(19)
(11)EP 2 090 351 A2

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
19.08.2009 Bulletin 2009/34

(21)Application number: 08291144.7

(22)Date of filing:  03.12.2008
(51)Int. Cl.: 
B01D 46/24  (2006.01)
B28B 11/00  (2006.01)
(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR
Designated Extension States:
AL BA MK RS

(30)Priority: 13.02.2008 WO PCT/JP2008/052374

(71)Applicant: Ibiden Co., Ltd.
Ogaki-shi, Gifu 503-8604 (JP)

(72)Inventor:
  • Sato, Hiroki
    Ibi-gun 501-0695 Gifu (JP)

(74)Representative: Uchida, Kenji et al
S.A. Fedit-Loriot et Autres Conseils en Propriété Industrielle 38, avenue Hoche
75008 Paris
75008 Paris (FR)

  


(54)Honeycomb structured body, exhaust-gas-purifying apparatus and method for manufacturing honeycomb structured body


(57) An object of the present invention is to provide a honeycomb structured body that can be efficiently manufactured, and the honeycomb structured body of the present invention comprises a honeycomb block including a pillar-shaped honeycomb fired body having a plurality of cells placed longitudinally in parallel with one another with a cell wall interposed therebetween and each having an end portion sealed with a plug portion formed by a plug material paste at either one end, wherein the plug portions include fired first plug portions on one end face side of the honeycomb fired body and unfired second plug portions on an other end face side of the honeycomb fired body.




Description

TECHNICAL FIELD



[0001] The present invention relates to a honeycomb structured body, an exhaust-gas-purifying apparatus and a method for manufacturing the honeycomb structured body.

BACKGROUND ART



[0002] Exhaust gases discharged from conventional internal combustion engines such as a diesel engine contain particulate matter (hereinafter, also referred to as PM). In recent years, the PM has raised serious problems because it is harmful to the environment and the human body.
For this reason, various honeycomb filters such as a honeycomb filter comprising a porous ceramic honeycomb structured body have been proposed as filters that capture PM in exhaust gases and purify the exhaust gases.

[0003] As such a honeycomb structured body, Patent Document 1 discloses a honeycomb structured body in which a plurality of filters comprising a porous ceramic sintered body are integrated by bonding peripheral faces of the filters with one another with a sealing material layer interposed therebetween (for example, see Patent Document 1).

[0004] A honeycomb structured body of this kind can be manufactured as follows.
First, a ceramic powder, a binder, a dispersant solution and the like are mixed to prepare a wet mixture.
Next, the wet mixture is extruded molded, and the extrusion-molded body is cut into a predetermined length to form a pillar-shaped honeycomb molded body.
Thereafter, a plug material paste is injected to a predetermined end of each cell of the honeycomb molded body to seal each cell at either one end. Next, the honeycomb molded body with the plug material paste filled therein is degreased and fired to form honeycomb fired bodies to be used as a filter.
Next, a plurality of the honeycomb fired bodies are combined with one another with a sealing material layer (adhesive layer) interposed therebetween to form an aggregated body of the honeycomb fired bodies. Thereafter, if necessary, the periphery of the aggregated body of the honeycomb fired bodies is cut and a coat layer is formed on the periphery of the aggregated body to manufacture a honeycomb structured body.

[0005] Patent Document 1: JP-A 2001-162121

DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION



[0006] In the method for manufacturing a honeycomb structured body described in Patent Document 1, upon manufacturing a honeycomb molded body by extrusion-molding, the honeycomb molded body is formed to have almost the same shape as that of a honeycomb fired body to be manufactured, and various treatments such as sealing (plugging), degreasing and firing are carried out to form the honeycomb fired body.
In such a manufacturing method, the honeycomb fired body becomes slightly smaller than the honeycomb molded body because of the firing treatment. Here, the reduction in the size inevitably occurs.
For this reason, upon manufacturing a honeycomb molded body, the honeycomb molded body is formed to have a slightly larger size than that of a honeycomb fired body to be manufactured in consideration of the size reduction.
However, since the amount of the size reduction is an estimated value, the manufactured honeycomb fired bodies may have variations in the size depending on firing conditions and the like.
In case of using honeycomb fired bodies having variations in the size, when a honeycomb structured body is manufactured by combining a plurality of the honeycomb fired bodies with one another, the manufactured honeycomb structured body may have irregular end faces, and thus require a grinding treatment to be carried out on the end faces in some cases.
However, the end-face grinding treatment is desirably omitted, if possible. This is because the grinding treatment may cause problems such as occurrence of cracks on the end faces of the honeycomb structured body and intrusion of ground powders into pores of the cell walls of the honeycomb structured body. Moreover, additional treatments such as the end-face grinding treatment and a washing treatment for removing the ground powders intruded into the pores of the cell walls directly cause an increase in the cost.

[0007] Moreover, when a honeycomb molded body having almost the same shape as that of the honeycomb fired body to be manufactured is formed and various treatments are carried out thereon, as described in the above-mentioned method for manufacturing a honeycomb structured body, the productivity tends to be lowered. In particular, this tendency becomes more apparent upon manufacturing a honeycomb structured body having a shorter length in the longitudinal direction.
This will be described more in detail.
In such a method as the above-mentioned method for manufacturing a honeycomb structured body, the firing treatment of the honeycomb molded bodies is usually carried out with a plurality of honeycomb molded bodies housed in a single firing jig. Here, in order to allow the molded bodies to be sintered positively and uniformly, the honeycomb molded bodies need to be housed with a certain distance interval therebetween.
For this reason, when a firing jig having a certain size is used, the smaller the honeycomb molded bodies housed in the firing jig are, the wider the area is occupied by a space (gap) between the honeycomb molded bodies, resulting in lower productivity of the honeycomb fired bodies.
In other words, in the firing jig having the certain size, for example, even when half-sized honeycomb molded bodies are used, the number of the honeycomb molded bodies that can be housed in the firing jig is not twice of the number of full-sized honeycomb molded bodies that can be housed in the firing jig, and less than twice thereof.
Moreover, a firing jig having a size that is best suited for the size of the honeycomb molded bodies is desirably used. Although it is preferable to prepare firing jigs having different sizes according to the sizes of the honeycomb molded bodies, the preparation of those firing jigs having different sizes causes an increase in the manufacturing cost.

DISCLOSURE OF THE INVENTION MEANS FOR SOLVING THE PROBLEMS



[0008] In order to solve the above-mentioned problems, the present inventors have intensively studied, and completed the present invention.
The honeycomb structured body according to claim 1 comprises: a honeycomb block including a pillar-shaped honeycomb fired body having a plurality of cells placed longitudinally in parallel with one another with a cell wall interposed therebetween and each having an end portion sealed with a plug portion formed by a plug material paste at either one end, wherein the plug portions include fired first plug portions on one end face side of the honeycomb fired body and unfired second plug portions on an other end face side of the honeycomb fired body.

[0009] The honeycomb structured body according to claim 1 can be efficiently manufactured by the method for manufacturing a honeycomb structured body of the present invention described below.
Moreover, in the honeycomb structured body according to claim 1, the honeycomb fired body constituting the honeycomb structured body has the fired plug portions on one end face side, and the unfired plug portions on the other end face side. For this reason, the unfired plug portions make it possible to alleviate a thermal stress, while the fired plug portions are less likely to cause cracks and peeling even under a high temperature, and therefore PM leakage is less likely to occur.

[0010] The honeycomb structured body according to claim 2 is one embodiment of the honeycomb structured body according to claim 1 in which the unfired second plug portions are solidified by heating.
As described above, when the unfired plug portions are formed as solidified plug portions, it is possible to positively seal ends of the cells, while maintaining the effect for alleviating a thermal stress.

[0011] The honeycomb structured body according to claim 3 is one embodiment of the honeycomb structured body according to claim 1 or 2 in which the second plug portions are formed by using a plug material paste containing at least inorganic particles and an inorganic binder.
Such a plug material paste is particularly suitable for forming the unfired plug portions, because the plug material paste has superior adhesiveness with the cell wall and a required strength.

[0012] The honeycomb structured body according to claim 4 is one embodiment of the honeycomb structured body according to any of claims 1 to 3 in which the honeycomb block comprises a plurality of the honeycomb fired bodies combined with one another with an adhesive layer interposed therebetween.
The honeycomb structured body according to claim 5 is one embodiment of the honeycomb structured body according to claim 4 in which composition of the second plug portion is almost the same as composition of the adhesive layer.
When the composition of the second plug portion is almost the same as the composition of the adhesive layer, as described above, an inner stress caused by a difference between the thermal expansion coefficients of the component members is less likely to occur, leading to further improvement of the reliability.

[0013] The honeycomb structured body according to claim 6 is one embodiment of the honeycomb structured body according to any of claims 1 to 3 in which the honeycomb block comprises a single honeycomb fired body.

[0014] The honeycomb structured body according to claim 7 is one embodiment of the honeycomb structured body according to any of claims 1 to 6 in which a coat layer is formed on a periphery of the honeycomb block.
The honeycomb structured body according to claim 7 has further improved reliability because PM is further less likely to leak from the peripheral side faces. Furthermore, the formation of the coat layer makes it possible to improve the peripheral accuracy (dimensional accuracy of peripheral side faces) of the honeycomb structured body.

[0015] The honeycomb structured body according to claim 8 is one embodiment of the honeycomb structured body according to claim 7 in which composition of the second plug portion is almost the same as composition of the coat layer.
When the composition of the second plug portion is almost the same as the composition of the coat layer, as described above, an inner stress caused by a difference between the thermal expansion coefficients of the component members is less likely to occur, leading to further improvement of the reliability.

[0016] The honeycomb structured body according to claim 9 is one embodiment of the honeycomb structured body according to any of claims 1 to 8 in which composition of the first plug portion is almost the same as composition of the honeycomb fired body.
When the composition of the first plug portion is almost the same as the composition of the honeycomb fired body, as described above, an inner stress caused by a difference between the thermal expansion coefficients of the component members is less likely to occur, leading to further improvement of the reliability. In particular, even under a high temperature close to 1000°C, the honeycomb structured body is less likely to deteriorate, and can maintain sufficient strength and superior reliability.

[0017] Moreover, in the honeycomb structured body according to claim 5, 8 or 9, the composition of each plug portion is almost the same as the composition of either of the adhesive layer, the coat layer or the honeycomb fired body. For this reason, upon manufacturing the honeycomb structured body, it is not necessary to separately prepare the plug material pastes to be used for forming the plug portions.

[0018] The honeycomb structured body according to claim 10 is one embodiment of the honeycomb structured body according to any of claims 1 to 9 in which the plurality of cells formed in the honeycomb fired body comprise large-capacity cells each having a comparatively larger cross-section perpendicular to the longitudinal direction, and small-capacity cells each having a comparatively smaller cross-section, the large-capacity cell having the first plug portion formed therein, the small-capacity cell having the second plug portion formed therein.
The honeycomb structured body having such cells has a configuration suitable for capturing a large amount of PM as well as suppressing an increase in the pressure loss.

[0019] The exhaust-gas-purifying apparatus according to claim 11 is an exhaust-gas-purifying apparatus provided with the honeycomb structured body according to any of claims 1 to 10 placed in a metal casing with a holding sealing member interposed therebetween, wherein the honeycomb structured body is placed in an orientation with the end face having the first plug portions formed therein on an exhaust-gas outlet side and the end face having the second plug portions formed therein on an exhaust-gas inlet side.

[0020] The exhaust-gas-purifying apparatus according to claim 11 is provided with the honeycomb structured body according to any of claims 1 to 10 as a honeycomb structured body. The first plug portions (fired plug portions) are located on the exhaust-gas outlet side and the second plug portions (unfired plug portions) are located on the exhaust-gas inlet side. This enables alleviation of a thermal stress caused by high-temperature exhaust gases on the exhaust-gas inlet side, and prevention of cracks in the plug portions and peeling between the honeycomb fired body and the plug portions on the exhaust-gas outlet side where temperature raises much higher in a regenerating process.

[0021] The method for manufacturing a honeycomb structured body according to claim 12 comprises molding a ceramic raw material to manufacture a pillar-shaped honeycomb molded body having a plurality of cells longitudinally placed in parallel with one another with a cell wall interposed therebetween; injecting a plug material paste to seal cells at predetermined positions on each end face of the honeycomb molded body; firing the honeycomb molded body to manufacture a honeycomb fired body having first plug portions formed therein; and manufacturing a honeycomb block including at least one of the honeycomb fired bodies, and further comprising: cutting the honeycomb fired body having the first plug portions formed at predetermined positions; forming second plug portions by injecting a plug material paste into end portions of the cells of the cut honeycomb fired body at predetermined positions, and solidifying the plug material paste through heating, the second plug portions formed on a side opposite to the side having the first plug portions formed thereon.

[0022] The method for manufacturing a honeycomb structured body according to claim 12 makes it possible to suitably manufacture the honeycomb structured body according to any of claims 1 to 10.
Moreover, in the method for manufacturing a honeycomb structured body according to claim 12, after a honeycomb fired body is manufactured by firing a honeycomb molded body, the resulting honeycomb fired body is cut.
Since the honeycomb fired body is cut after being fired as described above, it is possible to manufacture honeycomb fired bodies with high dimensional accuracy in the longitudinal direction and a smaller variation in the size.

[0023] Moreover, the method for manufacturing a honeycomb structured body according to claim 12 is particularly suitable for manufacturing a honeycomb structured body that has a short length in the longitudinal direction.
In the method for manufacturing a honeycomb structured body, the honeycomb molded body is housed in the firing jig and then fired. As described above, when a firing jig having a certain size is used, the smaller honeycomb molded bodies are used, the lower the productivity thereof becomes.
In contrast, in the method for manufacturing a honeycomb structured body according to claim 12, the honeycomb fired body having a predetermined length is manufactured by firing the honeycomb molded body and then cutting the obtained honeycomb fired body.
For this reason, even when a honeycomb structured body having a short length is manufactured, superior productivity can be achieved.
For example, even when a honeycomb structured body having a half length of a general length in the longitudinal direction is manufactured, the same firing jig as that generally used can be used.
Therefore, the honeycomb fired body is preferably cut into two equal pieces. Needless to say, the honeycomb fired body may be cut into three or more pieces. When cut into three or more pieces, the honeycomb fired bodies located at a position other than the two ends (located at the center) may be used for manufacturing another honeycomb structured body.

[0024] The method for manufacturing a honeycomb structured body according to claim 13 is one embodiment of the method for manufacturing a honeycomb structured body according to claim 12 which comprises cutting the honeycomb fired body after manufacturing the honeycomb fired body having the first plug portions formed therein; and manufacturing the honeycomb block after forming the second plug portions.

[0025] The method for manufacturing a honeycomb structured body according to claim 14 is one embodiment of the method for manufacturing a honeycomb structured body according to claim 12 or 13 which comprises manufacturing the honeycomb block by using a single honeycomb fired body.
The method for manufacturing a honeycomb structured body according to claim 15 is one embodiment of the method for manufacturing a honeycomb structured body according to claim 12 or 13 which comprises manufacturing the honeycomb block by combining a plurality of honeycomb fired bodies with one another with an adhesive layer interposed therebetween.

[0026] The method for manufacturing a honeycomb structured body according to claim 16 is one embodiment of the method for manufacturing a honeycomb structured body according to claim 12 which comprises manufacturing a honeycomb block having the first plug portions formed at both ends thereof by manufacturing the honeycomb fired bodies having the first plug portions formed therein and then combining a plurality of the honeycomb fired bodies with one another with an adhesive layer interposed therebetween; and forming the second plug portions at an opposite end of the honeycomb block to the end having the first plug portions formed, after cutting the honeycomb block having the honeycomb fired bodies combined with one another with the adhesive layer interposed therebetween.
The method for manufacturing a honeycomb structured body according to claim 17 is one embodiment of the method for manufacturing a honeycomb structured body according to claim 15 or 16 in which composition of the second plug portion is almost the same as composition of the adhesive layer.
When the composition of the second plug portion is almost the same as the composition of another component member of the honeycomb structured body, as described above, an inner stress caused by a difference between the thermal expansion coefficients of the component members is less likely to occur in the honeycomb structured body thus manufactured.

[0027] The method for manufacturing a honeycomb structured body according to claim 18 is one embodiment of the method for manufacturing a honeycomb structured body according to any of claims 12 to 17 which comprises manufacturing the honeycomb fired body to have the plurality of cells including large-capacity cells each having a comparatively larger cross-section perpendicular to the longitudinal direction and small-capacity cells each having a comparatively smaller cross-section, forming the first plug portions in the large-capacity cells, and forming the second plug portions in the small-capacity cells.
The method for manufacturing a honeycomb structured body according to claim 18 makes it possible to manufacture a honeycomb structured body that has a configuration suitable for capturing a large amount of PM as well as suppressing an increase in the pressure loss.

[0028] The method for manufacturing a honeycomb structured body according to claim 19 is one embodiment of the method for manufacturing a honeycomb structured body according to any of claims 12 to 18 which comprises forming a coat layer by applying a coating material paste to a periphery of the honeycomb block and solidifying the coating material paste after manufacturing the honeycomb block.
As described above, the formation of the coat layer on the periphery of the honeycomb block makes it possible to manufacture a honeycomb structured body having further improved reliability. Moreover, the formation of the coat layer makes it possible to manufacture a honeycomb structured body having a high peripheral accuracy (dimensional accuracy of the peripheral side face).

[0029] The method for manufacturing a honeycomb structured body according to claim 20 is one embodiment of the method for manufacturing a honeycomb structured body according to claim 19 in which composition of the second plug portion is almost the same as composition of the coat layer.
When the composition of the second plug portion is almost the same as the composition of another component member of the honeycomb structured body, as described above, an inner stress caused by a difference between the thermal expansion coefficients of the component members is less likely to occur in the honeycomb structured body thus manufactured.

[0030] The method for manufacturing a honeycomb structured body according to claim 21 is one embodiment of the method for manufacturing a honeycomb structured body according to any of claims 12 to 20 in which the plug material paste used for forming the second plug portion contains at least inorganic particles and an inorganic binder.
Such a plug material paste is particularly suitable for forming the second plug portions (unfired plug portions), because the plug material paste has superior adhesiveness with the cell wall and a required strength.

[0031] The method for manufacturing a honeycomb structured body according to claim 22 is one embodiment of the method for manufacturing a honeycomb structured body according to any of claims 12 to 21 in which composition of the first plug portion is almost the same as composition of the honeycomb fired body.
When the composition of the first plug portion is almost the same as the composition of another component member of the honeycomb structured body, as described above, an inner stress caused by a difference between the thermal expansion coefficients of the component members is less likely to occur in the honeycomb structured body thus manufactured. In particular, even under a high temperature close to 1000°C, the honeycomb structured body is less likely to deteriorate, and can maintain sufficient strength and superior reliability.

[0032] Moreover, in the method for manufacturing a honeycomb structured body according to claim 17, 20 or 22, the composition of each plug portion is almost the same as the composition of either of the adhesive layer, the coat layer and the honeycomb fired body. For this reason, upon manufacturing the honeycomb structured body, it is not necessary to separately prepare the plug material paste, and a wet mixture to be used for forming the adhesive paste, the coating material paste or the honeycomb molded body may be used as the plug material paste.

BEST MODE FOR CARRYING OUT THE INVENTION



[0033] The above, and the other objects, features and advantages of the present invention will be made apparent from the description of preferred embodiments, given as non-limiting examples, with reference to the accompanying drawings in which:

Figs. 1(a) to 1(h) are explanatory views each illustrating manufacturing processes of a first embodiment;

Fig. 2 is a perspective view schematically illustrating one example of a honeycomb structured body of the first embodiment;

Fig. 3(a) is a perspective view schematically illustrating one example of a honeycomb fired body constituting the honeycomb structured body of the first embodiment;

Fig. 3 (b) is a B-B line cross-sectional view of Fig. 3 (a);

Fig. 4 is a cross-sectional view schematically illustrating one example of an exhaust-gas-purifying apparatus of the first embodiment in which a honeycomb structured body is installed;

Figs. 5(a) to 5(f) are explanatory views each illustrating manufacturing processes of the second embodiment;

Figs. 6(a) to 6(g) are explanatory views each illustrating manufacturing processes of the third embodiment;

Fig. 7 is a flow chart of the methods for manufacturing a honeycomb structured body according to the first to third embodiments;

Fig. 8(a) is a perspective view illustrating another example of a honeycomb fired body constituting the honeycomb structured body of an embodiment of the present invention;

Fig. 8 (b) is a B-B line cross-sectional view of Fig. 8 (a); and

Figs. 9(a) to 9(c) are perspective views each illustrating another example of a honeycomb fired body manufactured in the method for manufacturing a honeycomb structured body according to an embodiment of the present invention, wherein:
10... Honeycomb structured body; 11... Adhesive layer; 12... Coat layer; 15... Honeycomb block; 20... Honeycomb fired body; 21... Cell; 22a... Unfired plug portion (second plug portion) ; 22b... Fired plug portion (First plug portion); 23... Cell wall.



[0034] The following description will discuss embodiments of the present invention.

(First Embodiment)



[0035] First, the following description will discuss a method for manufacturing a honeycomb structured body according to the present embodiment in the order of processes.
Figs. 1(a) to 1(h) are explanatory views each illustrating manufacturing processes of a first embodiment.
(1) As a ceramic raw material, silicon carbide powders having different average particle diameters are used and mixed with an organic binder, a plasticizer, a lubricant and water to prepare a wet mixture.

[0036] (2) The wet mixture is charged into an extrusion-molding apparatus and extrusion-molded to form a honeycomb molded body 130 having a predetermined shape (see Fig. 1(a)). Here, an extrusion-molding metal die that forms each cell 121 into a predetermined shape is selected.
Here, the honeycomb molded body 130 is manufactured to have a longitudinal length almost twice as long as a designed value of a longitudinal length of a honeycomb structured body to be manufactured. At this time, the length of the honeycomb molded body is determined in consideration of the amount of shrinkage at the time of firing and a cutting margin to be cut out.
Moreover, the honeycomb molded body is dried by using a drying apparatus.

[0037] (3) Next, a predetermined amount of a plug material paste 122 is injected into a predetermined end portion of each cell 121 of the honeycomb molded body 130 to seal the respective cells 121. Upon sealing the cells, a sealing mask is applied to an end face of the honeycomb molded body, and the plug material paste is injected only into the cells needed to be sealed (see Fig. 1(b)).
Here, the plug material paste is injected in such a manner that in a honeycomb structured body to be manufactured at the end the cells are sealed in a checkered pattern on each end face and each cell is sealed only at either one end thereof.
Here, a composition having almost the same composition as that of the wet mixture (almost the same composition as that of the honeycomb molded body) is used as the plug material paste.
Although the plug material paste may have the same composition as that of the wet mixture, for example, the viscosity thereof may be adjusted in consideration of the filling property thereof to fill the cells. The adjustment of the viscosity may be carried out by changing the blending amount of the organic solvent, water or the like.

[0038] (4) After the honeycomb molded body 130 having cells each being sealed at a predetermined end is placed on a firing jig, a degreasing treatment is carried out to remove the organic components in the honeycomb molded body 130 by heating the honeycomb molded body 130 in a degreasing furnace.
Subsequently, the degreased honeycomb molded body is charged into a firing furnace while being on the firing jig, and a firing treatment is carried out at a predetermined temperature (for example, 2200 to 2300°C) to manufacture a honeycomb fired body 120 (see Fig. 1(c)).
Here, in the present invention, plug portions 22b formed through the firing treatment is referred to as first plug portions.
Moreover, in the present invention, a "honeycomb molded body" includes a molded body on which the drying treatment or the degreasing treatment has been carried out in addition to a raw molded body immediately after being extrusion-molded.

[0039] (5) Next, the honeycomb fired body 120 manufactured in the process (4) is cut into two pieces having an equal longitudinal length to obtain honeycomb fired bodies 20 (see Fig. 1(d)).
The honeycomb fired body is cut by using a diamond cutter, an OD (outside diameter) diamond blade, an ID (inner diameter) diamond blade, a multi-wire, a multi-blade or the like.
By carrying out such a cutting treatment, the honeycomb fired bodies 20, which have a longitudinal length equal to a designed value of a longitudinal length of a honeycomb structured body to be manufactured, can be manufactured.
Here, in the honeycomb fired body 20 obtained by cutting, only predetermined cells are sealed on one end face side.

[0040] (6) Next, in the honeycomb fired body manufactured in the process (5), the plug material paste is injected into end portions of predetermined cells on the unsealed end of the honeycomb fired body to seal each cell at either one end thereof.
Here, as the plug material paste to be injected, for example, a plug material paste containing an inorganic binder, an organic binder and inorganic particles is used. The plug material paste may further contain at least one of inorganic fibers and whiskers.
Next, the plug material paste injected in the process is solidified by heating, and formed into unfired plug portions (solidified plug portions) 22a (see Fig. 1(e)). Here, in the present invention, the unfired (solidified) plug portions are referred to as second plug portions.
Here, the plug material paste injected in the process (3) is formed into the fired plug portions 22b through the firing treatment in the process (4).

[0041] (7) Next, an adhesive paste for forming an adhesive layer is applied to side faces of the honeycomb fired bodies 20 having the cells each being sealed at the predetermined end to form an adhesive paste layer. Repeatedly another honeycomb fired body is laminated on the adhesive paste layer to manufacture an aggregated body 110 of the honeycomb fired bodies in which a predetermined number of the honeycomb fired bodies 20 are combined with one another. Here, the honeycomb fired bodies are laminated so that the first plug portions are all located on the same end face side (the second plug portions are all located on the other end face side).
Here, as the adhesive paste, an adhesive paste having almost the same composition as that of the plug material paste injected in the process (6) is used.
Subsequently, the aggregated body 110 of the honeycomb fired bodies is heated so that the adhesive paste layer is solidified and formed into an adhesive layer 11 (see Fig. 1(f) and Fig. 1(g)).
Here, Fig. 1(g) is a partially enlarged A-A line cross-sectional view of Fig. 1(f).

[0042] (8) Thereafter, the aggregated body 110 of the honeycomb fired bodies is cut along a broken line in Fig. 1(f) by using a diamond cutter to form a honeycomb block. A coating material paste is applied to the periphery of the honeycomb block and solidified to form a coat layer 12. Thus, a honeycomb structured body 10 is manufactured (see Fig. 1(h)).
Here, for example, a paste-form composition having almost the same composition as that of the adhesive paste is used as the coating material paste.

[0043] Next, with reference to the figures, the following description will discuss a honeycomb structured body manufactured by such a manufacturing method.
Fig. 2 is a perspective view schematically illustrating one example of a honeycomb structured body of the first embodiment. Fig. 3(a) is a perspective view schematically illustrating one example of a honeycomb fired body constituting the honeycomb structured body of the first embodiment, and Fig. 3(b) is a B-B line cross-sectional view of Fig. 3(a).

[0044] In the honeycomb structured body 10 of the present embodiment, as shown in Fig. 2, the plurality of honeycomb fired bodies 20 are combined with one another with the adhesive layer 11 interposed therebetween to form a honeycomb block 15. Additionally, the coat layer 12 is formed on the periphery of the honeycomb block 15.
Moreover, as shown in Figs. 3(a) and 3(b), the honeycomb fired body 20 has a configuration in which a large number of cells 21 are placed in parallel with one another in the longitudinal direction (direction of arrow a in Fig. 3 (a)). The cell wall 23 partitioning the cells 21 functions as a filter.

[0045] That is, as shown in Fig. 3 (b), each of the cells 21 formed in the honeycomb fired body 20 is sealed either on the exhaust-gas inlet side with the plug portion 22a formed by the plug material paste, or on the exhaust-gas outlet side with the plug portion 22b formed by the plug material paste. Therefore, exhaust gases that have flowed in one cell 21 having a sealed end on the exhaust-gas outlet side, are discharged from another cell 21 having a sealed end on the exhaust-gas inlet side, after having always passed through the cell wall 23 partitioning the cells 21. When the exhaust gases pass through the cell wall 23, PM is captured in the cell wall 23 so that the exhaust gases are purified.
Here, the plug portions 22b which seal the end portions on the exhaust-gas outlet side are plug portions (first plug portions) formed by carrying out the firing treatment on the plug material paste. In contrast, the plug portions 22a which seal the end portions on the exhaust-gas inlet side are unfired plug portions (second plug portions) formed by solidifying the plug material paste without carrying out the firing treatment thereon.
Moreover, in the honeycomb structured body 10, the coat layer 12 and the plug portions 22a are formed by using almost the same paste as the paste used for forming the adhesive layer 11.
Here, in Fig. 3(b), arrows indicate exhaust gas flows.

[0046] As described above, in the honeycomb structured body 10, the plug portions 22b are formed through the firing treatment and the plug portions 22a are formed without carrying out the firing treatment thereon. Therefore, the plug portions 22b and the plug portions 22a have mutually different mechanical properties such as hardness (for example, Vickers hardness, Rockwell hardness and the like), strength (bending strength, compression strength, breaking strength and the like), Young's modulus, elastic modulus, and thermal conductivity.
In the embodiment of the present invention, plug portions having a low strength and a low thermal conductivity are formed on one end of the honeycomb structured body, and plug portions having a high strength and a high thermal conductivity are formed on the other end of the honeycomb structured body. The honeycomb structured body is preferably placed so that end portions with the plug portions having a low strength and a low thermal conductivity are located on an inlet side of an exhaust-gas-purifying apparatus and end portions with the plug portions having a high strength and a high thermal conductivity are located on an outlet side of the exhaust-gas-purifying apparatus.

[0047] In the present description, the firing refers to a process in which instable components (moisture, binder, and the like) in the molded body are decomposed and removed, and reactions among the respective components (including recrystallizing) are allowed to progress to form a stable compound. The firing further improves the strength. In contrast, the solidification refers to a process in which, by removing moisture and the like in the composition, the state of the composition is changed by physical actions to exert an adhesive property (to improve the hardness of the composition) without allowing any reactions among the respective components in the composition to take place.

[0048] Next, with reference to the figures, the following description will discuss an exhaust-gas-purifying apparatus provided with such a honeycomb structured body.
Fig. 4 is a cross-sectional view schematically illustrating one example of an exhaust-gas-purifying apparatus of the present embodiment in which a honeycomb structured body is installed.

[0049] As shown in Fig. 4, an exhaust-gas-purifying apparatus 40 is mainly configured by a honeycomb structured body 10, a casing (metal container) 41 that covers the outside of the honeycomb structured body 10 and a holding sealing material 42 made of alumina interposed between the honeycomb structured body 10 and the casing 41, and an introducing pipe 43 coupled to an internal combustion engine such as an engine, is connected to an end of the casing 41 on the side from which exhaust gases are introduced, and an exhaust pipe 44 coupled to the outside is connected to the other end of the casing 41.
Here, the honeycomb structured body 10 is installed in the casing 41 so that the side on which the plug portions 22a (unfired plug portions) are formed is located on the exhaust-gas inlet side, and the side on which the plug portions 22b (fired plug portions) are formed is located on the exhaust-gas outlet side. Therefore, in the exhaust-gas-purifying apparatus 40, the plug portions 22b having higher mechanical properties are located on the exhaust-gas outlet side.
Here, in Fig. 4, arrows indicate exhaust-gas flows.

[0050] In the exhaust-gas-purifying apparatus 40 having such a configuration, exhaust gases discharged from the internal combustion engine such as an engine are introduced into the casing 41 through the introducing pipe 43, and allowed to flow into the honeycomb structured body 10 from the cells having an opening on the inlet side. Thereafter, the exhaust gases pass through the cell wall, and PM is captured in the cell wall to purify the exhaust gases. Then, the purified gases are discharged out of the honeycomb structured body from the cells having an opening on the outlet side, and discharged the outside through the exhaust pipe 44.

[0051] When a large amount of PM is accumulated on the cell walls of the honeycomb structured body 10 to cause an increase in the pressure loss, a regenerating process of the honeycomb structured body 10 is carried out.
In the regenerating process, gases heated by a heater (not shown) are allowed to flow in the cells of the honeycomb structured body. Thereby, the honeycomb structured body 10 is heated, and the PM accumulated on the cell walls are burned and eliminated. Alternatively, the PM may be burned and eliminated by using a post-injection system.
In particular, the exhaust-gas outlet side of the honeycomb structured body tends to have a larger amount of PM accumulated thereon than that on the exhaust-gas inlet side, and upon burning and eliminating the PM, temperature tends to rise higher on the exhaust-gas outlet side of the honeycomb structured body compared to the exhaust-gas inlet side. Therefore, in the present embodiment, the plug portions having higher mechanical properties are located on the exhaust-gas outlet side where temperature tends to rise higher, while the plug portions having lower mechanical properties are located on the exhaust-gas inlet side.

[0052] The following description will explain the effects of the first embodiment.
  1. (1) In the present embodiment, upon manufacturing a honeycomb structured body, after the firing treatment is carried out on a honeycomb molded body to manufacture a honeycomb fired body, the resulting honeycomb fired body is cut.
    By carrying out the cutting treatment after the firing treatment as described above, it is possible to manufacture honeycomb fired bodies each having superior dimensional accuracy in the longitudinal direction, thus leading to a smaller variation in the size of the honeycomb fired bodies. Therefore, the present embodiment can be suitably used for manufacturing a honeycomb structured body that has little irregularity on the end faces thereof and does not particularly need a grinding treatment.
    More specifically, a fired body may be formed to have a dimension larger than the designed value, and the fired body is cut at positions the designed value from the respective end faces to obtain two pieces of honeycomb fired bodies. Here, the center portion may be designed to be eliminated in the cutting treatment, or may be discarded as a cutting margin. Alternatively, in the case where the center portion of the honeycomb fired body is not discarded, this portion may be used for manufacturing another honeycomb structured body.
    Moreover, in the present embodiment, since the manufactured fired body is cut to have the dimension of the designed value, a grinding treatment does not need to be carried out on the end faces. Therefore, no grinding powders remain in the pores in the cell walls of the honeycomb fired body, and no washing treatment following the end-face grinding treatment is required.


[0053] Moreover, since after a honeycomb fired body is manufactured, the resulting honeycomb fired body is cut, two honeycomb fired bodies can be manufactured from a single honeycomb molded body. Therefore, it is possible to efficiently manufacture honeycomb fired bodies. As a result, the productivity of the honeycomb structured body is improved, and the number of honeycomb structured bodies manufactured per unit time can be increased, leading to a reduction in the manufacturing costs.

[0054] (2) In the present embodiment, since after a plug material paste is injected, the plug portions for sealing the predetermined end of each cell are formed by carrying out the firing treatment on the plug material paste or solidifying the plug material paste by heating, the predetermined end of each cell can be positively sealed.

[0055] (3) In the present embodiment, since a coat layer is formed on the periphery of the honeycomb structured body, it is possible to prevent PM leakage from the peripheral side faces of the honeycomb structured body when the honeycomb structured body is used for purifying exhaust gases, leading to improvement of the reliability. Moreover, the formation of the coat layer improves the dimensional accuracy of the peripheral side faces of the honeycomb structured body.

[0056] (4) In the present embodiment, since the unfired plug portions, the adhesive layer and the coat layer which constitute the honeycomb structured body are formed by using almost the same material, an inner stress caused by a difference between the thermal expansion coefficients of the component members in the honeycomb structured body is less likely to occur, making it possible to further improve the reliability.
Moreover, the fired plug portions constituting the honeycomb structured body are formed by using almost the same composition as that of the honeycomb fired body. Therefore, even upon occurrence of a thermal impact during the regenerating process, cracks, peeling and the like are less likely to occur between the cell walls and the plug portions, thereby making it possible to improve the reliability and also to positively prevent leakage of soot.

[0057] (5) In an exhaust-gas-purifying apparatus of the present embodiment, since the plug portions formed through the firing treatment (first plug portions) are located on the exhaust-gas outlet side and the plug portions formed without carrying out the firing treatment (second plug portions) are located on the exhaust-gas inlet side, the above-mentioned effect described in (4) is most effectively exerted. Therefore, it is possible to easily alleviate an inner stress caused by high temperature exhaust gases on the exhaust-gas inlet side. On the exhaust-gas outlet side, although a large amount of PM tends to accumulate and the temperature tends to rise upon carrying out the regenerating process, the fired plug portions tend to prevent occurrence of cracks between the cell walls and the plug portions, thereby making it possible to positively capture PM.

[0058] Hereinafter, an example that discloses the first embodiment of the present invention more specifically is shown, but the present invention is not limited to this example.

(Example 1)



[0059] (1) An amount of 52.8% by weight of a silicon carbide coarse powder having an average particle diameter of 22 µm and an amount of 22.6% by weight of a silicon carbide fine powder having an average particle diameter of 0.5 µm were mixed, and to the obtained mixture were added 2.1% by weight of an acrylic resin, 4.6% by weight of an organic binder (methyl cellulose), 2.8% by weight of a lubricant (UNILUB, manufactured by NOF Corp.), 1.3% by weight of glycerin, and 13.8% by weight of water, and then mixed and kneaded to obtain a wet mixture. The wet mixture was then extrusion-molded to provide raw honeycomb molded bodies having almost the same shape as that shown in Fig. 3(a) with its cells unsealed.

[0060] (2) Subsequently, the raw honeycomb molded bodies were dried by using a microwave drying apparatus to obtain a dried honeycomb molded bodies. Thereafter, predetermined cells of the dried honeycomb molded bodies were filled in with a paste having the same composition as that of the wet mixture. Specifically, a paste having the same composition as that of the wet mixture was injected to seal each cell at either one end thereof. Thereafter, the honeycomb molded bodies were dried again by the drying apparatus.

[0061] (3) Next, after the dried honeycomb molded bodies were placed on a firing jig, and then degreased at a temperature of 400°C. Thereafter, a firing treatment was carried out at a temperature of 2200°C under a normal-pressure argon atmosphere for 3 hours to manufacture honeycomb fired bodies comprising a silicon carbide sintered body. The manufactured honeycomb fired bodies had a porosity of 45%, an average pore diameter of 15 µm, a size of 34.3 mm × 34.3 mm × 300.5 mm, the number of cells (cell density) of 300 pcs/inch2 and a thickness of a cell wall of 0.25 mm (10 mil).

[0062] (4) Next, each of the honeycomb fired bodies were cut into two equal pieces by using an OD diamond blade having a board thickness of 0.5 mm to obtain honeycomb fired bodies having a size of 34.3 mm × 34.3 mm × 150 mm. In the obtained honeycomb fired bodies, predetermined cells are sealed only at either one end thereof.

[0063] (5) In the honeycomb fired bodies obtained in the process (4), a plug material paste was injected to end portions of unsealed cells to seal each cell at either one end thereof.
Here, as the plug material paste, a plug material paste containing 30.0% by weight of a silicon carbide powder having an average particle diameter of 0. 6 µm, 21.4% by weight of silica sol, 8.0% by weight of carboxymethyl cellulose and 40.6% by weight of water was used.
Thereafter, the plug material paste injected in the process was solidified by heating with a hot air at 180°C for 15 minutes to form plug portions.

[0064] (6) Next, an adhesive paste was applied to side faces of the honeycomb fired bodies manufactured through the processes (1) to (5), and 16 pieces of the honeycomb fired bodies were bonded to one another with the adhesive paste interposed therebetween. Furthermore, the adhesive paste was solidified by heating at 180°C for 20 minutes to manufacture a rectangular pillar-shaped aggregated body of the honeycomb fired bodies. Subsequently, the periphery of the aggregated body of the honeycomb fired bodies was cut by using a diamond cutter to manufacture a round pillar-shaped honeycomb block with the adhesive layer having a thickness of 1 mm.
Here, as the adhesive paste, a paste having the same composition as that of the plug material paste used in the process (5) was used.

[0065] (7) Next, a coating material paste was applied to the periphery of the honeycomb block to form a coating material paste layer. Then, the coating material paste layer was solidified at 120°C to manufacture a round pillar-shaped honeycomb structured body having a size of 143.8 mm in diameter × 150 mm in length with a coat layer formed on the periphery.
Here, a paste having the same composition as that of the plug material paste used in the process (5) was used as the coating material paste.

(Comparative Example 1)



[0066] (1) Raw honeycomb molded bodies having almost the same shape as that shown in Fig. 2(a) with its cells unsealed were manufactured by following the same procedure as in the process (1) of Example 1, except that the manufactured raw honeycomb molded bodies was designed to have a length of 150 mm after being fired.

[0067] (2) Next, the raw honeycomb molded bodies were dried by using a microwave drying apparatus to form dried honeycomb molded bodies. Thereafter, a plug material paste was injected to end portions of predetermined cells to seal each cell at either one end thereof.
Here, a composition having the same composition as that of the wet mixture was used as the plug material paste.

[0068] (3) Next, the degreasing treatment and the firing treatment were carried out on the honeycomb molded bodies with the plug material paste filled therein under the same conditions as those in the process (3) of Example 1 to manufacture honeycomb fired bodies.
Here, each of the manufactured honeycomb fired bodies comprises a silicon carbide sintered body and has a porosity of 45%, an average pore diameter of 15 µm, a size of 34.3 mm × 34.3 mm × 150 mm, the number of cells (cell density) of 300 pcs/inch2 and a thickness of a cell wall of 0.25 mm (10 mil).

[0069] (4) Next, by using the honeycomb fired bodies manufactured in the process (3), a honeycomb structured body comprising a plurality of the honeycomb fired bodies combined with one another with an adhesive layer interposed therebetween was manufactured by following the same method as in the processes (6) and (7) of Example 1.

(Evaluation of Honeycomb Structured Body)


(1) Measurement of Pressure Loss



[0070] An exhaust-gas-purifying apparatuses 40 shown in Fig. 4 was assembled using each of the honeycomb structured bodies manufactured in Example 1 and Comparative Example 1. Then, a 2L common-rail-type diesel engine was coupled to an introduction pipe 43 of the exhaust-gas-purifying apparatus 40. Pressure gauges were attached in front of and behind the honeycomb structured body.
The engine was driven at the number of revolutions of 1500 min-1 and a torque of 50 Nm. A pressure difference was measured five minutes after the start of the driving operation.

[0071] The results showed that the pressure loss of the honeycomb structured body of Example 1 was 2.3 kPa, and the pressure loss of the honeycomb structured body of Comparative Example 1 was 2.4 kPa.
Accordingly, the honeycomb structured body manufactured in Example 1 showed the similar degree of the pressure loss to that of the honeycomb structured body manufactured in Comparative Example 1 (conventional method).

[0072] (2) Measurement of Regeneration Limit Value
An exhaust-gas-purifying apparatuses 40 shown in Fig. 4 was assembled using each of the honeycomb structured bodies manufactured in Example 1 and Comparative Example 1. Then, a 2L common-rail-type diesel engine was coupled to an introduction pipe 43 of the exhaust-gas-purifying apparatus 40.
An experiment in which the engine was driven at the number of revolutions of 2000 min-1 and a torque of 50 Nm for a predetermined time period and a regenerating process was carried out was successively conducted while increasing the time period of the operation, and the honeycomb structured body (especially, the plug portions) was observed whether cracks had occurred.
The amount of PM having been captured upon the occurrence of cracks was defined to be regeneration limit value.

[0073] The results showed that the regeneration limit value of the honeycomb structured body of Example 1 was 7.9 g/l, and the regeneration limit value of the honeycomb structured body of Comparative Example 1 was 7.7 g/l.
Accordingly, the honeycomb structured body manufactured in Example 1 showed the similar degree of the regeneration limit value to that of the honeycomb structured body manufactured in Comparative Example 1 (conventional method).

[0074] (Second Embodiment)
In the present embodiment, the sequence of the processes in the method for manufacturing a honeycomb structured body was different from the sequence of the processes in the method for manufacturing a honeycomb structured body of the first embodiment.
Figs. 5(a) to 5(f) are explanatory views each illustrating manufacturing processes of the second embodiment.
(1) In the method for manufacturing a honeycomb structured body of the present embodiment, honeycomb fired bodies 120 are manufactured by following the same method as in the processes (1) to (4) in the method for manufacturing a honeycomb structured body of the first embodiment (see Fig. 5(a)).

[0075] (2) Next, an adhesive paste for forming an adhesive layer was applied to side faces of the manufactured honeycomb fired bodies 120 to form an adhesive paste layer. Repeatedly another honeycomb fired body is laminated on the adhesive paste layer to manufacture an aggregated body 110' of the honeycomb fired bodies in which a predetermined number of the honeycomb fired bodies 120 are combined with one another.
Here, as the adhesive paste, an adhesive paste having almost the same composition as that of a plug material paste used in the process (4) described below is used.
Further, in the process, after the honeycomb fired bodies were combined, the adhesive paste layer is solidified to form an adhesive layer 11 by heating the aggregated body of the honeycomb fired bodies (see Fig. 5(b)).

[0076] (3) Next, the aggregated body 110' of the honeycomb fired bodies manufactured in the process (2) is cut into two pieces having an equal longitudinal length to form aggregated bodies 110 of the honeycomb fired bodies (see Fig. 5(c)).
The honeycomb fired body is cut by using a diamond cutter, an OD diamond blade, an ID diamond blade, a multi-wire, a multi-blade or the like.
By carrying out such a cutting treatment, the aggregated bodies 110 of the honeycomb fired bodies, which have a longitudinal length equal to a designed value of a longitudinal length of a honeycomb structured body to be manufactured, can be manufactured.

[0077] (4) Next, in the aggregated body 110 of the honeycomb fired bodies cut in the process (3), the plug material paste is injected to end portions of unsealed cells out of cells needed to be sealed so that each cell is sealed at either one end thereof.
Thereafter, the injected plug material paste is solidified by heating to form plug portions 22a (Figs. 5 (d) and 5(e)).
Fig. 5(e) is a partially enlarged C-C line cross-sectional view of Fig. 5(d).
Here, as the plug material paste, for example, a plug material paste containing an inorganic binder, an organic binder and inorganic particles is used. The plug material paste may further contain at least one of inorganic fibers and whiskers.

[0078] (5) Thereafter, the aggregated body 110 of the honeycomb fired bodies is cut along a broken line in Fig. 5(d) by using a diamond cutter to form a honeycomb block. A coating material paste is applied to the periphery of the honeycomb block and solidified by heating to form a coat layer 12. Thus, a honeycomb structured body 10 is manufactured (see Fig. 5(f)).
Here, as the coating material paste, for example, a coating material paste having almost the same composition as that of the plug material paste used in the process (4) is used.

[0079] In the present embodiment, a honeycomb structured body can be manufactured through the processes as described above.
Here, the configuration of the honeycomb structured body manufactured by the manufacturing method of the present embodiment is the same as the configuration of the honeycomb structured body of the first embodiment. The configuration of an exhaust-gas-purifying apparatus provided with the honeycomb structured body manufactured by the manufacturing method of the present embodiment is the same as the configuration of the exhaust-gas-purifying apparatus of the first embodiment.

[0080] The honeycomb structured body, the exhaust-gas-purifying apparatus and the method for manufacturing a honeycomb structured body according to the second embodiment can exert the same effects as those of the first embodiment.

[0081] Hereinafter, an example that discloses the second embodiment of the present invention more specifically is shown, but the present invention is not limited to the example. (Example 2)
(1) Honeycomb fired bodies comprising a silicon carbide sintered body and having a porosity of 45%, an average pore diameter of 15 µm, a size of 34.3 mm × 34.3 mm × 300.5 mm, the number of cells (cell density) of 300 pcs/inch2 and a thickness of a cell wall of 0.25 mm (10 mil) were manufactured by following the same procedure as in the processes (1) to (3) of Example 1.

[0082] (2) Next, an adhesive paste was applied to side faces of the honeycomb fired bodies manufactured in the process (1), and 16 pieces of the honeycomb fired bodies were bonded to one another with the adhesive paste interposed therebetween. Furthermore, the adhesive paste was solidified by heating at 180°C for 20 minutes to manufacture a rectangular pillar-shaped aggregated body of the honeycomb fired bodies.
Subsequently, the aggregated body of the honeycomb fired bodies was cut by using an OD diamond blade having a board thickness of 0.5 mm into two equal pieces to obtain aggregated bodies of the honeycomb fired bodies having a longitudinal length of 150 mm. In the obtained aggregated bodies of the honeycomb fired bodies, predetermined cells are sealed only at either one end thereof.
In the process, as the adhesive paste, an adhesive paste containing 30.0% by weight of a silicon carbide powder having an average particle diameter of 0. 6 µm, 21.4% by weight of silica sol, 8.0% by weight of carboxymethyl cellulose and 40.6% by weight of water was used.

[0083] (3) Next, in the aggregated body of the honeycomb fired body obtained in the process (2), a plug material paste was injected to end portions of unsealed cells to seal each cell at either one end thereof. Subsequently, the injected plug material paste was solidified by heating with a hot air at 180°C for 15 minutes to form plug portions.
Here, as the plug material paste, a paste having the same composition as that of the adhesive paste used in the process (2) was used.

[0084] (4) Next, the periphery of the aggregated body was cut by using a diamond cutter to manufacture a round pillar-shaped honeycomb block with the adhesive layer having a thickness of 1 mm.
Thereafter, a coating material paste was applied to the periphery of the honeycomb block to form a coating material paste layer. Then, the coating material paste layer was dried at 180°C for 20 minutes to manufacture a round pillar-shaped honeycomb structured body having a size of 143.8 mm in diameter × 150 mm in length with the coat layer formed on the periphery thereof.
Here, as the coating material paste, a paste having the same composition as that of the adhesive paste used in the process (2) was used.

[0085] As described above, in the honeycomb structured body manufactured in Example 2, the plug portions on one end face side were formed through the firing treatment, and the plug portions on the other end face side were formed without carrying out the firing treatment.
The pressure loss and the regeneration limit value were measured on the honeycomb structured body manufactured in the present Example by following the same method as in Example 1 to give 2.3 kPa and 7.9 g/l, respectively.
Accordingly, the honeycomb structured body manufactured in Example 2 showed the similar degree of the pressure loss and the regeneration limit value to those of the honeycomb structured body manufactured in Comparative Example 1 (conventional method).

[0086] (Third Embodiment)
In the present embodiment, the sequence of the processes in the method for manufacturing a honeycomb structured body was different from the sequence of the processes in the method for manufacturing a honeycomb structured body of the first embodiment.
Figs. 6(a) to 6(g) are explanatory views each illustrating the manufacturing processes of the third embodiment.
(1) In the method for manufacturing a honeycomb structured body of the present embodiment, honeycomb fired bodies 20 each having a longitudinal length equal to a designed value of a longitudinal length of a honeycomb structured body to be manufactured were manufactured by following the same method as in the processes (1) to (5) in the method for manufacturing a honeycomb structured body of the first embodiment (see Figs. 6(a) and 6(b)).

[0087] (2) Next, an adhesive paste for forming an adhesive layer is applied to side faces of the honeycomb fired bodies 20 manufactured in the process (1) to form an adhesive paste layer. Repeatedly another honeycomb fired body is laminated on the adhesive paste layer to manufacture an aggregated body 110 of the honeycomb fired bodies in which a predetermined number of the honeycomb fired bodies are combined with one another.
Here, in the process, after the honeycomb fired bodies are combined with one another, the aggregated body of the honeycomb fired bodies is heated to form the adhesive paste layer into the adhesive layer 11 (see Figs. 6(c) and 6(d)).
Fig. 6(d) is a partially enlarged D-D line cross-sectional view of Fig. 6(c).
Here, as the plug material paste, a paste having almost the same composition as the composition of a plug material paste used in the following process (3) is used.

[0088] (3) Next, in the aggregated body 110 of the honeycomb fired bodies manufactured in the process (2), the plug material paste is injected to end portions of unsealed cells out of cells needed to be sealed so that each cell is sealed at either one end thereof.
Thereafter, the injected plug material paste is solidified by heating to form plug portions 22a (see Figs. 6 (e) and 6(f)).
Fig. 6(f) is a partially enlarged E-E line cross-sectional view of Fig. 6(e).
Here, as the plug material paste, for example, a plug material paste containing an inorganic binder, an organic binder and inorganic particles is used. The plug material paste may further contain at least one of inorganic fibers and whiskers.

[0089] (4) Thereafter, the aggregated body 110 of the honeycomb fired bodies is cut along a broken line in Fig. 6(e) by using a diamond cutter to form a honeycomb block. A coating material paste is applied to the periphery of the honeycomb block and solidified by heating to form a coat layer 12. Thus, a honeycomb structured body 10 is manufactured (see Fig. 6(g)).
Here, as the coating material paste, for example, a coating material paste having almost the same composition as that of the plug material paste injected in the process (3) is used.

[0090] In the present embodiment, a honeycomb structured body can be manufactured through the processes as described above.
Here, the configuration of the honeycomb structured body manufactured by the manufacturing method of the present embodiment is the same as the configuration of the honeycomb structured body of the first embodiment. The configuration of an exhaust-gas-purifying apparatus provided with the honeycomb structured body manufactured by the manufacturing method of the present embodiment is the same as the configuration of the exhaust-gas-purifying apparatus of the first embodiment.

[0091] The honeycomb structured body, the exhaust-gas-purifying apparatus and the method for manufacturing a honeycomb structured body according to the third embodiment can exert the same effects as those of the first embodiment.

[0092] Hereinafter, an example that discloses the third embodiment of the present invention more specifically is shown, but the present invention is not limited to the example. (Example 3)
(1) First, honeycomb fired bodies having a size of 34.3 mm × 34.3 mm × 150 mm in which predetermined cells are sealed only at either one end thereof were manufactured by following the same procedure as in the processes (1) to (5) of Example 1.

[0093] (2) Next, by following the same procedure as in the process (2) of Example 2, an adhesive paste was applied to side faces of the honeycomb fired bodies manufactured in the process (1), and 16 pieces of the honeycomb fired bodies were bonded to one another with the adhesive paste interposed therebetween. Furthermore, the adhesive paste was solidified by heating at 180°C for 20 minutes to manufacture a rectangular pillar-shaped aggregated body of the honeycomb fired bodies.
Here, as the adhesive paste, an adhesive paste containing 30.0% by weight of a silicon carbide powder having an average particle diameter of 0. 6 µm, 21.4% by weight of silica sol, 8.0% by weight of carboxymethyl cellulose and 40.6% by weight of water was used.

[0094] (3) Next, plug portions were formed by following the same procedure as in the process (3) of Example 2 to seal each cell at either one end thereof.
Here, as the plug material paste for forming the plug portions, a paste having the same composition as that of the adhesive paste used in the process (2) was used.

[0095] (4) Next, the periphery of the aggregated body of the honeycomb fired bodies was cut and a coat layer was formed thereon by following the same procedure as in the process (4) of Example 2 to manufacture a round pillar-shaped honeycomb structured body having a size 143.8 mm in diameter × 150 mm in length with the coat layer formed on the periphery.
Here, as the coating material paste for forming the coat layer, a paste having the same composition as the composition of the adhesive paste used in the process (2) was used.

[0096] As described above, in the honeycomb structured body manufactured in Example 3, the plug portions on one end face side were formed through the firing treatment, and the plug portions on the other end face side were formed without carrying out the firing treatment.
The pressure loss and the regeneration limit value were measured on the honeycomb structured body manufactured in the present Example by following the same method as in Example 1 to give 2.5 kPa and 7.9 g/l, respectively.
Accordingly, the honeycomb structured body manufactured in Example 3 showed the similar degree of the pressure loss and the regeneration limit value to those of the honeycomb structured body manufactured in Comparative Example 1 (conventional method).

[0097] Although the methods for manufacturing a honeycomb structured body according to the first to third embodiments described above are different, the honeycomb structured bodies manufactured in the respective embodiments have the same configurations, and the exhaust-gas-purifying apparatuses provided with the respective honeycomb structured bodies have the same configurations.
The processes of the methods for manufacturing a honeycomb structured body according to the respective embodiments are shown in Fig. 7.

[0098] Fig. 7 is a flow chart of the methods for manufacturing a honeycomb structured body of the first to third embodiments.
As shown in Fig. 7, the timing for cutting the honeycomb fired bodies, the timing for combining the plurality of honeycomb fired bodies and the timing for injecting the plug material paste to the cells of the honeycomb fired bodies obtained by cutting are different among the methods for manufacturing a honeycomb structured body according to the first to third embodiments.

[0099] (Fourth Embodiment)
In the honeycomb structured bodies according to the first to third embodiments, all of the cells have the same rectangular cross-section perpendicular to the longitudinal direction of the honeycomb fired body. However, in the honeycomb structured body of the present embodiment, the cross-sectional shapes of the respective cells perpendicular to the longitudinal direction of the honeycomb fired body may be, for example, an octagonal shape and a rectangular shape.
Fig. 8(a) is a perspective view illustrating another example of a honeycomb fired body constituting the honeycomb structured body of the embodiment of the present invention, and Fig. 8(b) is a B-B line cross-sectional view of Fig. 8(a).

[0100] A honeycomb fired body 70, shown in Figs. 8 (a) and 8(b), has a configuration in which a large number of cells 71a and 71b are placed in parallel with one another in the longitudinal direction (direction of arrow b in Fig. 8(a)) with a cell wall 73 interposed therebetween. The respective cells 71a and 71b are sealed with a plug portion at either one end thereof. More specifically, in the cell 71a, an end portion on the exhaust-gas inlet side is sealed with an unfired plug portion (second plug portion) 72a, and in the cell 71b, an end portion on the exhaust-gas outlet side is sealed with a fired plug portion (first plug portion).
Here, the cross-sectional shape perpendicular to the longitudinal direction of the cell 71a is a rectangular shape, and the cross-sectional shape perpendicular to the longitudinal direction of the cell 71b is an octagonal shape.

[0101] Therefore, the plurality of cells formed in the honeycomb fired body 70 include large-capacity cells having a comparatively larger cross-sectional area perpendicular to the longitudinal direction and small-capacity cells having a comparatively smaller cross-sectional area. The first plug portions are formed in the large-capacity cells, and the second plug portions are formed in the small-capacity cells.

[0102] The honeycomb fired body 70 also has a configuration in which exhaust gases that have flowed in the cell 71b is discharged from the cell 71a after having always passed through the cell wall 73.
Therefore, also in the honeycomb fired body 70, the cell wall 73 functions as a filter for capturing PM and the like.
In the honeycomb fired body 70, the capacity of the cell (the cell 71b having the octagonal cross-section) having an opening on the exhaust-gas inlet side is larger than the capacity of the cell (the cell 71a having the square cross-section) having an opening on the exhaust-gas outlet side. Therefore, the honeycomb structured body 70 has a configuration suitable for capturing a large amount of PM as well as suppressing an increase in the pressure loss.

[0103] Moreover, in the honeycomb fired body having the large-capacity cells and the small-capacity cells, the combination of the cross-sectional shapes of the large-capacity cell and the small-capacity cell is not particularly limited to the octagonal shape and the rectangular shape, and a combination of any shapes such as a combination of two kinds of rectangular shapes having different cross-sectional areas may be used.

[0104] (Other Embodiments)
In the methods for manufacturing a honeycomb structured body of the first to fourth embodiments, a plurality of rectangular pillar-shaped honeycomb fired bodies are combined to form an aggregated body of the honeycomb fired bodies, and then the aggregated body is cut to manufacture a honeycomb block. However, in the method for manufacturing a honeycomb structured body of the embodiment of the present invention, the honeycomb block may be manufactured by combining honeycomb fired bodies which have been formed to have a predetermined shape.

[0105] Figs. 9(a) to 9(c) are perspective views each illustrating another example of a honeycomb fired body manufactured in the method for manufacturing a honeycomb structured body of the embodiment of the present invention.
Namely, a honeycomb block may be manufactured by combining honeycomb fired bodies 220, 230 and 240 each of which has a plurality of cells 221, 231 or 241 with a cell wall 223, 233 or 243 interposed therebetween.
Here, upon manufacturing the honeycomb block 15 shown in Fig. 2, the honeycomb fired bodies 220, 230 and 240 are used four pieces each.

[0106] In the honeycomb structured body according to the embodiments of the present invention described above, there is no description on supporting of a catalyst on the honeycomb structured body. However, in the embodiments of the present invention, a catalyst may be supported on the honeycomb structured body.
By supporting a catalyst on the honeycomb structured body, the honeycomb structured body with a catalyst supported thereon and an exhaust-gas-purifying apparatus provided with the honeycomb structured body make it possible to convert toxic components such as CO, HC and NOx contained in exhaust gases. Moreover, the supported catalyst may lower the burning temperature of PM.

[0107] As the catalyst, a catalyst containing a noble metal, an alkali metal, an alkaline-earth metal, an oxide thereof or the like may be used. In addition, the catalyst is preferably supported on the honeycomb structured body in such a manner that the catalyst is on the surface of a layer of an oxide having a high specific surface area such as alumina.

[0108] In the embodiments of the present invention, when a paste containing at least inorganic particles and an inorganic binder is used as the plug material paste, examples of the inorganic particles include carbides, nitrides and the like, more specifically, inorganic particles including silicon carbide, silicon nitride or boron nitride, and the like. Each of these may be used alone, or two or more kinds of these may be used in combination. Silicon carbide is preferably used among these inorganic particles due to its superior thermal conductivity.
Examples of the inorganic binder include silica sol, alumina sol and the like. Each of these may be used alone, or two or more kinds of these may be used in combination. Silica sol is preferably used among the inorganic binders.

[0109] In addition, the plug material paste may contain at least one of inorganic fibers and whiskers. Here, examples of the inorganic fibers and the whiskers include ceramic fibers such as silica-alumina, mullite, alumina and silica, and the like. Each of these may be used alone, or two or more kinds of these may be used in combination. Alumina fibers are preferably used among the inorganic fibers and the whiskers.

[0110] As described above, the plug material paste may have almost the same composition as that of the wet mixture used for manufacturing the honeycomb fired body by extrusion-molding.
Here, the former material (the plug material paste containing at least inorganic particles and an inorganic binder) is preferably used as the plug material paste for forming the plug portions formed without carrying out the firing treatment thereon, and the latter material (paste having almost the same composition as that of the wet mixture) is preferably used for forming the plug portions formed through the firing treatment.
However, the former plug material paste may be used as the material for the plug portions formed through the firing treatment, or the latter plug material paste may be used as the material for the plug portions formed without carrying out the firing treatment thereon.

[0111] Moreover, in the first to fourth embodiments, all of the plug portions formed without carrying out the firing treatment thereon, the adhesive layer and the coat layer are formed by using the pastes having almost the same composition. However, these material pastes do not necessarily need to have almost the same composition.

[0112] The shape of the honeycomb structured body of the embodiments of the present invention is not limited to the round pillar shape shown in Fig. 2, and the shape may be an optional pillar shape such as cylindroid pillar shape and polygonal pillar shape.

[0113] A porosity of the honeycomb fired body according to the embodiments of the present invention is preferably 35 to 60%.
An average pore diameter of the honeycomb fired body is preferably 5 to 30 µm.
Here, the porosity and the average pore diameter can be measured by the conventionally known methods such as mercury porosimetry method, an Archimedes' method, a measuring method using a scanning electron microscope (SEM).

[0114] The main component of the constituent materials of the honeycomb fired body is not limited to silicon carbide, and examples of other main components of the constituent materials include nitride ceramics such as aluminum nitride, silicon nitride, boron nitride, and titanium nitride; carbide ceramics such as zirconium carbide, titanium carbide, tantalum carbide, and tungsten carbide; oxide ceramics such as alumina, zirconia, cordierite, mullite, and aluminum titanate; and the like.
Among these components, non-oxide ceramics are preferable, and silicon carbide is more preferable because this is excellent in thermal resistance properties, mechanical strength, thermal conductivity and the like. Moreover, silicon-containing ceramics, in which metallic silicon is blended with the above described ceramics, as well as a ceramic material such as ceramic bound by silicon or silicate compounds, may be used. And among these, those ceramics (silicon-containing silicon carbide) in which metallic silicon is blended with silicon carbide are preferably used.
Especially, silicon-containing silicon carbide ceramics containing 60% by weight or more of silicon carbide are preferable.

[0115] A particle diameter of the ceramic powder in the wet mixture extrusion-molded in the method for manufacturing a honeycomb structure body of the embodiments of the present invention is not particularly limited, and a ceramic powder which tends not to cause the case where a size of the honeycomb structured body manufactured by the following firing treatment becomes smaller than that of a degreased honeycomb molded body is preferable.
For example, a ceramic powder containing 100 parts by weight of a powder having an average particle diameter of 1.0 to 50.0 µm and 5 to 65 parts by weight of a powder having an average particle diameter of 0.1 to 1.0 µm is preferable.

[0116] An organic binder contained in the wet mixture to be extrusion-molded in the method for manufacturing a honeycomb structured body of the embodiments of the present invention is not particularly limited, and examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol and the like. Methyl cellulose is preferable among these.
A plasticizer contained in the wet mixture is not particularly limited, and examples thereof include glycerin, and the like.
A lubricant contained in the wet mixture is not particularly limited, and examples thereof include polyoxyalkylene-based compounds such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether, and the like.
The specific examples of the lubricant include polyoxyethylene monobutyl ether, polyoxypropylene monobutyl ether, and the like.
Here, depending on the case, a plasticizer and a lubricant may not be contained in the wet mixture.

[0117] Also, a dispersion medium may be used upon preparing the wet mixture, and examples thereof include water, an organic solvent such as benzene, alcohol such as methanol, and the like.
Moreover, a forming auxiliary may be added to the wet mixture.
The forming auxiliary is not particularly limited, and examples thereof include ethylene glycol, dextrin, fatty acids, fatty acid soap, polyalcohol, and the like.

[0118] Furthermore, a pore-forming agent such as balloons that are fine hollow spheres comprising oxide-based ceramics, spherical acrylic particles, and graphite may be added to the wet mixture as needed.
The balloons are not particularly limited, and examples thereof include alumina balloons, glass micro balloons, shirasu balloons, fly ash balloons (FA balloons), mullite balloons, and the like. Alumina balloons are preferable among these.

[0119] Moreover, in the first to fourth embodiments, upon combining the plurality of honeycomb fired bodies with one another, the method is used in which the adhesive paste is applied to the side faces of the respective honeycomb fired bodies, and the honeycomb fired bodies are successively laminated. However, the plurality of honeycomb fired bodies may be combined with one another as follows. A spacer is attached to the surface of each honeycomb fired body so as to ensure a space between the honeycomb fired bodies. The honeycomb fired bodies are arranged with the spacer interposed therebetween, and then an adhesive paste is injected into the space between the honeycomb fired bodies to combine the honeycomb fired bodies with one another.

[0120] In the first to fourth embodiments, the honeycomb block is manufactured by combining the plurality of honeycomb fired bodies with one another. However, in the honeycomb structured body and the exhaust-gas-purifying apparatus of the embodiments of the present invention, the honeycomb block does not necessarily need to be formed by the plurality of honeycomb fired bodies, but the honeycomb block may be formed by a single honeycomb fired body.
Here, upon manufacturing such a honeycomb structured body comprising a honeycomb block formed by a single honeycomb fired body, upon extrusion-molding a wet mixture, a honeycomb molded body which has almost the same cross-sectional shape perpendicular to the longitudinal direction thereof as the cross-sectional shape of a honeycomb block perpendicular to the longitudinal direction thereof, may be manufactured.


Claims

1. A honeycomb structured body comprising:

a honeycomb block including a pillar-shaped honeycomb fired body having a plurality of cells placed longitudinally in parallel with one another with a cell wall interposed therebetween and each having an end portion sealed with a plug portion formed by a plug material paste at either one end,

wherein
said plug portions include fired first plug portions on one end face side of said honeycomb fired body and unfired second plug portions on an other end face side of said honeycomb fired body.
 
2. The honeycomb structured body according to claim 1,
wherein
said unfired second plug portions are solidified by heating.
 
3. The honeycomb structured body according to claim 1 or 2,
wherein
said second plug portions are formed by using a plug material paste containing at least inorganic particles and an inorganic binder.
 
4. The honeycomb structured body according to any of claims 1 to 3,
wherein
said honeycomb block comprises a plurality of the honeycomb fired bodies combined with one another with an adhesive layer interposed therebetween.
 
5. The honeycomb structured body according to claim 4,
wherein
composition of said second plug portion is almost the same as composition of said adhesive layer.
 
6. The honeycomb structured body according to any of claims 1 to 3,
wherein
said honeycomb block comprises a single honeycomb fired body.
 
7. The honeycomb structured body according to any of claims 1 to 6,
wherein
a coat layer is formed on a periphery of said honeycomb block.
 
8. The honeycomb structured body according to claim 7,
wherein
composition of said second plug portion is almost the same as composition of said coat layer.
 
9. The honeycomb structured body according to any of claims 1 to 8,
wherein
composition of said first plug portion is almost the same as composition of said honeycomb fired body.
 
10. The honeycomb structured body according to any of claims 1 to 9,
wherein
the plurality of cells formed in said honeycomb fired body comprise large-capacity cells each having a comparatively larger cross-section perpendicular to said longitudinal direction, and small-capacity cells each having a comparatively smaller cross-section,
said large-capacity cell having said first plug portion formed therein,
said small-capacity cell having said second plug portion formed therein.
 
11. An exhaust-gas-purifying apparatus provided with the honeycomb structured body according to any of claims 1 to 10 placed in a metal casing with a holding sealing member interposed therebetween,
wherein
said honeycomb structured body is placed in an orientation with the end face having said first plug portions formed therein on an exhaust-gas outlet side and the end face having said second plug portions formed therein on an exhaust-gas inlet side.
 
12. A method for manufacturing a honeycomb structured body comprising:

molding a ceramic raw material to manufacture a pillar-shaped honeycomb molded body having a plurality of cells longitudinally placed in parallel with one another with a cell wall interposed therebetween;

injecting a plug material paste to seal cells at predetermined positions on each end face of said honeycomb molded body;

firing said honeycomb molded body to manufacture a honeycomb fired body having first plug portions formed therein; and

manufacturing a honeycomb block including at least one of said honeycomb fired bodies, and

further comprising:

cutting said honeycomb fired body having said first plug portions formed at predetermined positions;

forming second plug portions by injecting a plug material paste into end portions of the cells of said cut honeycomb fired body at predetermined positions, and solidifying said plug material paste through heating, said second plug portions formed on a side opposite to the side having the first plug portions formed thereon.


 
13. The method for manufacturing a honeycomb structured body according to claim 12, comprising:

cutting said honeycomb fired body after manufacturing said honeycomb fired body having said first plug portions formed therein; and

manufacturing said honeycomb block after forming said second plug portions.


 
14. The method for manufacturing a honeycomb structured body according to claim 12 or 13, comprising:

manufacturing said honeycomb block by using a single honeycomb fired body.


 
15. The method for manufacturing a honeycomb structured body according to claim 12 or 13, comprising:

manufacturing said honeycomb block by combining a plurality of honeycomb fired bodies with one another with an adhesive layer interposed therebetween.


 
16. The method for manufacturing a honeycomb structured body according to claim 12, comprising:

manufacturing a honeycomb block having said first plug portions formed at both ends thereof by manufacturing the honeycomb fired bodies having said first plug portions formed therein and then combining a plurality of said honeycomb fired bodies with one another with an adhesive layer interposed therebetween; and

forming said second plug portions at an opposite end of said honeycomb block to the end having said first plug portions formed, after cutting said honeycomb block having said honeycomb fired bodies combined with one another with the adhesive layer interposed therebetween.


 
17. The method for manufacturing a honeycomb structured body according to claim 15 or 16,
wherein
composition of said second plug portion is almost the same as composition of said adhesive layer.
 
18. The method for manufacturing a honeycomb structured body according to any of claims 12 to 17, comprising:

manufacturing said honeycomb fired body to have the plurality of cells including large-capacity cells each having a comparatively larger cross-section perpendicular to said longitudinal direction and small-capacity cells each having a comparatively smaller cross-section,

forming said first plug portions in said large-capacity cells, and

forming said second plug portions in said small-capacity cells.


 
19. The method for manufacturing a honeycomb structured body according to any of claims 12 to 18, further comprising:

forming a coat layer by applying a coating material paste to a periphery of said honeycomb block and solidifying said coating material paste after manufacturing said honeycomb block.


 
20. The method for manufacturing a honeycomb structured body according to claim 19,
wherein
composition of said second plug portion is almost the same as composition of said coat layer.
 
21. The method for manufacturing a honeycomb structured body according to any of claims 12 to 20,
wherein
said plug material paste used for forming said second plug portion contains at least inorganic particles and an inorganic binder.
 
22. The method for manufacturing a honeycomb structured body according to any of claims 12 to 21,
wherein
composition of said first plug portion is almost the same as composition of said honeycomb fired body.
 




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REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description