with each other through a conductor filled in a through hole 150.
The diffusion layer 12 has permeability to gases and is made of alumina ceramic having a porosity of 14.6±0.6%.
The sensor layer 13 is a solid electrolyte having oxygen ion conductivity and is made of dense zirconia ceramic having a porosity of 2% or less.
The duct layer 14 is made of dense alumina ceramic having a porosity of 2% or less.
The shield layer 11 and the heater layer 15 a substantially made of the same material as the duct layer 14.
Hereinafter is described a method for manufacturing the gas sensing element (ceramic stack) 1.
In fabricating the gas sensing element 1, sheet materials are provided first by mixing organic materials, such as binders, dispersants and plasticizers, into a ceramic material. The sheet materials are then each formed into the ceramic sheets 11 to 15 structuring the respective layers. Specifically, the present embodiment provides the shield sheet 11 that serves as a shield layer, the diffusion sheet 12 that serves as a diffusion layer, the sensor sheet 13 that serves as a sensor layer and the duct sheet 14 that serves as a duct layer.
These plural types of ceramic sheets 11 to 15 having different ceramic components and different porosities as required after baking are stacked and baked for integration to fabricate the gas sensing element 1.
In particular, as shown in
At sub-step S21, a relation is obtained between the organic-volume rates of the ceramic sheets 11 to 15 before baking and the baking shrinkages of the ceramic sheets 11 to 15 resulting from being baked at a predetermined temperature in the baking step.
At sub-step S22, the organic-volume rates of the ceramic sheets 11 to 15 are selected so that all the ceramic sheets 11 to 15 may have substantially the same baking shrinkage as desired, based on the relation between the organic-volume rates and the baking shrinkages, which has been obtained at sub-step S21.
At sub-step S41, the organic materials are mixed into a ceramic material on the basis of the organic-volume rates selected at sub-step S22 to provide sheet materials for the respective ceramic sheets 11 to 15. The sheet materials are then each formed into the ceramic sheets 11 to 15.
At sub-step S42, the ceramic sheets 11 to 15 are stacked and baked for integration to fabricate the ceramic stack 1.
More details are provided below.
Among the ceramic sheets 11 to 15 to be fabricated, the diffusion sheet 12, or a diffusion layer, is ensured to have an after-baking porosity that falls within the range of 14.6 0.6%.
To this end, as shown in
<Sub-Step S11 of Measuring Porosity>
A ceramic material is prepared for the diffusion sheet 12 whose after-baking porosity is to be adjusted.
At this sub-step, an alumina mixed powder (adjusted ceramic material) is used as the ceramic material for the diffusion sheet 12. The alumina mixed powder is obtained by mixing two types of alumina powders “a” and “b” (adjustment materials) having different particle sizes and tap densities. In the present embodiment, the alumina powder “a” has a mean particle diameter of 0.3 m and a tap density of 1.40 g/cc, and the alumina powder “b” has a mean particle diameter of 0.4 m and a tap density of 0.81 g/cc.
The present embodiment makes use of the two adjustment materials which are different both in the mean particle diameter and the tap density. However, the two adjustment materials may be different only in the mean particle diameter or in the tap density.
Then, various diffusion sheets 12 having organic materials by a volume rate of 50% are fabricated using the alumina mixed powders having different mixture ratios of alumina powders “a” and “b”. Then, porosities of these diffusion sheets 12 obtained after being baked in the baking step are measured. It should be appreciated that the organic-volume rates of the diffusion sheets 12 are optionally selected.
Thus, as shown in
<Sub-Step S12 of Selecting Mixture Ratio>
Subsequently, based on the relation between the mixture ratio and the after-baking porosity (see
As can be seen from
<Sub-Step S13 of Making Adjusted Ceramic Material>
Subsequently, based on the mixture ratio selected at step S12, the alumina powders “a” and “b” are mixed at the ratio of 2:8 to make an alumina mixed powder M12 (adjusted ceramic material).
It should be appreciated that, at a later step, this alumina mixed powder M12 made at this sub-step is used as the ceramic material for the diffusion sheet 12.
Then, as shown in
It should be appreciated that the shield sheet 11 and the heater sheet 15 are made of substantially the same ceramic material as the duct sheet 14. Step S2 of the present embodiment therefore is performed to match the baking shrinkage of the diffusion sheet 12, the sensor sheet 13 and the duct sheet 14.
<Sub-Step S21 of Measuring Shrinkage>
Ceramic materials for the ceramic sheets 12 to 14 are prepared first.
At this sub-step, the alumina mixed powder M12 made at sub-step S13 is used as the ceramic material for the diffusion sheet 12. A zirconia powder with yttria solid solution, for example, is used as the ceramic material for the sensor sheet 13. Also, an alumina powder “c” having small mean particle diameter and high tap density is used as the ceramic material for the duct sheet 14.
Using the ceramic materials mentioned above, various ceramic sheets having different organic-volume rates are made for each of the ceramic sheets 12 to 14. Baking shrinkage of each of these ceramic sheets 12 to 14 is measured on the condition that baking is performed at a predetermined temperature in the baking step. The baking temperature in the present embodiment is 1,460 C.
As shown in
<Sub-Step S22 of Selecting Organic-Volume Rate>
Subsequently, based on the relation between the organic-volume rate and the baking shrinkage (see
In the present embodiment, the diffusion sheet 12 having organic materials by a volume rate of 50%, which has been made using the alumina mixed powder M12, is used as a reference sheet, and the baking shrinkage of each of the sensor sheet 13 and the duct sheet 14 is adjusted to the reference sheet. The reason for using the diffusion sheet 12 as a reference sheet is that the after-baking porosity of the diffusion sheet 12 has previously been adjusted, and that the baking shrinkage of the sensor sheet 13 and the duct sheet 14 is adjusted to that of the diffusion sheet 12.
As can be seen from
Then, a step S3 of
It should be appreciated that, as at step S2 of adjusting baking shrinkage, step S3 of matching profiles is performed subjecting the diffusion sheet 12, the sensor sheet 13 and the duct sheet 14 (the shield and the heater sheets 11 and 15 are made of substantially the same ceramic material as the duct sheet 14). It should also be appreciated that the diffusion sheet 12 that has been made with the alumina mixed powder M12 and having organic materials by a volume rate of 50% is used as a reference sheet for matching the baking-shrinkage profiles of the sensor sheet 13 and the duct sheet 14.
<Sub-Step S31 of Measuring Profile for Every Time Period>
The ceramic materials for the sensor sheet 13 and the duct sheet 14 are prepared first.
At this sub-step, the ceramic material used for the sensor sheet 13 is a disintegrated zirconia powder (disintegrated ceramic powder) obtained by granulating zirconia powder using spray-drying technique, degreasing the granulated zirconia powder (granulated ceramic powder), followed by mixing a solvent, and disintegrating the resultant using a ball mill. The ceramic material used for the duct sheet 14 is a disintegrated alumina powder (disintegrated ceramic powder) obtained by granulating an alumina powder “c” using a spray-drying technique, degreasing the granulated alumina powder (granulated ceramic powder), followed by mixing a solvent, and disintegrating the resultant using a ball mill.
Subsequently, each of the granulated zirconia powder and the granulated alumina powder is disintegrated for various time periods. The various disintegrated zirconia and alumina powders obtained in this way using various disintegration time periods are formed into various sensor sheets 13 and duct sheets 14, respectively. In this case, the organic-volume rates of the sensor sheet 13 and the duct sheet 14 are ensured to be 38.5% and 39%, respectively, as selected at sub-step S22. Then, baking-shrinkage profiles are measured for the sensor sheets 13 and the duct sheets 14 on the condition that those sheets 13 and 14 are baked in the baking step.
Thus, as shown in
<Sub-Step S32 of Selecting Disintegration Time Period>
Then, based on the relations between the baking-shrinkage profiles and the disintegration time periods (see
As can be seen from
<Sub-Step S33 of Making Disintegrated Ceramic Material>
Subsequently, based on the disintegration time period selected at sub-step S32, the granulated zirconia powder obtained by granulating the zirconia powder is disintegrated for 24 hours to make a disintegrated zirconia powder M13 (disintegrated ceramic material). Similarly, based on the disintegration time period selected at sub-step S32, the granulated alumina powder obtained by granulating the alumina powder “c” is disintegrated for 8 hours to make a disintegrated alumina powder M14 (disintegrated ceramic material).
At a later step, these disintegrated zirconia powder M13 and disintegrated alumina powder M14 are used as the ceramic materials for the sensor sheet 13 and the duct sheet 14, respectively.
The next step is a step S4 of fabricating a ceramic stack 1. Step S4 includes a sub-step S41 of forming sheets and a sub-step S42 of baking.
<Sub-Step S41 of Forming Sheets>
The ceramic sheets 11 to 15 (see
As will be appreciated from the above description, in fabricating the diffusion sheet 12, the alumina mixed powder M12 is prepared by mixing the alumina powders “a” and “b” at a ratio of 2:8, and then organic materials, such as a binder, a dispersant and a plasticizer, are mixed into the alumina mixed powder M12 so that the organic-volume rate may be 50% as have been selected in advance. This diffusion sheet material is then formed into the diffusion sheet 12 by using the doctor-blade technique.
As will be appreciated from the above description, in fabricating the sensor sheet 13, the disintegrated zirconia powder M13 is prepared by granulating the zirconia powder and disintegrating the granulated zirconia powder for 24 hours, and then organic materials, such as a binder, a dispersant and a plasticizer, are mixed into the disintegrated zirconia powder M13 so that the organic-volume rate may be 38.5% as have been selected in advance. This sensor sheet material is then formed into the sensor sheet 13 by using the doctor blade technique.
As will be appreciated from the above description, in fabricating the duct sheet 14, the disintegrated alumina powder M14 is prepared by granulating the alumina powder “c” and disintegrating the granulated alumina powder for 8 hours, and then organic materials, such as a binder, a dispersant and a plasticizer, are mixed into the disintegrated alumina powder M14 so that the organic-volume rate may be 39% as have been selected in advance. This duct sheet material is then formed into the duct sheet 14 by using the doctor blade technique.
The shield sheet 11 and the heater sheet 15 are fabricated in the same manner as the duct sheet 14 by using the same materials as the duct sheet 14.
A plural number of duct sheets 14 are stacked and the groove portion 141 is formed therein, as shown in
Further, the heater sheet 15 is provided with the heater element 19, the lead portion 191 and the terminal portion 192. Then, the through hole 150 is formed and filled with a conductor.
<Sub-Step S42 of Baking>
As shown in
In this way, the gas sensing element (ceramic stack) 1 can be obtained, in which a plurality of ceramic layers are stacked in the order of the shield layer 11, the diffusion layer 12, the sensor layer 13, the duct layer 14 and the heater layer 15.
The advantageous effects of the method for manufacturing the ceramic stack 1 of the present embodiment are explained below.
In the manufacturing method according to the present embodiment, step S2 is performed to match the baking shrinkage of the ceramic sheets 11 to 15. Specifically, at sub-step S21 of measuring baking shrinkage, a relation between the organic-volume rates and the baking shrinkages after being baked is obtained for the ceramic sheets 11 to 15. More specifically, investigation is made as to how the baking shrinkage varies depending on the organic-volume rate of each of the ceramic sheets 11 to 15. Then, at sub-step S22, the organic-volume rate of each of the ceramic sheets 11 to 15 is selected based on the relation between the organic-volume rate and the baking shrinkage obtained at the previous sub-step, so that all of the ceramic sheets 11 to 15 may have substantially the same baking shrinkage as desired.
Thus, the ceramic sheets 11 to 15 obtained at sub-step S41 should have substantially been fabricated as having the same baking shrinkage. Accordingly, the plural types of ceramic sheets 11 to 15, when they are stacked and baked for integration at sub-step S42, may all exhibit substantially the same baking shrinkage. Thus, distortion, separation, cracking and the like of the ceramic sheets 11 to 15, which may result from baking, can be suppressed, and hence the ceramic stack 1 to be obtained may have high dimensional accuracy and high qualities.
In the present embodiment, the after-baking porosity of the diffusion sheet 12 is adjusted at step S1. Thus, a desired after-baking porosity can be determined for the diffusion sheet 12.
Further, the baking-shrinkage profile of each of the ceramic sheets 11 to 15 is adjusted at step S3. Accordingly, the baking-shrinkage profiles of all the ceramic sheets 11 to 15 can be more approximated. Thus, distortion, separation, cracking and the like of the ceramic sheets 11 to 15, which may result from baking, can be further suppressed, and hence the ceramic stack 1 to be obtained may have higher dimensional accuracy and higher qualities.
As described above, the granulated zirconia powder and the granulated alumina powder are made utilizing the spray-drying technique. Use of this spray-drying technique may facilitate the granulation of the zirconia powder and the alumina powder. Also, the spray-drying technique may enable adjustment of the degree of agglomeration of the zirconia powder and the alumina powder. As a result, more accurate adjustment may advantageously be ensured in the baking-shrinkage profiles of the ceramic sheets 11 to 15.
At sub-step S41, the sheet materials are formed into the ceramic sheets 11 to 15 using the doctor-blade technique. This may reduce such defect as voids in the after-baking ceramic sheets 11 to 15. Thus, the strength of the ceramic sheets 11 to 15 after baking can be enhanced, which may enhance the durability of the ceramic stack 1 to be obtained.
Advantageously, the difference between the maximum and minimum baking shrinkages is 1% or less in the plural types of ceramic sheets 11 to 15 baked for integration at sub-step S42. Thus, distortion, separation, cracking and the like of the ceramic sheets 11 to 15, which may result from baking, can be sufficiently suppressed, and hence the ceramic stack 1 to be obtained may have higher dimensional accuracy and higher qualities.
As mentioned above, the ceramic stack 1 can be applied to a gas sensing element. The excellent characteristics of the ceramic stack 1, i.e. dimensional accuracy and high qualities, may be prominently exerted in the application to such a gas sensing element. In particular, in light of the fact that the downsizing has increasingly advanced in gas sensors lately, and that the gas sensors have come to be used under higher-temperature circumstances, the gas sensors are now required to have higher dimensional accuracy and durability. The application of the high-quality ceramic stack 1 to a gas sensing element may realize downsizing of the gas sensor, and at the same time, may provide a gas sensor having excellent durability.
As described above, according to the method of manufacturing a ceramic stack of the present embodiment, distortion, separation, cracking and the like can be suppressed in stacking and baking for integration of the plural types of ceramic sheets.
In the above description, the plural types of ceramic sheets of the present embodiment have included a ceramic sheet whose after-baking porosity is to be adjusted. Further, all of the ceramic sheets in the present embodiment have been matched as to the baking shrinkage and the baking-shrinkage profile by performing various steps, as shown in
Alternatively, for example, where the plural types of ceramic sheets are to be matched as to the baking shrinkage alone, steps S2 and 54 alone may be performed as shown in
Also, as shown in
Further, as shown in
The present invention may be embodied in several other forms without departing from the spirit thereof. The embodiments and modifications described so far are therefore intended to be only illustrative and not restrictive, since the scope of the invention is defined by the appended claims rather than by the description preceding them. All changes that fall within the metes and bounds of the claims, or equivalents of such metes and bounds, are therefore intended to be embraced by the claims.
Number | Date | Country | Kind |
---|---|---|---|
2006-164238 | Jun 2006 | JP | national |