# Patent

## Title
Silicon carbide ceramic and honeycomb structure

## Abstract

A silicon carbide ceramic is provided which has a small amount of resistivity change due to changes in temperature and which is capable of generating heat by current application. The silicon carbide ceramic contains silicon carbide crystals having 0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals, preferably having a nitrogen content of 0.01 mass % or less, more preferably containing two or more kinds of silicon carbide particles containing silicon carbide crystals and silicon for binding the silicon carbide particles to each other and having a silicon content of from 10 to 40 mass %.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a silicon carbide ceramic and a honeycomb structure. More specifically, the invention relates to a silicon carbide ceramic having a small amount of resistivity change due to temperature change and being capable of generating heat by current application, and a honeycomb structure using such a silicon carbide ceramic as a material thereof.
2. Description of Related Art
Silicon carbide is a compound semiconductor with good conductivity and has an excellent thermal resistance and chemical stability. Therefore, silicon carbide has been utilized as a current application heating element to be used in high-temperature electric furnaces and the like. Generally, silicon carbide exhibits the behavior that “the resistivity rapidly decreases and it converts to increase at about 400° C. as a minimal” with a temperature increase due to current application heat generation. This has been considered on the basis that silicon carbide is a semiconductor. That is, since silicon carbide is a semiconductor, the number of conduction electrons capable of being excited from an impurity level to a conduction band increases with a temperature increase. The resistivity decreases within a range from normal temperature to about 400° C. by this behavior. At temperatures exceeding about 400° C., since the mobility of conduction electrons decreases due to thermal vibration of lattice, it has been considered that the resistivity exhibits a slightly increasing tendency.
Thus, the silicon carbide exhibits the negative property that the resistivity change depending on temperature is a negative (property of showing a decrease in resistivity with a temperature increase) within a range of from normal temperature to about 400° C. Therefore, there were following problems in the case of using silicon carbide as a heating element and increasing the temperature from the normal temperature to about 400° C. by current application. That is, since the resistivity of the silicon carbide (heating element) decreases with the above-mentioned temperature increase, and an electric current may be rapidly increased. In addition, it is very difficult for a heating element exhibiting a large change rate in the above-mentioned “resistivity change depending on temperature” {100×(magnitude of a change in resistivity)/(magnitude of a temperature chancre)} to control the temperature.
In contrast to this, there has been proposed a silicon carbide heating element being made of a “silicon carbide sintered body containing at least 10% of β-SiC crystal particles and having nitrogen dissolved therein” in attempt to reducing the resistivity change depending on temperature (see, for example, Patent Document 1). There has been also proposed a conductive silicon carbide ceramic material composed mainly of “silicon carbide containing 90% or less of 6H—SiC with respect to the entire crystal system and having nitrogen dissolved therein” and having a predetermined temperature coefficient of resistance (see, for example, Patent Document 2).
RELATED ART DOCUMENTS
Patent Documents
Patent Document 1: JP-A-H07-89764
Patent Document 2: JP-A-H07-53265
SUMMARY OF THE INVENTION
The silicon carbide heating element disclosed in Patent Document 1 contains at least 10% of β-SiC (3C—SiC) crystal particles being a metastable phase. Therefore, there is a possibility of them being transformed into 4H—SiC or 6H—SiC due to thermal history when a current application is performed at a high voltage, which may lead to a reduction in thermal resistance.
In the conductive silicon carbide ceramic materials disclosed in Patent Document 2, though temperature dependence of electric resistance is low, each of the resistivity at normal temperature is as small as 1Ω·cm or less. So, a current may flow excessively through this conductive silicon carbide ceramic material when a current application is performed at a high voltage, and thereby, it may damage electric circuits and the like so that they are not preferred.
The present invention has been made in view of such problems of the related art. The present invention provides a silicon carbide ceramic having a small amount of resistivity change due to temperature change and being capable of generating heat by current application, and a honeycomb structure using such a silicon carbide ceramic as a material.
According to the present invention, the silicon carbide ceramic and the honeycomb structure as shown below are provided.
According to a first aspect of the present invention, a silicon carbide ceramic containing silicon carbide crystals is provided, wherein 0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals are contained in the silicon carbide crystals.
According to a second aspect, a silicon carbide ceramic according to the first aspect is provided, wherein a content amount of a nitrogen is 0.01 mass % or less.
According to a third aspect, a silicon carbide ceramic according to the first or second aspect is provided, containing a plurality of silicon carbide particles containing the silicon carbide crystals and a silicon for binding the silicon carbide particles to each other, wherein a content ratio of the silicon is 10 to 40 mass %.
According to a fourth aspect, a silicon carbide ceramic according to the third aspect is provided, wherein an average particle diameter of the silicon carbide particles is 10 to 50 μm.
According to a fifth aspect, a silicon carbide ceramic according to any one of the first to fourth aspects is provided, wherein a porosity is 30 to 65%.
According to a sixth aspect, a silicon carbide ceramic according to any one of the first to fifth aspects is provided, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.
According to a seventh aspect, a honeycomb structure using a silicon carbide ceramic according to any one of the first to sixth aspects is provided as a material.
According to an eighth aspect, a current application heat-generating catalyst carrier having a honeycomb structure according to the seventh aspect is provided and generates heat by current application.
The silicon carbide ceramic of the invention contains 0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals. Therefore, the silicon carbide ceramic of the present invention has a small amount of resistivity change due to temperature change and is capable of generating heat by current application.
The honeycomb structure of the present invention uses the silicon carbide ceramic of the present invention as a material. Therefore, the honeycomb structure of the present invention has a small amount of resistivity change due to temperature change and is capable of generating heat by current application, and the generation of defects and the like at partition walls is also prevented.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view schematically showing one embodiment of the honeycomb structure of the present invention; and
FIG. 2 is a schematic view showing the cross-section, which is parallel to a cell extending direction, of one embodiment of the honeycomb structure of the present invention.



DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the embodiments of the present invention will be described, but the invention is not limited to the following embodiments. It should be understood that modifications, improvements and the like suitably added to the following embodiments based on the ordinary knowledge of a person skilled in the art without departing from the scope of the present invention are also included in the scope of the present invention.
(1) Silicon Carbide Ceramic:
One embodiment of the silicon carbide ceramic according to the present invention contains silicon carbide crystals, wherein “0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals” are contained in the silicon carbide crystals.
Thus, the silicon carbide ceramic according to the present embodiment contains 0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals. Therefore, the silicon carbide ceramic according to the present embodiment has a small amount of resistivity change due to temperature change and is capable of generating heat stably by current application.
In the silicon carbide ceramic according to the present embodiment, the silicon carbide crystals to be contained therein preferably contain 4H—SiC silicon carbide crystals, 6H—SiC silicon carbide crystals, and 15R—SiC silicon carbide crystals, and are more preferably made of these crystals.
Examples of the structure of silicon carbide crystals include “hexagonal 2H—SiC, 4H—SiC, and 6H—SiC structures”, “cubic 3C—SiC structure”, and “rhombohedral 15R—SiC structure”. These crystal structures are typically present in (throughout) silicon carbide crystals as a mixture and “amount of resistivity change due to temperature change (a resistivity change depending on temperature)” differs with the kind of the crystal structure.
The content ratio of the 4H—SiC silicon carbide crystals in the silicon carbide crystals is 0.1 to 25 mass %, preferably 0.1 to 17 mass %, more preferably 0.1 to 5 mass %. And, in the silicon carbide crystals, crystal components other than the 4H—SiC silicon carbide crystals are preferably 6H—SiC silicon carbide crystals and 15R—SiC silicon carbide crystals. When the content ratio of the 4H—SiC silicon carbide crystals in the silicon carbide crystals is less than 0.1 mass %, it is not preferable because electrical conduction is mainly occurred through the crystal phase of the 6H—SiC silicon carbide crystals to increase the amount of resistivity change due to temperature change. When the content ratio of the 4H—SiC silicon carbide crystals in the silicon carbide crystals is more than 25 mass %, it is not preferable because the resistivity decreases and an electric current may flow excessively at the time of current application so that electric circuits and the like may be damaged.
In the silicon carbide crystals, 15R—SiC silicon carbide crystals may be contained at a ratio of 0.1 to 20 mass %, more preferably 0.1 to 12 mass %. The band gap of the 15R—SiC silicon carbide crystals is smaller than that of the 4H—SiC silicon carbide crystals. Therefore, the influence on the inversion layer channel mobility due to the trap density of an oxide film in the vicinity of the interface is small. Further, since the bulk mobility of the 15R—SiC silicon carbide crystals is low anisotropy, there is an effect for stabilizing the resistance at the time of current application. On the other hand, when the content ratio of the 15R—SiC silicon carbide crystals in the silicon carbide crystals is more than 20 mass %, it is impossible to reduce an amount of resistivity change due to temperature change because conductivity due to the 15R—SiC silicon carbide crystals is mainly occurred.
The 3C—SiC silicon carbide crystals contained in the silicon carbide crystals is preferably 5 mass % or less, more preferably 3 mass % or less. Since the 3C—SiC silicon carbide is a metastable phase, it is transformed into 4H—SiC or 6H—SiC due to thermal history. Therefore, when the content ratio of the 3C—SiC silicon carbide crystals in the silicon carbide crystals is more than 5 mass %, the thermal resistance may deteriorate.
When the 15R—SiC silicon carbide crystals, the 3C—SiC silicon carbide crystals, or both the 15R—SiC silicon carbide crystals and the 3C—SiC silicon carbide crystals are contained in the silicon carbide crystals, the remaining components in the silicon carbide crystals are preferably 6H—SiC silicon carbide crystals. The term “the remaining components” as used herein means “components other than 4H—SiC silicon carbide crystals, 15R—SiC silicon carbide crystals, and 3C—SiC silicon carbide crystals”.
In the silicon carbide ceramic according to the present embodiment, the content amount (content amount in solid solution) of nitrogen is preferably 0.01 mass % or less. When the content amount in solid solution of nitrogen is more than 0.01 mass %, it is not preferable because excessive current may damage electric circuits and the like. The reason is that, in the case that the content amount in solid solution of nitrogen is more than 0.01 mass %, the resistivity decreases to flow an electric current excessively at the time of current application. The content amount of nitrogen is a value measured by using ICP (Inductively Coupled Plasma: high-frequency inductively coupled plasma) emission spectroscopic analysis.
The silicon carbide ceramic according to the present embodiment is preferably a porous fired body (sintered body). When the silicon carbide ceramic according to the present embodiment is porous, the porosity is preferably 30 to 65%, more preferably 35 to 50%. When the porosity is smaller than 30%, an excessive electric current may damage electric circuits and the like. The reason is that, in the case that the porosity is smaller than 30%, the resistivity decreases and an electric current may flow excessively at the time of current application. Further, when the porosity is smaller than 30%, since the thermal capacity increases, a temperature elevating rate may become slow at the time of current application. When the porosity is larger than 65%, the resistivity becomes high easily and an electric current hardly flows at a time of current application so that it may be difficult to generate heat sufficiently. Further, when the porosity is larger than 65%, the strength decreases so that the cracks may be generated due to “thermal cycle or temperature distribution at the time of current application”. The porosity is a value measured by using a mercury porosimeter. In addition, the average pore diameter is preferably 2 to 30 μm, more preferably 4 to 20 μm. When the average pore diameter is smaller than 2 μm, the resistivity may become high excessively. When the average pore diameter is larger than 30 μm, the resistivity may become small extremely. The average pore diameter is a value measured by using a mercury porosimeter.
The silicon carbide ceramic according to the present embodiment is preferably 2 to 100 Ω·cm of a resistivity at 20° C. (R20), more preferably 20 to 80 Ω·cm. In addition, it is preferably 1 to 25 Ω·cm of a resistivity at 400° C., more preferably 5 to 20 Ω·cm. This makes it possible to cause the silicon carbide ceramic according to the present embodiment to generate heat properly by current application. When the resistivity at 400° C. is larger than 25 Ω·cm, since electric current flows hardly at the time of current application, it may be difficult to generate heat sufficiently. When the resistivity at 400° C. is smaller than 1 Ω·cm, an electric current may flow excessively at the time of current application to damage the electric circuits and the like. It is to be noted that the resistivity at 400° C. is a value obtained by elevating the temperature of the silicon carbide ceramic to 400° C. by current application heat generation.
Moreover, in the silicon carbide ceramic according to the present embodiment, a difference (R20−RMin) between the resistivity at 20° C. (R20) and the minimum resistivity (RMin) is preferably 80 Ω·cm or less, more preferably 40 Ω·cm or less. In this way, when a difference between the resistivity at 20° C. and the minimum resistivity is small, a change in resistivity due to current application heat generation decreases at the time of current application. Therefore, this makes it possible to prevent an electric current from flowing excessively. When above difference of the resistivity is larger than 80 Ω·cm, an electric current may flow excessively at the time of current application to damage the electric circuits and the like. The term “minimum resistivity” as used herein means a value in which the resistivity of the silicon carbide ceramic reaches the minimum value when a temperature of the silicon carbide ceramic is changed.
Moreover, in the silicon carbide ceramic according to the present embodiment, the temperature (TR-Min) at which the resistivity reaches the minimum value (minimum resistivity) is preferably 500° C. or less, more preferably 400° C. or less. By converting the resistivity to increase at a lower temperature, it is possible to avoid an electric current from flowing excessively to prevent damage of electric circuits and the like.
The entirety of the silicon carbide ceramic according to the present embodiment may be formed by bonding silicon carbides to each other or may be formed by bonding of a plurality of silicon carbide particles via silicon (metal silicon: Si). Of these, the entirety of the silicon carbide ceramic is preferably formed by bonding of a plurality of silicon carbide particles via silicon. In other words, the silicon carbide ceramic according to the present embodiment preferably contains a plurality of silicon carbide particles and silicon for binding these silicon carbide particles to each other. At this time, it is preferred that the silicon carbide particles contain the above-mentioned silicon carbide crystals (silicon carbide crystals containing “0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals”). It is more preferred that the silicon carbide particles are made of the above-mentioned silicon carbide crystals.
Thus, when the silicon carbide ceramic according to the present embodiment contains “a plurality of silicon carbide particles and silicon for binding these silicon carbide particles to each other”, it is possible to decrease the resistivity. In addition, in this case, the content ratio of silicon (the content ratio of silicon with respect to the total of silicon carbide particles and silicon) is preferably 10 to 40 mass %, more preferably 15 to 35 mass %. When the content ratio of silicon is less than 10 mass %, the porosity becomes high and the resistivity may tend to become high easily, and thereby, an electric current may flow hardly at the time of current application so that it may be difficult to generate heat sufficiently. Further, when the content ratio of silicon is less than 10 mass %, the strength decreases and cracks may be generated due to the thermal cycle or temperature distribution at the time of current application. When the content ratio of silicon is more than 40 mass %, an excessive current may damage electric circuits and the like. The reason is that, in the case that the content ratio of silicon is more than 40 mass %, since the porosity becomes low, the resistivity may become low easily, and thereby, an electric current may flow excessively at the time of current application. Further, when the content ratio of silicon is more than 40 mass %, the thermal capacity becomes large so that a temperature elevating rate may become slow at the time of current application.
Moreover, when the silicon carbide ceramic according to the present embodiment contains “a plurality of silicon carbide particles and silicon for binding these silicon carbide particles to each other”, an average particle diameter of the silicon carbide particles is preferably 10 to 50 μm, more preferably 15 to 35 μm. By adjusting the average particle diameter of the silicon carbide particles within such a range, it is possible to support a small amount of resistivity change due to temperature change small and a desired resistivity at the same time. When the average particle diameter of the silicon carbide particles is smaller than 10 μm, the resistivity tends to become high easily, and thereby, an electric current hardly flows at the time of current application so that it is difficult to generate heat sufficiently. When the average particle diameter of the silicon carbide particles is larger than 50 μm, since the porosity tends to become low easily and the thermal capacity tends to become large easily, a temperature elevating rate may become slow at the time of current application. The average particle diameter of the silicon carbide particles contained in the silicon carbide ceramic is a value determined by observing the cross-section and surface of the silicon carbide ceramic with SEM and analyzing them by an image processing software. As the image processing software, ImageJ (product of NIH (National Institute of Health)) can be used. Specifically, for example, a sample for observing the “cross-section” and “surface” is cut out from a silicon carbide ceramic firstly. With regard to the cross-section of the silicon carbide ceramic, the asperities of the cross-section are filled with a resin, followed by polishing, and then the cross-section thus polished is observed. On the other hand, with regard to the surface of the silicon carbide ceramic, the sample (partition wall) cut out therefrom is used for observation. An arithmetic average of the observation results of five fields of view for the “cross-section” and five fields of view for the “surface” is designated as an average particle diameter of silicon carbide particles contained in the silicon carbide ceramic.
When a voltage of, for example, 100 to 800V is applied to the silicon carbide ceramic according to the present embodiment, it becomes 400 to 900° C. due to heat generation.
(2) Honeycomb Structure:
One embodiment of the honeycomb structure of the present invention has, as a material thereof, the above-mentioned one embodiment of the silicon carbide ceramic of the present invention. As shown in FIGS. 1 and 2, a honeycomb structure 100 according to the present embodiment is a cylindrical structure having partition walls 1 defining “a plurality of cells 2 extending from one end face 11 to another end face 12” to form a through channel of a fluid, and an outer peripheral wall 3 located at the most outer periphery. Incidentally, the honeycomb structure according to the present embodiment is not necessarily equipped with the outer peripheral wall.
Thus, since the honeycomb structure according to the present embodiment uses, as a material thereof, above one embodiment of the silicon carbide ceramic of the present invention, an amount of resistivity change due to temperature change is small, and it is possible to generate heat by current application. Therefore, the honeycomb structure according to the present embodiment can be used as a “current application heating element” which generates heat by current application. Further, when the honeycomb structure according to the present embodiment is used as a catalyst carrier (current application heat-generating catalyst carrier) for purifying an exhaust gas by loading a catalyst thereon, it is possible to conduct the temperature control stably during current application heat generation. The reason is that the honeycomb structure (current application heat-generating catalyst carrier) according to the present embodiment has a small change in resistivity even when the temperature changes greatly.
In the honeycomb structure 100 according to the present embodiment, a thickness of the partition walls is preferably 50 to 200 μm, more preferably 70 to 130 μm. By adjusting the thickness of the partition walls within such a range, even if a catalyst is loaded on the honeycomb structure 100 while using it as a catalyst carrier, it is possible to suppress an excessive increase in pressure loss when an exhaust gas is flowed into. When the thickness of the partition walls is thinner than 50 μm, the strength of the resulting honeycomb structure may decrease. When the thickness of the partition walls is thicker than 200 μm, a pressure loss may increase in the case of loading a catalyst on the honeycomb structure 100 while using it as a catalyst carrier.
In the honeycomb structure 100 according to the present embodiment, a cell density is preferably 40 to 150 cells/cm2, more preferably 70 to 100 cells/cm2. By adjusting the cell density within such a range, it is possible to improve the purifying performance of the catalyst at a state that a pressure loss becomes lower when an exhaust gas is flowed into. When the cell density is smaller than 40 cells/cm2, a catalyst loading area may decrease. When the cell density is more than 150 cells/cm2, a pressure loss at the time of flowing an exhaust gas into may increase in the case of loading a catalyst on the honeycomb structure 100 while using it as a catalyst carrier.
The partition walls 1 are preferably porous. When the partition walls 1 are porous, a porosity of the partition walls 1 is preferably 30 to 65%, more preferably 35 to 50%. When the porosity is smaller than 30%, the thermal capacity becomes large so that a temperature elevating rate may become slow at the time of current application. When the porosity is larger than 65%, the strength decreases so that cracks may be generated due to a thermal cycle or temperature distribution at the time of current application.
Moreover, when the partition walls 1 are porous, an average pore diameter of the partition wall 1 is preferably 2 to 30 μm, more preferably 4 to 20 μm. When the average pore diameter is smaller than 2 μm, the resistivity may become high excessively. When the average pore diameter is larger than 30 μm, the resistivity may become small extremely.
Moreover, the thickness of the outer peripheral wall 3 constituting the most outer periphery of the honeycomb structure 100 according to the present embodiment is preferably 0.1 to 2 mm. When the thickness is thinner than 0.1 mm, the strength of the resulting honeycomb structure 100 may deteriorate. When the thickness is thicker than 2 mm, an area of the partition wall for loading a catalyst thereon may decrease.
In the honeycomb structure 100 according to the present embodiment, the shape of the cell 2 at the cross-sectional perpendicular to the extending direction of the cell 2 is preferably rectangular, hexagonal, or octagonal, or combination thereof. When the cell has such a shape, a pressure loss becomes lower at the time of flowing an exhaust gas into the honeycomb structure 100 so that it exhibits an excellent purifying performance of the catalyst.
There is not particularly limited on the shape of the honeycomb structure according to the present embodiment. Examples of the shape of the honeycomb structure of the present embodiment includes a cylindrical shape with a circumferentially round bottom (cylindrical), a cylindrical shape with a circumferentially oval bottom, or a cylindrical shape with a circumferentially polygonal bottom (such as rectangular, pentagonal, hexagonal, heptagonal, or octagonal). Moreover, in the size of the honeycomb structure, the area of the whole bottom surface is preferably 2000 to 20000 mm2, more preferably 4000 to 10000 mm2. In addition, the length in the central axis direction of the honeycomb structure is preferably 50 to 200 mm, more preferably 75 to 150 mm.
An isostatic strength of the honeycomb structure 100 according to the present embodiment is preferably 1 MPa or more, more preferably 3 MPa or more. Although the isostatic strength is preferably more, the upper limit is about 10 MPa in consideration of the material, structure, and the like of the honeycomb structure 100. When the isostatic strength is less than 1 MPa, the honeycomb structure may be easily broken in the case of using it as a catalyst carrier or the like. The isostatic strength is a value measured by applying a hydrostatic pressure thereon in water.
(3) Current Application Heat-Generating Catalyst Carrier:
One embodiment of the current application heat—generating catalyst carrier of the present invention is a catalyst carrier equipped with the above-mentioned one embodiment of the honeycomb structure of the present invention and generates heat by current application. The term “current application heat-generating catalyst carrier” means a “catalyst carrier” which generates heat by current application (by applying an electric current).
Thus, since the current application heat-generating catalyst carrier according to the present embodiment is equipped with the above-mentioned one embodiment of the honeycomb structure of the present invention, an amount of resistivity change due to temperature change is small and it is possible to generate heat by current application. Therefore, when a catalyst body is prepared by loading a catalyst on the current application heat-generating catalyst carrier according to the present embodiment and the resulting catalyst body is used for purifying an exhaust gas, it is possible to perform heat generation stably due to current application. The reason is that the current application heat-generating catalyst carrier according to the present embodiment exhibits a small change in resistivity even if temperature changes.
The current application heat-generating catalyst carrier of the present invention may consist of the above-mentioned one embodiment of the honeycomb structure of the present invention or may be equipped with a constituting element other than the above-mentioned one embodiment of the honeycomb structure of the present invention. Examples of the constituting element other than the above-mentioned one embodiment of the honeycomb structure of the present invention include an electrode for applying a voltage. That is, the current application heat-generating catalyst carrier according to the present embodiment is preferably equipped with the one embodiment of the honeycomb structure of the present invention and “an electrode for applying a voltage to the one embodiment of the honeycomb structure of the present invention”.
(4) Method for producing silicon carbide ceramic:
(4-1) There is not particularly limited on the method for producing a silicon carbide ceramic according to the present embodiment. Examples of the method for producing a silicon carbide ceramic according to the present embodiment include a method having a forming raw material preparing step, a forming step, and a firing step. The forming raw material preparing step is preferably a step of mixing a plural kinds of silicon carbide ceramic powders “containing 4H—SiC silicon carbide crystals at respectively different content ratio” to prepare a forming raw material. The forming step is preferably a step of forming above forming raw material to form a formed body. The firing step is preferably a step of firing above formed body to prepare a silicon carbide ceramic being adjusted at the content ratio of the 4H—SiC silicon carbide crystals to a desired value. In this case, the content ratio of silicon carbide in the silicon carbide ceramic to be used for preparation of the forming raw material is preferably 60 mass % or more. In addition, the content ratio of silicon (metal silicon) in the silicon carbide ceramic to be used for the preparation of the forming raw material is preferably 40 mass % or less. The term “a plural kinds” of the “a plural kinds of silicon carbide ceramic powders” as used herein means “a plural kinds” when the silicon carbide ceramic powders are classified (distinguished) by the “content amount of 4H—SiC silicon carbide crystals contained therein”. In other words, the silicon carbide ceramic powders different in the content amount of 4H—SiC silicon carbide crystals are regarded as different kinds of silicon carbide ceramic powders. And, the term “a plural kinds of silicon carbide ceramic powders” means a plurality of “silicon carbide ceramic powders respectively different in the content amount of 4H—SiC silicon carbide crystals”.
This makes it possible to obtain a silicon carbide ceramic having a desired 4H—SiC silicon carbide crystal content ratio in the silicon carbide crystals. That is, firstly, two or more kinds of predetermined silicon carbide ceramic powders (which have different content ratio of 4H—SiC silicon carbide crystals at respectively) are prepared. They are mixed at a predetermined ratio. This makes it possible to adjust the content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals of the resulting silicon carbide ceramic to a desired value. The number of the kinds of the silicon carbide ceramic powders to be mixed is preferably 2 to 5, more preferably 2.
Incidentally, it may be only one kind of silicon carbide ceramic powders as the silicon carbide ceramic powders to be contained in the forming raw material. In this case, it is preferred that 0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9 mass % of 6H—SiC silicon carbide crystals are contained in the silicon carbide ceramic powders contained in above silicon carbide ceramic powders.
The content ratio of the 4H—SiC silicon carbide crystals in the silicon carbide ceramic contained in the forming raw material is adjusted so that a silicon carbide ceramic to be obtained therefrom has a desired content ratio of 4H—SiC silicon carbide crystals. It is to be noted that the term “content ratio of 4H—SiC silicon carbide crystals” means a content ratio of 4H—SiC silicon carbide crystals with respect to the entire silicon carbide crystals of a silicon carbide ceramic (or silicon carbide ceramic powders) unless otherwise particularly specified.
With respect to “desired content ratio of 4H—SiC silicon carbide crystals”, silicon carbide ceramic powders having a “content ratio of 4H—SiC silicon carbide crystals” equal to or smaller than it are called “low 4H—SiC silicon carbide ceramic powders” or “low 4H—SiC silicon carbide powders”. In addition, silicon carbide ceramic powders having a “content ratio of 4H—SiC silicon carbide crystals” equal to or larger than it are called “high 4H—SiC silicon carbide ceramic powders” or “high 4H—SiC silicon carbide powders”. A plural kinds of silicon carbide ceramic powders “containing 4H—SiC silicon carbide crystals at respectively different content ratio” are composed of “low 4H—SiC silicon carbide ceramic powders” and “high 4H—SiC silicon carbide ceramic powders”. The number of the kinds of the “low 4H—SiC silicon carbide ceramic powders” constituting the plural kinds of the silicon carbide ceramic powders “containing 4H—SiC silicon carbide crystals at respectively different content ratio” may be either one or more. Moreover, the number of the kinds of the “high 4H—SiC silicon carbide ceramic powders” constituting the plural kinds of the silicon carbide ceramic powders “containing 4H—SiC silicon carbide crystals at respectively different content ratio” may be either one or more. The term “desired content ratio of 4H—SiC silicon carbide crystals” means the content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals in the “silicon carbide ceramic to be prepared (desired silicon carbide ceramic)”. The term “content ratio of 4H—SiC silicon carbide crystals” in the silicon carbide ceramic powders means a content ratio of 4H—SiC silicon carbide crystals with respect to the entire silicon carbide crystals in the silicon carbide ceramic powders.
The content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals in the “low 4H—SiC silicon carbide ceramic powders” is preferably 0.01 to 15 mass %. And, the content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals in the “high 4H—SiC silicon carbide ceramic powders” is preferably 0.5 to 40 mass %. The term “content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals” used herein means the content ratio of 4H—SiC silicon carbide crystals with respect to the entire silicon carbide crystals.
The “content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals in the low 4H—SiC silicon carbide ceramic powders” is called “content ratio of 4H—SiC silicon carbide crystals in the low 4H—SiC silicon carbide powders”. The “content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals in the high 4H—SiC silicon carbide ceramic powders” is called “content ratio of 4H—SiC silicon carbide crystals in the high 4H—SiC silicon carbide powders”. A difference between the “content ratio of 4H—SiC silicon carbide crystals in the low 4H—SiC silicon carbide powders” and the “content ratio of 4H—SiC silicon carbide crystals in the high 4H—SiC silicon carbide powders” is preferably 30 mass % or less, more preferably 15 mass % or less. When the difference is more than 30 mass %, since the resistance decreases in a part, there is a possibility of an uneven temperature distribution. When either one or both of the low 4H—SiC silicon carbide powders and the high 4H—SiC silicon carbide powders are present in a plural kinds, it preferably satisfies the following condition. That is, it is preferable that a difference between the “content ratio of 4H—SiC silicon carbide crystals in the low 4H—SiC silicon carbide powders” and the “content ratio of 4H—SiC silicon carbide crystals in the high 4H—SiC silicon carbide powders” becomes within the above-described range even if any one of ones among above a plural kinds is selected.
In addition, in the silicon carbide crystals in the low 4H—SiC silicon carbide ceramic powders, 6H—SiC silicon carbide crystals are preferably contained mainly, in addition to the 4H—SiC silicon carbide crystals. The term “6H—SiC silicon carbide crystals are contained mainly, in addition to the 4H—SiC silicon carbide crystals” means that except trace components being 1 mass % or less, only 6H—SiC silicon carbide crystals are contained, in addition to the 4H—SiC silicon carbide crystals. In addition, similarly, in the silicon carbide crystals in the high 4H—SiC silicon carbide ceramic powders, 6H—SiC silicon carbide crystals are preferably contained mainly, in addition to the 4H—SiC silicon carbide crystals.
Moreover, in the silicon carbide crystals in the low 4H—SiC silicon carbide ceramic powders, 15R—SiC silicon carbide crystals or 3C—SiC silicon carbide crystals may be contained, in addition to the 4H—SiC silicon carbide crystals and 6H—SiC silicon carbide crystals. In addition, similarly, in the silicon carbide crystals in the high 4H—SiC silicon carbide ceramic powders, 15R—SiC silicon carbide crystals or 3C—SiC silicon carbide crystals may be contained, in addition to the 4H—SiC silicon carbide crystals and 6H—SiC silicon carbide crystals. When a silicon carbide ceramic containing 15R—SiC silicon carbide crystals is produced, it is preferable that the 15R—SiC silicon carbide crystals are contained in either one of the low 4H—SiC silicon carbide ceramic powders or the high 4H—SiC silicon carbide ceramic powders or “both of them”. The term “both of them” means “both of the low 4H—SiC silicon carbide ceramic powders and the high 4H—SiC silicon carbide ceramic powders”.
The method for producing a silicon carbide ceramic according to the present embodiment is described more specifically. Although there is not particularly limited on the shape of the silicon carbide ceramic, a method for producing a honeycomb structural silicon carbide ceramic (honeycomb structure) is described in the following description on the production method.
(4-2) When a silicon carbide ceramic (silicon-silicon carbide ceramic) “containing a plurality of silicon carbide particles and silicon (metal silicon) for binding these silicon carbide particles to each other” is produced, it is preferred to produce the silicon carbide ceramic by using the following method.
Firstly, a plural kinds of silicon carbide ceramic powders “containing 4H—SiC silicon carbide crystals at respectively different content ratio” are mixed to prepare a forming raw material (step of preparing a forming raw material). More specifically, low 4H—SiC silicon carbide ceramic powders and high 4H—SiC silicon carbide ceramic powders are mixed so as to adjust the “content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals of a silicon carbide ceramic to be prepared” to a desired value. Further, the resulting mixture is mixed with metal silicon powders to prepare a forming raw material. At this time, if necessary, it is preferred to mix further with additives ordinarily used for the production of a silicon-silicon carbide ceramic such as binder, surfactant, pore forming material, and water. Incidentally, there is not particularly limited on the mixing order of these raw materials. In addition, the low 4H—SiC silicon carbide ceramic powders and the high 4H—SiC silicon carbide ceramic powders may be collectively called “silicon carbide ceramic raw material”.
An average particle diameter of the silicon carbide ceramic powders is preferably 10 to 50 μm, more preferably 15 to 35 μm. When the average particle diameter is smaller than 10 μm, since the resistivity becomes high easily, an electric current flows hardly at the time of current application so that it may be difficult to generate heat sufficiently. When the average particle diameter is larger than 50 μm, since the porosity becomes low easily, the thermal capacity becomes large easily so that a temperature elevating rate may become slow at the time of current application. An average particle diameter of the silicon carbide ceramic powders is a value of 50% particle size measured by a laser diffraction/scattering particle size distribution analyzer (for example, “LA-920”, product of Horiba, Ltd.) using the Fraunhofer diffraction theory or Mie scattering theory as a measurement principle.
The total of the content ratio of the metal silicon and the content ratio of the silicon carbide ceramic raw material in the forming raw material is preferably 30 to 90 mass %.
A ratio (mass ratio) of the metal silicon in the forming raw material with respect to the total of the metal silicon and the silicon carbide ceramic raw material is preferably 10 to 40 mass %, more preferably 15 to 35 mass %.
Examples of the binder include methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. Of these, it is preferable that methyl cellulose is used in combination with hydroxypropoxyl cellulose. The content amount of the binder is preferably 2.0 to 10.0 parts by mass based on 100 parts by mass of the total mass of the silicon carbide ceramic raw material and the metal silicon.
The content amount of water is preferably 20 to 60 parts by mass based on 100 parts by mass of the total mass of the silicon carbide ceramic raw material and the metal silicon.
Examples of the surfactant include ethylene glycol, dextrin, fatty acid soap, and polyalcohol. These surfactants may be used either singly or in combination. The content amount of the surfactant is preferably 0.1 to 2.0 parts by mass based on 100 parts by mass of the total mass of the silicon carbide ceramic raw material and the metal silicon.
The pore forming material is not particularly limited insofar as it forms pore after firing, and examples thereof include graphite, starch, resin balloon, water absorbing resin, and silica gel. The content amount of the pore forming material is preferably 0.5 to 10.0 parts by mass based on 100 parts by mass of the total mass of the silicon carbide ceramic raw material and the metal silicon. The average particle diameter of the pore forming material is preferably 10 to 30 μm. When an average particle diameter is smaller than 10 μm, it may not form pore sufficiently. When an average particle diameter is larger than 30 μm, it may be clogged at a die during forming. The average particle diameter of the pore forming material is a value measured by using a laser diffraction method.
Next, the forming raw material is kneaded to form a kneaded clay. There is not particularly limited on the method for kneading the forming raw material to form a kneaded clay, and examples thereof include a method using a kneader or a vacuum kneader machine.
Next, it is preferred to extrude the kneaded clay (forming raw material) to form a honeycomb formed body (forming step). The honeycomb formed body is a cylindrical formed body having porous partition walls defining “a plurality of cells each extending from the one end face to another end face” to form a through channel of a fluid; and an outer peripheral wall located at the most outer periphery. It is to be noted that the honeycomb formed body is not necessarily equipped with the outer peripheral wall.
In extrusion, it is preferably used a die having a desired entire shape, a cell shape, a thickness of partition walls, a cell density, and the like. The material of the die is preferably a superalloy being hardly worn away.
The external shape, size, thickness of the partition wall, cell density, thickness of the outer peripheral wall, and the like of the honeycomb formed body can be appropriately determined depending on the structure of the honeycomb structure to be produced while considering the shrinkage during drying or firing.
The honeycomb formed body thus obtained is preferably dried. There is not particularly limited on the drying method, and examples thereof include electromagnetic wave heating methods such as microwave heating drying and high-frequency induction heating drying, and external heating methods such as hot air drying and overheat water vapor drying. Of these methods, it is preferred to dry the formed body to remove a predetermined water content by the electromagnetic wave heating method, followed by drying to remove the remaining water content by the external heating method. This makes it possible to dry the entirety of the formed body quickly and uniformly while preventing crack generation. As drying conditions, it is preferred to remove a water content of 30 to 99 mass % with respect to the water content before drying by the electromagnetic wave heating method, and then reduce the water content to 3 mass % or less by the external heating method. As the electromagnetic wave heating method, induction heating drying is preferred, and as the external heating method, hot air drying is preferred.
When a length of the honeycomb formed body in a central axis direction is not a desired length, it is preferable that both end faces (both end portions) are cut to obtain the desired length. Although there is not particularly limited on a cutting method, examples thereof include a method using a circular saw cutter machine.
Next, it is preferred to conduct calcination for removing the binder and the like. The calcination is conducted preferably at 400 to 550° C. for 0.5 to 20 hours under the atmosphere. There is not particularly limited on the calcination method, and it can be conducted using an electric furnace, gas furnace, or the like.
Next, the honeycomb formed body subjected to calcination is fired to prepare a honeycomb structure (honeycomb structural silicon carbide ceramic) being adjusted at a content ratio of the 4H—SiC silicon carbide crystals to a desired value preferably (firing step). As the firing conditions, the firing is preferably performed at the temperature of 1400 to 1500° C. for 1 to 20 hours under an inert atmosphere such as nitrogen or argon. In addition, after the firing, oxidation treatment is preferably conducted at 1200 to 1350° C. for 1 to 10 hours in order to improve durability. There is not particularly limited on the firing method, and it can be conducted using an electric furnace, a gas furnace, or the like.
Since above method for producing the one embodiment of the silicon carbide ceramic of the present invention is a method for producing a honeycomb structure using, as a material thereof, the one embodiment of the silicon carbide ceramic of the present invention, it is also a method for producing one embodiment of the honeycomb structure of the present invention. Further, the method for producing one embodiment of the honeycomb structure of the present invention is also a method for producing an current application heat-generating catalyst carrier equipped with the one embodiment of the honeycomb structure of the present invention.
(4-3) When a silicon carbide ceramic formed by binding silicon carbides to each other (not containing silicon as a binder) is produced, it is preferred to prepare the silicon carbide ceramic by following method.
Firstly, low 4H—SiC silicon carbide ceramic powders (low 4H—SiC powders) are mixed with high 4H—SiC silicon carbide ceramic powders (high 4H—SiC powders) to prepare a forming raw material (a forming raw material preparing step). Upon preparing the forming raw material, above “low 4H—SiC powders” and above “high 4H—SiC powders” are mixed so as to obtain a “desired content ratio of 4H—SiC silicon carbide crystals in the silicon carbide crystals of a silicon carbide ceramic to be produced”. And additives are then added if necessary without adding metal silicon to obtain the forming raw material.
Moreover, when a silicon carbide ceramic containing 15R—SiC silicon carbide crystals is prepared, it is preferred that 15R—SiC silicon carbide crystals are contained in the low 4H—SiC silicon carbide ceramic powders or the high 4H—SiC silicon carbide ceramic powders, or in “both of them”. Above term “both of them” means “both of the low 4H—SiC silicon carbide ceramic powders and high 4H—SiC silicon carbide ceramic powders”.
Next, the forming raw material is formed into a desired structure such as honeycomb structure, if necessary, by extrusion or the like to form a formed body (forming step).
Then, the formed body thus obtained is fired in a known manner to obtain a silicon carbide ceramic being adjusted at a content ratio of 4H—SiC silicon carbide crystals to a desired value (firing step).
EXAMPLES
The silicon carbide ceramic of the present invention will be described more specifically by Examples, but the present invention is not limited to or by these Examples.
Example 1
Silicon carbide powders having a content ratio of 4H—SiC silicon carbide crystals of 0.1 mass %, silicon carbide powders having a content ratio of 4H—SiC silicon carbide crystals of 26.0 mass %, and metal silicon powders were mixed at a mass ratio of 70.0:0.0:30.0. The silicon carbide powders are silicon carbide ceramic powders. Hydroxypropylmethyl cellulose as a binder, a water absorbing resin as a pore forming material, and water were added to mixture to prepare a forming raw material. The forming raw material thus prepared was kneaded by using a vacuum kneader machine to obtain a cylindrical kneaded clay. The silicon carbide powders and the metal silicon powders may be called (collectively) “ceramic raw material”. In addition, the silicon carbide powders having a content ratio of 4H—SiC silicon carbide crystals of 0.1 mass % are “low 4H—SiC silicon carbide powders”. And, the silicon carbide powders having a content ratio of 4H—SiC silicon carbide crystals of 26.0 mass % are “high 4H—SiC silicon carbide powders”. The content amount of the binder was 7 parts by mass based on 100 parts by mass of the total amount of the ceramic raw material. Moreover, the content amount of the pore forming material was 3 parts by mass based on 100 parts by mass of the total amount of the ceramic raw material. Further, the content amount of water was 42 parts by mass based on 100 parts by mass of the total amount of the ceramic raw material. The average particle diameter of the silicon carbide powders was 30 μm and the average particle diameter of the metal silicon powders was 6 μm. Moreover, the average particle diameter of pore forming material was 25 μm. The average particle diameter of each of the silicon carbide powders, metal silicon powders, and pore forming material were a value measured by a laser diffraction method.
The cylindrical kneaded clay thus obtained was formed by using an extruder to obtain a cylindrical honeycomb formed body. The honeycomb formed body thus obtained was subjected to high-frequency induction heat drying, followed by drying at 120° C. for 2 hours by using a hot air drier, and then a predetermined amount of both end portions was cut.
Thereafter, the honeycomb formed body was degreased, fired, and further subjected to oxidation treatment to obtain a honeycomb structure (silicon carbide ceramic). The degreasing condition was set at 550° C. for 3 hours. The firing condition was set at 1450° C. for 2 hours under an argon atmosphere. The oxidation treatment condition was set at 1300° C. for 1 hour. Nitrogen has not been dissolved in solid solution in the honeycomb structure thus obtained.
In the honeycomb structure thus obtained, an average pore diameter of partition wall was 15 μm and a porosity was 40%. The average pore diameter and porosity are values as measured using a mercury porosimeter. In addition, in the honeycomb structure, the thickness of the partition wall was 120 μm and the cell density was 90 cells/cm2. Further, the bottom surface of the honeycomb structure was a circle with a diameter of 90 mm and the length of the honeycomb structure was 100 mm in the cell extending direction. The isostatic strength of the honeycomb structure thus obtained was 7 MPa. The isostatic strength is breaking strength measured while applying a hydrostatic pressure in water. Moreover, the average particle diameter of the silicon carbide particles constituting the partition wall of the honeycomb structure was 30 μm. The average particle diameter of the silicon carbide particles constituting the partition wall of the honeycomb structure thus obtained is a value determined by observing the cross-section of the silicon carbide ceramic with SEM and analyzing them by using an image processing apparatus.
The “resistivity (R20, RMin, R20−Rmin)”, “temperature to give the minimum resistivity (TR-Min)”, “stability at the time of current application”, and “thermal resistance” of the honeycomb structure thus obtained were measured by the following methods, respectively. In addition, the ratio of crystal structures in the silicon carbide ceramic (honeycomb structure) was measured by the following method. The results were shown in Table 2.
In Table 2, the column of “crystal structure ratio (mass %)” showed the ratios (mass %) of respective crystal structures (4H—SiC silicon carbide crystals, 6H—SiC silicon carbide crystals, and the like) with respect to the total of silicon carbide crystals in the silicon carbide ceramic of the fired body. The column of an average particle diameter (μm) showed the average particle diameter (μm) of the silicon carbide particles in the silicon carbide ceramic. It is a value determined by observing the cross-section and film surface of the silicon carbide ceramic with SEM and analyzing them with an image processing software (ImageJ). Moreover, the content ratio (mass %) of metal silicon showed a content ratio of the metal silicon with respect to the total of the total of the silicon carbide particles and the metal silicon in the silicon carbide ceramic. The content ratio of the metal silicon is a value measured by using a fluorescent X-ray analysis. Moreover, the porosity showed a porosity of the partition wall of the honeycomb structure made of the silicon carbide ceramic.
Moreover, in the column of “stability during current application” in Table 2, when the temperature distribution in the carrier was 50° C. or less during current application, it was evaluated as “A”. And, when the temperature distribution in the carrier was 100° C. or less (and more than 50° C.) during current application, it was evaluated as “B”. Further, when the temperature distribution in the carrier was more than 100° C. during current application, it was evaluated as “C”. The term “temperature distribution in the carrier” in the “temperature distribution in the carrier was 50° C. or less” as used herein means a difference between the maximum temperature and the minimum temperature in the carrier. The evaluation of “A” and “B” are both within the acceptable level. Moreover, in the column of “thermal resistance” in Table 2, when a transformation ratio of 3C—SiC silicon carbide crystals was 5% or less of the original one, it was evaluated as “A”. And, when a transformation ratio of 3C—SiC silicon carbide crystals was 10% or less of the original one (and more than 5%), it was evaluated as “B”. The evaluation of “A” and “B” are both within the acceptable level.
(Measurement of Resistivity)
From the honeycomb structure (silicon carbide ceramic), a 4 mm×2 mm×40 mm test piece was cut and resistance of it was measured using a four terminal method. The resistance was measured at 20° C. and then measured at each 100° C. from 100° C. to 800° C. The resistivity is calculated based on the resistance thus obtained.
(Measurement of Ratios of Crystal Structures)
A quantitative determination of the crystal polymorphic forms of silicon carbide was performed by using the X-ray diffraction method of a powder sample (method proposed by Ruska (J. Mater. Sci., 14, 2013-2017 (1979))).
(Temperature to Give the Minimum Resistivity)
In the “measurement of resistivity”, the temperature at which the resistivity reaches the minimum value was designated as “temperature (TR-Min) to give the minimum resistivity”.
(Stability During Current Application)
Stability during current application was evaluated by measuring a temperature distribution in the carrier when current application was performed at a voltage of 600V by using a thermocouple (measuring the temperature at 39 positions uniformly scattered in the honeycomb structure) and determining a temperature distribution when the average temperature in the carrier reached 500° C.
(Thermal Resistance)
Thermal resistance was, similar to above test of “stability during current application”, performed by applying a voltage of 600V until the average temperature in the carrier was reached 500° C., and then voltage application was stopped to cool the temperature to 50° C. after the average temperature reached 500° C. This heating and cooling was regarded as 1 cycle, and a transformation ratio of 3C—SiC silicon carbide crystals after this cycle was repeated 100 times was found to evaluate. The transformation ratio of 3C—SiC silicon carbide crystals is a value obtained by subtracting the content ratio of 3C—SiC silicon carbide crystals after the thermal resistance test from the content ratio of 3C—SiC silicon carbide crystals before the thermal resistance test, dividing the difference by the content ratio of 3C—SiC silicon carbide crystals before the thermal resistance test, and then multiplying the value thus obtained by 100.











TABLE 1









low 4H—SiC silicon carbide powders
high 4H—SiC silicon carbide powders

















Content
Crystal structure ratio
Average particle
Content
Crystal structure ratio
Average particle
metal silicon
pore forming material



ratio
(mass %)
diameter
ratio
(mass %)
diameter
Content ratio
Content amount






















(mass %)
4H—SiC
6H—SiC
15R—SiC
3C—SiC
(μm)
(mass %)
4H—SiC
6H—SiC
15R—SiC
3C—SiC
(μm)
(mass %)
(parts by mass)

























Comp. Ex. 1
70.0
0.0
100.0
0.0
0.0
30
0.0
26.0
67.0
4.0
3.0
30
30
1.0


Example 1
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
1.0


Example 2
100.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
0
1.0


Example 3
67.5
0.1
92.9
5.0
2.0
30
2.5
26.0
67.0
4.0
3.0
30
30
1.0


Example 4
62.1
0.1
92.9
5.0
2.0
30
7.9
26.0
67.0
4.0
3.0
30
30
1.0


Example 5
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
1.0


Example 6
0.0
0.1
92.9
5.0
2.0
30
70.0
5.0
90.0
4.0
1.0
30
30
1.0


Example 7
43.3
0.1
92.9
5.0
2.0
30
26.7
26.0
67.0
4.0
3.0
30
30
1.0


Example 8
0.0
0.1
92.9
5.0
2.0
30
70.0
10.0
87.0
3.0
0.0
30
30
1.0


Example 9
45.0
12.0
84.0
3.0
1.0
30
25.0
26.0
67.0
4.0
3.0
30
30
1.0


Example 10
0.0
12.0
84.0
3.0
1.0
30
70.0
17.0
79.0
3.0
1.0
30
30
1.0


Example 11
5.0
12.0
84.0
3.0
1.0
30
65.0
26.0
67.0
4.0
3.0
30
30
1.0


Example 12
7.1
12.0
84.0
3.0
1.0
30
92.9
26.0
67.0
4.0
3.0
30
0
1.0


Comp. Ex. 2
0.0
12.0
84.0
3.0
1.0
30
70.0
26.0
67.0
4.0
3.0
30
30
1.0


Example 13
56.7
0.1
92.9
0.1
6.9
30
13.3
26.0
67.0
0.1
6.9
30
30
1.0


Example 14
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
5.0
2.0
30
30
1.0


Example 15
56.7
0.1
88.9
9.0
2.0
30
13.3
26.0
47.0
25.0
2.0
30
30
1.0


Example 16
56.7
0.1
79.1
18.8
2.0
30
13.3
26.0
47.0
25.0
2.0
30
30
1.0


Example 17
56.7
0.1
77.9
20.0
2.0
30
13.3
26.0
47.0
25.0
2.0
30
30
1.0


Example 18
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
62.0
5.0
7.0
30
30
1.0


Example 19
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
51.0
5.0
18.0
30
30
1.0


Example 20
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
51.0
5.0
23.0
30
30
1.0


Example 21
5.0
12.0
47.0
3.0
38.0
30
65.0
26.0
50.2
21.3
2.5
30
30
1.0


Comp. Ex. 3
5.0
12.0
47.0
3.0
38.0
30
65.0
27.1
49.1
21.3
2.5
30
30
1.0


Example 22
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
0.2


Example 23
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
0.3


Example 24
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
0.5


Example 25
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
1.5


Example 26
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
2.0


Example 27
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
2.1


Example 28
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
4.0


Example 29
56.7
0.1
92.9
5.0
2.0
30
13.3
26.0
67.0
4.0
3.0
30
30
4.3


Example 30
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
0.2


Example 31
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
0.3


Example 32
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
0.5


Example 33
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
1.5


Example 34
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
2.0


Example 35
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
2.1


Example 36
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
4.0


Example 37
70.0
0.1
92.9
5.0
2.0
30
0.0
26.0
67.0
4.0
3.0
30
30
4.3


Example 38
56.7
0.1
92.9
5.0
2.0
7
13.3
26.0
67.0
4.0
3.0
7
30
1.0


Example 39
56.7
0.1
92.9
5.0
2.0
9
13.3
26.0
67.0
4.0
3.0
9
30
1.0


Example 40
56.7
0.1
92.9
5.0
2.0
10
13.3
26.0
67.0
4.0
3.0
10
30
1.0


Example 41
56.7
0.1
92.9
5.0
2.0
15
13.3
26.0
67.0
4.0
3.0
15
30
1.0


Example 42
56.7
0.1
92.9
5.0
2.0
35
13.3
26.0
67.0
4.0
3.0
35
30
1.0


Example 43
56.7
0.1
92.9
5.0
2.0
50
13.3
26.0
67.0
4.0
3.0
50
30
1.0


Example 44
56.7
0.1
92.9
5.0
2.0
51
13.3
26.0
67.0
4.0
3.0
51
30
1.0


Example 45
70.0
0.1
92.9
5.0
2.0
6
0.0
26.0
67.0
4.0
3.0
6
30
1.0


Example 46
70.0
0.1
92.9
5.0
2.0
9
0.0
26.0
67.0
4.0
3.0
9
30
1.2


Example 47
70.0
0.1
92.9
5.0
2.0
10
0.0
26.0
67.0
4.0
3.0
10
30
1.2


Example 48
70.0
0.1
92.9
5.0
2.0
15
0.0
26.0
67.0
4.0
3.0
15
30
0.9


Example 49
70.0
0.1
92.9
5.0
2.0
35
0.0
26.0
67.0
4.0
3.0
35
30
0.9


Example 50
70.0
0.1
92.9
5.0
2.0
50
0.0
26.0
67.0
4.0
3.0
50
30
0.9


Example 51
70.0
0.1
92.9
5.0
2.0
51
0.0
26.0
67.0
4.0
3.0
51
30
0.9




















TABLE 2









Silicon carbide ceramic
Metal silicon













Crystal structure ratio (mass %)
Average particle
Content ratio
Porosity















4H—SiC
6H—SiC
15R—SiC
3C—SiC
diameter (μm)
(mass %)
(%)





Comp. Ex. 1
0.0
100
0.0
0.0
30
30
40


Example 1
0.1
92.9
5.0
2.0
30
30
40


Example 2
0.1
92.9
5.0
2.0
30
0
40


Example 3
1.0
92.0
5.0
2.0
30
30
40


Example 4
3.0
90.0
4.9
2.1
30
30
40


Example 5
5.0
88.0
4.8
2.2
30
30
40


Example 6
5.0
90.0
4.0
1.0
30
30
40


Example 7
10.0
83.0
4.6
2.4
30
30
40


Example 8
10.0
87.0
3.0
0.0
30
30
40


Example 9
17.0
77.9
3.4
1.7
30
30
40


Example 10
17.0
79.0
3.0
1.0
30
30
40


Example 11
25.0
68.2
3.9
2.9
30
30
40


Example 12
25.0
68.2
3.9
2.9
30
0
40


Comp. Ex. 2
26.0
67.0
4.0
3.0
30
30
40


Example 13
5.0
88.0
0.1
6.9
30
30
40


Example 14
5.0
88.0
5.0
2.0
30
30
40


Example 15
5.0
80.9
12.0
2.0
30
30
40


Example 16
5.0
73.0
20.0
2.0
30
30
40


Example 17
5.0
72.0
21.0
2.0
30
30
40


Example 18
5.0
87.0
5.0
3.0
30
30
40


Example 19
5.0
84.9
5.0
5.0
30
30
40


Example 20
5.0
84.9
5.0
6.0
30
30
40


Example 21
25.0
50.0
20.0
5.0
30
30
40


Comp. Ex. 3
26.0
49.0
20.0
5.0
30
30
40


Example 22
5.0
88.0
4.8
2.2
30
30
29


Example 23
5.0
88.0
4.8
2.2
30
30
30


Example 24
5.0
88.0
4.8
2.2
30
30
35


Example 25
5.0
88.0
4.8
2.2
30
30
45


Example 26
5.0
88.0
4.8
2.2
30
30
50


Example 27
5.0
88.0
4.8
2.2
30
30
51


Example 28
5.0
88.0
4.8
2.2
30
30
65


Example 29
5.0
88.0
4.8
2.2
30
30
66


Example 30
0.1
92.9
5.0
2.0
30
30
29


Example 31
0.1
92.9
5.0
2.0
30
30
30


Example 32
0.1
92.9
5.0
2.0
30
30
35


Example 33
0.1
92.9
5.0
2.0
30
30
45


Example 34
0.1
92.9
5.0
2.0
30
30
50


Example 35
0.1
92.9
5.0
2.0
30
30
51


Example 36
0.1
92.9
5.0
2.0
30
30
65


Example 37
0.1
92.9
5.0
2.0
30
30
66


Example 38
5.0
88.0
4.8
2.2
7
30
66


Example 39
5.0
88.0
4.8
2.2
9
30
51


Example 40
5.0
88.0
4.8
2.2
10
30
46


Example 41
5.0
88.0
4.8
2.2
15
30
42


Example 42
5.0
88.0
4.8
2.2
35
30
38


Example 43
5.0
88.0
4.8
2.2
50
30
34


Example 44
5.0
88.0
4.8
2.2
51
30
33


Example 45
0.1
92.9
5.0
2.0
6
30
67


Example 46
0.1
92.9
5.0
2.0
9
30
52


Example 47
0.1
92.9
5.0
2.0
10
30
47


Example 48
0.1
92.9
5.0
2.0
15
30
41


Example 49
0.1
92.9
5.0
2.0
35
30
37


Example 50
0.1
92.9
5.0
2.0
50
30
33


Example 51
0.1
92.9
5.0
2.0
51
30
32























Stability









during




R20
RMin
R20 − RMin
TR-Min
current
Thermal




(Ω · cm)
(Ω · cm)
(Ω · cm)
(° C.)
application
resistance







Comp. Ex. 1
200
20
180
800
A
A



Example 1
70
31
39
500
A
A



Example 2
100
25
75
500
A
A



Example 3
60
25
35
450
A
A



Example 4
55
21
34
425
A
A



Example 5
40
15
25
400
A
A



Example 6
50
20
30
400
A
A



Example 7
25
10
15
390
A
A



Example 8
30
12
18
390
A
A



Example 9
7
3
4
370
A
A



Example 10
10
3
7
370
A
A



Example 11
2.5
1.2
1.3
360
A
A



Example 12
5
2
3
350
A
A



Comp. Ex. 2
0.5
0.1
0.4
330
A
A



Example 13
45
22
23
370
A
B



Example 14
41
16
25
400
A
A



Example 15
44
22
22
405
A
A



Example 16
43
18
25
430
A
A



Example 17
41
12
29
450
B
A



Example 18
42
16
26
400
A
A



Example 19
39
15
24
400
A
A



Example 20
38
13
25
400
A
B



Example 21
2
1
1
350
A
A



Comp. Ex. 3
0.3
0.1
0.2
550
A
A



Example 22
10
4
6
400
A
A



Example 23
20
11
9
400
A
A



Example 24
30
13
17
400
A
A



Example 25
60
25
35
400
A
A



Example 26
100
40
60
400
A
A



Example 27
150
70
80
400
A
A



Example 28
170
87
83
400
A
A



Example 29
200
110
90
400
A
A



Example 30
40
17
23
500
A
A



Example 31
60
29
31
500
A
A



Example 32
80
42
35
500
A
A



Example 33
103
65
38
500
A
A



Example 34
150
80
70
500
A
A



Example 35
170
90
80
500
A
A



Example 36
200
110
90
500
A
A



Example 37
270
160
110
500
A
A



Example 38
250
150
100
400
A
A



Example 39
200
120
80
400
A
A



Example 40
70
30
40
400
A
A



Example 41
62
23
39
400
A
A



Example 42
36
15
21
400
A
A



Example 43
27
8
19
400
A
A



Example 44
25
12
13
400
A
A



Example 45
225
145
80
500
A
A



Example 46
170
95
75
500
A
A



Example 47
115
58
57
500
A
A



Example 48
90
51
39
500
A
A



Example 49
66
32
34
500
A
A



Example 50
50
20
30
500
A
A



Example 51
31
11
20
500
A
A










Examples 2 to 51, Comparative Examples 1 to 3
In a manner similar to Example 1 except some of the production conditions were changed as shown in Table 1, honeycomb structures (silicon carbide ceramics) were produced. The “resistivity” of the honeycomb structures thus obtained was measured by the above-described method. The results are shown in Table 2. Incidentally, in Table 1, the column of “content ratio (mass %)” of “low 4H—SiC silicon carbide powders” showed the content ratio of “low 4H—SiC silicon carbide powders” with respect to the total of the whole silicon carbide powders and metal silicon. Moreover, the column of “content ratio (mass %)” of “high 4H—SiC silicon carbide powders” showed the content ratio of “high 4H—SiC silicon carbide powders” with respect to the total of the whole silicon carbide powders and metal silicon. The column of “crystal structure ratio (mass %)” of “low 4H—SiC silicon carbide powders” showed the ratio (mass %) of each of the crystal structures (4H—SiC silicon carbide crystals, 6H—SiC silicon carbide crystals and the like) with respect to the whole silicon carbide crystals in the low 4H—SiC silicon carbide powders. Moreover, the column of “crystal structure ratio (mass %)” of “high 4H—SiC silicon carbide powders” showed the ratio (mass %) of each of the crystal structures (4H—SiC silicon carbide crystals, 6H—SiC silicon carbide crystals and the like) with respect to the whole silicon carbide crystals in the high 4H—SiC silicon carbide powders. Further, the content ratio (mass %) of the metal silicon is a content ratio of the metal silicon with respect to the total amount of the whole silicon carbide powders and the metal silicon. Moreover, the content amount of the pore forming material is indicated by a content ratio (part by mass) based on 100 parts by mass of the “total amount of the whole silicon carbide powders and the metal silicon”.
It has been found from Table 1 and Table 2 that the silicon carbide ceramics (honeycomb structures) obtained in Examples 1 to 51 has a small difference (R20−Rmin) between the resistivity (R20) at 20° C. and the minimum resistivity (RMin), and has a small temperature of resistivity. On the other hand, since the silicon carbide ceramic of Comparative Example 1 did not contain 4H—SiC silicon carbide crystals, it has been found that an R20−RMin difference is large and the one has a large temperature change of resistivity. It has also been found that the temperature to give the minimum resistivity is high. Moreover, the silicon carbide ceramic of Comparative Example 2 has a large content ratio of 4H—SiC silicon carbide crystals. Therefore, the one has a small resistivity at 20° C. (R20) and it has been considered that the one is less effective for generating heat by current application. Further, the silicon carbide ceramic of Comparative Example 3 has a large content ratio of 4H—SiC silicon carbide crystals and a small content ratio of 6H—SiC silicon carbide crystals. Therefore, it has been found that the one has a small resistivity (R20) at 20° C. and a temperature to give the minimum resistivity is also high.
Industrial Applicability
The silicon carbide ceramic of the present invention is suitably utilized as a heating element. In addition, the honeycomb structure of the present invention and the current application heat-generating catalyst carrier of the present invention are suitably utilized as a catalyst carrier for exhaust gas purifying apparatus for purifying an exhaust gas of automobiles.
Description of Reference Numerals


    1: partition wall
    2: cell
    3: outer peripheral wall
    11: one end face
    12: another end face
    100: honeycomb structure.

## Claims

1. A silicon carbide ceramic comprising silicon carbide crystals wherein 0.1 to 25 mass % of 4H—SiC silicon carbide crystals and 50 to 99.9mass % of 6H—SiC silicon carbide crystals are contained in the silicon carbide crystals, and wherein a difference (R20−Rmin) between the resistivity at 20° C. (R20) and the minimum resistivity (Rmin) of the silicon carbide ceramic is 80 Ω·cm or less.

2. A silicon carbide ceramic according to claim 1, wherein the resistivity at 20° C. (R20) of the silicon carbide ceramic is 2 to 100 Ω·cm.

3. A silicon carbide ceramic according to claim 1, wherein a content amount of nitrogen is 0.01 mass % or less.

4. A silicon carbide ceramic according to claim 3, comprising a plurality of silicon carbide particles containing the silicon carbide crystals and silicon for binding the silicon carbide particles to each other;
wherein a content ratio of the silicon is 10 to 40 mass %.

5. A silicon carbide ceramic according to claim 4, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

6. A silicon carbide ceramic according to claim 4, wherein an average particle diameter of the silicon carbide particles is 10 to 50 μm.

7. A silicon carbide ceramic according to claim 6, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

8. A silicon carbide ceramic according to claim 3, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

9. A silicon carbide ceramic according to claim 1, comprising a plurality of silicon carbide particles containing the silicon carbide crystals and silicon for binding the silicon carbide particles to each other;
wherein a content ratio of the silicon is 10 to 40 mass %.

10. A silicon carbide ceramic according to claim 9, wherein an average particle diameter of the silicon carbide particles is 10 to 50 μm.

11. A silicon carbide ceramic according to claim 10, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

12. A silicon carbide ceramic according to claim 9, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

13. A silicon carbide ceramic according to claim 9, wherein an average particle diameter of the silicon carbide particles is 15 to 35 μm.

14. A silicon carbide ceramic according to claim 1, wherein a porosity is 30 to 65%.

15. A silicon carbide ceramic according to claim 14, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

16. A silicon carbide ceramic according to claim 1, wherein 0.1 to 20 mass % of 15R—SiC silicon carbide crystals are contained in the silicon carbide crystals.

17. A honeycomb structure comprising the silicon carbide ceramic according to claim 1 as a material.

18. A current application heating catalyst carrier comprising the honeycomb structure according to claim 17 and generating heat by current application.