CN101058049B - Ceramic honeycomb structure, manufacturing method thereof, and coating used for the manufacture - Google Patents
Ceramic honeycomb structure, manufacturing method thereof, and coating used for the manufacture Download PDFInfo
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- CN101058049B CN101058049B CN2007100063015A CN200710006301A CN101058049B CN 101058049 B CN101058049 B CN 101058049B CN 2007100063015 A CN2007100063015 A CN 2007100063015A CN 200710006301 A CN200710006301 A CN 200710006301A CN 101058049 B CN101058049 B CN 101058049B
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Abstract
A ceramic honeycomb structure comprising a ceramic honeycomb body comprising axial grooves on its periphery, and cell walls constituting a larger number of flow paths inside the grooves, and a peripheral wall layer covering the grooves, wherein there are stress release portions at least partially in the peripheral wall layer and/or between the peripheral wall layer and the grooves. The thermal expansion coefficient of the peripheral wall layer is preferably smaller than those of the cell walls in a radial direction. The peripheral wall layer is preferably formed on the ceramic honeycomb body formed by removing a peripheral wall from a ceramic green body, before or after sintering the ceramic honeycomb body.
Description
The application is that application number is 03800080.6, the applying date be June 7, denomination of invention in 2003 be ceramic honeycomb structure and manufacture method thereof and make in used be coated with dividing an application of material.
Technical field
The present invention relates to prevent ceramic honeycomb structure and the manufacture method thereof peeling off or crack from the honeycomb main body of periphery parietal layer, promptly be used in the exhaust gas purification that at high temperature is subjected to thermal shock easily with catalytic converter or absorb particulate with also not cracking in the filter and ceramic honeycomb structure and the manufacture method thereof that fragmentation etc. has sufficient mechanical strength can not taking place yet for vibrating etc. even particularly relate to.
Background technology
From protecting the area and even the environment of the whole earth,, use exhaust gas purification based on ceramic honeycomb structure with catalytic converter or absorb the particulate filter at present for the harmful substance of the graphite particle in the exhaust of removing diesel engine etc.As shown in Figure 1, honeycomb structure 1 has the cellular unit wall 4 of incorporate periphery wall 3 and a plurality of cellular units 6 of formation.Honeycomb structure 1, the hold assembly between the inner peripheral surface by being disposed at metal system accommodating container (not shown) and the periphery wall 3 of honeycomb structure 1 is securely held.
Honeycomb structure 1 was by following operation preparation in the past.To stir the ceramic base soil extrusion molding that cordierite generates material powder, shaping additive, pore creating material and water gained, obtain having the formed body of periphery wall 3 and cellular unit wall 4 incorporate ojosas.Dry this formed body, and then remove the shaping additive etc. of bonding agent in the formed body etc. by heating after, make its shape with regulation and intensity by sintering, thereby obtain by periphery wall 3 with fine pores and the cellular unit wall 4 integrated honeycomb structures that constitute 1.
But, at Production Example such as external diameter be more than the 150mm, length is the use for diesel engine large size ceramic honeycomb structure more than the 150mm or during the slim honeycomb structure of the thickness of making cellular unit wall 4 below 0.2mm, because the overweight or undercapacity of formed body, can not support deadweight, and the problem that exists near the cellular unit wall 4 the periphery wall 3 to distort or be out of shape.
As the method that addresses this problem, Japan's patent the 2nd, 604, the method of following formation periphery parietal layer is disclosed for No. 876, promptly, the ceramic base soil extrusion molding of cordierite raw material, shaping additive and/or pore creating material gained will be stirred, drying and sintering, have the sintered body of ojosa in formation after, remove the periphery wall 3 of sintered body and near the cellular unit wall it by grinding with this ojosa, after being coated with material on the cellular unit wall that exposes, carry out drying and curing, thereby form the periphery parietal layer.In the method, owing to remove the periphery wall 3 of sintered body and near the cellular unit wall 4 it, therefore can remove periphery wall 3 and near the distortion cellular unit it with this ojosa by grinding.Even it is very low to have the circularity of sintered body of ojosa, owing to be to form the periphery parietal layer by grinding, after improving circularity, so also can improve dimensional accuracy.If use the material that is coated with that contains ceramic fibre and inorganic bond, can also form high-intensity periphery parietal layer.
In addition, as the ceramic honeycomb structure behind the anti-fissility that improves the periphery parietal layer, Japan's patent the 2nd, the periphery parietal layer is disclosed in 613, No. 729 by cordierite particle and/or ceramic fibre and the ceramic honeycomb structure that is made of the noncrystalline matrix of oxide that the aluminium oxide of the silica of colloidal state or colloidal state constitutes.
One example structure of ceramic honeycomb structure 1 as shown in Figures 2 and 3.Ceramic honeycomb main body 10, have a plurality of cellular units 6 that separated by cellular unit wall 4 and the axis direction groove 14 that on the most peripheral of ceramic honeycomb main body 10, forms, by on groove 14, being coated with the spreading material and periphery parietal layer 12 being set, can prevent that in use periphery parietal layer 12 is peeled off, can also suppress the reduction of the thermal shock strength of honeycomb structure 1 simultaneously.
But, use Japan's patent the 2nd, 604, No. 876 and No. the 2nd, 613,729, Japan's patent in the catalytic converter used as exhaust gas purification of the ceramic honeycomb structure of record and when absorbing particulate and using filter, knownly have a following problem.
Using ceramic honeycomb structure as catalyst carrier and when absorbing particulate and using filter, ceramic honeycomb structure, in the metal container made by support component by firm grip.The high-temperature exhaust air owing in a plurality of openings of ceramic honeycomb structure, circulate, therefore the especially rapid temperature rising of local generation when initiating, in ceramic honeycomb structure, produce thermal stress owing to the temperature difference between portion of ceramic honeycomb main center and the periphery parietal layer makes, therefore crack on the perine outside.In addition, when using with filter as the absorption particulate, owing to burning is deposited in regenerate heat in handling of particulate on the filter, especially near particulate is piled up the centre of more ceramic honeycomb structure, produce local temperature and raise, also have because of thermal stress to make the problem that cracks on the periphery parietal layer.
If crack on the perine outside and this crackle extends on the cellular unit wall always, then the cellular unit wall comes off and the purifying property of exhaust is reduced, and perhaps entrance side is communicated with outlet side and makes atomic absorptivity decline.
Make that external diameter is more than the 150mm, length is large, honeycomb tectosome more than the 150mm or cellular unit wall thickness when being thin-walled honeycomb tectosome below the 0.15mm, then be extruded in the body, it is more to produce the bad phenomenon of distorting or being out of shape near the cellular unit the periphery wall, its result has shaping followed and dry residual stress.If directly carry out sintering under the situation of this bad phenomenon having, then to locally discharge residual stress, thereby crack from bad, might expand and be extended down to whole sintered body.Even remove the periphery wall of sintered body and near cellular unit wall thereof, can not remove this crackle fully, thereby fabrication yield is descended.
In addition,, therefore, as shown in Figure 4, on the cellular unit wall 4 of the most peripheral that constitutes groove 14, be easy to generate incomplete 4a, form the incomplete incomplete groove 14a of a part of cellular unit wall 4 easily because the ceramic honeycomb sintered body is hard and crisp.Because the groove 14 of periphery is little with the contact area of cellular unit wall 4, so the isobaric intensity of honeycomb structure 1 reduces or causes easily peeling off of periphery parietal layer 12.If as catalytic converter or absorption particulate filter, use this honeycomb structure, then because engine luggine or road vibration, the periphery parietal layer is peeled off from honeycomb structure, in reservoir vessel, can not guarantee the chucking power that suits, therefore honeycomb structure moves in reservoir vessel, thus the breakage that may produce honeycomb structure.
In No. the 2nd, 604,876, Japan's patent, in order to remove the periphery wall of ceramic honeycomb sintered body, using with peripheral speed is that 750～2100m/ divides the emery wheel of rotation at a high speed, and the process velocity that divides with 0.7～0.9mm/ carries out grinding.But, when the cellular unit wall of grinding honeycomb structure, owing to be the interrupted processing of the interrupted conflict of machining tool, the processing capacity of therefore have to less control feeding or incision etc., process time is just elongated like this.Therefore in addition because sintered body is hard and crisp, be necessary to use high price emery wheel as abrasive grinding wheel resemble the skive.
In addition, in above-mentioned conventional art, the material that is coated with that is made of cordierite particle and inorganic adhesive owing to coating on the outer peripheral face of the honeycomb main body that is made of cordierite forms the periphery parietal layer, therefore the thermal coefficient of expansion of periphery parietal layer big than honeycomb main body, outside after the drying and sintering of perine, can be outside residual tensile stress on the perine, residual compression stress on the cellular unit wall.The reason that the thermal coefficient of expansion of periphery parietal layer becomes bigger than honeycomb main body, be because the potter's clay particle (hexagonal plate crystal) in the raw material is oriented in (wall is interior) in the slit jaw by extrusion molding with the narrow slits of mouthful mould, differently-oriented directivity for the potter's clay particle that forms by sintering, the cordierite crystalline orientation of hexagonal column is the right angle, so with respect to the thermal coefficient of expansion of cellular unit wall is little and the periphery parietal layer is made of randomly-oriented cordierite particle and the big inorganic adhesive of thermal coefficient of expansion.
In order to be accommodated in the container, when the clamping honeycomb structure, sometimes also outside perine produce tensile stress.If act on the state of periphery parietal layer with tensile stress the temperature of the central part of honeycomb structure is sharply risen, then because of the temperature difference of cellular unit wall in the periphery parietal layer, the tensile stress in the periphery parietal layer can increase, and also is easy to generate crackle outside on the perine.
Summary of the invention
Therefore, the purpose of this invention is to provide on the cellular unit wall and to be difficult to extend the crackle that produces based on thermal shock, to have the good resistance to sudden heating and the ceramic honeycomb structure of reliability.
Another object of the present invention provides when using with filter with catalytic converter or absorption particulate as exhaust gas purification, and the crackle ceramic honeycomb structure of thermal stress is followed in difficult generation.
Another purpose of the present invention provides the periphery parietal layer and the honeycomb main body is difficult to peel off, have good isobaric intensity and the ceramic honeycomb structure that can make efficiently.
Another object of the present invention provides the manufacture method of making this ceramic honeycomb structure.
Ceramic honeycomb structure of the present invention, comprise: have the axis direction groove of periphery and the ceramic honeycomb main body that forms the cellular unit wall of a plurality of openings in described groove inboard, with the periphery parietal layer that covers described groove, wherein, the thermal coefficient of expansion of described periphery parietal layer is littler than the thermal coefficient of expansion of the footpath direction of described cellular unit wall, is 10.0 * 10
-7/ ℃ below.
In described ceramic honeycomb structure, preferred periphery parietal layer is made of the mixture that contains amorphous silica particle and noncrystalline matrix of oxide.
In addition, the noncrystalline matrix of oxide preferably is made of the silica of colloidal state and/or the aluminium oxide of colloidal state.The periphery parietal layer more preferably has the composition of the noncrystalline matrix of oxide of the amorphous silica particle that contains 100 mass parts and 2～35 mass parts.
The manufacture method of ceramic honeycomb structure of the present invention, shaping has extrusion molding pottery base soil and makes the ceramic honeycomb structure of periphery wall and the incorporate ojosa of cellular unit wall, remove described formed body or to described formed body carry out sintering and the periphery wall of sintered body and near the cellular unit wall it, utilization is coated with material and covers the axis direction groove that exposes and form the periphery parietal layer, wherein, contain amorphous silica particle and noncrystalline matrix of oxide at the described material that is coated with, the thermal coefficient of expansion of described periphery parietal layer is 10.0 * 10
-7/ ℃ below.
In the manufacture method of above-mentioned ceramic honeycomb structure, preferably with respect to amorphous silica particle 100 mass parts, the content of described noncrystalline matrix of oxide is 2～35 mass parts, and further preferred described noncrystalline matrix of oxide is made of colloidal silica particles and/or colloidal alumina.
The invention provides a kind of material that is coated with of the periphery parietal layer that is used to form ceramic honeycomb structure, wherein, the thermal coefficient of expansion of described periphery parietal layer is 10.0 * 10
-7/ ℃ below, and be divided into benchmark with solid formation, contain the amorphous silica particle of 100 mass parts and the colloidal silica and/or the colloidal alumina of 2～35 mass parts.
In preferred implementation of the present invention, the cellular unit wall of ceramic honeycomb structure preferably has the average pore footpath of 50～80% the porosity and 10～50 μ m.
In addition, in preferred implementation of the present invention, the cell-wall of preferred described ceramic honeycomb structure has thickness and the above unit interval of 1.3mm of 0.1～0.5mm.
When ceramic honeycomb structure of the present invention is purified the catalyst carrier of usefulness or absorbs the particulate filter use as emission gases, has the effect that is difficult to produce the crackle of following thermal stress.
Description of drawings
Fig. 1 (a) is a stereogram of representing ceramic honeycomb structure in the past, and Fig. 1 (b) is the stereogram of the broken section of expression ceramic honeycomb structure of the present invention.
Fig. 2 is a routine partial sectional view of representing ceramic honeycomb main body used among the present invention.
Fig. 3 is the expression partial sectional view of the ceramic honeycomb structure of the structure of the ceramic honeycomb body recess of coverage diagram 2 with having periphery parietal layer imporosity.
Fig. 4 is a partial sectional view of representing the ceramic honeycomb main body that the part of cellular unit wall is lacked after removing periphery wall in the past.
Fig. 5 is illustrated in the partial sectional view that has the space part state on the periphery parietal layer of groove of ceramic honeycomb main body of coverage diagram 2.
Fig. 6 is illustrated in the scan microscope photo that shows crackle shape space part on the periphery wall laminar surface of ceramic honeycomb structure of the present invention.
Fig. 7 (a) is the stereogram of space part one example that is illustrated on the periphery parietal layer of ceramic honeycomb structure of the present invention, extends along axis direction,
Fig. 7 (b) is another the routine stereogram of space part that is illustrated on the periphery parietal layer of ceramic honeycomb structure of the present invention, extends along axis direction,
Fig. 7 (c) is the stereogram of the another example of space part that is illustrated on the periphery parietal layer of ceramic honeycomb structure of the present invention, extends along axis direction,
Fig. 7 (d) is the stereogram of the another example of space part that is illustrated on the periphery parietal layer of ceramic honeycomb structure of the present invention, extends along axis direction and circumferencial direction,
The stereogram of Fig. 7 (e) another example of space part that to be expression extend along the axis direction of ceramic honeycomb structure of the present invention and circumferencial direction,
Fig. 7 (f) is the stereogram that is illustrated in the another example of space part that is the extension of tortoise plastron shape on the ceramic honeycomb structure of the present invention.
Fig. 8 is illustrated in the partial sectional view that has the ceramic honeycomb structure of space part between periphery parietal layer and the groove.
Fig. 9 is the local amplification view of presentation graphs 8 space parts.
Figure 10 (a) is that expression will be removed the stereogram that honeycomb formed article behind the periphery wall is positioned in state on the sintering platform,
To be expression carry out the stereogram of state behind the sintering to the honeycomb formed article of Figure 10 (a) to Figure 10 (b),
Figure 10 (c) is a stereogram of representing to divide from the large-diameter portion that the honeycomb sintered body excision of Figure 10 (b) is docked with the sintering platform state.
Figure 11 (a) is that expression will be positioned in the stereogram of state on the sintering platform with the honeycomb formed article behind the sintering platform butted part undergauge,
Figure 11 (b) is the stereogram of expression by the sintered body of the honeycomb formed article gained of Figure 11 (a).
Figure 12 (a) be expression in order on the honeycomb main body, to form the periphery parietal layer side view at the state of the two ends of honeycomb main body fixed clamp member,
Figure 12 (b) is the side view that is illustrated in the broken section of the state that forms the periphery parietal layer on the honeycomb main body of Figure 12 (a).
Figure 13 (a) is the figure of a routine manufacture method of expression ceramic honeycomb structure of the present invention.
Figure 13 (b) is the figure of another routine manufacture method of expression ceramic honeycomb structure of the present invention.
The specific embodiment
[1] embodiment
The ceramic honeycomb structure of embodiment of the present invention, it is characterized in that, comprise: have the axis direction groove of periphery and the ceramic honeycomb main body that forms the cellular unit wall of a plurality of openings in described groove inboard, with the periphery parietal layer that covers described groove, and the thermal coefficient of expansion of periphery parietal layer is littler than the thermal coefficient of expansion of the footpath direction of cellular unit wall.Will be by thermal coefficient of expansion poor than the thermal coefficient of expansion of the hot nest cell-wall of cellular unit wall and periphery parietal layer, residual compression stress on the perine outside, and on the cellular unit wall residual tensile stress.Therefore, especially when initiating, even the temperature of the central part of ceramic honeycomb structure than periphery wall floor height, but owing to have compression stress on the perine outside, therefore can prevent to crack on the perine outside.
The thermal coefficient of expansion of the periphery parietal layer preferably thermal coefficient of expansion than cellular unit wall footpath direction is little by 0.1 * 10
-7/ ℃ more than.Under the situation of cordierite honeycomb tectosome, because the thermal coefficient of expansion of cellular unit wall footpath direction is roughly 10.1～20.0 * 10
-7/ ℃, therefore if the thermal coefficient of expansion of periphery parietal layer is roughly 10.0 * 10
-7/ ℃ below the time, the crackle of the different periphery parietal layers that cause of the thermal expansion amount of the temperature difference between the periphery parietal layer that can prevent the honeycomb structure that produces owing to based on common use time the and the central part.The thermal coefficient of expansion of the periphery parietal layer more preferably thermal coefficient of expansion than cellular unit wall footpath direction is little by 1.0 * 10
-7/ ℃ more than, 9.0 * 10
-7/ ℃ below, preferred especially little by 2.0 * 10
-7/ ℃ more than, 8.0 * 10
-7/ ℃ below.
If use and contain thermal coefficient of expansion 10.0 * 10
-7/ ℃ below extremely low amorphous silica particle and with the material that is coated with of the good high strength noncrystalline matrix of oxide of amorphous silica particle zygosity, then can obtain the periphery parietal layer of thermal coefficient of expansion less than the cellular unit wall.In addition, the aggregate by the amorphous silica particle constitutes owing to the height of No. the 2nd, 604,876, hardness ratio Japan patent and the 2nd, 613, No. 729 disclosed cordierite aggregates of Japan's patent, therefore can improve the hardness of periphery parietal layer.
It all is the amorphous silica particle that the ceramic particle of periphery parietal layer (aggregate) need not, as long as just can obtain the periphery parietal layer of low thermal coefficient of expansion more than 50% for the amorphous silica particle.In addition, if not the average grain diameter of crystalloid silicon dioxide granule is 1～100 μ m, then can obtain all good periphery parietal layer of intensity and resistance to sudden heating.If not the average grain diameter of crystalloid silicon dioxide granule is lower than 1 μ m, then owing to the noncrystalline matrix of oxide that need be used to engage the amorphous silica particle in a large number, so the resistance to sudden heating of periphery parietal layer is low excessively.In addition, if not the average grain diameter of crystalloid silicon dioxide granule surpasses 100 μ m, then the intensity of periphery parietal layer descends.The average grain diameter of preferred silicon dioxide granule is 5～40 μ m.
The shape of amorphous silica particle gets over that subglobular is then unreasonable to be thought.For example, if not the length-width ratio of crystalloid silicon dioxide granule (ratio of major diameter/minor axis) is below 20, then because the surface area of amorphous silica particle is little, therefore the amount that is used in conjunction with the noncrystalline matrix of oxide of amorphous silica particle can be reduced, thereby the good periphery parietal layer of resistance to sudden heating can be obtained.The amount of noncrystalline titanium dioxide thing matrix, thus the good periphery parietal layer of resistance to sudden heating can be obtained.The length-width ratio of amorphous silica particle is preferably below 10, more preferably below 5.
Under the situation of making the honeycomb structure that is made of cordierite, the ceramic base soil that cordierite is generated raw material carries out extrusion molding, carries out sintering behind the formed body that obtains cellular unit wall and the incorporate honeycomb structure of periphery wall.But, perine and cellular unit wall are incorporate outside is extruded in the body, the thickness of periphery parietal layer is than cellular unit wall thickness, and the degree of orientation of the cordierite crystallization in the periphery wall is lower than cellular unit wall, so the thermal coefficient of expansion of periphery parietal layer is bigger than the thermal coefficient of expansion of cellular unit wall.So, after will removing fully with the incorporate periphery wall of cellular unit wall, can form the thermal coefficient of expansion periphery parietal layer littler than cellular unit wall by machining, be desirable therefore.
By on the axis direction groove that exposes on the honeycomb external side of main body face, being coated with material and forming the periphery parietal layer, not only can engage honeycomb main body and periphery parietal layer securely, but also the cellular unit wall of distortion that can be by removing periphery wall improves the mechanical strength of honeycomb structure.In addition, even under the low situation of the whole circularity of the whole honeycomb structure behind the sintering,, therefore can improve dimensional accuracy owing to be after the grinding by periphery wall improves circularity, to form the periphery parietal layer.
Removing of periphery wall, can also can carry out with the state of honeycomb formed article, but the viewpoint from cutting down finished cost is preferably carried out dried honeycomb formed article with the state of sintered body, from guaranteeing the viewpoint of dimensional accuracy, preferably sintered body is carried out.Under the situation that is coated with material that contains amorphous silica particle and noncrystalline ceramic substrate, because fusing point is lower than the pottery (cordierite etc.) that constitutes the ceramic honeycomb main body, therefore preferably after the honeycomb main body of removing periphery wall is carried out sintering, is coated with the spreading material and carries out drying and sintering.Thus, can form be fixed in securely on the groove, since thermal coefficient of expansion than the little of cellular unit wall and the periphery parietal layer that resistance to sudden heating is good.
The periphery parietal layer with respect to amorphous silica particle 100 mass parts, preferably contains the noncrystalline matrix of oxide of 2～35 mass parts with being coated with material.If not the crystalloid matrix of oxide is lower than 2 mass parts, then can not be securely in conjunction with the amorphous silica particle.In addition, if not the crystalloid matrix of oxide surpasses 35 mass parts, then when drying or sintering or owing to thermal shock, crack on the perine outside easily.Oxide colloid by the aluminium oxide of the silica of colloidal state and/or colloidal state constitutes because the raising effect of screening characteristics is very big, therefore is suitable for the noncrystalline ceramic substrate.The periphery parietal layer can contain ceramic fibre, cement etc. with being coated with material, also can further contain organic adhesive etc.
The periphery parietal layer that the noncrystalline matrix of oxide that constitutes by the aluminium oxide by the silica of amorphous silica particle and colloidal state and/or colloidal state forms preferably contains the above SiO of 70 quality %
2, also can contain an amount of Al
2O
3, MgO, Fe
2O
3, TiO
2, Na
2O, K
2O, CaO etc.Preferred SiO
2Content more than 80 quality %, preferred SiO
2Content is more than 90 quality %.
After removing the periphery wall of cordierite honeycomb formed body or sintered body by machining, by forming the periphery parietal layer that is coated with the material formation by the noncrystalline matrix of oxide (silica of preferred colloidal state and/or the aluminium oxide of colloidal state) of amorphous silica particle that contains 100 mass parts and 2～35 mass parts (being divided into benchmark) with solid formation, can obtain such ceramic honeycomb structure, promptly, promptly be used in the exhaust gas purification that applies big thermal shock with catalytic converter or absorb in the filter that particulate uses, also be not easy to crack on the perine outside, when operation, also be not easy to crack on the perine outside.Be coated with material, except that above-mentioned basis, can also contain ceramic fibre, cement etc., also can further contain organic adhesive.In addition, also can after forming the periphery parietal layer, apply the oxide colloid of colloidal silica and/or colloidal alumina etc. again on the surface of periphery parietal layer.
In embodiments of the present invention, be before sintering, remove honeycomb formed article periphery wall and near the cellular unit wall.Behind sintering,, then not only on the cellular unit wall, produce shortcoming easily, and machining needs spended time because therefore the hardness height of periphery wall and cellular unit wall will remove periphery wall and near cellular unit wall thereof by cutting.In contrast, if before sintering, carry out machining because the hardness of periphery wall and cellular unit wall is low easily, therefore can remove periphery wall and near cellular unit wall thereof by machining and can not produce the shortcoming of cellular unit wall with the very short time.
By carrying out with ojosa be dried under the situation of removing periphery wall 3 on the body, when removing the periphery wall 3 of sintered body, be not easy to produce the problem of the shortcoming 4a of cellular unit wall 4, can guarantee the contact area of cellular unit wall 4 and periphery parietal layer 12 fully.In addition, if remove periphery wall 3, then, therefore process time can be shortened owing to can carry out machining in the stage that is dried to body.In addition, owing to can use skive, and therefore the cutting element of use superhard cutter etc. can cut down finished cost.
Behind the periphery wall 3 of removing dried ceramic honeycomb formed body, if before or after sintering, on groove 14, be coated with spreading material [reaching (b)] and carry out drying and sintering with reference to Figure 13 (a), then can form and groove 14 incorporate periphery parietal layers 12.This periphery parietal layer 12, owing to be difficult to peel off from honeycomb main body 10, so honeycomb structure has good isobaric intensity.
In addition, when list claims " periphery wall " in this manual,, can be understood as the periphery wall that not only contains honeycomb formed article or sintered body, but also contain near the periphery wall of its cellular unit wall if be not particularly limited.Under the situation of also removing near the cellular unit wall 4 the periphery wall 12, preferably remove more than 2 cellular unit parts from periphery at least, more preferably remove 3 to 4 cellular unit parts.
Also can behind the periphery wall of removing the drying of ceramic honeycomb formed article, carry out sintering, then the outer peripheral face that exposes finally be processed, thereby form periphery parietal layer 12.In addition, also can form periphery parietal layer 12, and then process the outer peripheral face of periphery parietal layer 12 according to purposes in periphery wall 3 backs of removing the ceramic honeycomb formed body.
If after being coated with the spreading material on the groove 14, carry out sintering, then make both the change in size unanimity of following sintering, not only can prevent from the crackle that produces because of sintering from can also make both integrated, since can make the cellular unit wall 4 and the adhesive strength of periphery parietal layer 12 become big, therefore preferred especially.
As shown in figure 10, when sintered ceramic honeycomb formed article 41, if an end of the axis direction of ceramic honeycomb formed body 41 mode with contact is positioned on the sintering platform 40, and behind sintering during the large-diameter portion 44 of the ceramic honeycomb main body 42 that is connected with sintering platform 40 of excision, the uniform honeycomb main body 43 of external diameter can be obtained, and the periphery wall layer thickness homogenising of honeycomb structure can be made.
Generally, cause that in the process that the ceramic post sintering reaction is carried out size reduces.If the size on whole honeycomb structure reduces consistent, then no problem, but under the situation of large size ceramic honeycomb structure that the exhaust gas purification of diesel engine is used (for example external diameter is more than the 150mm, length be more than the 150mm), though also depend on material, but, the degree difference that reduces in the size everywhere of ceramic honeycomb structure.For example, the open end of the honeycomb formed article that docks with the sintering platform limits owing to be sintered platform, so the size minimizing is little.
Shown in Figure 10 (a), have uniform external diameter though be dried to body 41, shown in Figure 10 (b), the open end 44 that docks with sintering platform 40 is subjected to the qualification of sintering platform 41, and is littler than other parts based on the undergauge of sintering, the circularity variation.In addition, shown in Figure 12 (a), the two ends of the uneven ceramic honeycomb sintered body of pair of discs 51,51 clamping external diameters by having the target external diameter, and on the peripheral groove 14 of ceramic honeycomb sintered body, be coated with the spreading material, in case form the identical periphery parietal layer 12 of external diameter and disk 51,51, then the thickness of periphery parietal layer 12 just becomes inhomogeneous, is easy to generate the be full of cracks based on thermal shock outside on the thick part of perine 12.Therefore, preferably shown in Figure 10 (c), remove the big open end of external diameter 44 and make the external diameter homogenising of ceramic honeycomb sintered body 43.
In addition, cause according to sintering and the predicted value of undergauge, can make the thickness homogenising of the periphery parietal layer of honeycomb structure by removing periphery wall.For example, when obtaining sintered body shown in Figure 10 (b) by the formed body shown in Figure 10 (a), calculate the size changing rate of the each several part of honeycomb structure, and formed body 45 is processed into shape shown in Figure 11 (a) (undergauges taking place with the butted part 47 of sintering platform 40) according to this rate of change, then shown in Figure 11 (b), can obtain the good sintered body of dimensional accuracy 46.If use this sintered body, then can use disk 51,51 shown in Figure 12 to form periphery parietal layer 12 with uniform thickness.
Even the section shape of honeycomb structure is different in the longitudinal direction, for example when the formed body of section toroidal during for the elliptoid sintered body of section roughly, can according to the three-dimensional measurement device measure become sintered body by formed body the time size changing rate, the cutting degree of the periphery wall of decision ceramic formation body, and be processed into body by three-dimensional machining tool thus.
In ceramic honeycomb structure of the present invention, cell-wall 4 preferably has 50～80% the porosity.If cell-wall 4 has the porosity more than 50%, the material that then constitutes periphery parietal layer 12 enters in the pore of cell-wall 4 easily, and promptly so-called grappling (anchor) effect is strong.By anchoring effect, periphery parietal layer 12 and groove 14 are by integrated, and the mechanical strength of honeycomb structure 1 increases.But if the porosity surpasses 80%, then the intensity of cell-wall 4 (thereby mechanical strengths such as isobaric intensity of honeycomb structure 1) became low.If mechanical strengths such as isobaric intensity became low, then as catalyst carrier or the use of absorption particulate filter the time, the mechanical stress of the vibration of honeycomb structure 1 easy launched machine or road vibration etc. is destroyed.
The average pore of cell-wall 4 directly is preferably 10～50 μ m.If average pore directly is more than the 10 μ m, the material that then constitutes periphery parietal layer 12 enters in the pore of cell-wall 4 easily, and promptly so-called grappling (anchor) effect is strong.But if average pore directly surpasses 50 μ m, then the intensity of cell-wall 4 reduces, and is therefore not preferred.
If cell-wall 4 satisfies the above-mentioned condition in the porosity and average pore footpath, then periphery parietal layer 12 and groove 14 can only be fixed, therefore specially permit No. 2604876 with Japan and Japan speciallys permit that resistance to sudden heating is very low in the ceramic honeycomb structure of No. 2613729 record compares, have and to suppress resistance to sudden heating in the ceramic honeycomb structure 1 of stress opening portion and reduce.For the mechanical strength of the cell-wall 4 that prevents honeycomb structure 1 reduces, preferably adjust the porosity and average pore footpath, concentrate for reducing simultaneously to the stress of thick pore, preferably the pore with cell-wall 4 forms the section circular.
Because ceramic honeycomb structure of the present invention mainly is as the carrier of the exhaust gas purification catalyst of automobile engine or the atomic filter that is used for removing the exhaust of diesel engine uses, therefore use the ceramic material of excellent heat resistance at least on the ceramic honeycomb main body, preferred especially use is selected from least by cordierite, aluminium oxide, malachite, silicon nitride, carborundum and LAS and constitutes a kind of ceramic material in one group.Wherein, cordierite, because cheapness and hear resistance and chemical resistance is good, coefficient of thermal expansion is low, therefore most preferably.
The thickness of the cellular unit wall 4 of ceramic honeycomb structure 1 is preferably 0.1～0.5mm.Especially surpass under the situation of large, honeycomb tectosome of 150mm at external diameter, if the thickness of cellular unit wall 4 is lower than 0.1mm, the undercapacity of cellular unit wall 4 then.On the other hand, if the thickness of cellular unit wall 4 surpasses 0.5mm, then the exhaust of cellular unit wall 4 becomes big by resistance (pressure loss).Therefore the more preferably thickness of cellular unit wall 4 is 0.2～0.4mm.
More than the preferred 1.3mm of the spacing of cellular unit wall 4.When if spacing is lower than 1.3mm, because the cellular unit wall opening area of honeycomb structure 1 is too small, so the pressure loss of honeycomb structure 1 is big, causes the output of engine to reduce.
In addition, if the isobaric intensity of ceramic honeycomb main body 10 is more than the 1.0MPa, then periphery parietal layer 12 is difficult for peeling off with honeycomb main body 10, guarantees suitable chucking power in accommodating container (not shown), and honeycomb structure 1 is damaged with regard to seldom moving in accommodating container.The isobaric intensity of ceramic honeycomb main body 10 is more preferably more than 1.5MPa.
Further the present invention is described in detail by following example, but the present invention is not limited thereto.The chemical composition of material therefor is as shown in table 1 in following embodiment and comparative example.
Table 1
Annotate: (1) porosity 35%.
(2) porosity 65%.
(3) solid formation divided 50 quality %.
(4) solid formation divided 30 quality %.
In each embodiment and comparative example, the porosity of ceramic honeycomb main body and average pore footpath are by mercury penetration method the test film that cuts out to be measured.In addition, the thermal coefficient of expansion of each ceramic honeycomb structure is the mean value of the thermal coefficient of expansion of room temperature to 800 ℃.
The assay method of heat shock resistance temperature, be to constitute by following operation, promptly, be set in temperature and put into each ceramic honeycomb structure in the electric furnace of (room temperature+400 ℃) and kept 30 minutes, after speed was chilled to room temperature, whether visualization had produced crackle on the cellular unit wall of the axis direction both ends of the surface of ceramic honeycomb structure, when not cracking on the cellular unit wall, make 25 ℃ of the each risings of furnace temperature, and measure repeatedly until cracking.The heat shock resistance temperature is the poor of the temperature that begins to crack and room temperature.
The assay method of isobaric intensity, be to constitute by following operation, promptly, car gage (JASO) M505-87 according to civic organization's automotive engineering meeting, butt joint thickness is the aluminium sheet of 20mm and both ends of the surface are airtight on the axis direction both ends of the surface of each ceramic honeycomb structure, after simultaneously connecting airtight the rubber that thickness is 2mm on the perine surface outside, put into pressure vessel, in pressure vessel, introduce water and on each ceramic honeycomb structure, apply hydrostatic pressing.Isobaric intensity is the pressure (MPa) when each ceramic honeycomb structure is destroyed.
Reference example 1～6
Modulation is the cordierite generation material powder of principal component with potter's clay powder, talcum powder, SiO 2 powder and alumina powder.Material powder is with the SiO of 48～52 quality %
2, 33～37 quality % Al
2O
3And the MgO of 12～15 quality % is principal component, and contains bonding agent, lubricant, the graphite (pore creating material) of methylcellulose, hydroxypropyl methylcellulose etc.Cordierite is generated material powder carry out after sufficient dry type mixes, add the water of ormal weight, stir fully and make plastic ceramic base soil.
Make the body that is extruded into periphery wall 3 and cellular unit wall 4 incorporate honeycomb structures by ceramic base soil, carry out drying and sintering, obtaining external diameter is that 280mm and total length are the cordierite honeycomb sintered body of 300mm.The cellular unit wall of each sintered body has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.By utilizing the cylinder grinding machine to remove the periphery wall of each cordierite honeycomb sintered body, make the ceramic honeycomb main body 10 (external diameter is that 265.7mm, total length are 300mm) that axis direction exposes groove.
Be divided into benchmark with solid formation, cordierite powder A (average grain diameter is 10 μ m) with respect to 100 mass parts, the colloidal silica that cooperates 10～15 mass parts, and then with respect to total 100 mass parts of cordierite powder A and colloidal silica, the methylcellulose of interpolation 1.2 mass parts, stir with water, making viscosity is the material that is coated with of 15000～19000cP.
On the peripheral groove 14 of honeycomb main body 10 coating above-mentioned be coated with material after, in the drying oven of each temperature shown in the table 2, carry out heated-air drying.Afterwards, be heated to 450 ℃, decompose and remove methylcellulose, obtaining groove 14 is that 266.7mm and total length are the ceramic honeycomb structure of 300mm with periphery parietal layer 12 incorporate external diameters.After will being coated with material viscosity and being adjusted into 15000～19000cP, fill the angle part of periphery parietal layer 12 until groove 14, owing to be after filling is coated with material, in 70 ℃～120 ℃ drying oven, each ceramic honeycomb structure to be heated immediately, therefore produce crooked crackle shape space part 21 on the perine 12 outside.
The space part 21 of the periphery parietal layer 12 of each ceramic honeycomb structure 1 of visualization is approximately each space part 21 straight line and calculates its length, calculates the combined length of the space part 21 that exists in the ceramic honeycomb structure 1.Calculate the total length of the combined length/honeycomb structure 1 of space part 21 thus.In addition, measure the heat shock resistance temperature and the isobaric intensity of each ceramic honeycomb structure 1.The result is as shown in table 2.
Table 2
Table 2 (continuing)
Reference example 7～11
Making the external diameter that periphery has groove by the mode identical with reference example 1 is that 265.7mm and total length are the ceramic honeycomb main body 10 of 300mm.The cellular unit wall of each ceramic honeycomb main body 10 has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.
In addition, be divided into benchmark with solid formation, cooperate the colloidal silica of 10 mass parts with respect to the cordierite powder B (average grain diameter is 20 μ m) of 100 mass parts, and then add an amount of methylcellulose and water stirs, thereby make the material that is coated with that viscosity is 25000～67000cP.On the periphery of honeycomb main body 10, be coated with the spreading material, with 40 ℃ of dryings after 24 hours, again with 70 ℃ of dryings 12 hours.Because initial baking temperature is low, therefore do not produce space part 21 on the perine 12 outside.Afterwards, be heated to 450 ℃ and decompose and to remove methylcellulose, producing groove 14 is that 266.7mm and total length are the ceramic honeycomb structure of 300mm with periphery parietal layer 12 incorporate external diameters.
The heat shock resistance temperature and the isobaric intensity of each ceramic honeycomb structure 1 have been measured.In addition, dissect at the axis direction of honeycomb structure 1 and to observe the periphery parietal layer 12 that is filled in groove 14 on the cross section, number goes out in whole grooves 14 and has the number of the groove 14 of space part 22 between the periphery parietal layer 12.The result is as shown in table 3.
Table 3
Table 3 (continuing)
| Sequence number | Drying condition | Has space part | The heat shock resistance temperature | Isobaric intensity |
| Groove number (%) | Degree (℃) | (MPa) | ||
| Reference example 7 | 40 ℃ 24 hours 70 |
2 | 475 | 2.5 |
| Reference example 8 | 40 ℃ 24 hours 70 |
7 | 525 | 2.5 |
| Reference example 9 | 40 ℃ 24 hours 70 |
49 | 575 | 2.3 |
| Reference example 10 | 40 ℃ 24 hours 70 |
90 | 600 | 1.8 |
| Reference example 11 | 40 ℃ 24 hours 70 |
97 | 600 | 1.5 |
Reference example 12～15
Making the external diameter that periphery has groove by the mode identical with reference example 1 is that 265.7mm and total length are the honeycomb main body 10 of 300mm.The cellular unit wall of each honeycomb main body 10 has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 03mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.Coating on the periphery wall of each tectosome 10 except that viscosity is 52000cP, remaining and the used identical material that is coated with of comparative example 2, as shown in table 5, in the drying oven of 70 ℃ or 100 ℃, carry out rapid draing by hot blast.Be heated to 450 ℃ and decompose and to remove methylcellulose afterwards, obtaining groove 13 is that 266.7mm, total length are the embodiment 12 of 300mm and the ceramic honeycomb structure of embodiment 13 with periphery parietal layer 12 incorporate external diameters.
Except using being coated with the material of making in the following manner, remaining is by obtaining the ceramic honeycomb structure of embodiment 14 and 15 with embodiment 12 and 13 same modes, it is the described material that is coated with, be divided into benchmark with solid formation, amorphous silica powders A (average grain diameter is 15 μ m) with respect to 100 mass parts, the colloidal silica that cooperates 7 mass parts, and then with respect to total 100 mass parts of amorphous silica powders A and colloidal silica, the methylcellulose that cooperates 1.2 mass parts, add an amount of water then and stir, thereby obtain the material that is coated with that viscosity is 45000cP.
For the ceramic honeycomb structure 1 of embodiment 12～15, heat shock resistance temperature and isobaric intensity have been measured by the mode identical with embodiment 1.The result is as shown in table 5.And the total length of the combined length/honeycomb structure of the form of the space part 21 of ceramic honeycomb structure 1, space part 21, in the ratio that all has the groove number of space part 22 between grooves China and foreign countries' perines 12 and the groove 14, as shown in table 4.
Table 4
Table 4 (continuing)
(the cellular unit wall has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 03mm, the spacing and 10.5 * 10 of 1.5mm to utilize the cylinder grinding machine to remove the cordierite honeycomb sintered body of making by the mode identical with reference example 1
-7/ ℃ the radial thermal expansion coefficient) periphery wall, making the external diameter that periphery has groove is that 264.7mm and total length are the honeycomb main body A of 300mm.The pasty state that can apply of match ratio shown in the coating table 6 is coated with material (adding organic adhesive and water stirs) on the outer peripheral face of each honeycomb main body A, make dried thickness be roughly 1mm, obtaining external diameter after the drying is that 266.7mm, total length are the ceramic honeycomb structure 1 of 300mm.
Make the Core Hardness Tester type PHK of George Fischer society system rotate for two weeks, on the periphery parietal layer 12 of ceramic honeycomb structure 1, produce scratch, the scratch degree of depth is measured by non-contacting three-dimensional measurement device quickvision (ITUTOYO of M Co., Ltd. system), measures the scraping of periphery parietal layer 12 of each ceramic honeycomb structure 1 and decreases the degree of depth (standard of case hardness).In addition, measure the heat shock resistance temperature for 3 ceramic honeycomb structures 1 of each example.In addition, cut out test film and measure 40 ℃ to 800 ℃ mean thermal expansion coefficients from periphery parietal layer 12.Its result is as shown in table 5.
The periphery parietal layer 12 of each ceramic honeycomb structure 1, because the silica by amorphous silica particle A and colloidal state constitutes, therefore the scratch degree of depth of periphery parietal layer 12 is practical going up below the no problem 0.45mm, in addition, since the thermal coefficient of expansion of periphery parietal layer 12 than the radial thermal expansion coefficient (10.5 * 10 of cellular unit wall 4
-7/ ℃) little, so the heat shock resistance temperature be practical no problem more than 550 ℃.
Embodiment 5～8
Identical with embodiment 1～4, on the outer peripheral face of honeycomb main body A, coating except match ratio shown in the table 5, remaining material that is coated with by the mode gained identical with embodiment 1～4, make dry thickness be roughly 1mm, carry out drying, and then 850 ℃ of sintering 2 hours, obtaining external diameter was that 266.7mm and total length are the ceramic honeycomb structure 1 of 300mm.
For each ceramic honeycomb structure 1, identical with embodiment 1, the scratch degree of depth, thermal coefficient of expansion and the heat shock resistance temperature of mensuration periphery parietal layer 12.The result is as shown in table 5.Because being the silica by amorphous silica particle B and colloidal state, the arbitrary periphery parietal layer 12 among the embodiment 5～8 constitutes, therefore case hardness (the scratch degree of depth) is practical going up below the no problem 0.45mm, in addition, since the thermal coefficient of expansion of periphery parietal layer 12 than the radial thermal expansion coefficient (10.5 * 10 of cellular unit wall 4
- 7/ ℃) little, so the heat shock resistance temperature be practical no problem more than 550 ℃.
Embodiment 9～12
To the external diameter that obtains by the mode identical with embodiment 1 is that 290mm, total length are after the honeycomb formed article of 320mm carries out drying, carry out sintering after removing periphery wall and both ends with lathe, prepare the external diameter that on periphery, has groove thus and be 264.7, total length is the honeycomb main body B of 300mm.On each honeycomb main body B, be coated with the spreading material in the same manner, obtain ceramic honeycomb structure 1 with embodiment 1～4.
For each ceramic honeycomb structure 1, identical with embodiment 1, the scratch degree of depth, thermal coefficient of expansion and the heat shock resistance temperature of mensuration periphery parietal layer 12.The result is as shown in table 5.Embodiment 9～12, and except being removes before sintering the periphery wall 3, remaining is identical with embodiment 1～4, and the scratch degree of depth of the periphery parietal layer 12 of its ceramic honeycomb structure 1 is practical going up below the no problem 0.45mm.In addition, since the thermal coefficient of expansion of the periphery parietal layer 12 of the ceramic honeycomb structure 1 of embodiment 9～12 than the radial thermal expansion coefficient (10.5 * 10 of cellular unit wall 4
-7/ ℃) little, so the heat shock resistance temperature be practical no problem more than 550 ℃.
Identical with embodiment 16, making external diameter is that 264.7mm, total length are the honeycomb main body A of 300mm.On each honeycomb main body A, except being coated with the material of match ratio shown in the coating table 6, remaining obtains external diameter by the mode identical with embodiment 1～4 is that 266.7mm, total length are the ceramic honeycomb structure 1 of 300mm.
For each ceramic honeycomb structure 1, identical with embodiment 1, the scratch degree of depth, thermal coefficient of expansion and the heat shock resistance temperature of mensuration periphery parietal layer 12.The result is as shown in table 5.Embodiment 28 is coated with material, stuff and other stuff 100 mass parts and colloidal silica 7 mass parts by 90 quality % amorphous silica particle A and 10 quality % quartz constitute, embodiment 29 is coated with material, is made of the noncrystalline particle A of 100 mass parts and the colloidal alumina of 7 mass parts.Therefore for arbitrary ceramic structural body 1, the scratch degree of depth of periphery parietal layer 12 is practical going up below the no problem 0.45mm, in addition, because the thermal coefficient of expansion of periphery parietal layer 12 is than the radial thermal expansion coefficient 10.5 * 10 of cellular unit wall 4
-7/ ℃ little, so the heat shock resistance temperature be practical no problem more than 550 ℃.
Comparative example 1
Identical with embodiment 1, after obtaining periphery wall 3 and cellular unit wall 4 incorporate honeycomb structures, do not remove periphery wall and directly carry out drying and sintering, obtaining external diameter is that 280mm, total length are the honeycomb main body C of 300mm.The cellular unit wall of this ceramic honeycomb main body C has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.For this ceramic honeycomb main body C, identical with embodiment 1, the scratch degree of depth, thermal coefficient of expansion and the heat shock resistance temperature of mensuration periphery wall 3.The result is as shown in table 5.Because the periphery wall 3 of this ceramic honeycomb structure is integrated with cellular unit wall 4, so the scratch degree of depth of periphery wall 3 is practical going up below the no problem 0.45mm.But, because the thermal coefficient of expansion of periphery wall 3 is than the radial thermal expansion coefficient (10.5 * 10 of cellular unit wall 4
-7/ ℃) big, so the heat shock resistance temperature is lower than 550 ℃.
Table 5
Annotate: (1) has the chemical composition shown in the table 1, and average grain diameter is 14.1 μ m.
(2) have the chemical composition shown in the table 1, average grain diameter is 30.1 μ m.
(3) have the chemical composition shown in the table 1, average grain diameter is 15.1 μ m.
(4) have the chemical composition shown in the table 1, average grain diameter is 15 μ m.
(5) have the chemical composition shown in the table 1, average grain diameter is 12 μ m.
(6) with the solid match ratio that is divided into benchmark that forms.
Table 5 (continuing)
Embodiment 15
Identical with reference example 1, obtain having the formed body of periphery wall 3 and cellular unit wall 4 incorporate ojosas.Make this formed body at medium drying oven inner drying.By the dried formed body of machining tool clamping on the lathe and it is rotated with 260rpm, remove the crushed element (degree of depth of 3 cellular unit parts) of periphery wall with superhard cutter and with the condition of incision 5mm and feeding 1.0mm/ second, make the honeycomb main body 10 that periphery is exposed groove.
Make side's openend of this honeycomb main body 10 be docked on the sintering platform of ojosa and put into sintering furnace, be warming up to 500 ℃ with 5 ℃/hour programming rates from room temperature, be warming up to 1425 ℃ with 20 ℃/hour programming rates from 500 ℃, under maximum temperature, kept 10 hours.Slowly cooling behind sintering, obtaining external diameter is that 264.7～265.7mm, total length are the honeycomb sintered body of 300mm.The cellular unit wall of this honeycomb sintered body has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.
By this honeycomb sintered body 10 of a pair of hold assembly shown in Figure 12 51,51 clampings, being coated with material (cooperating organic adhesive and water at the cordierite particle (average grain diameter 10 μ m) of 100 mass parts and in the solid colloidal silica that forms 7 mass parts that are divided into benchmark) at coating pasty state on the outer peripheral face of honeycomb sintered body 10, to make external diameter be 266.7mm, then 120 ℃ of dryings 2 hours, again 850 ℃ of following sintering 2 hours.The thickness of the periphery parietal layer 12 of gained honeycomb structure is 0.5～1.5mm (with reference to Figure 13 (a)).
With with reference to 1 identical, measured the isobaric intensity of honeycomb structure 1.Isobaric intensity is made as zero more than 1.0MPa and when being lower than 1.5MPa, is made as ◎ when 1.5MPa is above, is made as when being lower than 1.0MPa *.In addition, isobaric intensity is qualified when 1.0MPa is above, is defective when being lower than 1.0MPa.In addition, identical with embodiment 1, the heat shock resistance temperature of mensuration ceramic honeycomb structure 1.The heat shock resistance temperature difference is being made as zero, is being made as ◎ in time more than 550 ℃, is being made as when being lower than 500 ℃ more than 500 ℃ *.Heat shock resistance temperature in addition is to be qualified more than 500 ℃ the time, is defective when being lower than 500 ℃.The result is as shown in table 7.
Embodiment 16
Identical with embodiment 15, make the honeycomb main body 10 of removing periphery wall.Generate the methylcellulose that adds 0.5 mass parts in material powder 100 mass parts at the cordierite identical with the honeycomb main body, and then add dispersant and water, the pasty state that obtains applying is coated with material.With this honeycomb main body 10 of a pair of hold assembly shown in Figure 12 51,51 clampings, make the thickness behind the sintering be coated with the spreading material with being about 1.6mm, form periphery parietal layer 12.
One side's open end is positioned on the sintering platform of ojosa the honeycomb main body 10 that ground connection will form periphery parietal layer 12, honeycomb main body 10 is put into sintering furnace, carry out sintering with the condition identical with embodiment 30, obtaining external diameter is that 266.7～267.7mm, total length are the honeycomb sintered body of 300mm.Because the change in size during sintering, the external diameter scope is 266.7～267.7mm, and therefore removing the big place of external diameter, to make external diameter be 266.7mm.The thickness of periphery parietal layer 10 is 0.6～1.6mm (with reference to the process chart of Figure 13 (b)).The isobaric intensity of gained honeycomb structure 1 and heat shock resistance temperature are measured by the mode identical with embodiment 30.The result is as shown in table 7.
Embodiment 17
Has the formed body of ojosa with embodiment 15 identical making.On the periphery 3 of formed body, has the part of being out of shape owing to the deadweight of formed body.Behind medium drying oven inner drying, make side's openend to ground connection formed body is positioned on the sintering platform of ojosa and put into sintering furnace, carry out sintering with the condition identical with embodiment 30, obtaining external diameter is that 274.7mm, total length are the honeycomb sintered body of 300mm.Owing to the honeycomb sintered body that the influence of the distortion of periphery wall 3 cracks is more.The cellular unit wall of this honeycomb sintered body has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.
The honeycomb sintered body that crackle will not take place in sintering circuit is installed on the periphery grinding machine, periphery wall 3 and near the cellular unit wall 4 it are ground to the degree of depth of about 4.5mm (3 cellular unit branch), and obtaining the external diameter that periphery has groove is the honeycomb main body 10 of 265.7mm.The peripheral speed of the skive that uses in the grinding is the 0.5mm/ branch as 2000m/ branch, feed speed.When removing periphery wall 3, on the part of cellular unit wall 4, produce shortcoming.Coating is identical with embodiment 30 on the outer peripheral face of the honeycomb main body 10 of removing periphery wall 3 is coated with material, and making its thickness is 0.8～1.2mm, then, 120 ℃ dry 2 hours down, follow 850 ℃ of following sintering 2 hours.The isobaric intensity of gained honeycomb structure 1 and heat shock resistance temperature, measure by the mode identical with embodiment 15.The result is as shown in table 6.
Embodiment 18
Except length is become the 50mm, remaining is identical with embodiment 15, has made the honeycomb formed article of removing periphery wall.Make side's openend to ground connection this honeycomb formed article is positioned on the sintering platform of ojosa and put into sintering furnace, carry out sintering with the condition identical with embodiment 30.Is that 264.7～265.7mm, length are that the honeycomb sintered body of 350mm cuts off by the position of the interface 50mm that starts from the sintering platform with the external diameter of gained, and obtaining external diameter is that 265.5～265.9mm, length are the honeycomb main body 10 of 300mm.The cellular unit wall of this honeycomb main body 10 has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.
On the outer peripheral face of this honeycomb main body 10, coating is identical with embodiment 15 is coated with material, and making its external diameter is 266.7mm, then with 120 ℃ of dryings 2 hours, follows 850 ℃ of following sintering 2 hours.The thickness of gained periphery parietal layer 12 is 0.8～1.2mm.To the isobaric intensity of gained honeycomb structure 1 and heat shock resistance temperature, measure by the mode identical with embodiment 15.The result is as shown in table 6.
Embodiment 19
Shown in Figure 11 (a), except being decides the external diameter that is dried to body according to the change in size based on sintering, remaining is identical with embodiment 15, makes the honeycomb main body 45 of removing periphery wall.Make side's openend to ground connection honeycomb main body 45 is positioned on the sintering platform 40 of ojosa and put into sintering furnace, carry out sintering with the condition identical with embodiment 30, obtaining external diameter is that 265.4～265.9mm, length are the honeycomb main body 10 of 300mm.The cellular unit wall of this honeycomb main body 10 has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.
On the outer peripheral face of honeycomb main body 10, coating except the colloidal silica of the cordierite particle that contains 100 mass parts and 5 mass parts, all the other identical with embodiment 15 materials that are coated with, making external diameter is 266.7mm, then, with 120 ℃ of dryings 2 hours, then with 850 ℃ of sintering 2 hours.The thickness of gained periphery parietal layer 12 is 0.8～1.2mm.The isobaric intensity of gained honeycomb structure 1 and heat shock resistance temperature are measured by the mode identical with embodiment 30.The result is as shown in table 6.
Embodiment 20
Obtain to remove the honeycomb structure of periphery wall in the same manner with embodiment 15, by the mode identical with embodiment 15 the dry body with this honeycomb structure is carried out sintering then, obtaining external diameter is that 264.7～265.7mm, length are the honeycomb sintered body of 300mm.The cellular unit wall of this honeycomb sintered body has 65% the porosity, the average pore footpath of 20 μ m, the thickness of 0.3mm, the spacing and 10.5 * 10 of 1.5mm
-7/ ℃ the radial thermal expansion coefficient.
On outer peripheral face with the honeycomb main body 10 of a pair of hold assembly 51,51 clampings, coating except the colloidal silica of the amorphous silica aggregate (average grain diameter is 14 μ m) that contains 100 mass parts and 7 mass parts, remaining identical with embodiment 15 material that is coated with, making external diameter is 266.7mm, then with 120 ℃ of dryings 2 hours, then with 850 ℃ of sintering 2 hours.The thickness of gained periphery parietal layer 12 is 0.5～15mm.To the isobaric intensity of gained honeycomb structure 1 and heat shock resistance temperature, measure by the mode identical with embodiment 15.The result is as shown in table 6.
Table 6
| Sequence number | The thickness of periphery parietal layer (mm) | Isobaric intensity | The heat shock resistance temperature |
| Embodiment 15 | 0.5～1.5 | ○ | ○ |
| Embodiment 16 | 0.6～1.6 | ◎ | ○ |
| Embodiment 17 | 0.8～1.2 | × | ○ |
| Embodiment 18 | 0.8～1.2 | ○ | ◎ |
| Embodiment 19 | 0.8～1.2 | ○ | ◎ |
| Embodiment 20 | 0.5～1.5 | ○ | ○ |
As shown in Table 6, the method according to this invention can obtain isobaric intensity and the good honeycomb structure of resistance to sudden heating.In addition, the in uneven thickness little embodiment 18 of periphery parietal layer and 19 honeycomb structure, resistance to sudden heating is especially good.
More than embodiments of the present invention are had been described in detail, but short of particular determination, the feature of each embodiment is also applicable to other embodiment.So, for example no matter whether outside has stress release portion at least a portion between perine and/or periphery parietal layer and the described groove, and the thermal coefficient of expansion of periphery parietal layer the radial thermal expansion coefficient than the cellular unit wall of ceramic honeycomb main body is little, all not only removing of periphery wall can be behind the sintered ceramic honeycomb formed article, carried out, also removing of periphery wall can be before sintering, carried out.
In addition,, the radial thermal expansion coefficient of the thermal coefficient of expansion of periphery wall layer can be made, therefore, resistance to sudden heating can be improved less than the cellular unit wall by constitute the periphery parietal layer of ceramic honeycomb structure by amorphous silica particle and noncrystalline matrix of oxide.Ceramic honeycomb structure with this feature is applicable to the catalytic converter that exhaust gas purification is used or absorbs the particulate filter.Especially be not easy to produce the crackle of following thermal shock, therefore be best suited for the catalytic converter that exhaust gas purification is used.
Claims (20)
1. ceramic honeycomb structure, comprise: have the axis direction groove of periphery and the ceramic honeycomb main body that forms the cellular unit wall of a plurality of openings in described groove inboard, with the periphery parietal layer that covers described groove, wherein, the thermal coefficient of expansion of described periphery parietal layer is 10.0 * 10 less than the radial thermal expansion coefficient of described cellular unit wall
-7/ ℃ below.
2. ceramic honeycomb structure, comprise: have the axis direction groove of periphery and the ceramic honeycomb main body that forms the cellular unit wall of a plurality of openings in described groove inboard, with the periphery parietal layer that covers described groove, wherein, described periphery parietal layer is made of the mixture that contains amorphous silica particle and noncrystalline matrix of oxide, and the thermal coefficient of expansion of described periphery parietal layer is 1.0 * 10
-7/ ℃ below.
3. ceramic honeycomb structure according to claim 2, wherein, described noncrystalline matrix of oxide is made of colloidal silica particles and/or colloidal alumina.
4. according to claim 2 or 3 described ceramic honeycomb structures, wherein, the consisting of of described periphery parietal layer: contain the amorphous silica particle of 100 mass parts and the noncrystalline matrix of oxide of 2～35 mass parts.
5. the manufacture method of a ceramic honeycomb structure, shaping has extrusion molding pottery base soil and makes the ceramic honeycomb structure of periphery wall and the incorporate ojosa of cellular unit wall, remove described formed body or to described formed body carry out sintering and the periphery wall of sintered body and near the cellular unit wall it, utilization is coated with material and covers the axis direction groove that exposes and form the periphery parietal layer, wherein, contain amorphous silica particle and noncrystalline matrix of oxide at the described material that is coated with, and the thermal coefficient of expansion of described periphery parietal layer is 1.0 * 10
-7/ ℃ below.
6. the manufacture method of ceramic honeycomb structure according to claim 5, wherein, with respect to amorphous silica particle 100 mass parts, the content of described noncrystalline matrix of oxide is 2～35 mass parts.
7. according to the manufacture method of claim 5 or 6 described ceramic honeycomb structures, wherein, described noncrystalline matrix of oxide is made of colloidal silica particles and/or colloidal alumina.
8. one kind is coated with material, is used to form the periphery parietal layer of ceramic honeycomb structure, and wherein, the thermal coefficient of expansion of described periphery parietal layer is 1.0 * 10
-7/ ℃ below, and be divided into benchmark with solid formation, contain the amorphous silica particle of 100 mass parts and the colloidal silica and/or the colloidal alumina of 2～35 mass parts.
9. according to any described ceramic honeycomb structure in the claim 1～4, wherein, the cell-wall of described ceramic honeycomb structure has 50～80% the porosity and the average pore footpath of 10～50 μ m.
10. according to the manufacture method of any described ceramic honeycomb structure in the claim 5～7, wherein, the cell-wall of described ceramic honeycomb structure has 50～80% the porosity and the average pore footpath of 10～50 μ m.
11. the material that is coated with according to claim 8, wherein, the cell-wall of described ceramic honeycomb structure has the average pore footpath of 50～80% the porosity and 10～50 μ m.
12. according to any described ceramic honeycomb structure in the claim 1～4, wherein, the external diameter of described ceramic honeycomb structure is more than the 150mm and total length is more than the 150mm.
13. according to the manufacture method of any described ceramic honeycomb structure in the claim 5～7, wherein, the external diameter of described ceramic honeycomb structure is more than the 150mm and total length is more than the 150mm.
14. the material that is coated with according to claim 8, wherein, the external diameter of described ceramic honeycomb structure is more than the 150mm and total length is more than the 150mm.
15. according to any described ceramic honeycomb structure in the claim 1～4, wherein, the cell-wall of described ceramic honeycomb structure has thickness and the above unit interval of 1.3mm of 0.1～0.5mm.
16. according to the manufacture method of any described ceramic honeycomb structure in the claim 5～7, wherein, the cell-wall of described ceramic honeycomb structure has thickness and the above unit interval of 1.3mm of 0.1～0.5mm.
17. the material that is coated with according to claim 8, wherein, the cell-wall of described ceramic honeycomb structure has thickness and the above unit interval of 1.3mm of 0.1～0.5mm.
18. according to any described ceramic honeycomb structure in the claim 1～4, wherein, described ceramic honeycomb structure is as catalyst carrier or absorb the particulate filter use.
19. according to the manufacture method of any described ceramic honeycomb structure in the claim 5～7, wherein, described ceramic honeycomb structure is as catalyst carrier or absorb the particulate filter use.
20. the material that is coated with according to claim 8, wherein, described ceramic honeycomb structure is as catalyst carrier or absorb the particulate filter use.
Applications Claiming Priority (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002175374 | 2002-06-17 | ||
| JP2002175374 | 2002-06-17 | ||
| JP2002175372 | 2002-06-17 | ||
| JP2002175372 | 2002-06-17 | ||
| JP2002-175372 | 2002-06-17 | ||
| JP2002-175374 | 2002-06-17 | ||
| JP2002-262088 | 2002-09-06 | ||
| JP2002262088 | 2002-09-06 | ||
| JP2002262088 | 2002-09-06 | ||
| JP2002326852 | 2002-11-11 | ||
| JP2002-326852 | 2002-11-11 | ||
| JP2002326852 | 2002-11-11 | ||
| JP2002355022 | 2002-12-06 | ||
| JP2002355022A JP4474633B2 (en) | 2002-06-17 | 2002-12-06 | Method for manufacturing ceramic honeycomb structure |
| JP2002-355022 | 2002-12-06 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038000806A Division CN100341623C (en) | 2002-06-17 | 2003-06-17 | Ceramic honeycomb structure, process for producing same and coat material for use in the production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058049A CN101058049A (en) | 2007-10-24 |
| CN101058049B true CN101058049B (en) | 2010-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101409665A Expired - Lifetime CN101147882B (en) | 2002-06-17 | 2003-06-17 | A ceramic honeycomb structure and its manufacturing method, and using coating material in manufacturing |
| CN2007100063015A Expired - Lifetime CN101058049B (en) | 2002-06-17 | 2003-06-17 | Ceramic honeycomb structure, manufacturing method thereof, and coating used for the manufacture |
| CN2007100063072A Expired - Lifetime CN101053974B (en) | 2002-06-17 | 2003-06-17 | Method for producing a ceramic honeycomb structure |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN2007101409665A Expired - Lifetime CN101147882B (en) | 2002-06-17 | 2003-06-17 | A ceramic honeycomb structure and its manufacturing method, and using coating material in manufacturing |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100063072A Expired - Lifetime CN101053974B (en) | 2002-06-17 | 2003-06-17 | Method for producing a ceramic honeycomb structure |
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| CN (3) | CN101147882B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102256912B (en) * | 2008-12-18 | 2014-04-16 | 陶氏环球技术有限责任公司 | Ceramic honeycomb filter with enhanced thermal shock resistance |
| EP2473269A1 (en) * | 2009-08-31 | 2012-07-11 | Corning Incorporated | Zoned monolithic reactor and associated methods |
| KR101714363B1 (en) * | 2015-04-16 | 2017-03-23 | 주식회사 엔바이온 | Honeycomb Structures With Enhanced Crack Resistance |
| JP6966984B2 (en) * | 2018-09-20 | 2021-11-17 | 日本碍子株式会社 | Peripheral coating material, outer peripheral coating honeycomb structure and dust collecting filter |
| CN113232243B (en) * | 2021-01-16 | 2022-12-06 | 温州南冠机械有限公司 | SCR denitration catalyst production mold and production method thereof |
| CN115075918B (en) * | 2021-03-16 | 2024-01-16 | 日本碍子株式会社 | Honeycomb structure, method for manufacturing electrically heated carrier, and filler press-fitting device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629067A (en) * | 1992-01-30 | 1997-05-13 | Ngk Insulators, Ltd. | Ceramic honeycomb structure with grooves and outer coating, process of producing the same, and coating material used in the honeycomb structure |
| EP0884459A3 (en) * | 1997-06-13 | 2002-12-11 | Corning Incorporated | Coated catalytic converter substrates and mounts |
| JP2001261428A (en) * | 2000-03-14 | 2001-09-26 | Ngk Insulators Ltd | Ceramic honeycomb structural body |
-
2003
- 2003-06-17 CN CN2007101409665A patent/CN101147882B/en not_active Expired - Lifetime
- 2003-06-17 CN CN2007100063015A patent/CN101058049B/en not_active Expired - Lifetime
- 2003-06-17 CN CN2007100063072A patent/CN101053974B/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| JP平5－269388A 1993.10.19 |
| US 5,629,067 A,1997.05.13,第3栏第15行～第8栏第53行，第16栏第25行～第17栏第14行权利要求1～7. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101147882A (en) | 2008-03-26 |
| CN101058049A (en) | 2007-10-24 |
| CN101053974A (en) | 2007-10-17 |
| CN101053974B (en) | 2011-03-23 |
| CN101147882B (en) | 2012-07-18 |
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