CERAMIC HONEYCOMB STRUCTURE AND ITS PRODUCTION METHOD, AND HONEYCOMB-MOLDING DIE

Abstract

A ceramic honeycomb structure comprising a ceramic honeycomb body having pluralities of longitudinal flow paths partitioned by square-lattice-cross-sectioned cell walls, and an outer peripheral wall formed on an outer periphery of the ceramic honeycomb body; the outermost peripheral cell wall of the ceramic honeycomb body having an outer peripheral surface shape reflecting the square lattice shapes of the cell walls; the thickness of the outer peripheral cell wall being larger than the thickness of the cell walls; and the outer peripheral wall being formed to cover an outer peripheral surface of the outer peripheral cell wall.

Claims

1. A ceramic honeycomb structure comprising a ceramic honeycomb body having pluralities of longitudinal flow paths partitioned by square-lattice-cross-sectioned cell walls, and an outer peripheral wall formed on an outer periphery of said ceramic honeycomb body; an outermost peripheral cell wall of said ceramic honeycomb body having an outer peripheral surface shape reflecting the square lattice shapes of said cell walls; the minimum thickness of said outer peripheral cell wall being larger than the thickness of said cell walls; and said outer peripheral wall being formed to cover an outer peripheral surface of said outer peripheral cell wall.

2. The ceramic honeycomb structure according to claim 1, wherein a ratio T/t of the minimum thickness T of said outer peripheral cell wall to the thickness t of said cell walls meets 1<T/t≦10.

3. The ceramic honeycomb structure according to claim 1, wherein the degree of flow path deformation D.sub.1/D.sub.0 in an axially viewed cross section is 0.9-1.1, wherein D.sub.1 represents a diameter of the largest circle inscribed in the outermost flow path cell wall, and D.sub.0 represents a diameter of the largest circle inscribed in an undeformed ideal flow path cell wall.

4. The ceramic honeycomb structure according to claim 1, wherein the minimum thickness T of said outer peripheral cell wall is 0.1-2 mm.

5. A method for producing a ceramic honeycomb structure comprising a ceramic honeycomb body having pluralities of longitudinal flow paths partitioned by square-lattice-cross-sectioned cell walls, and an outer peripheral wall formed on an outer periphery of said ceramic honeycomb body, comprising the steps of extrusion-molding a moldable ceramic material to form a ceramic honeycomb green body integrally comprising square-lattice-cross-sectioned cell walls defining pluralities of longitudinal flow paths, and an outermost peripheral cell wall having an outer peripheral surface shape reflecting the square lattice shapes of said cell walls for constituting an outermost periphery of said ceramic honeycomb body; drying and sintering said ceramic honeycomb green body to obtain said ceramic honeycomb body; and applying a coating material to an outer peripheral surface of said outer peripheral cell wall of said ceramic honeycomb body, and heat-treating said coating material to form said outer peripheral wall; a die used in said extrusion-molding step comprising a die body comprising supply holes for supplying said moldable ceramic material, and square-lattice-patterned slits formed on the opposite surface side to a surface apertured for having said supply holes, such that they are communicating with said supply holes to extrusion-mold said moldable ceramic material supplied through said supply holes to a honeycomb shape, and a guide ring arranged on the slit-grooved surface side for regulating an outer peripheral surface shape of an outer peripheral cell wall of said ceramic honeycomb green body; said grooved surface having a cell-walls-forming region for forming said square-lattice-cross-sectioned cell walls, and an outer peripheral region positioned outside said cell-walls-forming region via a step H, such that said cell-walls-forming region constitutes an elevated surface; said cell-walls-forming region having an outer peripheral shape reflecting the square lattice shapes of said slits; and said guide ring surrounding said cell-walls-forming region such that it has an inner peripheral shape along an outer peripheral shape of said cell-walls-forming region, with a gap smaller than said step H disposed between said guide ring and the grooved surface in said outer peripheral region to supply said moldable ceramic material for forming said outer peripheral cell wall.

6. The method for producing a ceramic honeycomb structure according to claim 5, wherein a ratio T/t of the minimum thickness T of said outer peripheral cell wall to the thickness t of said cell walls meets 1<T/t≦10.

7. The method for producing a ceramic honeycomb structure according to claim 5, wherein said coating material comprises ceramic aggregate particles and an inorganic binder as main components.

8. The method for producing a ceramic honeycomb structure according to claim 5, wherein said ceramic aggregate particles are made of at least one selected from the group consisting of cordierite, silica, alumina, mullite, silicon carbide, silicon nitride and aluminum titanate.

9. A honeycomb-molding die for forming a ceramic honeycomb green body having pluralities of longitudinal flow paths partitioned by square-lattice-cross-sectioned cell walls by extrusion molding, comprising a die body comprising supply holes for supplying a moldable material, and square-lattice-patterned slits formed on the opposite surface side to a surface apertured for having said supply holes, such that they are communicating with said supply holes to mold said moldable material to a honeycomb shape; and a guide ring arranged on the slit-grooved surface side for regulating an outer peripheral surface shape of said outermost peripheral cell wall of said honeycomb green body; said grooved surface having a cell-walls-forming region for forming said square-lattice-cross-sectioned cell walls, and an outer peripheral region positioned outside said cell-walls-forming region via a step H, such that said cell-walls-forming region constitutes an elevated surface; said cell-walls-forming region having an outer peripheral shape reflecting the square lattice shapes of said slits; and said guide ring surrounding said cell-walls-forming region such that it has an inner peripheral shape along an outer peripheral shape of said cell-walls-forming region, with a gap smaller than said step H disposed between said guide ring and the grooved surface in said outer peripheral region to supply a moldable material for forming said outer peripheral cell wall.

10. The honeycomb-molding die according to claim 9, wherein the relation of ts<d≦(s+ts) is met in a direction perpendicular to said square-lattice-patterned slits, wherein “d” represents the smallest gap between the inner peripheral surface of said guide ring and an outermost periphery of a cell-walls-forming region, “s” represents an interval between adjacent square-lattice-shaped slits, and “ts” represents a slit width.

11. The honeycomb-molding die according to claim 9, wherein an angle θ between an inner peripheral surface of said guide ring and said grooved surface meets the relation of 30°≦θ<90°.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIG. 1(a) is a schematic view showing an example of ceramic honeycomb bodies.

[0044] FIG. 1(b) is a schematic view showing an example of the ceramic honeycomb structures of the present invention.

[0045] FIG. 2(a) is a partial cross-sectional view showing an outer peripheral cell wall of the ceramic honeycomb structure of the present invention.

[0046] FIG. 2(b) is a partial cross-sectional view showing an outer peripheral cell wall of the ceramic honeycomb structure of the present invention.

[0047] FIG. 3(a) is a partial cross-sectional view schematically showing an example of ceramic honeycomb bodies.

[0048] FIG. 3(b) is a partial cross-sectional view schematically showing another example of ceramic honeycomb bodies.

[0049] FIG. 3(c) is a partial cross-sectional view schematically showing a further example of ceramic honeycomb bodies.

[0050] FIG. 3(d) is a partial cross-sectional view schematically showing a still further example of ceramic honeycomb bodies.

[0051] FIG. 4(a) is a schematic cross-sectional view showing the largest circle inscribed in an undeformed ideal flow path.

[0052] FIG. 4(b) is a schematic cross-sectional view showing an example of the largest circle inscribed in a deformed flow path.

[0053] FIG. 4(c) is a schematic cross-sectional view showing another example of the largest circle inscribed in a deformed flow path.

[0054] FIG. 4(d) is a schematic cross-sectional view showing a further example of the largest circle inscribed in a deformed flow path.

[0055] FIG. 5(a) is a schematic view showing an example of flow-path-direction cross sections of the ceramic honeycomb structure of the present invention.

[0056] FIG. 5(b) is a schematic view showing another example of flow-path-direction cross sections of the ceramic honeycomb structure of the present invention.

[0057] FIG. 5(c) is a schematic view showing a further example of flow-path-direction cross sections of the ceramic honeycomb structure of the present invention.

[0058] FIG. 5(d) is a schematic view showing a still further example of flow-path-direction cross sections of the ceramic honeycomb structure of the present invention.

[0059] FIG. 6(a) is a front view showing an example of the ceramic honeycomb-molding dies of the present invention when viewed from the slit side.

[0060] FIG. 6(b) is an enlarged front view showing an example of the ceramic honeycomb-molding dies of the present invention when viewed from the supply hole side.

[0061] FIG. 6(c) is a schematic cross-sectional view taken along the line A-A in FIG. 6(b).

[0062] FIG. 6(d) is an exploded view of FIG. 6(c).

[0063] FIG. 7(a) is a schematic cross-sectional view showing the flow of a moldable material in the ceramic honeycomb-molding die of the present invention.

[0064] FIG. 7(b) is a schematic cross-sectional view showing the flow of a moldable material in a conventional ceramic honeycomb-molding die.

[0065] FIG. 8(a) is a front view showing another example of the ceramic honeycomb-molding dies of the present invention.

[0066] FIG. 8(b) is an enlarged schematic cross-sectional view taken along the line B-B in FIG. 8(a).

[0067] FIG. 9 is a schematic view showing an example of conventional ceramic honeycomb structures.

[0068] FIG. 10(a) is a schematic view showing a skinless honeycomb structure described in JP 2008-155594 A.

[0069] FIG. 10(b) is an enlarged schematic cross-sectional view showing a portion C in FIG. 10(a).

[0070] FIG. 11 is a schematic view showing the die described in JP 2008-155594 A.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0071] The embodiments of the present invention will be specifically explained below without intention of restricting the present invention thereto. It should be noted that proper modifications and improvements can be made based on the usual knowledge of those skilled in the art within the scope of the present invention.

[0072] [1] Ceramic Honeycomb Structure

[0073] As shown in FIGS. 1(a) and 1(b), the ceramic honeycomb structure 10 of the present invention comprises a ceramic honeycomb body 11 having pluralities of longitudinal flow paths 13 partitioned by square-lattice-cross-sectioned cell walls 12 [FIG. 1(a)], and an outer peripheral wall 15 formed around an outer periphery of the ceramic honeycomb body 11; the outermost peripheral cell wall 12a of the ceramic honeycomb body 11 being in a shape of an outer peripheral surface 14 reflecting the square lattice shapes of the cell walls 12; and the outer peripheral wall 15 covering the not-machined outer peripheral surface 14 of the outer peripheral cell wall 12a of the ceramic honeycomb body 11. The outer peripheral surface shape reflecting the square lattice shapes of cell walls means an outer peripheral surface shape constituted by one or two outward exposed cell walls (outer peripheral cell wall 12a) among four cell walls constituting square flow paths in the outermost periphery. The outer peripheral cell wall 12a in a shape of the outer peripheral surface 14 reflecting the square lattice shapes of cell walls 12 is constituted by outermost cell walls of the square-lattice-cross-sectioned cell walls 12, which is thicker than the other cell walls 12. The outer peripheral surface 14 of the outer peripheral cell wall 12a preferably has such a shape in an axial cross section as to provide the minimum diameter difference between the largest circle inscribed in the outer peripheral surface 14 and the smallest circle circumscribed on the outer peripheral surface 14.

[0074] With the outer peripheral cell wall 12a of the ceramic honeycomb body 11 in a shape of the outer peripheral surface 14 reflecting the square-lattice-cross-sectioned cell walls 12, as shown in FIG. 1(a), all cell walls 12 constituting the ceramic honeycomb body 11 including the outermost peripheral cell wall 12a are in a complete lattice shape, without incomplete cell walls 52 having outward exposed end portions 55 as shown in FIGS. 10(a) and 10(b). As a result, in drying and sintering the extrusion-molded ceramic honeycomb green body 11, and in handling the dried and sintered ceramic honeycomb body 11 to form an outer peripheral wall 15 on the outer peripheral surface 14, the outer peripheral surface 14 of the ceramic honeycomb green body 11 is less damaged, resistant to the propagation of cracks inside the ceramic honeycomb structure, and thus resistant to decrease in heat shock resistance. Further, the ceramic honeycomb structure of the present invention 10 has sufficient isostatic strength because of less deformation in the outermost flow paths.

[0075] The minimum thickness T of the outer peripheral cell wall 12a of the ceramic honeycomb body 11 is larger than the thickness t of the cell walls 12 not existing in the outermost periphery, namely T>t. The minimum thickness T of the outer peripheral cell wall 12a is the minimum of the thicknesses of the outer peripheral cell wall 12a measured in arbitrary directions perpendicular to the cell walls 12. In practice, each of arbitrary flow paths (for example, 20 flow paths) positioned in the outermost periphery is measured with respect to thickness in one or two sides of its outer peripheral cell wall 12a, and the minimum thickness is regarded as T. As shown in FIG. 2(a), an outer peripheral cell wall 12a having the minimum thickness T is preferably expressed by a locus of a square of T in each side smoothly moving with its one side partially or entirely in contact with the outermost peripheral surface without rotation. FIG. 2(b) shows the locus on five arbitrary continuous flow paths (flow paths 13a to 13e) in the outermost periphery.

[0076] As shown in FIG. 2(b), the outer peripheral cell wall preferably exists completely between a circle of the minimum diameter X.sub.1 circumscribed on the outer peripheral cell wall and a circle of a diameter X.sub.2 inside the above circle, X.sub.2<X.sub.1. When a circle of the diameter X.sub.2 is the largest circle inscribed in the outer peripheral cell wall, the outer peripheral cell wall is preferably shaped to provide the minimum difference between the diameter X.sub.1 of the smallest circle circumscribed on the outer peripheral cell wall and the diameter X.sub.2 of the largest circle circumscribed on the outer peripheral cell wall. The diameters X.sub.1 and X.sub.2 meet preferably 0.9≦X.sub.2/X.sub.1, more preferably 0.93≦X.sub.2/X.sub.1, most preferably 0.95≦X.sub.2/X.sub.1. Incidentally, X.sub.1 represents the diameter of the honeycomb body.

[0077] With the minimum thickness T of the outer peripheral cell wall 12a larger than the thickness t of cell walls 12 not existing in the outermost periphery, cell walls in the outer peripheral surface 14 of the ceramic honeycomb green body 11 (outer peripheral cell wall 12a) are less damaged in handling the ceramic honeycomb green body 11. The minimum thickness T of the outer peripheral cell wall 12a is preferably 10 times or less of the cell wall thickness t, a ratio T/t meeting 1<T/t≦10. The ratio T/t meets more preferably 1.5<T/t≦7, further preferably 1.5<T/t≦5. The cross sections of ceramic honeycomb green bodies 11, in which the minimum thickness T of the outer peripheral cell wall 12a meets T=3t, T=5t, T=7t, and T=10t, respectively, are schematically shown in FIGS. 3(a), 3(b), 3(c) and 3(d).

[0078] As shown in FIGS. 4(a) to 4(d), the degree of deformation of a flow path is evaluated by a diameter of the largest circle inscribed in at least two cell walls among four cell walls of the flow path, which may be called “the largest inscribed circle,” in a cross section perpendicular to the axis of the ceramic honeycomb structure. Namely, the degree of deformation of a flow path is expressed by D.sub.1/D.sub.0, wherein D.sub.0 represents a diameter (designed value) of the largest circle inscribed in an undeformed ideal flow path, and D.sub.1 represents a diameter of the largest circle inscribed in an arbitrary flow path. For example, a flow path may be rhombically deformed as shown in FIG. 4(b) from an ideal square flow path [FIG. 4(a)] without the deformation of cell walls, or a cell wall may be further deformed as shown in FIGS. 4(c) and 4(d). In the present invention, the degree of flow path deformation D.sub.1/D.sub.0 in the outermost flow paths is preferably in a range of 0.9-1.1, more preferably in a range of 0.92-1.08. The degree of flow path deformation D.sub.1/D.sub.0 in the outermost flow paths is expressed by an average of values measured on arbitrarily selected 20 outermost flow paths (flow paths in the outermost periphery).

[0079] In the ceramic honeycomb structure 10 of the present invention, the flow paths 13 after forming the outer peripheral wall 15 may be substantially parallel to the center axis z of the ceramic honeycomb structure 10 as shown in FIG. 5(a), or may be inclined from the center axis z of the ceramic honeycomb structure as shown in FIG. 5(b). Further, the flow paths may be curved as shown in FIG. 5(c), or may have increasing cross section areas as shown in FIG. 5(d).

[0080] [2] Production Method of Ceramic Honeycomb Structure

[0081] The method of the present invention for producing a ceramic honeycomb structure comprising a ceramic honeycomb body having pluralities of longitudinal flow paths partitioned by square-lattice-cross-sectioned cell walls, and an outer peripheral wall formed on an outer periphery of the ceramic honeycomb body, comprises the steps of

[0082] (a) extrusion-molding a moldable ceramic material to form a ceramic honeycomb green body integrally comprising square-lattice-cross-sectioned cell walls defining pluralities of longitudinal flow paths, and an outermost peripheral cell wall having an outer peripheral surface shape reflecting the square lattice shapes of the cell walls for constituting the outermost periphery of a ceramic honeycomb body;

[0083] (b) drying and sintering the ceramic honeycomb green body to obtain the ceramic honeycomb body; and

[0084] (c) applying a coating material to an outer peripheral surface of the outermost peripheral cell wall of the ceramic honeycomb body, and heat-treating the coating material, to form an outer peripheral wall;

[0085] a die used in the extrusion-molding step comprising (1) a die body comprising supply holes for supplying the moldable ceramic material, and square-lattice-patterned slits formed on the opposite surface side to a surface apertured for having the supply holes, such that they are communicating with the supply holes to extrusion-mold the moldable ceramic material supplied through the supply holes to a honeycomb shape, and (2) a guide ring arranged on the slit-grooved surface side for regulating an outer peripheral surface shape of the outer peripheral cell wall of the ceramic honeycomb green body;

[0086] the grooved surface having a cell-walls-forming region for forming the square-lattice-shaped cell walls, and an outer peripheral region positioned outside the cell-walls-forming region via a step H, such that the cell-walls-forming region constitutes an elevated surface;

[0087] the cell-walls-forming region having an outer peripheral shape reflecting the square lattice shapes of the slits; and

[0088] the guide ring surrounding the cell-walls-forming region such that it has an inner peripheral shape along the outer peripheral shape of the cell-walls-forming region, with a gap smaller than the step H disposed between the guide ring and the grooved surface in the outer peripheral region to supply the moldable ceramic material for forming the outer peripheral cell wall.

[0089] A ceramic honeycomb green body formed by a moldable ceramic material extrusion-molded by the above die integrally comprises square-lattice-cross-sectioned cell walls defining pluralities of longitudinal flow paths, and an outer peripheral cell wall having an outer peripheral surface shape reflecting the square lattice shapes of the cell walls and thicker than the cell walls, with few deformed flow paths near the outer periphery and no incomplete flow paths not in a square lattice shape, so that cell walls on the outer peripheral surface of the ceramic honeycomb green body are resistant to damage while handling the extrusion-molded ceramic honeycomb green body. A ceramic honeycomb body obtained by drying and sintering the ceramic honeycomb green body can be provided with an outer peripheral wall on an outer peripheral surface of the not-machined outer peripheral cell wall. Because of no deformed flow paths near the outer periphery, a ceramic honeycomb structure having high isostatic strength can be obtained.

[0090] (1) Coating Material

[0091] The coating material preferably comprises ceramic aggregate particles and an inorganic binder as main components. The coating material comprises ceramic aggregate particles as aggregate, and an inorganic binder for bonding the aggregate. With the coating material comprising ceramic aggregate particles and an inorganic binder as main components, the outer peripheral wall is well bonded to the outer peripheral surface of the ceramic honeycomb body after coating and heat-treating without machining, resulting in a ceramic honeycomb structure having good heat shock resistance with less cracking inside the ceramic honeycomb body. The inorganic binder may be colloidal oxides such as colloidal silica, colloidal alumina, etc. The coating material may contain ceramic fibers.

[0092] Because the ceramic honeycomb structure of the present invention is used in an exhaust-gas-cleaning apparatus, the ceramic aggregate particles are preferably at least one selected from cordierite, silica, alumina, mullite, silicon carbide, silicon nitride and aluminum titanate having good heat resistance. Among them, the use of cordierite and/or amorphous silica reduces the thermal expansion coefficient of the outer peripheral wall, resulting in higher heat shock resistance.

[0093] (2) Honeycomb-Molding Die

[0094] As shown in FIGS. 6(a) to 6(d), a die 30 comprises supply holes 31 open on an apertured surface 31a for supplying a moldable material (for example, moldable ceramic material), and square-lattice-patterned slits 32 open on grooved surfaces 32a, 32b opposite to the apertured surface 31a having the supply holes 31, such that slits 32 are communicating with the supply holes 31. The grooved surface 32a is in a cell-walls-forming region 33a for forming square-lattice-cross-sectioned cell walls of the honeycomb green body, and the grooved surface 32b is in an outer peripheral region 33b outside the cell-walls-forming region 33a. The cell-walls-forming region 33a has an outer peripheral shape reflecting the square lattice shapes of the slits 32. The grooved surface 32b in the outer peripheral region 33b is connected to the grooved surface 32a in the cell-walls-forming region 33a via a step H, such that the grooved surface 32a constitutes an elevated surface. Namely, the step H is provided in a boundary between the cell-walls-forming region 33a and the outer peripheral region 33b. The step H is formed by using slits 32c defining the outer peripheral wall of the honeycomb green body. Namely, the outermost periphery 33c of the cell-walls-forming region 33a is in accordance with inside surfaces of the slits 32c (on the center side of the die) defining the outer peripheral cell walls. The outer peripheral shape of the cell-walls-forming region 33a in an axial cross section is preferably designed to provide the minimum diameter difference between the largest circle inscribed in the outer peripheral shape and the smallest circle circumscribed on the outer peripheral shape.

[0095] The guide ring 35 for regulating a shape of the outer peripheral surface 14 of the outer peripheral cell wall 12a of the honeycomb green body 11 is arranged on the grooved surface 32b in the outer peripheral region 33b, such that it encloses the outermost periphery 33c of the cell-walls-forming region 33a. The guide ring 35 comprises a surface 35b in contact with the grooved surface 32b, and a non-contact surface 35p providing a clearance L with the grooved surface 32b, the clearance L being smaller than the step H between the grooved surface 32a and the grooved surface 32b (L<H). The inner peripheral surface 35a of the guide ring 35 has a shape along the outer peripheral shape of the cell-walls-forming region 33a, when viewed from the extrusion direction. The cell-walls-forming region 33a and the guide ring 35 are selected to determine the outer diameter of the honeycomb body for the desired diameter of the honeycomb structure, taking into consideration the thickness of the outer peripheral wall.

[0096] With the die of the present invention having such a structure (the slits 32c is located at the position of the step H, and the clearance L of the guide ring is smaller than the step H), a moldable material discharged from the slit 32 of the grooved surface 32b receives only a force in the extrusion direction, when the flow direction of the moldable material changes to the extrusion direction (axial direction) at the outermost periphery 33c of the cell-walls-forming region 32a (at the step H) as shown in FIG. 7(a), so that the outermost flow paths of the ceramic honeycomb green body are unlikely deformed. On the other hand, when the guide ring does not have an inner peripheral shape along the outer peripheral surface shape of the outer peripheral cell wall of the ceramic honeycomb green body (for example, circular shape) as in the die described in JP 2009-61683 A, there are regions without the slits 32c at the step H, for example, as shown in FIG. 7(b), resulting in a small gap s1 between the outermost periphery 33c and the adjacent slit 32d. As a result, a moldable material for forming the outer peripheral cell wall receives a force toward a center of the honeycomb green body, so that the outermost flow paths are likely deformed.

[0097] An angle θ between the inner peripheral surface 35a of the guide ring and the non-contact surface 35p (or the grooved surface 32b in the outer peripheral region 33b) is preferably less than 90°, more preferably 300≦θ<900, as shown in FIGS. 8(a) and 8(b). When 0 is less than 30°, the guide ring 35 has such low strength that it may be undesirably deformed by the pressure of a moldable material discharged from the grooved surface 32b, resulting in the deformation of the outer peripheral wall and the outermost flow paths.

[0098] A moldable ceramic material extrusion-molded, for example, by such die can suitably provide a ceramic honeycomb green body integrally comprising square-lattice-cross-sectioned cell walls defining pluralities of longitudinal flow paths, and an outer peripheral wall having an outer peripheral surface shape reflecting the square lattice shapes of the cell walls and thicker than the cell walls as shown in FIG. 1(a). Cell walls in the outer peripheral surface of the ceramic honeycomb green body are unlikely damaged during handling, and the outermost flow paths are unlikely deformed during extrusion molding. With an outer peripheral wall formed by a coating material applied to an outer peripheral surface of the outer peripheral cell wall, a ceramic honeycomb structure having high isostatic strength can be obtained.

[0099] To produce such a honeycomb green body suitably, a ratio L/H of the clearance L between the non-contact surface 35p and the grooved surface 32b to the step H between the grooved surface 32a and the grooved surface 32b preferably meets 0.1≦L/H≦0.9. When the ratio L/H of the clearance L to the height of the step H is less than 0.1, a moldable material cannot be discharged from the grooved surface 32b easily, making it difficult to form the outer peripheral cell wall. On the other hand, when the ratio L/H is more than 0.9, a moldable material discharged from the grooved surface 32b receives a force toward a center of the honeycomb green body, so that the outer peripheral cell wall and the outermost flow paths are easily deformed. 0.2≦L/H≦0.8 is preferably met.

[0100] In the die used in the present invention, the smallest gap d between the inner peripheral surface 35a of the guide ring 35 and the outermost periphery 33c of the cell-walls-forming region 32a should be larger than the slit width ts, and is preferably equal to or less than the sum (s+ts) of the interval s of adjacent slits and the slit width ts. Namely, the smallest gap d, the interval s between adjacent slits, and the slit width ts preferably meet the relation of ts<d≦(s+ts). A sum of the interval s and the slit width ts corresponds to a slit pitch. When the smallest gap d is larger than (s+ts), a moldable ceramic material supplied for forming the outer peripheral wall is not directed to the outer peripheral region 33b, so that the outer peripheral wall may not be formed well. With d≦(s+ts) met, a honeycomb green body integrally comprising square-lattice-cross-sectioned cell walls defining pluralities of longitudinal flow paths, and an outermost peripheral cell wall having an outer peripheral surface shape reflecting the square lattice shapes of the cell walls and thicker than the cell walls for constituting the outermost flow paths can be suitably obtained.

[0101] Further, (Lp+d) is preferably equal to or more than (s+2ts), wherein Lp represents the length of the non-contact surface 35p of the guide ring 35 from the inner peripheral surface 35a. When (Lp+d) is (s+2ts) or more, a moldable ceramic material supplied through two or more slits [three slits in the die shown in FIGS. 6(b) and 8(b)] in the outer peripheral region 33b is extruded from the smallest gap d to form the outer peripheral wall. The length Lp is determined such that the range of (Lp+d) includes preferably 2-15 slits, more preferably 3-12 slits, most preferably 4-10 slits, in the outer peripheral region 33b.

[0102] The present invention will be explained in more detail by Examples below without intention of restriction.

Examples 1-3 and Comparative Example 1

[0103] Kaolin powder, talc powder, silica powder and alumina powder were mixed to have a cordierite composition comprising 50% by mass of SiO.sub.2, 36% by mass of Al.sub.2O.sub.3 and 14% by mass of MgO, and fully dry-mixed with methylcellulose or hydroxypropyl methylcellulose as a binder, a lubricant, and a balloon-type foamed resin as a pore-forming material, and then sufficiently blended with a predetermined amount of water to prepare a plasticized moldable ceramic material.

[0104] This moldable ceramic material was extrusion-molded by the die 30 shown in FIGS. 6(a) to 6(c) in Examples 1-3, and by the die shown in FIG. 11 (described in JP 2008-155594 A) in Comparative Example 1. The structure of each die is shown in Table 1. “L” represents a clearance between the non-contact surface 35p of the guide ring 35 and the grooved surface 32b; “H” represents a step height between the grooved surface 32a and the grooved surface 32b; “d” represents the smallest gap between the inner peripheral surface 35a of the guide ring 35 and the outermost periphery 33c of the cell-walls-forming region 33a; “s” represents an interval between the adjacent slits 32, 32; “ts” represents a slit width; and “n” represents the number of slits in a range of (Lp+d) [see FIGS. 6(a) to 6(c)], namely the number of slits supplying a moldable ceramic material, which was extruded from the smallest gap d to form the outer peripheral wall.

TABLE-US-00001 TABLE 1 Inner Surface Shape of Guide L H d s ts θ No. Ring (mm) (mm) (mm) (mm) n.sup.(1) d/s (mm) (°) Exam- Lattice 1.5 3 0.2 1.47 5 0.14 0.14 90 ple 1 Shape.sup.(2) Exam- Lattice 1.5 3 0.5 1.47 5 0.34 0.14 90 ple 2 Shape.sup.(2) Exam- Lattice 1.5 3 0.7 1.47 5 0.48 0.14 60 ple 3 Shape.sup.(2) Com. Circular — — — 1.47 — — 0.14 90 Ex. 1 Note: .sup.(1)The number of slits supplying a moldable ceramic material to form the outer peripheral cell wall. .sup.(2)A shape reflecting the lattice shapes of cell walls.

[0105] The moldable ceramic material was extrusion-molded through the above die, cut to a predetermined length to obtain a ceramic honeycomb green body. Each ceramic honeycomb green body of Examples 1-3 integrally comprised, as shown in FIG. 1(a), square-lattice-cross-sectioned cell walls defining pluralities of longitudinal flow paths, and an outermost peripheral cell wall having an outer peripheral surface shape reflecting the square lattice shapes of the cell walls; and the ceramic honeycomb green body of Comparative Example 1 was, as shown in FIGS. 10(a) and 10(b), a skinless honeycomb green body 50 comprising end portions 55 of cell walls 52 exposed to the peripheral side without having an outermost peripheral cell wall in the honeycomb green body.

[0106] Each green body was dried, and then sintered at 1410° C. to obtain a cordierite-type ceramic honeycomb body having an outer diameter of 264 mm, a length of 305 mm, a cell wall thickness of 0.13 mm, a flow path pitch of 1.57 mm, and a cell wall porosity of 61%. The outer peripheral wall thickness and cell wall thickness of these ceramic honeycomb bodies are shown in Table 2. The outer diameter is a diameter of the smallest circle entirely including the outer peripheral cell wall 12a, namely a diameter of a cylinder circumscribed on the ceramic honeycomb body.

TABLE-US-00002 TABLE 2 t .sup.(1) T .sup.(2) X.sub.1 .sup.(3) X.sub.2 .sup.(4) No. (mm) (mm) T/t (mm) (mm) X.sub.2/X.sub.1 Example 1 0.13 0.2 1.7 264 256 0.97 Example 2 0.13 0.5 4.2 264 248 0.94 Example 3 0.13 0.8 5.8 264 240 0.91 Com. Ex. 1 0.13 — — — — Note: .sup.(1) Cell wall thickness t. .sup.(2) The minimum thickness T of the outer peripheral cell wall. .sup.(3) X.sub.1 represents a diameter of the minimum circle circumscribed on the outer peripheral cell wall. .sup.(4) X.sub.2 represents a diameter of the largest circle inscribed in the outer peripheral cell wall.

[0107] A coating material comprising aggregate and an inorganic binder shown in Table 3, and methylcellulose (organic binder) and water was applied to an outer peripheral surface of each ceramic honeycomb body, and dried at 1400C for 2 hours to obtain a cylindrical ceramic honeycomb structure having a diameter of (outer diameter of ceramic honeycomb body+2 mm).

TABLE-US-00003 TABLE 3 Aggregate Average Particle Inorganic Binder Size Type and Amount .sup.(2) No. Type (μm) Concentration .sup.(1) (% by mass) Example 1 Cordierite 10 Colloidal Silica (20) 20 Example 2 Cordierite 10 Colloidal Silica (20) 20 Example 3 Cordierite 10 Colloidal Silica (20) 20 Com. Ex. 1 Cordierite 10 Colloidal Silica (20) 20 Note: .sup.(1) The concentration is expressed by “% by mass.” .sup.(2) The amount of the inorganic binder per aggregate.

[0108] With respect to Examples 1-3 and Comparative Example 1, evaluation was conducted on the degree of flow path deformation D.sub.1/D.sub.0 of the ceramic honeycomb body before applying the coating material to the outer peripheral surface, handling damage during applying the coating material, and the isostatic strength of the ceramic honeycomb structure obtained by applying the coating material to the outer peripheral surface.

[0109] Degree of Flow Path Deformation

[0110] The degree of flow path deformation was evaluated by a ratio D.sub.1/D.sub.0, wherein D.sub.1 represents a diameter of the largest circle inscribed in an arbitrary outermost flow path cell wall, which was determined by the maximum diameter of a circular-cross-sectioned steel wire insertable into the arbitrary outermost flow path, and D.sub.0 represents a design diameter of an undeformed ideal flow path. The degree of flow path deformation D.sub.1/D.sub.0 was measured on 20 arbitrarily selected outermost flow paths, and the measured values were averaged. The results are shown in Table 4.

[0111] Damage in Handling

[0112] In the step of applying a coating material to the outer peripheral surface of the ceramic honeycomb green body, damage generated on the outer peripheral surface was observed by the naked eye. The evaluation results are expressed by “No” when no damage was found, and “Yes” when at least one damage was found.

[0113] Isostatic Strength

[0114] The isostatic strength test was conducted according to the Japanese Automobile Standard Organization (JASO) standard M505-87 of the Society of Automotive Engineers of Japan. With both axial end surfaces of the ceramic honeycomb structure sealed with 20-mm-thick aluminum plates, and a 2-mm-thick rubber sheet attached to the outer peripheral wall surface, each ceramic honeycomb structure sample was put in a pressure container, into which water was charged to apply isostatic pressure to the outer peripheral wall surface. Pressure measured when the ceramic honeycomb structure was broken was regarded as isostatic strength. The isostatic strength was evaluated by the following standard:

Excellent: The isostatic strength was 2 MPa or more;
Good: The isostatic strength was 1.5 MPa or more and less than 2 MPa;
Fair: The isostatic strength was 1.0 MPa or more and less than 1.5 MPa;
and
Poor: The isostatic strength was less than 1.0 MPa.
The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Degree of Flow Path Isostatic Damage in No. Deformation D.sub.1/D.sub.0 Strength Handling Example 1 0.97 Good No Example 2 0.97 Good No Example 3 0.96 Good No Com. Ex. 1 0.75 Poor Yes

[0115] It is clear from Table 1 that the ceramic honeycomb structures of Examples 1-3 of the present invention had low degrees of flow path deformation and good isostatic strength. On the other hand, the outer peripheral wall was easily damaged in Comparative Example 1, suffering poor isostatic strength.