Patent Application
20110121493
1. Field of the Invention
The present invention relates to a method for manufacturing a ceramic fired body and a method for manufacturing a honeycomb structured body.
2. Discussion of the Background
In recent years, particulates such as soot in exhaust gases that are discharged from internal combustion engines for vehicles such as a bus and a truck, construction equipment and the like, have raised serious problems as contaminants harmful to the environment and the human body. For this reason, various applications in which honeycomb structured bodies made of porous ceramics are used as filters for capturing particulates in exhaust gases to purify the exhaust gases have been proposed.
As such a honeycomb structured body, for example, there is employed a honeycomb structured body having plural pillar-shaped honeycomb fired bodies combined with one another with an adhesive layer interposed therebetween. Here, the honeycomb fired bodies are manufactured by carrying out extrusion-molding, degreasing, firing or the like on a mixture comprising a ceramic raw material such as silicon carbide.
A honeycomb fired body is manufactured by molding and degreasing a ceramic raw material and firing the resultant honeycomb degreased body in a firing furnace.
Japanese Patent Application Publication (KOKAI) 2002-193670 and Japanese Patent Application Publication (KOKAI) 2006-46865 disclose a method for firing a degreased silicon carbide molded body.
Japanese Patent Application Publication (KOKAI) 2002-193670 discloses a method for firing a silicon carbide molded body in which a pillar-shaped silicon carbide molded body containing a silicon carbide powder, a binder, and a dispersion medium is degreased, and thereafter placed on a firing jig and fired.
Japanese Patent Application Publication (KOKAI) 2002-193670 specifically discloses a method in which plural layers of firing jigs each with the degreased silicon carbide molded body placed thereon are laminated to form a laminated body, a heater is disposed over the laminated body, an other heater is disposed under the laminated body, and the laminated body is heated with the heater.
Japanese Patent Application Publication (KOKAI) 2006-46865 discloses a firing furnace used for firing a degreased silicon carbide molded body. Japanese Patent Application Publication (KOKAI) 2006-46865 discloses that in this firing furnace, a muffle is provided in a firing chamber, electrodes are disposed so as to vertically sandwich the muffle, the muffle is heated with resistance heating when electric power is supplied to the muffle, and the firing objects contained in the muffle are fired.
Japanese Patent Application Publication (KOKAI) 2006-46865 also discloses a method in which a platform member is arranged in a closed-end box firing jig having a lid formed with a conductive material, firing objects are disposed on the platform member, and the firing jigs and the firing objects are energized, and the firing objects are heated. Specific examples of the heating method with energizing heating disclosed in Japanese Patent Application Publication (KOKAI) 2006-46865 are a method in which electrodes are disposed so as to vertically sandwich the muffle, an energizing auxiliary member is disposed between the muffle and the firing jigs, and the firing jigs are energized, and a method in which electrodes are arranged on the left and right of plural lines of firing jigs, and an energizing auxiliary member is disposed between the plural lines of firing jigs, and the firing jigs are energized.
The contents of Japanese Patent Application Publication (KOKAI) 2002-193670 and Japanese Patent Application Publication (KOKAI) 2006-46865 are incorporated herein by reference in their entirety.
According to one aspect of the present invention, a method for manufacturing a ceramic fired body includes molding and degreasing a ceramic raw material to manufacture a ceramic degreased body. The ceramic degreased body is fired in a continuous firing furnace. In the continuous firing furnace, a lower plate is disposed on the bottom of the ceramic degreased body. An upper plate is disposed on the upper surface of the ceramic degreased body. A lower energizing electrode is brought into contact with the lower plate. An upper energizing electrode is brought into contact with the upper plate. A resistance heating mechanism is disposed over the upper plate. An other resistance heating mechanism is disposed under the lower plate. The firing step includes preheating the ceramic degreased body up to a preheating temperature of at least about 1500° C. and at most about 2000° C. by resistance heating with the resistance heating mechanism. High-temperature firing includes heating the ceramic degreased body from the preheating temperature to a firing temperature of at least about 2000° C. and at most about 2300° C. by both the resistance heating with the resistance heating mechanism and direct energizing heating in which the ceramic degreased body is energized and heated by applying a voltage between the lower plate and the upper plate. The temperature of the ceramic degreased body is held at the firing temperature.
A method is for manufacturing a honeycomb structured body. Plural ceramic fired bodies manufactured by the above-described method for manufacturing a ceramic fired body are combined with one another with an adhesive layer interposed between the plural ceramic fired bodies.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
A ceramic degreased body obtained by molding and degreasing a ceramic raw material can be fired with a firing furnace, a so-called continuous firing furnace.
In the firing with the continuous firing furnace, a firing jig containing a ceramic degreased body is charged into the firing furnace from an input port, the ceramic degreased body is moved in the firing furnace with a transport mechanism such as a belt conveyor.
The temperature of the ceramic degreased body increases when the ceramic degreased body is moved in the firing furnace. When it reaches a predetermined firing temperature (for example, about 2200° C.), the temperature of the degreased body is held for a while. Thereafter, the ceramic degreased body is removed from the exit port of the firing furnace.
In the firing method with the continuous firing furnace, the temperature of the ceramic degreased body is desirably raised up to a firing temperature in a short period of time for improvement in manufacturing efficiency.
In the case of using the method of Japanese Patent Application Publication (KOKAI) 2002-193670 in which ceramic degreased bodies are placed in firing jigs in such a continuous firing furnace and vertically heated with heaters, the temperature-rise of the ceramic degreased bodies is problematically late.
Especially problematically, it takes time to raise the temperature of the ceramic degreased bodies in the vicinity of the center of each of the firing jigs distant from the heater with radiant heat transfer from the periphery.
Even in the case of using the method of Japanese Patent Application Publication (KOKAI) 2006-46865 in which firing jigs and ceramic degreased bodies are energized and heated, the temperature-rise of the ceramic degreased bodies is slow. Thus, the temperature of the ceramic degreased bodies is required to be raised up to a firing temperature in a short period of time.
The present inventors tried to raise the temperature up to a firing temperature by both resistance heating with a heater described in Japanese Patent Application Publication (KOKAI) 2002-193670 and direct energizing heating described in Japanese Patent Application Publication (KOKAI) 2006-46865 in order to increase a temperature-rise rate.
However, when the temperature of the ceramic degreased body was quickly raised by such a method, thermal shock is more likely to cause cracks in the ceramic degreased body, and the ceramic degreased body was not favorably fired.
For this reason, a firing method that enables raising of a temperature up to a firing temperature in a short period of time and also enables prevention of cracks in a ceramic degreased body is required to be developed.
As a result of further investigations to solve the above problems, the present inventors have found that the case of raising a temperature-rise rate too high in the temperature range up to about 2000° C. is more likely to cause cracks in a honeycomb degreased body. The present inventors have also found that it especially takes time to raise the temperature from about 2000° C. to a firing temperature (for example, at least about 2000° C. and at most about 2300° C.).
Then, the present inventors have tried to raise the temperature-rise rate not too high in the temperature range up to about 2000° C. and also tried to shorten the temperature from about 2000° C. to a firing temperature (for example, at least about 2000° C. and at most about 2300° C.). The present inventors have found that when a ceramic degreased body is preheated up to about 2000° C. only with resistance heating so as not to raise the temperature-rise rate too high, and heated by both direct energizing heating and resistance heating until the temperature reaches a firing temperature from about 2000° C., the temperature-rise time is shortened and cracks tend not to occur in the ceramic degreased body in the firing.
The present inventors also have found that without using a firing jig or a platform member, a lower plate is disposed on the bottom of a ceramic degreased body, an upper plate is disposed on the upper surface, and direct energizing heating is efficiently performed by applying a voltage between the lower plate and the upper plate.
Then, the present inventors have made the present invention based on the above findings.
That is, a method for manufacturing a ceramic fired body according to the embodiments of the present invention comprises: molding and degreasing a ceramic raw material to manufacture a ceramic degreased body; and firing the ceramic degreased body in a continuous firing furnace, wherein in the continuous firing furnace, a lower plate is disposed on the bottom of the ceramic degreased body, an upper plate is disposed on the upper surface of the ceramic degreased body, a lower energizing electrode is brought into contact with the lower plate, an upper energizing electrode is brought into contact with the upper plate, a resistance heating mechanism is disposed over the upper plate, and an other resistance heating mechanism is disposed under the lower plate, wherein the firing comprises: preheating the ceramic degreased body up to a preheating temperature of at least about 1500° C. and at most about 2000° C. by resistance heating with the resistance heating mechanism; and high-temperature firing, comprising: heating the ceramic degreased body from the preheating temperature to a firing temperature of at least about 2000° C. and at most about 2300° C. by both resistance heating with the resistance heating mechanism and direct energizing heating in which the ceramic degreased body is energized and heated by applying a voltage between the lower plate and the upper plate; and holding the temperature of the ceramic degreased body at the firing temperature.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, the ceramic degreased body is preheated up to a preheating temperature of at least about 1500° C. and at most about 2000° C. by resistance heating with the resistance heating mechanism. If preheating is performed only with the resistance heating mechanism, the temperature-rise rate is not too high, and cracks are more likely to be prevented in the ceramic degreased body.
In addition, the ceramic degreased body is heated from the preheating temperature to a firing temperature of at least about 2000° C. and at most about 2300° C. by both resistance heating and direct energizing heating. The combination of the two heating methods for heating tends to shorten the temperature-rise time in this temperature range.
Thus, resistance heating and direct energizing heating are selectively performed depending on the temperature range in the continuous firing furnace, whereby it is possible to shorten temperature-rise time and fire the ceramic degreased body so as not to cause cracks in the ceramic degreased body.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, the lower plate is disposed on the bottom of a first ceramic degreased body, a first upper plate is disposed on the upper surface of the first ceramic degreased body, a second ceramic degreased body is disposed on the upper surface of the first upper plate, a second upper plate is disposed on the upper surface of the second ceramic degreased body to manufacture a laminated body having two layers in which ceramic degreased bodies are laminated, and the energizing heating is performed by applying a voltage between the lower plate and the second upper plate.
Thus, ceramic degreased bodies having two layers can be energized in both up and down directions simultaneously, and a large number of honeycomb fired bodies can be efficiently manufactured.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, the lower plate is disposed on the bottom of a first ceramic degreased body, a first upper plate is disposed on the upper surface of the first ceramic degreased body, a second ceramic degreased body is disposed on the upper surface of the first upper plate, a second upper plate is disposed on the upper surface of the second ceramic degreased body, and then an other ceramic degreased body and an other upper plate are alternately disposed on the second upper plate to manufacture a laminated body having three or more layers in which ceramic degreased bodies are laminated, and the energizing heating is performed by applying a voltage between the lower plate and the highest upper plate.
Thus, plural ceramic degreased bodies can be energized in both up and down directions simultaneously, and a large number of honeycomb fired bodies can be efficiently manufactured.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, plural lines of the ceramic degreased bodies are arranged in the continuous firing furnace, and plural lines of the upper and lower energizing electrodes are aligned with plural lines of the ceramic degreased bodies, and direct energizing heating is performed.
Thus, current can be uniformly applied to each of plural lines of ceramic degreased bodies, and plural honeycomb fired bodies can be efficiently manufactured.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, the area of the lower plate and the area of the upper plate are each larger than the area of the side face of the ceramic degreased body.
Thus, if direct energizing heating is performed starting from such larger areas, plural lines of ceramic fired bodies tend to be heated uniformly.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, the lower plate and the upper plate comprise carbon.
Since carbon is conductive, a ceramic degreased body can be energized via the lower plate and the upper plate. In addition, since carbon is heat resistant, it is suitable for use in a firing furnace.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, a temperature-rise rate in the preheating is at least about 2° C./min and at most about 8° C./min.
Such a temperature-rise rate is more likely to suitably prevent cracks in the ceramic fired body in the preheating.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, a temperature-rise rate in the high-temperature firing is at least about 6° C./min and at most about 12° C./min.
Such a temperature-rise rate can shorten the temperature-rise time in the high-temperature firing.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, the ceramic fired body comprises porous silicon carbide having a large number of cells longitudinally disposed in parallel with one another with a cell wall interposed therebetween.
If porous silicon carbide having such a shape is manufactured, variations in pore diameters tend to be reduced in comparison with the porous silicon carbide fired only by resistance heating.
In the method for manufacturing a ceramic fired body according to the embodiments of the present invention, either one of the ends of each of the large number of cells is alternately plugged.
In a method for manufacturing a honeycomb structured body according to the embodiments of the present invention, plural ceramic fired bodies manufactured by any one of the above methods for manufacturing a ceramic fired body are combined with one another with an adhesive layer interposed therebetween.
As described above, ceramic fired bodies can be manufactured efficiently by such a method. Accordingly, a honeycomb structured body can be manufactured efficiently.
The embodiments will now be described with reference to the accompanying drawings, wherein like reference numerals designate corresponding or identical elements throughout the various drawings.
Hereinafter, the first embodiment, which is one embodiment of the method for manufacturing a ceramic fired body of the present invention and the method for manufacturing a honeycomb structured body, will be described with reference to the drawings.
First, a continuous firing furnace used in the firing of the present embodiment will be described.
In the oblong body frame 22 of the continuous firing furnace 20 illustrated in
A transport mechanism configured to transport a firing object is disposed in the muffle 23. A transport mechanism is driven, whereby the firing object is moved from the inlet part 23a to the exit part 23b, that is, from the left side to the right side in
The region where the muffle 23 is disposed in the continuous firing furnace 20 is divided into a preheating section P, a high-temperature firing section H, and a cooling section C in this order from the left in
The preheating section P is a section to preheat the temperature up to a preheating temperature of at least about 1500° C. and at most about 2000° C. by resistance heating with a resistance heating mechanism.
The high-temperature firing section H is a section to perform high-temperature firing that comprises: heating the ceramic degreased body from the preheating temperature to a firing temperature of at least about 2000° C. and at most about 2300° C. by both resistance heating with the resistance heating mechanism and direct energizing heating; and holding the temperature of the ceramic degreased body at the firing temperature.
The cooling section C is a section to cool the ceramic degreased body after the high-temperature firing down to room temperature.
Hereinafter, the preheating section P, the high-temperature firing section H, and the cooling section C of the continuous firing furnace 20 will be described.
The preheating section P illustrated in
A lower plate 30 is placed on the rollers 28, a ceramic degreased body 10 as a firing object is placed on the lower plate 30, and an upper plate 31 is placed on the ceramic degreased body 10.
The plural rollers 28 are provided in a longitudinal direction of the continuous firing furnace (transverse direction illustrated in
The material of the lower plate 30 and the upper plate 31 is not particularly limited, and is desirably carbon. It is because carbon is conductive and heat resistant.
A resistance heating mechanism 40 is provided over the muffle 23, and an other resistance heating mechanism 40 is provided under the muffle 23. As a resistance heating mechanism, a graphite heater or the like can be suitably used.
The resistance heating mechanisms 40 are energized and thereby heated. The muffle 23 is heated with the heat, whereby the ceramic degreased body 10 that is a firing object in the muffle 23 is heated.
A heat insulating layer 41 is provided outside the resistance heating mechanism 40.
The high-temperature firing section H illustrated in
The energizing electrodes are composed of a lower electrode 50 disposed under a lower plate 30 and an upper electrode 51 disposed on the upper plate 31. The lower electrode 50 and the upper electrode 51 pass through a muffle 23.
The lower electrode 50 is disposed between the rollers 28 so as not to contact the rollers 28.
The lower electrode 50 and the upper electrode 51 can be moved up and down.
As illustrated in
When direct energizing heating is not performed, as illustrated in
In the high-temperature firing section H, the resistance heating mechanism 40 is provided over the muffle 23, and an other resistance heating mechanism is provided under the muffle 23, as in the preheating section P. The temperature of the ceramic degreased body 10 can be raised up to a firing temperature by both direct energizing heating and resistance heating and held at the firing temperature.
The cross-sectional view of the cooling section C is not illustrated. The cooling section C has substantially the same configuration as that of the preheating section P illustrated in
Since the heating mechanism is not provided, the temperature of the firing object that passes through the cooling section C gradually decreases.
The temperature and length of the cooling section C, and the transport rate in the cooling section C are adjusted so that the firing object reaches approximately room temperature (for example, about 25° C.) in the vicinity of the exit part of the muffle.
A cooling mechanism such as a blower, which promotes cooling of a firing object by blowing air to the firing object, may be provided in the cooling section C.
Next, the method for manufacturing a ceramic fired body according to the present embodiment by using such a continuous firing furnace will be described.
First, a ceramic degreased body that is a firing object is manufactured.
The ceramic degreased body is manufactured by, for example, molding a wet mixture that contains a ceramic powder made of porous silicon carbide and a binder to from a ceramic molded body, drying the molded body, degreasing the molded body at a predetermined temperature, and heating and removing an organic matter in the molded body.
In the present embodiment, the subsequent processes will be described, for example, by the method for manufacturing a substantially rectangular-pillar shaped ceramic fired body comprising porous silicon carbide having a large number of cells longitudinally disposed in parallel with one another with a cell wall interposed therebetween.
An example of the shape of the ceramic fired body will be described later by the method for manufacturing a honeycomb structured body.
Next, such a ceramic degreased body is charged into the continuous firing furnace illustrated in
First, as illustrated in
Then, as illustrated in
Subsequently, as illustrated in
Thus, the lower plate 30, the ceramic degreased bodies 10, and the upper plate 31 are disposed to form a transport object 32.
It is to be noted that the positions of the lower plate 30 and the upper plate 31 are different, but these are made of the same carbon plates.
In the present embodiment, the area of the lower plate and the area of the upper plate are each larger than the area of the side face of the ceramic degreased body. The area of the side face of the ceramic degreased body means the area of the surface indicated by the numeral 11 in
The area of the lower plate and the area of the upper plate mean the area of the main surface (largest surface) of the lower plate and that of the upper plate.
The assembled transport object 32 is disposed in the input part 25 of the continuous firing furnace 20 illustrated in
The transport object 32 is transported to the preheating section P in the muffle 23 of the continuous firing furnace 20.
In the preheating section P, the ceramic degreased body is preheated from room temperature (for example, about 25° C.) to a preheating temperature of at least about 1500° C. and at most about 2000° C. by resistance heating with a resistance heating mechanism.
In the present embodiment, a temperature-rise rate in the preheating is at least about 2° C./min and at most about 8° C./min, and the temperature-rise rate is not particularly limited.
The gas atmosphere in the preheating section in the present embodiment is an argon atmosphere, and it is sufficient that the gas atmosphere is optionally adjusted depending on the kind and shape of the honeycomb degreased body.
The preheated transport object 32 is transported to the high-temperature firing section H in the muffle 23.
In the high-temperature firing section H, the ceramic degreased body is heated from the preheating temperature to a firing temperature of at least about 2000° C. and at most about 2300° C. by both resistance heating with the resistance heating mechanism and direct energizing heating in which the ceramic degreased body is energized and heated by applying a voltage between the lower plate and the upper plate.
In the present embodiment, a temperature-rise rate from the preheating temperature to the firing temperature is at least about 6° C./min and at most about 12° C./min, and the temperature-rise rate is not particularly limited.
Hereinafter, direct energizing heating will be described in detail with reference to
Before the transport object 32 is transported to the high-temperature firing section H, the lower electrode 50 is disposed on the lower side and the upper electrode 51 is disposed on the upper side, as illustrated in
Then, when the transport object 32 is transported to a predetermined position in the high-temperature firing section H, that is, the position sandwiched by the lower electrode 50 and the upper electrode 51, the rollers 28 that serve as a transport mechanism are stopped.
Next, as illustrated in
Subsequently, the ceramic degreased body 10 is energized between the lower plate 30 and the upper plate 31 by applying a voltage between the lower electrode 50 and the upper electrode 51. Thereby, direct energizing heating of the ceramic degreased body 10 is performed.
In the case of performing direct energizing heating, force is desirably applied from the upper electrode to the upper plate and also from the lower electrode to the lower plate in order to secure contact between the electrodes and the upper plate and the lower plate.
It is necessary to adjust the force to be applied depending on the strength of the upper plate and the lower plate, etc. For example, in the case where the upper plate and the lower plate have a thickness of about 16 mm and are made of carbon, the force is desirably at least about 400 kgf and at most about 800 kgf.
The applied voltage in direct energizing heating is optionally adjusted depending on the temperature-rise rate and the material of the ceramic degreased body.
For example, the voltage is desirably at least about 3 V and at most about 100 V, and the current is desirably at least about 50 A and at most about 5000 A.
In the high-temperature firing section, direct energizing heating and resistance heating with the resistance heating mechanism are performed together. The ratio of the amount of heat applied by direct energizing heating to the amount of heat applied by resistance heating is not particularly limited, and it is sufficient that the ratio is adjusted so as to reach a predetermined temperature-rise rate. If the ratio of the amount of heat applied by direct energizing heating is relatively increased, the electrical energy used upon applying the same amount of heat to a ceramic degreased body can be decreased.
In the high-temperature firing section, the ceramic degreased body is heated up to a firing temperature of at least about 2000° C. and at most about 2300° C. Thereafter, the ceramic degreased body is held at the firing temperature.
Also upon holding the ceramic degreased body at the firing temperature, direct energizing heating and resistance heating with the resistance heating mechanism are performed together. Also in this case, the amount of heat applied by direct energizing heating and resistance heating is appropriately adjusted, so that the temperature of the ceramic degreased body is held at a predetermined firing temperature.
The gas atmosphere in the high-temperature firing section in the present embodiment is an argon atmosphere, and it is sufficient that the gas atmosphere is optionally adjusted depending on the kind and shape of the honeycomb degreased body.
The high-temperature firing performed in the high-temperature firing section means the process comprising raising the temperature from a preheating temperature to a firing temperature and holding the temperature at the firing temperature. Through this high-temperature firing, a ceramic degreased body is fired and changed into a ceramic fired body. In the high-temperature firing, the transport mechanism is stopped, the lower electrode is brought and kept in contact with the lower plate, and the upper electrode is brought and kept in contact with the upper plate. Thereby, it is possible to sequentially raise the temperature up to a firing temperature and holding the temperature at the firing temperature.
After the high-temperature firing, the transport mechanism is driven, and the ceramic fired body fired through the high-temperature firing is transported into a cooling section C in the muffle 23 (see
In the cooling section C, the temperature of the ceramic fired body is gradually decreased. When the temperature of the ceramic fired body reaches approximately room temperature (for example, about 25° C.), the transport object 32 is removed from the exit part 23b (see
In the exit purge chamber 26, the furnace atmosphere is adjusted from an inert gas atmosphere such as argon and nitrogen to an air atmosphere, if necessary.
Then, the transport object 32 is removed from the exit part 27 of the continuous firing furnace 20, and the firing is completed.
Next, the method for manufacturing a honeycomb structured body of the present embodiment will be described.
In the present embodiment, the ceramic degreased body that is a firing object is a honeycomb degreased body having a honeycomb shape, and the honeycomb degreased body is fired to manufacture a honeycomb fired body. Then, plural honeycomb fired bodies are combined with one another to manufacture a honeycomb structured body.
First, the honeycomb structured body and the honeycomb fired body manufactured in the present embodiment will be described.
In the honeycomb structured body 100 illustrated in
In the honeycomb fired body 110 illustrated in
Therefore, the cell wall 113 functions as a filter for capturing PMs and the like.
Hereinafter, the method for manufacturing a honeycomb structured body according to the present embodiment will be described.
In the first place, silicon carbide powders having different average particle diameters as a ceramic raw material, and an organic binder are mixed to prepare a mixed powder. Then, a liquid plasticizer, a lubricant, and water are mixed to prepare a wet mixture for manufacturing a molded body.
Subsequently, molding is performed by charging the wet mixture into an extrusion-molding apparatus and extrusion-molding the mixture to manufacture a honeycomb molded body having a predetermined shape.
Next, the two ends of the honeycomb molded body are cut with a cutting machine so that the honeycomb molded body is cut into a predetermined length. Then, the cut honeycomb molded body is dried with a drying apparatus.
Subsequently, a predetermined amount of a plug material paste to be a plug is charged into an end of either one of cells to seal the cells. A honeycomb molded body with plugged cells is manufactured through such processes.
Next, degreasing is performed by heating organic matters of the honeycomb molded body with the plugged cells in a degreasing furnace to manufacture a honeycomb degreased body. The shape of the honeycomb degreased body is substantially the same as the shape of the honeycomb fired body illustrated in
Subsequently, the honeycomb degreased body is transported into a firing furnace, and then fired in the firing of the method for manufacturing a ceramic fired body according to the present embodiment to manufacture a honeycomb fired body having a shape illustrated in
Subsequently, bonding is performed by forming an adhesive paste layer between the honeycomb fired bodies, heating and solidifying the adhesive paste layer to form a adhesive layer, and bonding plural honeycomb fired bodies by interposing an adhesive layer to form an aggregated body of the honeycomb fired bodies.
Then, peripheral cutting is performed by cutting the outer periphery of the aggregated body with a diamond cutter to form a ceramic block having a substantially round pillar shape.
Further, formation of the sealing material layer is performed by applying a sealing material paste to the peripheral surface of the ceramic block having a substantially round pillar shape, and drying and solidifying the sealing material paste to form a sealing material layer.
It is to be noted that the same paste as the sealing material paste used for formation of the sealing material paste layer can be used as the adhesive paste.
The honeycomb structured body is manufactured by the above processes.
Hereinafter, the effects of the method for manufacturing a ceramic fired body and the method for manufacturing a honeycomb structured body according to the present embodiment will be described.
(1) In the method for manufacturing a ceramic fired body of the present embodiment, the ceramic degreased body is preheated up to a preheating temperature of at least about 1500° C. and at most about 2000° C. by resistance heating with the resistance heating mechanism. As preheating is performed only with a resistance heating mechanism, the temperature-rise rate is not too high, and cracks are more likely to be prevented in the ceramic degreased body.
(2) In the method for manufacturing a ceramic fired body of the present embodiment, the ceramic degreased body is heated from the preheating temperature to a firing temperature of at least about 2000° C. and at most about 2300° C. by both resistance heating and direct energizing heating. The combination of the two heating methods for heating tends to shorten the temperature-rise time in this temperature range.
(3) In the method for manufacturing a ceramic fired body of the present embodiment, the area of the lower plate and the area of the upper plate are each larger than the area of the side face of the ceramic degreased body.
As direct energizing heating is performed starting from such larger areas, plural lines of ceramic fired bodies are more likely to be heated uniformly.
(4) In the method for manufacturing a ceramic fired body of the present embodiment, the lower plate and the upper plate are made of carbon.
Since carbon is conductive, the ceramic degreased body can be suitably energized through the lower plate and the upper plate. Since carbon is also heat resistant, it is suitably used in a firing furnace.
(5) In the method for manufacturing a ceramic fired body of the present embodiment, a temperature-rise rate in the preheating is at least about 2° C. and at most about 8° C./min. The temperature-rise rate tends to suitably prevent cracks in the ceramic fired body in the preheating.
(6) In the method for manufacturing a ceramic fired body of the present embodiment, a temperature-rise rate in the high-temperature firing is at least about 6° C./min and at most about 12° C./min.
The temperature-rise rate tends to shorten the temperature-rise time in the high-temperature-firing.
(7) In the method for manufacturing a ceramic fired body of the present embodiment, the ceramic fired body comprises porous silicon carbide having a large number of cells longitudinally disposed in parallel with one another with a cell wall interposed therebetween. In the case where the porous silicon carbide of such a shape is manufactured, variations in pore diameters are more likely to be reduced compared with the porous silicon carbide fired only with resistance heating.
(8) In the method for manufacturing a honeycomb structured body of the present embodiment, plural ceramic fired bodies manufactured by the method for manufacturing a ceramic fired body according to the present embodiment are combined with one another with an adhesive layer interposed therebetween.
Ceramic fired bodies can be manufactured efficiently by such a method. Accordingly, a honeycomb structured body can be manufactured efficiently.
The following description will discuss examples that more specifically disclose the first embodiment of the present invention, and the present invention is not intended to be limited only by these examples.
In the following examples and comparative examples, honeycomb fired bodies of the shape as illustrated in
An amount of 52.8% by weight of coarse powder of silicon carbide having an average particle diameter of 22 μm and 22.6% by weight of fine powder of silicon carbide having an average particle diameter of 0.5 μm were mixed. To the resulting mixture, 2.1% by weight of acrylic resin, 4.6% by weight of an organic binder (methylcellulose), 2.8% by weight of a lubricant (UNILUB, made by NOF Corporation), 1.3% by weight of glycerin, and 13.8% by weight of water were added, and then kneaded to prepare a mixture composition. The mixture composition was extrusion-molded and cut into a predetermined length, so that a raw honeycomb molded body having substantially the same shape as the shape illustrated in
Next, the raw honeycomb molded body was dried with a microwave drying apparatus to give a dried body of the honeycomb molded body comprising a silicon carbide, with a size of 34.3 mm×34.3 mm×150 mm, the number of cells (cell density) of 46.5 pcs/cm2, and a thickness of the cell wall of 0.25 mm (10 mil). A paste (mixture composition) having the same composition as the raw molded body was then charged into predetermined cells, and the honeycomb molded body was again dried with a drying apparatus.
The dried honeycomb molded body was degreased at 400° C. to manufacture a honeycomb degreased body having substantially the same shape as illustrated in
The manufactured honeycomb degreased body was fired with a continuous firing furnace as illustrated in
First, by following the procedure illustrated in
The transport object has a structure in which six honeycomb degreased bodies are disposed on the lower plate, and the upper plate is disposed on the honeycomb degreased bodies.
As the lower plate and the upper plate, a carbon plate having a thickness of 16 mm and a size of the main surface of 300 mm×300 mm was used.
Then, the transport object was placed on rollers of the continuous firing furnace, the rollers were driven, and then transport objects were sequentially transported into a muffle. Argon gas was flowed in the muffle, which was then filled with argon atmosphere.
In the first place, the transport object was transported to a preheating section in the muffle. Then, preheating was performed as follows. First, resistance heating is performed with a resistance heating mechanism (carbon heater) while the transport object is transported, and thereafter the honeycomb degreased body was heated until the temperature thereof reached 2000° C. It took 325 minutes to start heating and raise the temperature of the honeycomb degreased body up to 2000° C.
Subsequently, the transport object was transported to a high-temperature firing section in the muffle. Then, a lower energizing electrode was brought into contact with the lower plate of the transport object, and an upper energizing electrode was brought into contact with the upper plate thereof. Thereafter, the honeycomb degreased body between the lower plate and the upper plate was energized by applying a voltage between the lower electrode and the upper electrode. Thereby, direct energizing heating of the honeycomb degreased body was performed.
In addition, resistance heating was performed with two resistance heating mechanisms (carbon heaters), one of which is provided over the muffle, and the other of which is provided under the muffle. The combination of direct energizing heating and resistance heating raised the temperature from the preheating temperature of the honeycomb degreased body of 2000° C. to the firing temperature of 2200° C. It took 30 minutes to raise the temperature from 2000 to 2200° C.
That is, it took 355 minutes to start heating and raise the temperature of the honeycomb degreased body up to 2200° C.
Thereafter, direct energizing heating and resistance heating with a resistance heating mechanism are performed together, the firing temperature of the honeycomb degreased body was held at 2200° C. for 60 minutes, and thereby the high-temperature firing was completed.
Through the high-temperature firing, the honeycomb degreased body was fired into a honeycomb fired body.
Subsequently, the transport object is transported into a cooling section in the muffle. The temperature of the honeycomb fired body was gradually decreased in the cooling section. The transport object was removed from the muffle when the temperature of the ceramic fired body reached approximately room temperature.
Then, the furnace was filled with air atmosphere in an exit purge chamber, the transport object was removed from the exit part of the continuous firing furnace, and the firing was completed.
Through the above processes, a honeycomb fired body made of a silicon carbide sintered body, with a porosity of 45%, an average pore diameter of 15 μm, a size of 34.3 mm×34.3 mm×150 mm, the number of cells (cell density) of 46.5 pcs/cm2 and a thickness of the cell wall of 0.25 mm (10 mil) was manufactured.
The temperature was raised to the preheating temperature of the honeycomb degreased body of 2000° in the same manner as in Example 1 in the preheating. However, in the high-temperature firing, direct energizing heating was not performed, and only resistance heating with a resistance heating mechanism was performed from the preheating temperature of 2000° C. to the firing temperature of 2200° C. It took 50 minutes to raise the temperature from 2000 to 2200° C.
That is, it took 375 minutes to start heating and raise the temperature of the honeycomb degreased body up to 2200° C.
The honeycomb fired body was manufactured in the same manner as in Example 1 in the preheating. However, in the high-temperature firing, direct energizing heating was performed, and resistance heating with a resistance heating mechanism was not performed. It took 60 minutes to raise the temperature from 2000 to 2200° C.
That is, it took 385 minutes to heat the honeycomb degreased body up to 2200° C.
A honeycomb fired body was manufactured by both resistance heating and direct energizing heating in both the preheating and the high-temperature firing, by using the same continuous firing furnace as the firing furnace in Example 1 which was provided with the same energizing heating mechanism in the preheating section as in the high-temperature firing section.
It took 120 minutes to raise the temperature to the preheating temperature of 2000° C., and it took 30 minutes to raise the temperature from 2000 to 2200° C.
That is, it took 150 minutes to start heating and raise the temperature of the honeycomb degreased body up to 2200° C.
In Comparative Example 3, two out of six manufactured honeycomb fired bodies had cracks.
The honeycomb fired bodies (six pieces each) manufactured in Example 1 and Comparative Example 1 were evaluated for the average pore diameter, pressure loss, and bending strength by the following procedure.
Part of the cell walls of the honeycomb fired body were cut, and the pore distribution of the cell walls was measured in a range of pore diameters from 0.1 to 360 μm with a porosimeter (AutoPore III 9420, manufactured by Shimadzu Corporation) by a mercury porosimetry. The average pore diameter and the variations thereof (σ) were calculated from the results.
In the exhaust gas pipe with the blower, a honeycomb fired body was fixed and disposed in a metal casing. Thereby, a pressure loss measuring apparatus to which a pressure gauge was attached so as to enable detection of pressure before and after the honeycomb fired body was manufactured.
The blower was driven so that the flow rate of exhaust gases was set to 750 m3/h, and a pressure difference (pressure loss) was measured after five minutes from the start of the driving operation. Plural honeycomb fired bodies were measured for pressure loss, and the average and variations thereof (σ) were calculated.
The three-point bending test was carried out on each of the honeycomb fired bodies in conformity with JIS R1601, and the bending strength (load) of the honeycomb fired bodies was measured.
Upon measurement of bending strength, the three-point bending test was conducted with an Instron tester, and the load (MPa) at break was measured. The distance between fulcrums was 135 mm.
The bending strength of plural honeycomb fired bodies was measured, and the average and variations thereof (σ) were calculated.
The contents of JIS R 1601 are incorporated herein by reference in their entirety.
Tables 1-1 and 1-2 summarizes the heating method and the temperature-rise time in firing of each example and comparative example, and measurement results of the average pore diameter, pressure loss, and bending strength of each of the honeycomb fired bodies manufactured in Example 1 and Comparative Example 1.
Since resistance heating and direct energizing heating are performed together in the high-temperature firing in Example 1, the temperature-rise time from 2000 to 2200° C. is 30 minutes, and 20 minutes shorter than that in Comparative Example 1 in which only resistance heating is performed in the high-temperature firing.
When the properties of the honeycomb fired bodies manufactured in Example 1 and Comparative Example 1 were compared, averages of average pore diameters, pressure loss, and bending strength thereof were equivalent, but variations in each of the measurement values were smaller in Example 1.
This showed that in the method for manufacturing a ceramic fired body of Example 1, the variations in the average pore diameter, pressure loss, and bending strength were small, and ceramic fired bodies were manufactured in a short period of time.
In Comparative Example 2, only direct energizing heating is performed in the high-temperature firing, and the temperature-rise time from 2000 to 2200° C. was as long as 60 minutes.
In Comparative Example 3, the temperature-rise time from the start of heating to 2200° C. was as short as 150 minutes. However, the temperature-rise rate in the preheating was so high that cracks occurred in the honeycomb fired bodies.
Hereinafter, the second embodiment, which is one embodiment of the present invention, will be described.
In the present embodiment, in the method for manufacturing a ceramic fired body and the method for manufacturing a honeycomb structured body according to the first embodiment, plural lines of the ceramic degreased bodies are arranged in the continuous firing furnace, plural lines of the upper and lower energizing electrodes are aligned with plural lines of the ceramic degreased bodies, and direct energizing heating was performed.
In
Two sets of lower electrodes 50 are disposed on the bottom of one set of the lower plate 30, and two sets of upper electrodes 51 are disposed on the upper surface of one set of the upper plate 31, so as to correspond to each of the two ceramic degreased bodies 10.
In addition, three lines of rollers 28 are provided so as not to contact the lower electrodes 50.
In the continuous firing furnace, plural transport objects 32 comprising one set of a lower plate 30, an upper plate 31, and two ceramic degreased bodies 10 are disposed, and a lower electrode 50 and an upper electrode 51 are disposed on the upper surface and bottom of each of the transport objects 32. When the transport objects and the energizing electrodes are thus disposed, direct energizing heating of a large number of ceramic degreased bodies can be performed at once.
In the present embodiment, the effects of (1) to (8) described also in the first embodiment can be exerted, so can the following effects.
(9) In the method for manufacturing the ceramic fired body of the present embodiment, plural lines of the ceramic degreased bodies are arranged in the continuous firing furnace, and plural lines of the upper and lower energizing electrodes are aligned with plural lines of the ceramic degreased bodies, and direct energizing heating is performed.
Thus, current can be equally applied to each of plural lines of the ceramic degreased bodies, and a large number of honeycomb fired bodies can be efficiently manufactured.
Hereinafter, the third embodiment, which is one embodiment of the present invention, will be described.
In the present embodiment, ceramic degreased bodies and carbon plates are alternately disposed to manufacture a laminated body in which ceramic degreased bodies and carbon plates are laminated in multiple layers. Direct energizing heating is performed by applying a voltage between the lowest carbon plate and the highest carbon plate.
In
A second layer of ceramic degreased bodies 10b, a second upper plate 31b, a third layer of ceramic degreased bodies 10c, and a third upper plate 31c are disposed in this order on the first upper plate 31a to form a laminated body 33.
A lower energizing electrode 50 is brought into contact with the lower plate 30, and an upper energizing electrode 51 is brought into contact with the highest third upper plate 31c. Thereby, direct energizing heating was performed.
In the case where two layers of ceramic degreased bodies are laminated, heating is performed in the following embodiment.
That is, in the method for manufacturing a ceramic fired body of the present embodiment, the lower plate is disposed on the bottom of a first ceramic degreased body, a first upper plate is disposed on the upper surface of the first ceramic degreased body, a second ceramic degreased body is disposed on the upper surface of the first upper plate, a second upper plate is disposed on the upper surface of the second ceramic degreased body to manufacture a laminated body having two layers in which ceramic degreased bodies are laminated, and the energizing heating is performed by applying a voltage between the lower plate and the second upper plate.
In the case where three or more layers of ceramic degreased bodies are laminated, heating is performed in the following embodiment.
That is, in the method for manufacturing a ceramic fired body of the present embodiment, the lower plate is disposed on the bottom of a first ceramic degreased body, a first upper plate is disposed on the upper surface of the first ceramic degreased body, a second ceramic degreased body is disposed on the upper surface of the first upper plate, a second upper plate is disposed on the upper surface of the second ceramic degreased body, and then an other ceramic degreased body and an other upper plate are alternately disposed on the second upper plate to manufacture a laminated body having three or more layers in which ceramic degreased bodies and upper plates are laminated, and the energizing heating is performed by applying a voltage between the lower plate and the highest upper plate.
In the present embodiment, the effects of (1) to (8) described also in the first embodiment can be exerted, so can the following effects.
(10) In the method for manufacturing the ceramic fired body of the present embodiment, a lower plate is disposed on the bottom of a first ceramic degreased body, an upper plate is disposed on the upper surface of the first ceramic degreased body, a second upper plate is disposed on the upper surface of a second ceramic degreased body, then an other ceramic degreased body and an other upper plate are alternatively disposed on the second upper plate to manufacture a laminated body having three or more layers in which ceramic degreased bodies are laminated, and the energizing heating is performed by applying a voltage between the lower plate and the upper plate at the highest layer.
In the above-mentioned two methods, thus, plural ceramic degreased bodies can be energized in both up and down directions simultaneously, and a large number of honeycomb fired bodies can be efficiently manufactured.
The continuous firing furnace described in the first embodiment of the present invention is a firing furnace in which a preheating section, a high-temperature firing section, and a cooling section are integrated. The cooling section may not be integrated with the preheating section and the high-temperature firing section, and may be a cooling device separate from the firing furnace. In this case, the cooling device is disposed on the outlet side from the high-temperature firing section, and transport objects removed from the high-temperature firing section are sequentially introduced into the cooling device.
Examples of the resistance heating mechanism used for resistance heating in the method for manufacturing a ceramic fired body of the present embodiment include, in addition to a graphite heater, a SiC heater, a C/C composite heater, and the like.
It is sufficient that the lower plate and the upper plate have the material and shape that enables direct energizing heating by interposing a ceramic degreased body, and these plates are not limited to carbon plates.
Examples of the material used for the lower plate and the upper plate include, in addition to carbon, SiC, a C/C composite, and the like.
The main constituent of the ceramic degreased body and the honeycomb fired body is not limited to silicon carbide. Examples of other ceramic raw materials include ceramic powders comprising: nitride ceramics such as aluminum nitride, silicon nitride, boron nitride and titanium nitride; carbide ceramics such as zirconium carbide, titanium carbide, tantalum carbide and tungsten carbide; oxide ceramics such as alumina, zirconia, cordierite, mullite, and aluminum titanate; and the like.
Of the above-mentioned possible constituents, non-oxide ceramics are desirable, and silicon carbide is particularly desirable. It is because silicon carbide is superior in heat resistance, mechanical strength, thermal conductivity, and the like. Moreover, the ceramic raw materials such as silicon-containing ceramic, in which metallic silicon is blended with the ceramics set forth above, as well as ceramic bound by silicon or silicate compounds can also be used as the constituents of the honeycomb fired body. Of these, those ceramics (silicon-containing silicon carbide) in which metallic silicon is blended with silicon carbide are desirably used.
The honeycomb structured body to be manufactured in the present embodiment is not limited to a honeycomb structured body with either one of the ends of the cells being plugged. A honeycomb structured body with either one of the ends of the cells being plugged can be preferably used as a honeycomb filter; whereas a honeycomb structured body with the cells not being plugged can be preferably used as a catalyst supporting carrier.
Accordingly, in the method for manufacturing a honeycomb structured body of the present embodiment, it is not always necessary to charge a plug material paste, but as needed.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/JP2009/069884 | Nov 2009 | JP | national |
The present application claims priority under 35 U.S.C. §119 to PCT Application No. PCT/JP2009/069884, filed Nov. 25, 2009, the contents of which are incorporated herein by reference in their entirety.
