KR100948325B1 - Joined body and method for manufacturing the same - Google Patents

Abstract

The present invention is a bonded body in which two or more to-be-joined objects are integrated through a bonding material layer formed of a bonding material composition, and the deformation of the bonded object due to thermal distortion can be suppressed to the bonding material layer, and the bonding material caused by stress It is an object of the present invention to provide a layer that does not easily break and that has excellent thermal shock resistance.

Two or more to-be-joined bodies are joined together through the bonding material layer 9 formed by the bonding material composition, The said bonding material composition has a plate-shaped particle, a non-critical particle, and an inorganic adhesive as a main component, The said bonding material layer The conjugate whose Young's modulus of (9) is 3 GPa or more.

Description

Joining body and its manufacturing method {JOINED BODY AND METHOD FOR MANUFACTURING THE SAME}

This invention relates to the joined body by which several to-be-joined body is joined together via a bonding material layer, and its manufacturing method.

A honeycomb structure is widely used as a diesel particulate filter (DPF) for trapping and removing particulate matter (particulate) contained in exhaust gases from a diesel engine or the like, for example. .

Such a honeycomb structure has a structure in which a plurality of cells serving as a flow path of a fluid formed and partitioned by a porous partition wall made of silicon carbide (SiC) or the like are parallel to each other in the direction of the central axis. In addition, the ends of adjacent cells are sealed alternately (in a checkered pattern). That is, one cell is open at one end and the other end is sealed, while the other cell adjacent to this is closed at one end and the other end is open.

With this structure, the exhaust gas flowing into the predetermined cell (inflow cell) from one end passes through the porous partition wall, and flows out through the cell (outflow cell) adjacent to the inflow cell, and is discharged when passing through the partition wall. By trapping particulate matter (particulate) in the gas in the partition wall, the exhaust gas can be purified.

In order to continuously use such a honeycomb structure (filter) for a long time, it is necessary to periodically regenerate the filter. That is, in order to reduce the pressure loss increased by the particles deposited in the filter over time and return the filter performance to the initial state, it is necessary to burn out and remove the particles deposited in the filter. When the filter is regenerated, a large thermal stress is generated, and this thermal stress causes a problem such as cracking or fracture in the honeycomb structure. In order to respond to the request for improving the thermal shock resistance against the thermal stress, a honeycomb structured body having a divided structure has been proposed, which has a function of distributing and alleviating thermal stress by integrally joining a plurality of honeycomb segments with a bonding material layer. The impact properties can be improved to some extent.

However, in recent years, the filter is required to be larger in size, and accordingly, the thermal stress generated during regeneration is also increased, and there is a strong demand for further improvement of the thermal shock resistance as a structure for solving the above-mentioned problems. In order to realize this heat shock resistance improvement, the bonding material layer for joining a plurality of honeycomb segments integrally is required to have excellent stress relaxation function and bonding strength.

Conventionally, a honeycomb structure is disclosed in which the Young's modulus of the bonding layer material between honeycomb segments is 20% or less of the honeycomb segment material for the purpose of improving the thermal shock resistance by the improvement of the bonding material layer (see Patent Document 1). The honeycomb structure is intended to reduce the thermal stress generated during use by reducing the Young's modulus of the bonding material layer. However, when the bonding material layer has a high porosity for reducing the Young's modulus, the bonding strength between the honeycomb segments becomes insufficient, resulting in a healthy bonded body. You may not get it.

In contrast, when the bonding material layer has a high Young's modulus, the deformation of the honeycomb segment due to thermal distortion can be suppressed by the bonding material layer. Only a problem arises that the bonding material layer is easily broken.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-190916

This invention is made | formed in view of the above-mentioned problem of the prior art, and the objective is the joining body in which two or more to-be-joined bodies are integrated through the joining material layer formed by the joining material composition, and deformation | transformation of a to-be-joined thing by heat distortion is carried out. In addition to being capable of suppressing the adhesion to the bonding material layer, the fracture of the bonding material layer due to stress is less likely to occur, and to provide an excellent thermal shock resistance.

In order to achieve the said objective, according to this invention, the following joined bodies and the manufacturing method of a joined body are provided.

[1] A bonding material in which two or more to-be-joined materials are integrated through a bonding material layer formed of a bonding material composition, wherein the bonding material composition comprises plate-shaped particles, non-critical particles, and an inorganic adhesive as a main component, and the Young's modulus of the bonding material layer is A conjugate that is 3 kPa or more.

[2] The bonded body according to [1], wherein the bonding material composition contains plate-shaped particles having a Young's modulus of 100 GPa or more as the plate-shaped particles.

[3] The joined body according to [1] or [2], in which the bonding material composition contains noncritical particles having a Young's modulus of 100 GPa or more as the noncritical particles.

[4] The joined body according to any one of [1] to [3], wherein a ratio of the plate-shaped particles contained in the bonding material composition is 1% by mass to 60% by mass of the entire main component.

[5] The conjugate according to any one of [1] to [4], wherein an aspect ratio of the plate-shaped particles is 3 or more (when paper is 1 or more in width).

[6] The joined body according to any one of [1] to [5], wherein the average particle diameter of the plate-shaped particles is 1 µm to 200 µm.

[7] The joined body according to any one of [1] to [6], wherein the plate-shaped particles are plate-shaped particles made of at least one material selected from the group consisting of mica, talc and glass flakes.

[8] The conjugate according to [7], wherein the mica is mica calcined at 800 ° C or higher, and the talc is talc calcined at 900 ° C or higher.

[9] The joined body according to any one of [1] to [8], wherein the porosity of the bonding material layer is less than 50%.

[10] The conjugate according to any one of [1] to [9], wherein the joined object is a honeycomb segment.

[11] A method for producing a joined body in which two or more joined objects are bonded together using a bonding material composition whose main component is plate-shaped particles, non-critical particles, and an inorganic adhesive, and whose Young's modulus after dry curing is 3 Pa or more.

Since the bonding material layer has a high Young's modulus of 3 kPa or more, the bonding material of the present invention can suppress deformation of the bonded object due to thermal distortion to the bonding material layer, and the plate-shaped particles contained in the bonding material composition forming the bonding material layer, Since the fracture resistance of the bonding material layer is improved, the bonding material layer is not easily broken by stress, and as a result, excellent thermal shock resistance is exhibited. Moreover, according to the manufacturing method of this invention, the joined body which has such excellent heat shock resistance can be manufactured.

Hereinafter, although this invention is demonstrated based on specific embodiment, this invention is not limited to this and interprets, and various changes, correction, and improvement are based on the knowledge of a person skilled in the art, unless it deviates from the range of this invention. Can be added.

As for the joined body of this invention, two or more to-be-joined bodies are integrated through the bonding material layer formed with the bonding material composition, The said bonding material composition consists of plate-shaped particle | grains, non-critical particle | grains, and an inorganic adhesive as a main component, Young's modulus is 3 ㎬ or more, which is the main feature. In addition, "the plate-shaped particle, a non-critical particle, and an inorganic adhesive as a main component" means here that the quantity which combined the plate-shaped particle, the non-critical particle, and an inorganic adhesive is 50 mass% or more of the whole bonding material composition. In addition, "the plate-shaped particle" has two or more relatively flat surfaces, and two of the flat surfaces are substantially parallel, and the distance between the substantially parallel surfaces is small compared with the long diameter of the surface, It is characterized by the above-mentioned. It means a particle. In addition, "non-plate-shaped particle" shall mean the particle | grains or ball-shaped particle which does not not only have the characteristics of the above-mentioned plate-shaped particle, but does not have the characteristics considered to be fibrous and needle-like.

In the joined body of the present invention, the Young's modulus of the bonded material layer is 3 GPa or more, preferably 4 GPa or more, more preferably 5 GPa or more. In this way, by providing a high Young's modulus to the bonding material layer that is bonded between the joined objects, the bonding material layer can suppress deformation of the bonded body due to thermal distortion. In addition, the Young's modulus of a bonding material layer cuts out the part of a bonding material layer to a predetermined shape (for example, 4 * 1 * 20mm rod shape) from a bonding body, and performs the 3-point bending test according to JIS R1602 with respect to the cut test piece, The displacement at the time of loading is measured and can be computed from the load-displacement curve.

In addition, in this invention, although the bonding material composition which forms a bonding material layer has plate-shaped particle | grains, non-critical particle | grains, and an inorganic adhesive as a main component, breakage resistance of a bonding material layer is improving by including especially plate-shaped particle | grains among these main components. . As described above, in the case of increasing the Young's modulus in the conventional bonding material layer, there is a problem that the deformation of the honeycomb segment can be suppressed while the stress caused by the bonding material layer is increased. It improves and the fracture | rupture of the bonding material layer by a stress does not produce easily, and it becomes a joining body excellent in a thermal shock resistance.

From a viewpoint of providing a high Young's modulus to a bonding material layer, it is preferable that the bonding material composition which forms a bonding material layer contains plate-shaped particle | grains whose Young's modulus is 100 GPa or more as plate-shaped particle | grains. In addition, from the same point of view, it is preferable that the bonding material composition contains noncritical particles having a Young's modulus of 100 GPa or more as noncritical particles. In addition, the Young's modulus of these plate-shaped particles or non-critical particles is, for example, a compression test according to JIS R1608 using a micro-compression tester, measures the displacement when a predetermined load is loaded, and is calculated from the load-displacement curve. can do.

It is preferable that the ratio of the said plate-shaped particle contained in a bonding material composition shall be 1 mass%-60 mass% of the main component (plate-shaped particle, non-critical particle | grain, and an inorganic adhesive agent) from a viewpoint of the strength and fracture resistance of a bonding material layer, It is more preferable to set it as 5 mass%-55 mass%, and it is more preferable to set it as 10 mass%-50 mass%. When the ratio of plate-shaped particle | grains is less than 1 mass% of the whole main component, the strength and fracture resistance of a bonding material layer may become inadequate, and when it exceeds 60 mass%, it may be difficult to apply.

The aspect ratio of the plate-shaped particles is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, from the viewpoint of the strength and the fracture resistance of the bonding material layer. When the aspect ratio of the plate-shaped particles is less than 3, the bonding material layer having sufficient strength and fracture resistance may not be obtained.

The average particle diameter of the plate-shaped particles is preferably 1 µm to 200 µm, more preferably 3 µm to 180 µm, further preferably 5 µm to 150 µm from the viewpoint of the strength and the fracture resistance of the bonding material layer. When the average particle diameter of plate-shaped particle | grains is less than 1 micrometer, the bonding material layer which has sufficient strength and fracture resistance may not be obtained, and when it exceeds 200 micrometers, it may be difficult to carry out construction.

As a specific material of plate-shaped particle | grains, mica, talc, glass flakes, etc. are mentioned, for example, In particular, mica can be used suitably. Regarding mica and talc, it is preferable to remove the hydroxyl groups in the structure in advance, so that the thermal stability of the resulting bonding material layer is improved. Therefore, calcined mica and calcined talc are preferred, and calcined mica is particularly preferred. . The calcination temperature is preferably 800 ° C or higher for mica and 900 ° C or higher for talc.

It is preferable that the ratio of the non-critical particle | grains contained in the bonding material composition of this invention as fillers other than the said plate-shaped particle shall be 1 mass%-50 mass% of the whole main component from a viewpoint of the strength of a bonding material layer, or breaking resistance, 5 It is more preferable to set it as the mass%-48 mass%, and it is more preferable to set it as 10 mass%-45 mass%. When the ratio of non-critical particle | grains is less than 1 mass% of the whole main component, it may be difficult to apply, and when it exceeds 50 mass%, the bonding material layer which has sufficient strength and fracture resistance may not be obtained.

It is preferable that it is 0.05 micrometer-200 micrometers, It is more preferable that it is 0.1 micrometer-150 micrometers from a viewpoint of the strength and fracture resistance of a bonding material layer, and, as for the average particle diameter of a non-type particle | grain, it is still more preferable if it is 1 micrometer-100 micrometers. . When the average particle diameter of plate-shaped particle | grains is less than 0.05 micrometer, it may be difficult to apply, and when it exceeds 200 micrometers, the bonding material layer which has sufficient strength and fracture resistance may not be obtained.

Specific materials for the non-critical particles include, for example, alumina, silica, mullite, zirconia, silicon carbide, silicon nitride, aluminum nitride, and glass.

It is preferable that the ratio of the inorganic adhesive agent contained as a matrix in the bonding material composition of this invention shall be 1 mass%-70 mass% of the whole main component from a viewpoint of the strength and fracture resistance of a bonding material layer, and are 5 mass%-65 mass% It is more preferable to set it as it, and it is further more preferable to set it as 10 mass%-60 mass%. When the ratio of an inorganic adhesive agent is less than 1 mass% of the whole main component, it may be difficult to carry out, and when it exceeds 70 mass%, the bonding material layer which has sufficient strength and fracture resistance may not be obtained.

Specific materials of the inorganic adhesive include colloidal silica (silica sol), colloidal alumina (alumina sol), various metal oxide sol, ethyl silicate, water glass, silica polymer, aluminum phosphate, and the like. It is particularly preferable to use colloidal silica because it is excellent in affinity with chemicals, chemical stability, heat resistance and the like.

In addition to the said main component, the bonding material composition may contain subcomponents, such as an organic binder, a dispersing agent, foaming resin, and water, as needed.

In the joined body of the present invention, the porosity of the bonded material layer is preferably less than 50%, more preferably less than 45%, and even more preferably less than 40%, from the viewpoint of the strength, the fracture resistance, or the Young's modulus of the joined material layer. When the porosity of the bonding material layer is 50% or more, sufficient Young's modulus may not be expressed.

Although the to-be-joined body which comprises the joined body of this invention is not specifically limited, For example, the ceramic member for obtaining a ceramic structure can be mentioned as a suitable to-be-joined body, Especially, the honeycomb segment for obtaining a honeycomb structure is especially suitable to be joined. It can be mentioned as water. The honeycomb structure obtained by joining such honeycomb segments can be suitably used for applications such as a diesel exhaust gas purification filter that is exposed to a harsh thermal environment, for example, in the regeneration process of the filter.

The manufacturing method of the joined body of this invention joins two or more to-be-joined bodies integrally using the bonding material composition which has plate-shaped particle | grains, non-critical particle | grains, and an inorganic adhesive as a main component, and the Young's modulus after dry hardening becomes 3 GPa or more. It is. The bonding material composition includes, as necessary, an organic binder (eg, methyl cellulose (MC), carboxymethyl cellulose (CMC), etc.), foamed resin, It can manufacture by adding a dispersing agent, water, etc., mixing and kneading it using a kneading machine, such as a mixer, to make a paste form.

In addition, when joining to-be-joined bodies using a bonding material composition, it is sufficient strength and joining that joining temperature is 1000 degrees C or less (more preferably, 50 degreeC-900 degreeC, More preferably, 100 degreeC-800 degreeC). It is preferable from a viewpoint that a state can be expressed. Although it can join together without a problem even if it exceeds 1000 degreeC, since the desired characteristic (Young's modulus etc.) cannot be acquired easily, it is unpreferable.

Next, the case where the joined body of the present invention is a honeycomb structure formed by joining a plurality of honeycomb segments (joints) will be described with reference to specific structural examples.

As shown in FIG. 1 and FIG. 2, the honeycomb structure 1 is arranged so that a plurality of cells 5 serving as flow paths of a fluid formed and partitioned by a porous partition wall 6 are parallel to each other in a central axis direction. The present invention provides a honeycomb segment (2) having a structure in which the whole structure is formed by attaching in a direction perpendicular to the central axis of the honeycomb structure (1) while each constitutes a part of the whole structure. It is comprised as the honeycomb segment joined body integrally joined by the bonding material layer 9 formed from the bonding material composition of this invention.

The honeycomb segment 2 integrally bonded by the bonding material layer 9 is ground after the bonding so that the entire cross-sectional shape thereof is circular, elliptical, triangular, square, or any other desired shape. Covered by 4). In addition, when using this honeycomb structure 1 as a DPF, as shown in FIG. 3 and FIG. 4 which is sectional drawing along the AA line, each cell 5 of the honeycomb segment 2 is each one edge part. WHEREIN: It seals by the filler 7 alternately.

In the predetermined cell 5 (inflow cell), the left end side in FIGS. 3 and 4 is opened, while the right end side is sealed along the filler 7, and the other cells 5 adjacent to this are closed. In the outflow cell, the left end side is sealed by the filler 7, but the right end side is open. By this sealing, as shown in FIG. 2, the end surface of the honeycomb segment 2 exhibits a checkered pattern.

In FIG. 4, the left side of the honeycomb segment 2 becomes an inlet of exhaust gas, and exhaust gas flows into the honeycomb segment 2 from the cell 5 (inflow cell) which is open without being sealed. The exhaust gas flowing into the cell 5 (inlet cell) passes through the porous partition wall 6 and flows out of the other cell 5 (outflow cell). And when passing through the partition wall 6, the particulate matter (particulate) containing soot in exhaust gas is captured by the partition wall 6. In this way, the exhaust gas can be purified. By this capture, since the particle | grains containing soot accumulate over time inside the honeycomb segment 2, and a pressure loss becomes large, the regeneration process which burns soot etc. is performed regularly. In addition, although the honeycomb segment 2 in which the whole cross-sectional shape is square is shown in FIGS. 2-4, shapes, such as a triangle and a hexagon, may be sufficient. In addition, the cross-sectional shape of the cell 5 may also be triangular, hexagonal, circular, elliptical, or other shapes.

As shown in FIG. 2, the bonding material layer 9 is formed from the bonding material composition, is applied to the outer circumferential surface of the honeycomb segment 2, and functions to bond the honeycomb segments 2 to each other. Application of the bonding material layer 9 may be performed on the outer circumferential surface of each honeycomb segment 2 adjacent to each other, but may be performed only on one side of the corresponding outer circumferential surface between the adjacent honeycomb segments 2. Application | coating only to one side of such a corresponding surface is preferable at the point which can save the usage-amount of the bonding material layer 9. The direction in which the bonding material layer 9 is applied is not particularly limited, such as the long longitudinal direction in the honeycomb segment outer circumferential surface, the direction perpendicular to the long length in the honeycomb segment outer circumferential surface, the direction perpendicular to the honeycomb segment outer circumferential surface, but the long length in the honeycomb segment outer circumferential surface. It is preferable to apply toward the longitudinal direction. The thickness of the bonding material layer 9 is determined in consideration of the bonding force between the honeycomb segments 2, and is appropriately selected in the range of, for example, 0.5 mm to 3.0 mm.

As a material of the honeycomb segment 2 used in the present embodiment, from the viewpoint of strength and heat resistance, a silicon-silicon carbide system formed of silicon carbide (SiC) and silicon carbide (SiC) as aggregate and silicon (Si) as a binder At least one selected from the group consisting of composite materials, silicon nitride, cordierite, mullite, alumina, spinel, silicon carbide-cordierite-based composites, lithium aluminum silicate, aluminum titanate, and Fe-Cr-Al-based metals. It may be configured. Especially, it is preferable to consist of a silicon carbide (SiC) or a silicon-silicon carbide type | system | group composite material.

The production of the honeycomb segment 2 is appropriately selected from the above materials, for example, and includes binders such as methyl cellulose, hydroxypropoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and polyvinyl alcohol, pore materials, surfactants, It can be performed by adding water as a solvent, making plastic clay, extruding the clay so as to have the above-described shape, and then drying by microwave, hot air or the like and then sintering.

As the filler 7 used for sealing the cell 5, the same material as the honeycomb segment 2 can be used. Sealing with the filler material 7 can be performed by filling the open cell 5 by immersing the end face of the honeycomb segment 2 in a slurry-like filler in a state of masking the cell 5 that is not sealed. Can be. Although the filling of the filler 7 may be performed before baking after the honeycomb segment 2 shaping | molding, or after baking, it is preferable to carry out before baking since the baking process completes once.

After the production of the honeycomb segment 2 as described above, a paste-like bonding material composition is applied to the outer circumferential surface of the honeycomb segment 2, the bonding material layer 9 is formed, and a predetermined three-dimensional shape (the whole of the honeycomb structure 1 is formed). Structure], the some honeycomb segment 2 is attached, and it crimps | bonds in this attached state, and heat-drys. In this way, the joined body in which the plurality of honeycomb segments 2 are integrally joined is produced. Thereafter, the bonded body is ground to the above-described shape, the outer circumferential surface is covered with the coating material 4, and heated and dried. In this way, the honeycomb structure 1 shown in FIG. 1 is produced. As a material of the coating material 4, the same thing as the bonding material layer 9 can be used. The thickness of the coating material 4 is suitably selected, for example in the range of 0.1 mm to 1.5 mm.

<Example>

Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

(Example 1)

[Production of Honeycomb Segments]

As the honeycomb segment raw material, SiC powder and metal Si powder were mixed at a mass ratio of 80:20, and a pore material, an organic binder, a surfactant, and water were added thereto to prepare a plastic clay. The clay was extruded and dried to form a honeycomb segment molded body having a thickness of 310 μm, a cell density of about 46.5 cells / cm 2 (300 cells / square inch), a square having a cross section of 35 mm on one side, and a length of 152 mm. Got it. Both ends of the cell were sealed in this honeycomb segment molded body so that the end face showed a checkered pattern. In other words, the adjacent cells were sealed so as to be sealed at ends opposite to each other. As a sealing material, the same material as the honeycomb segment raw material was used. Both ends of the cell were sealed, dried, degreased at about 400 ° C. in an air atmosphere, and then calcined at about 1450 ° C. in an Ar inert atmosphere to have a porous structure in which SiC crystal grains were bonded to Si. Obtained honeycomb segment.

(Preparation of bonding material composition)

Under the conditions shown in Tables 1 and 2, a dispersant, a foamed resin, and an organic binder (CMC) were mixed with the plate-shaped particles and / or the non-shaped particles, and colloidal silica was added as an inorganic adhesive, and kneading was carried out with a mixer for 30 minutes. It carried out and obtained paste type bonding material composition (bonding material composition No.1-No.16), respectively. The calcined mica used as the plate-shaped particles in the bonding material composition No. 13 was calcined at 800 ° C, and the calcined talc used as the plate-shaped particles in the bonding material composition No. 14 was calcined at 900 ° C. In Table 1 and Table 2, the ratio of the plate-shaped particle | grains which are a main component, non-critical particle | grains, and an inorganic adhesive agent was shown by each mass% when these sum total was 100. In addition, the ratio of the dispersing agent, foaming resin, and organic binder which are subcomponents was shown by the mass% of the external multiple when this was made into 100 main components. The aspect ratio of the plate-shaped particles was calculated as the "long diameter / thickness" of this particle | grain, and the said "long diameter" and the "thickness" were measured by the electron microscope observation. That is, it observed from the arbitrary direction perpendicular | vertical to the thickness direction of plate-shaped particle | grains, and measured the thickness by image-processing the electron microscope photograph. Moreover, in the same image, the length of the particle | grains of the direction perpendicular | vertical to the thickness direction was made into long diameter, and the long diameter was measured by image processing. In addition, this measurement was performed about ten or more particle | grains selected at random from the observation visual field, and made the average value of these aspect ratios into the aspect ratio of plate-shaped particle | grains.

[Production of Honeycomb Structure]

On the outer wall surface of the honeycomb segment, the bonding material composition No. 1 was coated to have a thickness of about 1 mm to form a bonding material layer, and the steps of stacking other honeycomb segments thereon were repeated. After making the whole honeycomb segment laminated body which consists of these, and applying the pressure from the exterior suitably, it dried at 140 degreeC for 2 hours, and obtained the honeycomb segment joined body. After the outer circumference of the obtained honeycomb segment joined body was cylindrically ground, the outer circumferential surface was coated with a coating material, and dried and cured at 700 ° C. for 2 hours to obtain a honeycomb structure.

(Evaluation of bonding material layer)

About the bonding material layer (bonding composition after hardening) of the obtained honeycomb structural body, strength, Young's modulus, and porosity were calculated | required by the following method. The results are shown in Table 3.

burglar:

The portion of the bonding material layer was cut out of the honeycomb structured body into a predetermined shape (4 × 1 × 20 mm rod), and the cut piece was measured by performing a three-point bending test according to JIS R1601.

Young's modulus:

In the measurement of the strength, the displacement when a predetermined load was loaded on the cut test piece was measured and calculated from the load-displacement curve (based on JIS R1602).

Porosity:

The portion of the bonding material layer was cut out from the honeycomb structured body into an arbitrary shape (10 × 10 × 1 mm plate) and calculated by the Archimedes method.

(Evaluation of Honeycomb Structures)

About the obtained honeycomb structured body, the joining state was confirmed by the following method, and rapid heating test (burner spalling (B-sp) test), rapid cooling test (electrically spalling (E-sp) test), and engine The test (E / G test) was done. The results are shown in Table 3.

Junction Status:

The state of the junction part after joining and hardening was visually observed, and the joint strength was observed by the hand texture. "(Circle)", the bonding state which peeled off or fell easily, or the state with many cracks or defects was made into "x" in the state without a crack and a defect in a firm bonding state.

Rapid heating test [burner spalling (B-sp) test]:

The test that makes the temperature difference between the center part and the outside part by flowing the air heated by the burner to the honeycomb structure, and evaluates the thermal shock resistance by the temperature at which the crack of the honeycomb structure does not occur (the higher the temperature, the higher the thermal shock resistance). to be.

Rapid cooling test [electrically spalling (E-sp) test]:

The honeycomb structured body is heated at 550 ° C for 2 hours with an electric furnace to a uniform temperature (450 ° C), and then taken out at room temperature and evaluated for thermal shock resistance by the presence or absence of cracking of the honeycomb structured body. "(Circle)" and the case where a crack was confirmed were made into "x" when the generation | occurrence | production of a crack was not recognized.

Engine test (E / G test):

It is a test which burns the particle | grains deposited for filter regeneration, and evaluates a thermal shock resistance by the presence or absence of the crack of a honeycomb structured structure on condition that the temperature of a honeycomb structure center part will be 1000 degreeC. "(Circle)" and the case where a crack was confirmed were made into "x" when the generation | occurrence | production of a crack was not recognized.

(Examples 2 to 14, Comparative Examples 1 and 2)

A honeycomb structural body was produced in the same manner as in Example 1 except that the bonding material composition No. 1 was changed to the bonding material composition Nos. 2 to 16 shown in Tables 1 and 2. The obtained honeycomb structures (Examples 2 to 14, Comparative Example 1 and Comparative Example 2) were evaluated in the same manner as in Example 1, respectively. The results are shown in Table 2.

Bonding composition NO. Plate-shaped particle Critic Inorganic adhesive Other ingredients material Young's modulus [㎬] Aspect ratio Average particle diameter [µm] Ratio of main component [mass%] material Young's modulus [㎬] Average particle diameter [µm] Ratio of main component [mass%] material Principal Components Ratio [mass%] Ratio (main fold) with respect to a main component [mass%] One mica 180 15 40 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 2 mica 180 20 40 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 3 mica 180 23 40 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 4 mica 180 20 20 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 5 mica 180 20 50 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 6 mica 180 20 40 20 SiC 400 1.5 60 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 7 mica 170 6 15 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 8 mica 170 6 20 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1

Bonding material composition No. Plate-shaped particle Critic Inorganic adhesive Other ingredients material Young's modulus [㎬] Aspect ratio Average particle diameter [µm] Ratio of main component [mass%] material Young's modulus [㎬] Average particle diameter [µm] Ratio of main component [mass%] material Proportion of main component [mass%] Ratio (main fold) with respect to a main component [mass%] 9 Glass flakes 70 15 40 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 10 Glass flakes 75 15 40 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 11 Glass flakes 70 60 160 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 12 Glass flakes 75 60 160 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 13 Calcined mica 180 20 42 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 14 Hassotal 170 6 16 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1 15 mica 180 20 40 30 SiC 400 1.5 40 Colloidal silica 30 Dispersant: 0.15 Foamed resin: 3 Organic binder: 0.1 16 ― ― ― ― ― SiC 400 1.5 65 Colloidal silica 35 Dispersant: 0.15 Foamed resin: 0.5 Organic binder: 0.1

Bonding material composition No. Strength of bonding material layer [MPa] Young's modulus of bonding material layer Porosity of the bonding material layer [%] Bonding type B-sp test [℃] E-sp test E / G test Example 1 One 10 8 44 ○ 800 ○ ○ Example 2 2 11 9 45 ○ 900 ○ ○ Example 3 3 14 9 43 ○ 900 ○ ○ Example 4 4 10 8 42 ○ 700 ○ ○ Example 5 5 13 9 44 ○ 800 ○ ○ Example 6 6 10 10 38 ○ 700 ○ ○ Example 7 7 9 6 40 ○ 700 ○ ○ Example 8 8 9 7 41 ○ 800 ○ ○ Example 9 9 7 5 45 ○ 700 ○ ○ Example 10 10 8 5 46 ○ 800 ○ ○ Example 11 11 7 6 46 ○ 700 ○ ○ Example 12 12 7 5 47 ○ 800 ○ ○ Example 13 13 12 9 48 ○ 900 ○ ○ Example 14 14 10 6 42 ○ 700 ○ ○ Comparative Example 1 15 0.9 0.8 75 × No test No test No test Comparative Example 2 16 2.2 4 42 ○ 500 × ×

As shown in Table 3, Examples 1 to 14 according to Examples of the present invention had high strength of the bonding material layer, good bonding state, and showed excellent thermal shock resistance. On the other hand, in Comparative Example 1 in which the Young's modulus of the bonding material layer was less than 3 GPa, the porosity of the bonding material layer was reduced to lower the Young's modulus. As a result, the strength of the bonding material layer was lowered and the bonding state was not good. It was in the state not to be able to perform, either. Moreover, although the bonding state was favorable, the comparative example 2 in which the plate-shaped particle is not contained in the bonding material composition which forms a bonding material layer was inferior to heat shock resistance.

INDUSTRIAL APPLICABILITY The present invention can be suitably used for the production of a honeycomb structure obtained by integrating a plurality of honeycomb segments used in a joined body obtained by joining and integrating a plurality of joined objects, for example, a DPF.

1 is a perspective schematic view showing an example of an embodiment of a joined body (honeycomb structure) according to the present invention;

2 is an enlarged view of an essential part showing an example of an embodiment of a joined body (honeycomb structure) according to the present invention;

3 is a perspective schematic view of a joined object (honeycomb segment) constituting a bonded body (honeycomb structure) according to the present invention;

4 is a sectional view taken along the line A-A in FIG.

<Explanation of symbols for the main parts of the drawings>

1: honeycomb structure 2: honeycomb segment

4: coating material 5: cell

6: partition wall 7: filling material

9: bonding material layer

Claims (11)

As a joined body in which two or more to-be-joined bodies are integrated through the bonding material layer formed of a bonding material composition, The said bonding material composition contains plate-shaped particle | grains, a non-strain particle, and an inorganic adhesive agent so that it may be 50 mass% or more of the whole said bonding material composition, and the Young's modulus of the said bonding material layer is 3 kPa or more. The conjugate according to claim 1, wherein the plate-shaped particles have a Young's modulus of 100 GPa or more. The conjugate according to claim 1 or 2, wherein the non-critical particles have a Young's modulus of 100 GPa or more. The ratio of the said plate-shaped particle | grains contained in the said bonding material composition is 1 mass%-60 mass% based on the total mass of the said plate-shaped particle | grains, the said non-critical particle | grains, and the said inorganic adhesive agent. Phosphorus conjugate. The conjugate according to claim 1 or 2, wherein an aspect ratio of the plate-shaped particles is 3 or more. The conjugate according to claim 1 or 2, wherein the average particle diameter of the plate-shaped particles is 1 µm to 200 µm. The conjugate according to claim 1 or 2, wherein the plate-shaped particles are plate-shaped particles made of at least one material selected from the group consisting of mica, talc, and glass flakes. The conjugate according to claim 7, wherein the mica is mica calcined at 800 ° C or higher, and the talc is talc calcined at 900 ° C or higher. The joined body according to claim 1 or 2, wherein the porosity of the bonding material layer is less than 50%. The conjugate of claim 1 or 2, wherein the joined object is a honeycomb segment. Bonding body which integrally joins two or more to-be-joined bodies using the bonding material composition containing plate-shaped particle | grains, a non-small particle, and an inorganic adhesive agent in 50 mass% or more of the whole bonding material composition, and the Young's modulus after dry hardening becomes 3 GPa or more. Manufacturing method.

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