Patent Application
20230294082
The present application claims the benefit of priority to Japanese Patent Application No. 2022-040159 filed on Mar. 15, 2022, the content of which is incorporated herein by reference in its entirety.
The present invention relates to a composite sintered body and a method of manufacturing the same, a honeycomb structure including the composite sintered body, and an electrically heating catalyst including the honeycomb structure.
Conventionally, in order to perform a purification treatment of toxic substances such as HC, CO, NOx, or the like contained in exhaust gas discharged from an engine of an automobile or the like, a catalytic converter having a columnar honeycomb structure or the like which supports a catalyst has been used. In the catalytic converter, the temperature of the catalyst needs to rise to an activation temperature in the purification treatment of exhaust gas, but since the temperature of the catalytic converter is low immediately after startup of the engine, or so on, there is a possibility that the exhaust gas purification performance may be reduced. Especially, in a plug-in hybrid electrical vehicle (PHEV) or a hybrid vehicle (HV), since the vehicle runs on motor only, the temperature of the catalyst easily decreases. Then, used is an electrically heating catalyst (EHC) in which a conductive catalytic converter is connected to a pair of electrodes and causes itself to generate heat by energization, to thereby preheat the catalyst.
Japanese Patent Application Laid-Open No. 2020-161413 (Document 1) discloses a technique for the honeycomb structure used in the electrically heating catalyst, in which surface bonding of silicon particles in an electrical resistance body forming the honeycomb structure is performed and a matrix containing borosilicate and cordierite is provided around the continuous body of the silicon particles. It is thereby possible to suppress an increase in the electric resistance (in other words, to improve the oxidation resistance) in the case where the honeycomb structure is exposed to a high temperature oxidation atmosphere.
WO 2012/128149 (Document 2) proposes a silicon carbide porous body which can be used for the electrically heating catalyst. The silicon carbide porous body contains 50 to 80 wt % of silicon carbide, 15 to 40 wt % of metallic silicon, and 1 to 25 wt % of cordierite, and the open porosity of the silicon carbide porous body is 10 to 40%. It is thereby possible to improve the thermal shock resistance and the resistance heat generation properties.
Furthermore, in the honeycomb structure disclosed in Document 1, since a potion in which the silicon particles are continuous is a local microstructure, it is thought that variation in the volume resistivity for all portions of the honeycomb structure is large and there is a limit in the improvement in the oxidation resistance. It is thought that this local microstructure is caused by inhibiting sintering of the silicon particles by borosilicate. Further, since the honeycomb structure contains borosilicate, sintering shrinkage becomes large and it is difficult to form the honeycomb structure with high dimensional accuracy.
The present invention is intended for a composite sintered body, and it is an object of the present invention to improve the oxidation resistance of a composite sintered body.
The composite sintered body according to one preferred embodiment of the present invention contains a silicon phase, a cordierite phase, and a high-resistance silicon carbide phase. In the composite sintered body of the present invention, the content of silicon in the composite sintered body to the composite sintered body is not lower than 30 mass % and not higher than 50 mass %. The content of cordierite in the composite sintered body to the composite sintered body is not lower than 10 mass % and not higher than 50 mass %. The content of high-resistance silicon carbide in the composite sintered body to the composite sintered body is not lower than 20 mass and not higher than 50 mass %.
According to the present invention, it is possible to improve the oxidation resistance of the composite sintered body.
Preferably, a median diameter of silicon particles, based on a volume standard, in the composite sintered body is not smaller than 9
Preferably, a porosity of the composite sintered body is not lower than 30% and not higher than 50%.
Preferably, an average pore diameter of the composite sintered body is not smaller than 2.5 μm and not larger than 4.0 μm.
Preferably, a volume resistivity of the composite sintered body at 20° C. is not lower than 1.0 Ω·cm and not higher than 100 Ω·cm.
Preferably, a change rate of a volume resistivity of a composite sintered body after exposing the composite sintered body to an atmosphere at 950° C. for 50 hours is not higher than 100%.
Preferably, the content of low-resistance silicon carbide in the composite sintered body is not higher than 1 mass %.
The present invention is also intended for a honeycomb structure. The honeycomb structure according to one preferred embodiment of the present invention includes a cylindrical outer wall and a lattice partition wall partitioning an inside of the outer wall into a plurality of cells. The outer wall and the partition wall are formed, including the above-described composite sintered body.
The present invention is still also intended for an electrically heating catalyst used for performing a purification treatment of exhaust gas discharged from an engine. The electrically heating catalyst according to one preferred embodiment of the present invention includes the above-described honeycomb structure and a pair of electrode terminals fixed to an outer surface of the honeycomb structure, for giving a current to the honeycomb structure.
The present invention is yet also intended for a method of manufacturing a composite sintered body. The method of manufacturing a composite sintered body according to one preferred embodiment of the present invention includes a) obtaining a green body by molding raw material powder containing a silicon raw material, a cordierite raw material, and a high-resistance silicon carbide raw material and b) obtaining a composite sintered body by sintering the green body. In the method of manufacturing a composite sintered body of the present invention, the composite sintered body contains a silicon phase, a cordierite phase, and a high-resistance silicon carbide phase. The content of silicon in the composite sintered body to the composite sintered body is not lower than 30 mass % and not higher than 50 mass %. The content of cordierite in the composite sintered body to the composite sintered body is not lower than 10 mass % and not higher than 50 mass %. The content of high-resistance silicon carbide in the composite sintered body to the composite sintered body is not lower than 20 mass % and not higher than 50 mass %.
Preferably, a sintering shrinkage of the composite sintered body to the green body is not higher than 7%.
These and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
The electrically heating catalyst 1 includes a honeycomb structure 2, a pair of electrode layers 31, and a pair of electrode terminals 41. The honeycomb structure 2, the pair of electrode layers 31, and the pair of electrode terminals 41 are each conductive. The honeycomb structure 2 is a substantially columnar member having a honeycomb construction, and is a carrier supporting a catalyst in the electrically heating catalyst 1. The pair of electrode layers 31 are fixed on an outer surface of the honeycomb structure 2. The pair of electrode layers 31 are foil-like or plate-like members which are arranged, facing each other with a central axis J1 sandwiched therebetween. The central axis J1 extends in a longitudinal direction of the honeycomb structure 2. Each of the electrode layers 31 is provided along the outer surface of the honeycomb structure 2. Further, in the electrically heating catalyst 1, the outer shape of the honeycomb structure 2 is not limited to the substantially columnar shape but may be changed into any one of various shapes. Furthermore, the respective numbers of and the arrangement of the electrode layers 31 and the electrode terminals 41 may be variously changed. In the electrically heating catalyst 1, the electrode layer 31 may be omitted and the electrode terminal 41 may be directly fixed to the honeycomb structure 2.
The pair of electrode terminals 41 are fixed on surfaces of the pair of electrode layers 31, respectively, by using a junction part 42. In other words, the pair of electrode terminals 41 are indirectly fixed on the outer surface of the honeycomb structure 2 with the pair of electrode layers 31 interposed therebetween. The electrode terminal 41 is, for example, a substantially strip-like member. The electrode terminal 41 is connected to a not-shown power supply. When the power supply applies a voltage across the pair of electrode layers 31 through the electrode terminals 41, a current flows in (in other words, a current is given to) the honeycomb structure 2 and the honeycomb structure 2 generates heat by the Joule heat. The catalyst supported by the honeycomb structure 2 is thereby preheated. The voltage applied to the electrically heating catalyst 1 ranges, for example, from 12 V to 900 V, and preferably ranges from 64 V to 600 V. Further, the voltage may be changed as appropriate.
The honeycomb structure 2 is a cell structure which is partitioned into a plurality of cells 23 inside. The honeycomb structure 2 includes an outer wall 21 and a partition wall 22. The outer wall 21 is a cylindrical portion extending in the longitudinal direction (i.e., the direction perpendicular to this paper of
The partition wall 22 is provided inside the outer wall 21 and is a lattice member partitioning the inside thereof into the plurality of cells 23. Each of the plurality of cells 23 is a space extending over substantially the full length of the honeycomb structure 2 in the longitudinal direction. Each cell 23 is a flow passage in which the exhaust gas flows, and the catalyst used for the purification treatment of the exhaust gas is supported by the partition wall 22. A cross-sectional shape of each cell 23 which is perpendicular to the longitudinal direction is, for example, a substantial rectangle. The cross-sectional shape may be any other shape such as a polygonal shape, a circular shape, or the like. In terms of reduction in the pressure loss in the flow of the exhaust gas in the cell 23, it is preferable that the cross-sectional shape should be a quadrangle or a hexagon. Further, in terms of an increase in the structural strength and the uniformity of heating in the honeycomb structure 2, it is preferable that the cross-sectional shape should be a rectangle. The plurality of cells 23 have the same cross-sectional shape in principle. The plurality of cells 23 may include some cells 23 each having a different cross-sectional shape.
The length of the outer wall 21 in the longitudinal direction is, for example, 30 mm to 200 mm. The outer diameter of the outer wall 21 is, for example, 25 mm to 120 mm. In terms of an increase in the heat resistance of the honeycomb structure 2, the area of an end surface of the honeycomb structure 2 (i.e., the area of a region surrounded by the outer wall 21 in the end surface of the honeycomb structure 2) is preferably 2000 mm2 to 20000 mm2, and further preferably 5000 mm2 to 15000 mm2. In terms of prevention of outflow of a fluid flowing in the cell 23, an increase in the strength of the honeycomb structure 2, and the strength balance between the outer wall 21 and the partition wall 22, the thickness of the outer wall 21 is, for example, 0.1 mm to 1.0 mm, preferably 0.15 mm to 0.7 mm, and more preferably 0.2 mm to 0.5 mm.
The length of the partition wall 22 in the longitudinal direction is substantially the same as that of the outer wall 21. In terms of an increase in the strength of the honeycomb structure 2 and reduction in the pressure loss in the flow of the exhaust gas in the cell 23, the thickness of the partition wall 22 is, for example, 0.07 mm to 0.3 mm and preferably 0.1 mm to 0.25 mm.
In terms of an increase in the area of the partition wall 22 which supports the catalyst and reduction in the pressure loss in the flow of the exhaust gas in the cell 23, the cell density of the honeycomb structure 2 (i.e., the number of cells 23 per unit area in the cross section perpendicular to the longitudinal direction) is, for example, 40 cells/cm2 to 150 cells/cm2, and preferably 70 cells/cm2 to 100 cells/cm2. The cell density can be obtained by dividing the number of all cells in the honeycomb structure 2 by the area of a region inside an inner peripheral edge of the outer wall 21 in the bottom surface of the honeycomb structure 2. The size of the cell 23, the number of cells 23, the cell density, and the like may be changed in various manners.
The outer wall 21 and the partition wall 22 in the honeycomb structure 2 are formed, including the composite sintered body described below. In the present preferred embodiment, the outer wall 21 and the partition wall 22 are formed of substantially only the composite sintered body.
The composite sintered body is porous ceramics containing a silicon phase, a cordierite phase, and a high-resistance silicon carbide phase. In the present specification, the “silicon phase” refers to a crystal phase formed mainly of silicon (Si). The silicon phase may contain impurities other than silicon (for example, a metal other than silicon). The content of impurities is not higher than 1 part by mass with respect to 100 parts by mass of silicon. Further, “silicon” refers to a (simple) substance formed of silicon element. The silicon phase contains a plurality of silicon particles serving as an aggregate of the composite sintered body. In the composite sintered body, the plurality of silicon particles become continuous, to thereby form a conductive path. Further, the composite sintered body may be used for any structure other than the honeycomb structure 2. For example, a structure having any one of various shapes, such as a substantially cylindrical shape, a substantially flat plate-like shape, or the like, may be formed, including the composite sintered body.
In the present specification, the “cordierite phase” refers to a crystal phase formed mainly of cordierite. The cordierite phase may contain impurities other than cordierite. As the impurity, for example, used is indialite which is a polymorph (also referred to as “polymorphism”) of cordierite. The cordierite phase exists mainly among a plurality of silicon particles and is a binder (i.e., a matrix) for binding the plurality of silicon particles. In the composite sintered body, it is preferable that the plurality of silicon particles should be so bound by the cordierite phase as to form a pore among the silicon particles. In the composite sintered body, since the cordierite phase having a relatively low thermal expansion coefficient is contained, the thermal shock resistance of the composite sintered body is improved.
In the present specification, the “high-resistance silicon carbide phase” refers to a crystal phase formed mainly of high-resistance silicon carbide. The high-resistance silicon carbide phase may contain impurities other than silicon carbide (SiC). The high-resistance silicon carbide refers to silicon carbide having relatively high content of impurities and relatively high volume resistivity. In the present specification, silicon carbide having a volume resistivity not lower than 1 k Ω cm (1000 Ω·cm) is referred to as high-resistance silicon carbide. Further, silicon carbide having a volume resistivity lower than 1 kΩ·cm (1000 Ω·cm) is referred to as “low-resistance silicon carbide”. Furthermore, the volume resistivity of the high-resistance silicon carbide is preferably not lower than 10 kΩ·cm. The volume resistivities of the high-resistance silicon carbide and the low-resistance silicon carbide are obtained by a method, for example, in which a sintered body is formed of silicon carbide powder by using a spark plasma sintering (SPS) method, a hot-press method, or the like and the sintered body is cut into a predetermined size and measured by a four-probe (four-terminal) method (JIS C2525).
The cordierite phase exists mainly among a plurality of silicon particles, and the conductive path among the plurality of silicon particles is divided, to thereby increase the volume resistivity of the composite sintered body. On the other hand, since the material of the composite sintered body includes high-resistance silicon carbide, when the composite sintered body is sintered, the silicon particles are aggregated due to low wettability of silicon and high-resistance silicon carbide, to be coarsened (in other words, the particle diameter of the silicon particles is increased). A binding portion of the silicon particles forming the conductive path is thereby thickened and the volume resistivity of the composite sintered body is reduced. As a result, the volume resistivity of the composite sintered body falls within a favorable range. Further, since the binding portion of the silicon particles forming the conductive path is thickened, blocking of the conductive path becomes hard to occur even when the binding portion is oxidized. Therefore, even when the composite sintered body is exposed to the high temperature oxidation atmosphere, a change in the volume resistivity of the composite sintered body is suppressed. In other word, the oxidation resistance of the composite sintered body is improved.
The content of silicon in the composite sintered body to the composite sintered body is not lower than 30 mass % and not higher than 50 mass %. The content of cordierite in the composite sintered body to the composite sintered body is not lower than 10 mass % and not higher than 50 mass %. The content of high-resistance silicon carbide in the composite sintered body to the composite sintered body is not lower than 20 mass % and not higher than 50 mass %. The content of silicon in the composite sintered body to the composite sintered body is preferably not lower than 32 mass % and not higher than 45 mass %, and more preferably not lower than 35 mass % and not higher than 45 mass %. The content of cordierite in the composite sintered body to the composite sintered body is preferably not lower than 12 mass % and not higher than 45 mass %, and more preferably not lower than 13 mass % and not higher than 35 mass %. The content of high-resistance silicon carbide in the composite sintered body to the composite sintered body is preferably not lower than 23 mass % and not higher than 50 mass %, and more preferably not lower than 25 mass % and not higher than 50 mass %.
In the composite sintered body of the present preferred embodiment, in terms of suppressing the volume resistivity from becoming excessively low, the content of low-resistance silicon carbide in the composite sintered body to the composite sintered body is preferably not higher than 1 mass %, and more preferably, the composite sintered body does not substantially contain low-resistance silicon carbide. In other words, the content of low-resistance silicon carbide in the composite sintered body is more preferably 0.0 mass % (in other words, not higher than the detection limit). Further, also in terms of suppressing the thermistor characteristics of the composite sintered body from becoming negative, the content of low-resistance silicon carbide in the composite sintered body to the composite sintered body is preferably 0.0 mass %.
The composite sintered body may further contain an amorphous phase. The amorphous phase is a phase of amorphous substance containing, for example, silicon, and the amorphous phase is an oxide phase formed mainly of amorphous silica (i.e., amorphous silicon dioxide (SiO2)). The amorphous phase exists mainly on surfaces of the silicon particles and partially or entirely coats the silicon particles. Even in a case where the composite sintered body is exposed to a high temperature oxidation atmosphere, oxidation of the silicon particles is thereby suppressed and a change in the volume resistivity of the composite sintered body is suppressed. In other words, the oxidation resistance of the composite sintered body is improved. Amorphous silica contained in the amorphous phase is generated by, for example, oxidizing the surfaces of the silicon particles. Further, the amorphous phase may contain an oxide other than amorphous silica and/or any amorphous substance other than an oxide.
The composite sintered body may further contain a cristobalite phase. In the present specification, the “cristobalite phase” refers to a crystal phase formed mainly of cristobalite. The cristobalite phase may contain impurities other than cristobalite. The cristobalite phase exists, for example, on the surfaces of the silicon particles, a surface and an inside of a film of the amorphous phase coating the silicon particles, and the like. The cristobalite phase is generated by, for example, oxidizing the surfaces of the silicon particles.
The composite sintered body may further contain a mullite phase. In the present specification, the “mullite phase” refers to a crystal phase formed mainly of mullite. The mullite phase may contain impurities other than mullite. The mullite phase exists, for example, on the surfaces of the silicon particles, the surface and the inside of the film of the amorphous phase coating the silicon particles, and the like. The mullite phase is generated by, for example, reaction firing or the like using and consuming cristobalite as a material, which is generated by oxidizing the surfaces of the silicon particles. The denseness of the composite sintered body is thereby increased, and the oxidation resistance and the strength of the composite sintered body are increased. Further, since the thermal expansion coefficient of the composite sintered body is reduced by reduction of the cristobalite phase, the thermal shock resistance of the composite sintered body is also improved.
The identification and the quantity determination of the composition of the composite sintered body can be performed by pattern fitting using a result of the powder X-ray diffraction method (XRD) by the WPPD (whole-powder-pattern decomposition) method. For these analyses, for example, software such as “TOPAS” of Bruker Corporation or the like can be used.
In the composite sintered body, the average particle diameter of the silicon particles in the silicon phase is preferably not smaller than 9 μm, and more preferably not smaller than 10 μm. The upper limit of the average particle diameter of the silicon particles is not particularly limited, but is preferably not larger than 30 μm, and more preferably not larger than 20 μm. Thus, by coarsening the silicon particles so that the average particle diameter thereof should be not smaller than 9 μm, it is possible to suitably achieve high oxidation resistance and high thermal shock resistance in the composite sintered body. In the present specification, the “average particle diameter” refers to a median diameter (D50) based on a volume standard, unless otherwise specified.
In the present specification, the average particle diameter of the silicon particles in the composite sintered body is obtained as follows. First, an arbitrary polished cross section of the composite sintered body is observed by a SEM (scanning electron microscope) at an arbitrary magnification (for example, 500 times) and one silicon particle within the field of view is extracted. Subsequently, the long and short diameters of this silicon particle are obtained. Specifically, two points on the outer circumference of the silicon particle are connected and the longest diameter passing the barycenter is obtained as the long diameter. Further, two points on the outer circumference of the silicon particle are connected and the shortest diameter passing the barycenter is obtained as the short diameter. For the measurement of the long and short diameters, for example, the image analysis software “Image Pro 9” of Media Cybernetics, Inc. can be used. Then, the arithmetic average of the long and short diameters is obtained as the particle diameter of the silicon particle. Furthermore, also with respect to the plurality of other silicon particles within the above-described field of view, respective particle diameters thereof are obtained by the same method. Then, the respective particle diameters obtained with respect to the plurality of silicon particles within the above-described field of view are volume-converted, and the particle diameter whose cumulative value of the volume is 50% is obtained as the median diameter (D50) of the silicon particles, based on the volume standard.
Next, the position of the field of view in the above-described polished cross section of the composite sintered body is changed, the particle diameter of each silicon particle included within the field of view is obtained by the same method as above, and the median diameter (D50) of the silicon particles, based on the volume standard is thereby obtained. Then, in each of a predetermined number (2 or more, for example, 3) of fields of view on the above-described cross section of the composite sintered body, an arithmetic average of the above-described D50 of the silicon particles obtained, respectively, is obtained as the average particle diameter of the silicon particles in the composite sintered body. The average particle diameter of other particles (for example, the cordierite particles and the high-resistance silicon carbide particles) in the composite sintered body can be obtained by the same method.
The volume resistivity of the composite sintered body at 20° C. is preferably not lower than 1.0 Ω·cm, more preferably not lower than 2.0 Ω·cm, and further preferably not lower than 10 Ω·cm. Further, the volume resistivity is preferably not higher than 100 Ω·cm, more preferably not higher than 85 Ω·cm, and further preferably not higher than 50Ω·cm. In the present specification, the “volume resistivity” refers to a volume resistivity at 20° C., unless otherwise specified. When the volume resistivity of the composite sintered body is made not higher than 100 Ω·cm, the electrical conductivity of the electrically heating catalyst 1 is increased and a quick rise of the temperature of the electrically heating catalyst 1 is achieved. Further, when the volume resistivity of the composite sintered body is made not lower than 1.0 Ω·cm, even in a case where a relatively high voltage is applied to the composite sintered body, damage of an electric circuit due to excessive current flow is prevented. Furthermore, when the volume resistivity of the composite sintered body is made not higher than 100 Ω·cm, the electrical conductivity of the composite sintered body is increased. As a result, in a case where the composite sintered body is used for the electrically heating catalyst, a quick rise of the temperature of the electrically heating catalyst can be achieved. The volume resistivity can be obtained by measurement performed by the four-probe (four-terminal) method (JIS C2525).
The change rate of the volume resistivity of the composite sintered body after exposing the composite sintered body to an atmosphere at 950° C., which is a high temperature oxidation atmosphere, for 50 hours (in other words, the change rate of the volume resistivity of the composite sintered body after exposure, which is hereinafter referred to as a “resistance change rate”) is preferably not higher than 100%. The resistance change rate is a result expressed by percentage, which is obtained by subtracting 1 from a value obtained by dividing the volume resistivity of the composite sintered body after the exposure thereof in the atmosphere at 950° C. for 50 hours by the volume resistivity (hereinafter, also referred to as “initial resistivity”) of the composite sintered body before the exposure. In the present specification, the “resistance change rate” refers to the change rate of the volume resistivity of the composite sintered body after the exposure in the atmosphere at 950° C. for 50 hours, unless otherwise specified.
When the resistance change rate of the composite sintered body is made not higher than 100%, even in the case where the composite sintered body is exposed to the high temperature oxidation atmosphere, the change in the volume resistivity of the composite sintered body is suitably suppressed. Various performances such as the energization performance and the like of the electrically heating catalyst 1 can be thereby kept within a desirable range. The resistance change rate of the composite sintered body is more preferably not higher than 50%. Further, there is a possibility that the volume resistivity of the composite sintered body may be reduced by the effects of the impurities contained in the silicon particles and the high-resistance silicon carbide particles, and the like. In this case, the resistance change rate is preferably not lower than −50%, and more preferably not lower than −10%. Since it is desirable that the volume resistivity of the composite sintered body should not be changed, it is desirable that the resistance change rate should be closer to 0%.
The porosity of the composite sintered body is preferably not lower than 30%, more preferably not lower than 32%, and further preferably not lower than 35%. Further, the porosity thereof is preferably not higher than 50%, and more preferably not higher than 45%. When the porosity is made not lower than 30%, it is possible to reduce the Young's modulus of the composite sintered body and improve the thermal shock resistance thereof. Furthermore, when the porosity is made not higher than 50%, the denseness of the composite sintered body is improved. As a result, the volume resistivity of the composite sintered body is reduced and the oxidation resistance and the strength of the composite sintered body are increased. The porosity can be obtained, for example, by the mercury porosimetry (mercury intrusion porosimetry) (JIS R1655) using a mercury porosimeter or the like.
The average pore diameter of the composite sintered body is preferably not smaller than 2.5 μm, more preferably not smaller than 2.8 μm, and further preferably not smaller than 3.0 μm. Further, the average pore diameter thereof is preferably not larger than 4.0 μm, more preferably not larger than 3.8 μm, and further preferably not larger than 3.5 μm. When the average pore diameter is made not smaller than 2.5 μm, it is thereby possible to prevent the specific surface area of the composite sintered body becoming excessively large, resulting in a reduction in the oxidation resistance. Further, when the average pore diameter is made not larger than 4.0 μm, the denseness of the composite sintered body is improved. As a result, the volume resistivity of the composite sintered body is reduced and the oxidation resistance and the strength of the composite sintered body are increased. In the present specification, the “average pore diameter” refers to the average pore diameter of the composite sintered body. The average pore diameter can be obtained, for example, by the mercury porosimetry (mercury intrusion porosimetry) (JIS R1655) using the mercury porosimeter or the like.
The electrode layer 31 extends in the longitudinal direction along the outer surface of the honeycomb structure 2 and spreads in a circumferential direction around the central axis J1 (hereinafter, also referred to simply as a “circumferential direction”). The electrode layer 31 spreads the current from the electrode terminal 41 in the longitudinal direction and the circumferential direction, to thereby increase the uniformity of heat generation of the honeycomb structure 2. The length of the electrode layer 31 in the longitudinal direction is, for example, 80% or more of the length of the honeycomb structure 2 in the longitudinal direction, and preferably 90% or more. More preferably, the electrode layer 31 extends over the full length of the honeycomb structure 2.
The angle of the electrode layer 31 in the circumferential direction (i.e., an angle formed by two line segments extending from both ends of the electrode layer 31 in the circumferential direction to the central axis J1) is, for example, 30° or more, preferably 40° or more, and more preferably 60° or more. On the other hand, in terms of suppressing the current flowing inside the honeycomb structure 2 from decreasing due to the pair of electrode layers 31 which are too close to each other, the angle of the electrode layer 31 in the circumferential direction is, for example, 140° or less, preferably 130° or less, and more preferably 120° or less.
In the exemplary case shown in
In terms of preventing the electric resistance from becoming excessively high and preventing any breakage in a case where the honeycomb structure 2 is put into a container (i.e., in canning), the thickness of the electrode layer 31 (i.e., the thickness in the radial direction) is, for example, 0.01 mm to 5 mm, and preferably 0.01 mm to 3 mm.
It is preferable that the volume resistivity of the electrode layer 31 should be lower than that of the honeycomb structure 2. The current thereby becomes easier to flow to the electrode layer 31 than to the honeycomb structure 2, and the current becomes easier to be spread in the longitudinal direction and the circumferential direction of the honeycomb structure 2. It is preferable that the volume resistivity of the electrode layer 31 should be not lower than one two-hundredth of that of the honeycomb structure 2 and not higher than one tenth thereof
The electrode layer 31 is formed of, for example, conductive ceramics, a metal, or a composite material of the conductive ceramics and the metal. The conductive ceramics is, for example, silicon carbide or a metal silicide such as tantalum silicide (TaSi2), chromium silicide (CrSi2), or the like. The metal is, for example, chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), silicon, or titanium (Ti). In terms of reduction in the thermal expansion coefficient, the material of the electrode layer 31 may be a composite material in which alumina, mullite, zirconia, cordierite, silicon nitride, aluminum nitride, or the like is added to one kind of or two or more kinds of metals.
It is preferable that the material of the electrode layer 31 should be a material which can be sintered at the same time as the honeycomb structure 2 is sintered. In terms of compatibility between the heat resistance and the conductivity, the material of the electrode layer 31 is preferably ceramics whose main component (specifically, containing 90 mass % or more) is silicon carbide or a silicon-silicon carbide (Si-SiC) composite material, and more preferably silicon carbide or a silicon-silicon carbide composite material. The silicon-silicon carbide composite material contains silicon carbide particles as an aggregate and silicon as a binder for binding the silicon carbide particles, and it is preferable that a plurality of silicon carbide particles should be so bound by silicon as to form a pore among the silicon carbide particles.
The electrode terminal 41 is formed of, for example, a simple metal or an alloy. In terms of having high corrosion resistance and appropriate volume resistivity and thermal expansion coefficient, the material of the electrode terminal 41 is preferably an alloy containing at least one kind of Cr, Fe, Co, Ni, Ti, and aluminum (Al). The electrode terminal 41 is preferably stainless steel and more preferably contains Al. Further, the electrode terminal 41 may be formed of a metal-ceramics mixed member. The metal contained in the metal-ceramics mixed member is, for example, a simple metal such as Cr, Fe, Co, Ni, Si, or Ti or an alloy containing at least one kind of metal selected from a group of these metals. The ceramics contained in the metal-ceramics mixed member is, for example, silicon carbide or a metal compound such as metal silicide (e.g., tantalum silicide (TaSi2) or chromium silicide (CrSi2)) or the like. As the ceramics, cermet (i.e., a composite material of ceramics and a metal) may be used. The cermet is, for example, a composite material of metallic silicon and silicon carbide, a composite material of metal silicide, metallic silicon, and silicon carbide, or a composite material in which one or more kinds of insulating ceramics such as alumina, mullite, zirconia, cordierite, silicon nitride, aluminum nitride, or the like are added to one or more kinds of the above-described metals.
Each of the junction parts 42 is formed of, for example, a composite material containing a metal and an oxide. The metal is, for example, one or more kinds of stainless steel, a Ni—Fe alloy, and Si. The oxide is one or more kinds of cordierite-based glass, silicon dioxide (SiO2), aluminum oxide (Al2O3), magnesium oxide (MgO), and a composite oxide of these oxides.
The junction part 42 may contain a conductive material other than any metal, instead of the above-described metal or additionally to the above-described metal. The conductive material is, for example, one or more kinds of a boride such as zinc boride, tantalum boride, or the like, a nitride such as titanium nitride, zirconium nitride, or the like, and a carbide such as silicon carbide, tungsten carbide, or the like.
Next, with reference to
To the above-described mixed powder, an aid may be added, additionally to the silicon raw material, the cordierite raw material, and the high-resistance silicon carbide material which are main raw materials. The aid contains, for example, Al. Further, it is preferable that the above-described mixed powder should not contain boron (B). In the manufacture of the composite sintered body, sintering inhibition among the silicon particles due to borosilicate is thereby prevented and variation in the volume resistivity for all portions of the honeycomb structure 2 is suppressed. Furthermore, since sintering shrinkage in the manufacture of the honeycomb structure 2 is reduced, the dimensional accuracy of the honeycomb structure 2 is increased.
As the binder included in the above-described mixed powder, for example, methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, or the like can be used. As the pore-forming agent, graphite, flour, starch, phenol resin, polymethylmethacrylate (poly (methyl methacrylate)), polyethylene, polyethylene terephthalate, foaming resin (acrylonitrile plastic balloon), water-absorbing resin, or the like can be used.
Subsequently, the above-described mixed powder, an appropriate amount of water, and the like are kneaded by a kneader, and body paste is produced from the kneaded product which is thereby obtained, by a tug mill (kneading machine). Then, by extrusion-molding the body paste, a green body having a honeycomb construction (hereinafter, also referred to as a “honeycomb green body”) is manufactured (Step S11). Next, microwave drying is performed on the honeycomb green body and then hot-air drying is performed thereon at 100° C. Further, degreasing is performed on the honeycomb green body after the drying, at 200° C. to 1000° C. for 1 to 10 hours in an air atmosphere.
The honeycomb green body after the degreasing is sintered at 1250° C. to 1800° C. (preferably, at 1300° C. to 1750° C.) for 0.5 to 5 hours in an inert gas atmosphere such as an argon (Ar) atmosphere or the like. The honeycomb structure 2 which is a sintered body having a honeycomb construction is thereby manufactured. (Step S12).
After Step S12 is ended, the sintering shrinkage of the honeycomb structure 2 to the honeycomb green body is preferably not higher than 7% and more preferably not higher than 5%. The sintering shrinkage is a result expressed by percentage, which is obtained by subtracting the arithmetic average of a value obtained by dividing the outer diameter of the honeycomb structure 2 after sintering by the outer diameter of the honeycomb structure 2 before sintering and another value obtained by dividing the height of the honeycomb structure 2 after sintering by the height of the honeycomb structure 2 before sintering, from 1.
In the manufacture of the honeycomb structure 2, after the sintering process in Step S12, an oxidation treatment of the honeycomb structure 2 may be performed (Step S13). The oxidation treatment is a preliminary oxidation treatment which is performed before exposing the honeycomb structure 2 to an oxidation atmosphere at the time of use, and is hereinafter also referred to as a “pre-oxidation treatment”. The pre-oxidation treatment is performed by, for example, heating the honeycomb structure 2 at 900° C. to 1300° C. for 5 to 20 hours in the air atmosphere. The pre-oxidation treatment is also referred to as “oxidation aging”. Further, the temperature, the time, the atmosphere, and the like in the pre-oxidation treatment may be changed in various manners. Furthermore, the temperature, the time, the atmosphere, and the like in the above-described drying, degreasing, and sintering of the honeycomb green body may be also changed in various manners.
In the manufacture of the honeycomb structure 2, the average particle diameter (in other words, the median diameter (D50) based on the volume standard) of the silicon raw material in the above-described raw material powder is preferably not smaller than 1 μm, and more preferably not smaller than 2 μm. The upper limit of the average particle diameter of the silicon particles in the raw material powder is not particularly limited, but actually, is preferably not larger than 30 μm, and more preferably not larger than 20 μm. It is thereby possible to suitably achieve coarsening of the silicon particles in the honeycomb structure 2. As a result, as described above, the volume resistivity of the composite sintered body falls within a favorable range, and the oxidation resistance of the composite sintered body is improved. In the present specification, unless otherwise specified, the average particle diameter of the particles in the raw material powder refers to a value obtained by the particle size distribution measurement performed by the laser diffraction scattering method (JIS R1629).
The electrically heating catalyst 1 is manufactured by fixing the pair of electrode layers 31 and the pair of electrode terminals 41 to the honeycomb structure 2 which is manufactured as described above. In the electrically heating catalyst 1, the catalyst is supported by inner surfaces of the plurality of cells 23 (i.e., a side surface of the partition wall 22) of the honeycomb structure 2. Further, the pair of electrode layers 31 may be formed at the same time as the honeycomb structure 2 is formed, by giving electrode layer paste which is a raw material of the electrode layer 31 to the honeycomb green body which is a precursor of the honeycomb structure 2 and sintering both the honeycomb green body and the electrode layer paste.
As described above, the method of manufacturing a composite sintered body includes a step (Step S11) of obtaining a green body by molding the raw material powder containing the silicon raw material, the cordierite raw material, and the high-resistance silicon carbide raw material and a step (Step S12) of obtaining a composite sintered body by sintering the green body. The composite sintered body contains the silicon phase, the cordierite phase, and the high-resistance silicon carbide phase. The content of silicon in the composite sintered body to the composite sintered body is not lower than 30 mass % and not higher than 50 mass %. The content of cordierite in the composite sintered body to the composite sintered body is not lower than 10 mass % and not higher than 50 mass %. The content of high-resistance silicon carbide in the composite sintered body to the composite sintered body is not lower than 20 mass % and not higher than 50 mass %. As described above, it is thereby possible to coarsen the silicon particles. As a result, it is possible to cause the volume resistivity of the composite sintered body to fall within a favorable range and improve the oxidation resistance of the composite sintered body. Further, it is also possible to improve the thermal shock resistance of the composite sintered body. Moreover, it is also possible to reduce the sintering shrinkage of the composite sintered body.
Further, it is preferable that the sintering shrinkage of the composite sintered body to the green body should be not higher than 7%. It is thereby possible to manufacture the composite sintered body with high dimensional accuracy. As a result, it is thereby possible to manufacture the honeycomb structure 2 and the electrically heating catalyst 1 with high dimensional accuracy.
Next, with reference to Tables 1 and 2, Examples of the honeycomb structure 2 in accordance with the present invention and Comparative Examples for comparison with the honeycomb structure 2 will be described. Tables 1 and 2 show respective sintered body properties of the honeycomb structure 2 in Examples and the honeycomb structure in Comparative Examples.
The respective contents of silicon, cordierite, high-resistance silicon carbide, and low-resistance silicon carbide in the honeycomb structure 2 shown in Table 1 are measured by the above-described powder X-ray diffraction method. As the X-ray diffraction apparatus, used is a sealed-tube X-ray diffraction apparatus (D8-ADVANCE manufactured by Bruker AXS). The measurement conditions are CuKα, 40 kV, and 40 mA, and 2θ=5-70°, and the step width in the measurement is 0.002°. Further, the volume resistivity of high-resistance silicon carbide used in Examples and Comparative Examples of Table 1 is 1000 k Ω·cm, and the volume resistivity of low-resistance silicon carbide is 1 Ω·cm.
The average particle diameter of silicon particles shown in Table 2 is obtained by the above-described method. Further, the porosity and the average pore diameter of the honeycomb structure 2 are measured by the mercury porosimetry (mercury intrusion porosimetry) (JIS R1655) using a mercury porosimeter.
The volume resistivity in Table 2 is the above-described initial resistivity and is measured by the four-probe (four-terminal) method (JIS C2525). The resistance change rate is obtained by the above-described method. Specifically, a specimen cut out from the partition wall 22 of the honeycomb structure 2 is exposed in the atmosphere at 950° C. for 50 hours, and then the volume resistivity of the specimen (hereinafter, also referred to as “post-exposure resistivity”) is measured by the four-probe (four-terminal) method. Then, the resistance change rate refers to a result expressed by percentage, which is obtained by subtracting 1 from a value obtained by dividing the post-exposure resistivity by the initial resistivity. The sintering shrinkage in Table 2 is obtained by the above-described method.
In Example 1, the honeycomb structure 2 is manufactured by Steps S11 to S13 described above. In Step S11, the mass ratio of the silicon raw material, the cordierite raw material, and the high-resistance silicon carbide material in the raw material powder is 36: 39: 25. The average particle diameter (in other words, the median diameter (D50) based on the volume standard) of the silicon raw material is 1.8 μm. The average particle diameter of the cordierite raw material is 8.0 μm. The average particle diameter of the high-resistance silicon carbide raw material is 9.3 μm. In Step S11, 12 parts by mass of the binder, 3 parts by mass of the pore-forming agent, and 6 parts by mass of aid are added with respect to 100 parts by mass of the main raw material (i.e., silicon, cordierite, and high-resistance silicon carbide). In Step S12, the sintering temperature and the sintering time of the honeycomb green body are 1375° C. and 2 hours, respectively. In Step S13, the pre-oxidation treatment temperature and the pre-oxidation treatment time are 1300° C. and 1 hour, respectively.
In Example 1, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure 2 are 34 mass %, 42 mass %, and 24 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure 2 is 10.4 μm. The porosity and the average pore diameter of the honeycomb structure 2 are 33% and 2.9 μm, respectively. The volume resistivity of the honeycomb structure 2 is 12 Ω·cm. The resistance change rate of the honeycomb structure 2 is 5%. The sintering shrinkage of the honeycomb structure 2 is 5.5%.
In Examples 2 to 5, the honeycomb structure 2 is manufactured by substantially the same manufactured method as that in Example 1 except that the mass ratio of the raw materials, the respective average particle diameters of the raw materials, and/or the addition amount of the pore-forming agent or the like are finely adjusted so that the composition of the honeycomb structure 2 should become the composition shown in Table 1. Substantially the same applies to the manufacture of the honeycomb structure in Comparative Examples 1 to 3. Further, in Comparative Examples 1 to 3, the raw material powder does not contain the high-resistance silicon carbide raw material, and the honeycomb structure does not include the high-resistance silicon carbide phase. Furthermore, the manufacture of the honeycomb structure in Comparative Example 4 is also substantially the same except that the raw material powder contains the low-resistance silicon carbide raw material (having an average particle diameter of 10.8 μm), instead of the high-resistance silicon carbide raw material, and the sintering temperature is 1450° C.
In Example 2, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure 2 are 43 mass %, 32 mass %, and 26 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure 2 is 11.8 μm. The porosity and the average pore diameter of the honeycomb structure 2 are 36% and 3.4 μm, respectively. The volume resistivity of the honeycomb structure 2 is 2 Ω·cm. The resistance change rate of the honeycomb structure 2 is 3%. The sintering shrinkage of the honeycomb structure 2 is 5.5%.
In Example 3, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure 2 are 32 mass %, 20 mass %, and 48 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure 2 is 9.5 μm. The porosity and the average pore diameter of the honeycomb structure 2 are 41% and 3.3 μm, respectively. The volume resistivity of the honeycomb structure 2 is 83 Ω·cm. The resistance change rate of the honeycomb structure 2 is 80%. The sintering shrinkage of the honeycomb structure 2 is 3.2%.
In Example 4, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure 2 are 36 mass %, 15 mass %, and 49 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure 2 is 10.5 μm. The porosity and the average pore diameter of the honeycomb structure 2 are 41% and 3.4 μm, respectively. The volume resistivity of the honeycomb structure 2 is 11Ω·cm. The resistance change rate of the honeycomb structure 2 is 2%. The sintering shrinkage of the honeycomb structure 2 is 2.9%.
In Example 5, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure 2 are 40 mass %, 12 mass %, and 48 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure 2 is 11.2 μm. The porosity and the average pore diameter of the honeycomb structure 2 are 41% and 3.6 μm, respectively. The volume resistivity of the honeycomb structure 2 is 6 Ω·cm. The resistance change rate of the honeycomb structure 2 is 2%. The sintering shrinkage of the honeycomb structure 2 is 3.0%.
In Comparative Example 1, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure are 31 mass %, 69 mass %, and 0 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure is 7.3 μm. The porosity and the average pore diameter of the honeycomb structure are 31% and 2.2 μm, respectively. The volume resistivity of the honeycomb structure is 16 Ω·cm. The resistance change rate of the honeycomb structure is 300%. The sintering shrinkage of the honeycomb structure is 7.9%.
In Comparative Example 2, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure are 27 mass %, 73 mass %, and 0 mass %, respectively. The average particle diameter of the silicon particles in the silicon phase of the honeycomb structure is 7.5 μm. The porosity and the average pore diameter of the honeycomb structure are 33% and 2.2 μm, respectively. The volume resistivity of the honeycomb structure is larger than 1000 Ω·cm. Since the volume resistivity of the honeycomb structure is excessively large, the resistance change rate of the honeycomb structure is not measured. The sintering shrinkage of the honeycomb structure is 7.9%.
In Comparative Example 3, the contents of silicon, cordierite, and high-resistance silicon carbide in the honeycomb structure are 59 mass %, 41 mass %, and 0 mass %, respectively. The silicon phase of the honeycomb structure is continuous and connected, and the silicon particle diameter cannot be measured. The porosity and the average pore diameter of the honeycomb structure are 26% and 2.6 μm, respectively. The volume resistivity of the honeycomb structure is 0.2 Ω·cm. Since the volume resistivity of the honeycomb structure is excessively small, the resistance change rate of the honeycomb structure is not measured. The sintering shrinkage of the honeycomb structure is 8.9%.
In comparison between Examples 1 to 5 and Comparative Examples 1 to 3, the content of high-resistance silicon carbide in the honeycomb structure 2 of Examples 1 to 5 is not lower than 20 mass % and not higher than 50 mass % while the content of high-resistance silicon carbide in the honeycomb structure of Comparative Examples 1 to 3 is lower than 20 mass %. As described above, the high-resistance silicon carbide phase in the composite sintered body divides the conductive path among the silicon particles, to thereby increase the volume resistivity of the composite sintered body, and on the other hand, the high-resistance silicon carbide phase in the composite sintered body coarsens the silicon particles and thickens the conductive path, to thereby reduce the volume resistivity of the composite sintered body. The volume resistivity of the composite sintered body thereby falls within a favorable range. Further, the high-resistance silicon carbide phase coarsens the silicon particles, to thereby suppress blocking of the conductive path due to oxidation of the binding portion of the silicon particles and achieve improvement of the oxidation resistance of the composite sintered body (in other words, reduction in the resistance change rate in the case of exposure in the high temperature oxidation atmosphere). Furthermore, the high-resistance silicon carbide phase coarsens the silicon particles, to thereby increase the average pore diameter and reduce the Young's modulus of the composite sintered body, and further to improve the thermal shock resistance of the composite sintered body. Further, the high-resistance silicon carbide phase reduces the sintering shrinkage of the composite sintered body.
In Examples 1 to 5, when the content of high-resistance silicon carbide is made not lower than 20 mass % and not higher than 50 mass %, the average particle diameter of the silicon particles in the honeycomb structure 2 becomes larger, i.e., not smaller than 9 The porosity of the honeycomb structure 2 is not lower than 30% and not higher than 50%, and the average pore diameter thereof is not smaller than 2.5 μm and not larger than 4.0 μm. Further, the volume resistivity of the honeycomb structure 2 is not lower than 1.0Ω·cm and not higher than 100 Ω·cm, falling within a favorable range, and the resistance change rate of the honeycomb structure 2 is low, i.e., not higher than 100%. Furthermore, the sintering shrinkage of the honeycomb structure 2 is low, i.e., not higher than 7%.
On the other hand, in Comparative Examples 1 to 3, since the content of high-resistance silicon carbide is lower than 20 mass %, the average particle diameter of the silicon particles in the honeycomb structure 2 is small, i.e., smaller than 9 In Comparative Example 3, the porosity is low, i.e., lower than 30%, and in Comparative Examples 1 and 2, the average pore diameter is small, i.e., smaller than 2.5 In Comparative Example 2, the volume resistivity is high, i.e., higher than 100 Ω·cm, and in Comparative Example 3, the volume resistivity is low, i.e., lower than 1.0 Ω·cm. In Comparative Example 1, the resistance change rate is high, i.e., 300%. In Comparative Example 2, since the resistance change rate is not measured and the average pore diameter is small, like in Comparative Example 1, it is thought that the resistance change rate is high like in Comparative Example 1. In Comparative Examples 1 to 3, the sintering shrinkage is higher than 7%.
In Comparative Example 4, since low-resistance silicon carbide of 69 mass % is contained, the volume resistivity is low, i.e., lower than 10 Ω·cm. Further, in Comparative Example 4, since a current flows in the silicon phase which is a positive thermistor and the low-resistance silicon carbide phase which is a negative thermistor, there is a possibility that the thermistor characteristic in the whole honeycomb structure may be negative. On the other hand, in Examples 1 to 5, since a current flows only in the silicon phase which is a positive thermistor, the thermistor characteristic in the whole honeycomb structure 2 is positive. In the electrically heating catalyst 1, in terms of increasing the temperature uniformity of the honeycomb structure 2, it is preferable that the thermistor characteristic should be positive so that a lower-temperature portion may have a low resistance, making it easy to carry a current and making the amount of heat generation large. Therefore, the honeycomb structure 2 in Examples 1 to 5 is more suitable for the electrically heating catalyst 1 than the honeycomb structure in Comparative Example 4.
In comparison between Examples 1, 2, 4 and 5 and Example 3, the average particle diameter of the silicon particles in Examples 1, 2, 4 and 5 ranges from 10.4 μm to 11.8 μm, and the average particle diameter of the silicon particles in Example 3 is 9.5 μm. Further, the resistance change rate in Examples 1, 2, 4 and 5 ranges 2 to 5% and the resistance change rate in Example 3 is 80%. Therefore, in terms of further reducing the resistance change rate (for example, to be 50% or lower), it is preferable that the average particle diameter of the silicon particles is not smaller than 10 μm.
As described above, the composite sintered body contains the silicon phase, the cordierite phase, and the high-resistance silicon carbide phase. The content of silicon in the composite sintered body to the composite sintered body is not lower than 30 mass % and not higher than 50 mass %. The content of cordierite in the composite sintered body to the composite sintered body is not lower than 10 mass % and not higher than 50 mass %. The content of high-resistance silicon carbide in the composite sintered body to the composite sintered body is not lower than 20 mass and not higher than 50 mass %. As described above, it is thereby possible to coarsen the silicon particles. As a result, it is possible to cause the volume resistivity of the composite sintered body to fall within a favorable range and improve the oxidation resistance of the composite sintered body. Further, it is also possible to improve the thermal shock resistance of the composite sintered body. Moreover, it is also possible to reduce the sintering shrinkage of the composite sintered body.
The configurations in the above-described preferred embodiment and variations may be combined as appropriate only if those do not conflict with one another.
While the invention has been shown and described in detail, the foregoing description is in all aspects illustrative and not restrictive. It is therefore understood that numerous modifications and variations can be devised without departing from the scope of the invention.
The present invention can be used for the electrically heating catalyst or the like which is used for the purification treatment of exhaust gas from an engine of an automobile or the like.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-040159 | Mar 2022 | JP | national |
