The present invention relates to a method of producing a honeycomb segment bonded article where a plurality of honeycomb segments are unitarily bonded by means of a bonding material layer.
A honeycomb structure is in heavy usage as a trapping filter for exhaust gas for environmental improvement, pollution prevention, and the like. At present, for example, an SiC DPF (diesel particulate filter) is produced by unitarily bonding a divided substrate (honeycomb segments) by means of a bonding material (ceramic cement) in order to inhibit a breakage due to a thermal shock (see, e.g., Patent Document 1). However, it has a problem of causing a breakage in a spot having low properties upon a heat resistant test because there is caused a difference in a texture of the bonding material layer after drying to generate a variance in properties.
Patent Document 1: JP-A-2003-10616
It is generally ideal that the bonding material is equally dried in all bonded spots in the bonded article. However, in a general production method, in the case of the bonded article obtained by bonding 12 pieces or more of the substrate (honeycomb segments), the bonding material on the outside is dried earlier to be solidified, before the bonding material on the inside is dried. Therefore, the drying manner is different between the bonding material on the outside and the bonding material on the inside, and the behavior of drying shrinkage and hardening of the bonding material according to the drying manner differs. Since, in the bonding material on the outside, which is dried and solidified first, the substrate is solidified with moving relatively uniformly according to the drying shrinkage and hardening of the bonding material, a variance in a texture of the bonding material layer is small, and the property variance is small. In contrast, since, in the bonding material on the inside, movement of the honeycomb segments according to the drying shrinkage and the hardening of the bonding material is not uniform, there arise a variance in the formation manner and a variance also in properties.
For example, a honeycomb segment hardens with moving in the direction where the bonding gap becomes small according to the shrinkage of the bonding material in a certain spot, while a honeycomb segment hardens without moving enough to match the shrinkage of the bonding material because one side of the honeycomb segment is already hardened in another spot. Alternatively, a honeycomb segment moves in the direction where the bonding gap is increased on the contrary to cause a variance in a texture of the bonding material layer, which leads to a variance in properties. Use of a bonding layer containing no inorganic fibers has been increasing from the viewpoint of health problems and the like. However, particularly, in the case of bonding with a bonding material, a variance in a texture of the bonding material layer is easily caused, and a variance in properties thereof is easily caused. Therefore, the thermal shock property deteriorates. In addition, in the case of producing a large-sized honeycomb structure, the drying manner is different between the bonding material on the outside and the bonding material on the inside of the bonded article. Therefore, since a variance in a texture of the bonding material layer is easily caused, and a variance in properties is easily caused, there is the case that the thermal shock property deteriorates.
The present invention aims to provide a method of producing a honeycomb segment bonded article, the method inhibiting decrease in strength properties due to a variance in a texture of the bonding material layer among a plurality of honeycomb segments unitarily bonded together by means of the bonding material layer formed of the bonding material.
The present inventors have found out that the above problem can be solved by unitarily bonding preliminary blocks together or honeycomb segments with a preliminary block after producing the preliminary block by bonding honeycomb segments. That is, according to the present invention, the following method of producing a honeycomb segment banded article is provided.
[1] A method of producing a honeycomb segment bonded article, the method comprising:
producing a preliminary block by unitarily bonding a plurality of honeycomb segments having a plurality of cells being partitioned by partition walls and passing through in the axial direction with a bonding material at a bonding face of each of the honeycomb segments and drying the honeycomb segments, and
integrally bonding the preliminary blocks together or honeycomb segments of one layer on an outer peripheral face of the preliminary block.
[2] The method of producing a honeycomb segment bonded article according to the above [1], wherein, in the preliminary block, the honeycomb segments are arranged in 5 rows or less along each of a first side and a second side perpendicular to the first side in a cross section in an axial direction to form an arrangement of 5 rows or less times 5 rows or less.
[3] The method of producing a honeycomb segment bonded article according to the above [1] or [2], wherein, in the preliminary block, no or one honeycomb segment is surrounded by the bonding layer formed of the bonding material at all outer peripheral walls.
[4] The method of producing a honeycomb segment bonded article according to any one of the above [1] to [3], wherein, in the preliminary block, the honeycomb segments are arranged in 2 rows or less on the first side and 2 rows or more on the second side perpendicular to the first side in a cross section in the axial direction.
[5] The method of producing a honeycomb segment bonded article according to any one of the above [1] to [3], wherein, in the preliminary block, the honeycomb segments are arranged in 3 rows on the first side and 3 rows on the second side perpendicular to the first side in a cross section in the axial direction to form an arrangement of 3 rows times 3 rows.
[6] The method of producing a honeycomb segment bonded article according to any one of the above [1] to [5], wherein, after the preliminary block is produced, the preliminary blocks are bonded together or the honeycomb segments are bonded in one layer on the outer peripheral face of the preliminary block, followed by drying, and the preliminary block or the honeycomb segment is further bonded.
[7] The method of producing a honeycomb segment bonded article according to any one of the above [1] to [6], wherein, in the honeycomb segment bonded article, the same number of the honeycomb segments are arranged on the first side and the second side perpendicular to the first side in a cross section in the axial direction.
After drying and solidifying at least one preliminary block bonded article previously produced before the whole is integrated, the preliminary blocks are bonded together or honeycomb segments are bonded on the outer peripheral face of the preliminary block, and they are dried for integration. This enables to obtain a structure capable of equally moving the honeycomb segments or the preliminary blocks in accordance with drying shrinkage and hardening of the bonding material, reducing a variance (unevenness) in the manner of formation of the bonding material layer, and reducing a variance in properties.
1: honeycomb segment bonded article, 2: partition wall, 3: cell, 5: bonding material layer, 7: outer peripheral wall, 8: end face, 10: honeycomb segment, 11: test piece, 13: small block, 14: medium-sized block, 20: vertical backing plate, 21: horizontal backing plate
Hereinbelow, an embodiment of the present invention will be described with referring to drawings. The present invention is by no means limited to the following embodiment, and changes, modifications, and improvements may be made as long as they do not deviate from the scope of the invention.
After hot air drying (S4), small blocks 13 are integrally bonded together or honeycomb segments 10 of one layer are integrally bonded to an outer peripheral face of the small block 13 to obtain a honeycomb segment bonded article 1 (S5). In addition, a plurality of small blocks or medium-sized blocks may unitarily be bonded together, or honeycomb segments of one layer may unitarily be bonded to the outer peripheral face of a small block or a medium-sized block to form a preliminary block. Incidentally, in the case of producing a larger honeycomb segment bonded article 1, a small block 13, a medium-sized block 14, or a honeycomb segment 10 is further bonded to form a final shape. That is, a preliminary block having 5 rows or less×5 rows or less is produced, and a honeycomb segment bonded article 1 is obtained using the preliminary block. Then, after the honeycomb segment bonded article 1 having the final shape is subjected to hot air drying (S6), calcination (S7) is performed. In the case that the bonding material is protruded upon production of the small block or the medium-sized block, it is preferable to apply a masking tape on the outer peripheral face of the honeycomb segment to inhibit adherence of the bonding material or to scrape the bonding material. In addition, it is preferable to perform hot air drying after leaving to stand at room temperature for a certain period of time before hot air drying after bonding to the small block or the medium-sized block, or after bonding into the final shape. Each of the production steps will be described with referring to
Further, in the case of using a honeycomb segment bonded article 1 of the present invention as a filter, it is preferable that a part of cells 3 are plugged at the end faces 8 of the honeycomb segment 10. In particular, it is preferable that adjacent cells 3 are alternately plugged in the mutually opposite end faces 8 in such a manner that the end faces 8 are plugged in a checkerwise pattern. By such plugging, for example, a fluid to be treated flowing into the segment from one end face 8 passes through the partition walls 2, and flows out from the other end face 84. When the fluid to be treated passes through the partition walls 2, the partition walls 2 function as a filter, and target substances can be removed.
In the present invention, it is preferable that the honeycomb segment 10 is made of at least one kind selected from the group consisting of cordierite, mullite, alumina, aluminum titanate, lithium aluminum silicate, silicon carbide, silicon nitride, and silicon carbide-metal silicon composite phase from the viewpoint of strength, heat resistance, and the like. However, in the case of using a honeycomb segment bonded article 1 of the present invention for a DPF, silicon carbide or silicon-silicon carbide based composite phase is preferably used from the viewpoint of high thermal resistance. In addition, cordierite is preferably used from the viewpoint of low thermal expansion coefficient and good thermal shock resistance. In addition, in the present invention, in the case that the honeycomb segment bonded article 1 is made from metal silicon (Si) and silicon carbide (SiC), when the Si content defined by Si/(Si+SiC) of the honeycomb segment bonded article 1 is too small, strength is low because an effect of adding Si cannot be obtained. When the content is above 50 mass %, effects in thermal resistance and high thermal conductivity, which are the characteristics of SiC, cannot be obtained. The Si content is preferably 5 to 50 mass %, more preferably 10 to 40 mass %.
To the above raw material are added a binder such as methyl cellulose and hydroxypropoxylmethyl cellulose, an organic pore former, a surfactant, and water to prepare kneaded clay having plasticity, and the kneaded clay is subjected to, for example, extrusion forming to form a quadrangular prism honeycomb formed article having a large number of cells 3 partitioned by partition walls 2 and extending through in the axial direction. After the honeycomb formed article is subjected to drying by, for example, microwaves and hot air, it is calcined to remove the binder and the organic pore former and then fired to produce the honeycomb segment 10.
In addition, it is preferable that the plugging portions in the case that the cells 3 are plugged in the end faces 8 contain as the main crystal phase at least one kind of a crystal phase selected from the aforementioned substances mentioned as suitable substances for the main crystal phase of the partition walls 2, and it is further preferable that a crystal phase similar to the main crystal phase of the honeycomb segment bonded article 1 is contained as the main crystal phase.
Specifically, as shown in
The bonding material of the bonding material layer 5 produced in S2 of
Next, as shown in
As described above, four honeycomb segments 10 of 2 rows×2 rows are bonded together by means of the bonding material layer 5 to form the small block 13. After the small block 13 is subjected to hot air drying (
As shown in the step 1 of
Further, as shown in the step 1 of
As shown in the step 1 of
In addition, as shown in the step 1 of
As shown in the step 1 of
As shown in the step 1 of
As shown in the step 1 of
Alternatively, as shown in
As shown in the step 1 of
As in the step 1 of
In the case of the bonding material containing fibrous particles such as ceramic fibers having little influence of drying, as shown in the step 2 of
As shown in the step 1 of
In the case of bonding material containing fibrous particles such as ceramic fibers having little influence of drying, as shown in the step 2 of
As shown in the step 1 of
As show in the step 1 of
In the case of a bonding material containing fibrous particles such as ceramic fibers having little influence of drying, the small block 13 of 4 rows×2 rows and the medium-sized block 14 of 4 rows×4 rows as shown in the stop 2 of
As shown in the step 1 of
In the case of a bonding material containing fibrous particles such as ceramic fibers having little influence of drying, the small block 13 of 4 rows×2 rows and the medium-sized block 14 of 4 rows×4 rows as shown in the step 2 of
Next, a method of producing a honeycomb bonded article of 9 rows×9 rows will be described. As shown in the step 1 of
Next, a method for producing a honeycomb bonded article of 10 rows×10 rows will be described. As shown in the step 1 of
In the case of a bonding material containing fibrous particles such as ceramic fibers having little influence of drying, the medium-sized block 14 of 4 rows×4 rows as shown in the step 2 of
As shown in the step 1 of
As described above, upon producing a honeycomb segment bonded article 1, by previously producing a small block 13 as a preliminary block having no or one or less honeycomb segment 10 surrounded by the bonding material layer 5 formed by a bonding material at the whole outer peripheral walls and unitarily bonding the small blocks 13 together or honeycomb segments 10 of one layer on the outer peripheral faces of the small block 13, a honeycomb segment bonded article 1 having improved thermal shock resistance can be produced. The small block 13 has one or less honeycomb segment 10 surrounded by the bonding material layer 5 formed by a bonding material. If there are two or more honeycomb segments 10 surrounded by the bonding material layer 5 at the whole outer peripheral walls as shown in
As described above, honeycomb segments 10 are bonded to produce a small block 13 (
In addition, in the case of a bonding material containing fibrous particles such as ceramic fibers having little influence of drying, the medium-sized block 14 of 4 rows×4 rows may directly be produced. Since the medium-sized block in this case have two or more honeycomb segments 10 surrounded by the bonding material layer at the whole outer peripheral faces like a honeycomb structure produced by a conventional production method, a variance in bonding strength is prone to be caused in a position surrounded by four honeycomb segments 10 in a cross section of the bonding material layer 5 upon drying. Therefore, when a honeycomb structure is produced by the use of such a medium-sized block, an effect in inhibiting unevenness of the bonding material layer 5 is decreased, and an effect in improving thermal shock resistance is reduced. However, since the step of producing a small block can be omitted to reduce the number of steps, a honeycomb structure can be produced at low costs. Therefore, in the case of a bonding material containing fibrous particles such as ceramic fibers having little influence of drying, it is also possible to select a production method where the step of producing small blocks is omitted depending on which of the variance in bonding strength and the production cost is emphasized from use environment and the like of the honeycomb structure.
Then, the outer periphery of the dried honeycomb segment bonded article 1 is ground into a cylindrical shape, and a coating material is applied on the outer peripheral face. Then, a thermal treatment is performed at about 700° C. for about 2 hours to obtain a honeycomb structure.
Hereinbelow, the present invention will be described in more detail on the basis of Examples. However, the present invention is by no means limited to the Examples.
(Production of Honeycomb Segment)
As raw materials for the honeycomb segment, an SiC powder and a metal Si powder were mixed together at a mass ratio of 80:20, and to the mixture were added a pore former an organic binder, a surfactant, and water to produce kneaded clay having plasticity. The kneaded clay was subjected to extrusion forming and drying to obtain a ceramic formed article having a partition wall thickness of 310 μm, a cell density of about 46.5 cells/cm2 (300 cells/in2), a cross section of a regular tetragon having a side of 35 mm, and a length of 178 mm. In the ceramic formed article, both the end faces were subjected to plugging in such a manner that the end faces show checkerwise patterns. That is, the plugging was performed in such a manner that adjacent cells were plugged in the mutually opposite end portions. As the plugging material, a material similar to the honeycomb segment raw material war used. After plugging both the end faces of the cells and dried, degreasing was performed at about 400° C. in an ambient atmosphere. Then, firing was performed at about 1450° C. in an Ar inert atmosphere to obtain a honeycomb segment where SiC crystal particles were bonded with Si.
(Preparation of Bonding Material)
Water was further mixed with a mixture of 41 mass % of SiC fine particles, 16.5 mass %, of SiC coarse particles, 22 mass % of mica, 20 mass % of colloidal silica, 0.5 mass % of bentonite, 1.5 mass % of an organic pore former (additional compounding based on 100 mass % of total main components of SiC, SiC coarse particles, mica, colloidal silica and bentonite), 0.4 mass % of an organic binder (additional compounding based on 100 mass % of total main components of SiC, SiC coarse particles, mica, colloidal silica and bentonite), and 0.04 mass % of a dispersant (additional compounding based on 100 mass % of total main components of SiC, Sic coarse particles, mica, colloidal silica and bentonite) as the bonding material 13, and kneading was performed for 30 minutes by a mixer to obtain a pasty bonding material. At this time, the amount of water added was adjusted in such a manner that the paste had a viscosity of 20 to 60 Pa·s. A mixture of SiC fine particles of 43 mass %, aluminosilicate fibers of 35 mass %, colloidal silica of 21 mass %, bentonite of 1 mass %, an organic pore former of 1.0 mass % (additional compounding based on total main components), an organic binder of 0.4 mass % (additional compounding based on total main components), and a dispersant of 0.04 mass % (additional compounding based on total main components) was adjusted as the bonding material 2 in the same manner as in the bonding material 1.
(Bonding)
The bonding material 1 was applied on the honeycomb segment bonded face, and the step of bonding honeycomb segments one by one under pressure was repeated to produce three kinds of bonded articles each having 12 honeycomb segments of four wide, three high (hereinbelow described as 3 rows×4 rows), 16 honeycomb segments of 4 rows×4 rows, or 35 honeycomb segments of 6 rows×6 rows (bonding method 1). Then, after drying at 140° C. for 2 hours by a hot air drier, a thermal treatment was performed at 700° C. for 2 hours in an electric furnace to obtain bonded articles (Comparative Examples 1 to 3). Bonded articles (Comparative Examples 4 to 6) were obtained by the use of the bonding material 2 in a similar manner.
Further, a bonded article (Comparative Example 7) having 64 honeycomb segments of 8 rows×8 rows was obtained in a similar manner using the bonding material 1. In addition, three kinds of bonded articles (Comparative Examples 8 to 10) each having 64 honeycomb segments of 8 rows×8 rows, 81 honeycomb segments of 9 rows×9 rows, or 100 honeycomb segments of 10 rows×10 rows were produced in a similar manner using the bonding material 2. Incidentally, a method where a bonded article is produced by drying only once without producing a preliminary block such as a small block is defined as the bonding method 1.
Production of a bonded article of 4 wide, 3 high (3 rows×4 rows):
In the first place, bonding was performed to give a small block shape of 2 rows×2 rows in a similar manner as in the bonded articles (Comparative Examples 1 to 10), and drying was performed at 140° C. for two hours by a hot air drier to produce a small block bonded article. Then, bonded articles were produced by the use of the bonding material 1 and the bonding material 2 by the bonding method 2 (
Production of a bonded article of 4 wide, 4 high (4 rows×4 rows):
In the first place, bonding was performed to give a small block shape of 2 rows×2 rows in a similar manner as in the bonded articles (Comparative Examples 1 to 10), and drying was performed at 140° C. for two hours by a hot air drier to produce a small block bonded article. Then, bonded articles were produced by the use of the bonding material and the bonding material 2 by the bonding method 4 (
Production of a bonded article of 5 wide, 6 high (6 rows×5 rows):
In the first place, bonding was performed to give a small block shape of 2 rows×2 rows in a similar manner as in the bonded articles (Comparative Examples 1 to 10), and drying was performed at 140° C. for two hours by a hot air drier to produce a small block bonded article. Then, bonded articles were produced by the use of the bonding material 1 and the bonding material 2 by the bonding method 6 (
Production of a bonded article of 8 wide, 8 high (8 rows×8 rows):
A bonded article of 8 rows×8 rows was produced by the use of the bonding material 1 or the bonding material 2 by the bonding method 12 (
In addition, a bonded article of 8 rows×8 rows was produced by the use of the bonding material 2 by the bonding method 13 (
Further, a bonded article of 8 rows×8 rows was produced by the use of the bonding material 2 by the bonding method 15 (
Production of a bonded article of 9 wide, 9 high (9 rows×9 rows):
A bonded article of 9 rows×9 rows was produced by the use of the bonding material 2 by a bonding method 17 (
Production of a bonded article of 10 wide, 10 high (10 rows×10 rows):
A bonded article of 10 rows×10 rows was produced by the use of the bonding material 2 by a bonding method 18 (
(Bending Strength of Bonded Portion)
A test piece having a width of 15 mm, a thickness of 10 mm, and a length of 70 mm as shown in
(Results of Bending Strength Property Evaluation)
From Table 1, each of the bonded articles (Comparative Examples 1 to 10) produced by the bonding method 1 had a small ratio of the minimum strength to the maximum strength to show a problem of a large variance in strength depending on the bonding positions. In particular, the tendency was remarkable in the case of using the bonding material 1 containing no fibrous particles such as ceramic fibers and in large sized bonded articles of 8 rows×8 rows or more. In contrast, in Examples 1 to 28, where bonding with a final shape was performed after producing small blocks or a medium-sized block, the strength ratio of the minimum strength to the maximum strength was improved to be nearly 1, and a variance depending on the bonding portions was little.
In addition, in comparison with a small block having honeycomb segments of 2 rows×2 rows, 3 rows×3 rows, 1 rows×4 rows, 2 rows×3 rows, or 2 rows×4 rows having one or less honeycomb segment surrounded by the bonding material layer and being formed by a bonding material layer at the all outer peripheral walls, the strength ratio of the minimum strength to the maximum strength of the cases (Examples 17, 19, 22, 24, 27, and 28) of using a large medium-sized block of 4 rows×4 rows or 5 rows×5 rows was small. However, it was improved in comparison with Comparative Examples (bonding method 1), and the number of drying times can be reduced with respect to the aforementioned cases using a small block. Therefore, it is also possible to produce a bonded article by the use of a large medium-sized block of 4 rows×4 rows or 5 rows×5 rows depending on the use conditions of the honeycomb structure.
(Evaluation for Thermal Resistance)
A honeycomb structure was obtained by bonding a bonded article having 16 honeycomb segments of 4 rows×4 rows produced under conditions similar to those for the bonded articles (Comparative Examples 2 and 5 and Examples 5 to 7) using the bonding material 1 or the bonding material 2 into a final shape, drying at 140° C., grinding the outer periphery into a cylindrical shape, applying a coating material on the outer peripheral faces thereof, and then thermally treating at 700° C. for two hours. In addition, a honeycomb structure was obtained by bonding a bonded article having 64 honeycomb segments of 8 rows×8 rows produced under conditions similar to those for the bonded articles (Comparative Examples 8 and Examples 16, 17 23, and 24) using the bonding material 2 into a final shape, drying at 140° C., grinding the outer periphery into a cylindrical shape, applying a coating material on the outer peripheral faces thereof, and then thermally treating at 700° C. for two hours. The honeycomb structures were subjected to a rapid heating test (burner spalling test) at a test temperature of 900° C., and presence/absence of a crack in the honeycomb structures after the test was checked by observation to give evaluations as good for no crack, fair for presence of a minimal crack, and bad for presence of a crack.
(Results of Thermal Resistance Evaluation)
From Table 2, while Examples 5 to 7 showed good results, Comparative Example 2 was evaluated as bad, having a problem in the thermal shock resistance property. Comparative Example 5 was evaluated as fair, where a minimal crack was found. Among the bonded articles of 8 rows×8 rows, while Examples 16 and 23 were evaluated as good, comparative Example 5 was evaluated as bad, having a problem in the thermal shock resistance property. Examples 17 and 24 were evaluated as fair, each having a minimal crack. Since Examples 17 and 24 employed a medium-sized block of 4 rows×4 rows, the strength ratio of the minimum strength to the maximum strength was about 0.4, which is small in comparison with 0.9 or more of Examples 11 and 23. Therefore, thermal shock resistance was decreased. However, it can be confirmed that the thermal shock resistance was improved in comparison with Comparative Example 8.
In producing a bonded article, it is ideal that drying and hardening of a bonding material and formation of a bonding material layer are caused at the same time in each bonding position. However, in the case of a large bonded article (bonding many honeycomb segments), in a bonded article obtained by applying a bonding material on a face to be bonded of a honeycomb segment, repeating bonding with pressurizing honeycomb segments one by one to bond the honeycomb segments into the final shape in one bonding step, and then drying as the Comparative Examples, there is a difference in a drying manner between the inside and the outside, and behaviors of drying shrinkage and hardening of the bonding material in accordance with the drying are different. For example, since the movement manner of the honeycomb segments in accordance with the drying shrinkage and hardening of the bonding material is not uniform at this time, a variance is caused in the manner of formation of the bonding material layer, and the properties also have variances.
For example, hardening is performed with honeycomb segments moving in the direction where the bonding gap is reduced in accordance with shrinkage of the bonding material in a certain position, while hardening is performed without movement which meets the shrinkage of the bonding material because one side of a honeycomb segment is already in a hardened condition in another position, or a honeycomb segment moves in a direction where the bonding gap increases. Thus, variances are caused in the texture and the properties of the bonding material layer. In the present invention, in order to solve such a problem, at least one small block bonded article where drying conditions are equivalent in each bonding position is produced and dried for solidification in advance before the whole is integrated, and then bonding and drying are performed for integration into a shape by which drying conditions are equivalent in each bonding position upon bonding the whole parts. For example, by the bonding structure, the movement of the honeycomb segments or small block bonded article(s) in accordance with drying shrinkage and hardening of the bonding material is uniformalized to reduce a variance in a formation manner of the bonding material layer and a variance in properties.
A method of producing a honeycomb segment of the present invention is useful as a trapping filter for exhaust gas, for example, as a production method of a diesel particulate filter (DPF) for trapping and removing particulate matter (particulates) contained in exhaust gas from diesel engine or the like.
Number | Date | Country | Kind |
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2007-009571 | Jan 2007 | JP | national |
Number | Date | Country | |
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Parent | PCT/JP2008/050520 | Jan 2008 | US |
Child | 12501893 | US |