JP5657981B2 - Method for producing ceramic-metal joined body, and ceramic-metal joined body - Google Patents

Description

  The present invention relates to a method for producing a ceramic-metal joined body and a ceramic-metal joined body. More specifically, a ceramic member made of a conductive ceramic material and a metal member can be joined well by brazing with a state in which high conductivity is secured between the members, that is, with low electrical resistance. The present invention relates to a method for manufacturing a ceramic-metal bonded body and a ceramic-metal bonded body manufactured by such a manufacturing method.

  As a method of joining a ceramic material and a metal material, a joining method by brazing has been conventionally used in many scenes. Usually, when joining a ceramic material and a metal material with a brazing material, since the wettability of the brazing material to the ceramic material is low, for example, the following two types of joining methods have been proposed (for example, patents). Reference 1 and 2).

  The first method is a method of performing metallization (metal coating) on the surface of the ceramic and indirectly brazing the ceramic material and metal material thus metallized, and the second method is as follows: By using a special metal brazing material containing noble metals such as gold (Au), platinum (Pt), palladium (Pd) and active metals such as Ti, Zr, and Be, and increasing the activity of ceramics and brazing material, In this method, the ceramic material and the metal material are directly brazed.

JP-A-8-119760 JP 2002-37679 A

  However, in such a conventional joining method by brazing, for example, conductive ceramics as a ceramic material, for example, conductive ceramics containing silicon carbide particles and silicon (hereinafter referred to as “Si—SiC ceramics” or “Si— When SiC is used, there is a problem in that the electrical resistance between the members increases at the bonding interface between the ceramic member and the metal member.

  That is, in the Si-SiC ceramic described above, a molded body having a predetermined shape is obtained using a ceramic raw material containing silicon carbide particles as an aggregate and silicon as a binder, and the obtained molded body is fired. In order to improve the durability of the ceramic member such as mechanical strength and corrosion resistance, the ceramic member is manufactured by firing as described above, and then, for example, a temperature of about 1200 ° C. Oxidation treatment may be performed to form a protective film made of silicon oxide on the surface of the ceramic member. Since the silicon oxide is an insulating material, it is presumed that the electrical resistance at the joint interface increases in a joined body in which a conductive ceramic member and a metal member are joined.

  Further, even when the above-described oxidation treatment is not performed, the ceramic surface may be oxidized by the firing atmosphere in the step of firing the ceramic raw material, and such oxidized ceramics are described above. Similar to the oxidation treatment, when a joined body is formed by joining metal members, the electrical resistance at the joining interface increases.

  The present invention has been made in view of the above-described problems, and is a state in which high electrical conductivity is ensured between members by brazing a conductive ceramic material and a metal material, that is, low electrical resistance. The present invention provides a method for producing a ceramic-metal joined body that can be satisfactorily joined with each other, and a ceramic-metal joined body produced by such a production method.

  In order to solve the above-described problems, the present invention provides the following method for producing a ceramic-metal joined body and a ceramic-metal joined body.

[1] A ceramic member made of a conductive ceramic material and having a first joint surface and a metal member made of a metal material and having a second joint surface are joined via a brazing material, A step of producing a ceramic-metal joined body in which a ceramic member and the metal member are joined via the brazing material, wherein the ceramic material constituting the ceramic member comprises silicon carbide particles as an aggregate and the carbonized material; It contains silicon as a binder for bonding silicon particles, and a reducing agent having a reducing property is applied to the first joint surface of the ceramic member to form an oxide film on the first joint surface. After reducing and removing, the first joining surface of the ceramic member from which the oxide film has been reduced and removed and the second joining surface of the metal member are joined via the brazing material. A method for producing a ceramic-metal bonded body (hereinafter sometimes referred to as “first production method”).

[2] A ceramic member made of a conductive ceramic material and having a first joint surface and a metal member made of a metal material and having a second joint surface are joined via a brazing material, A step of producing a ceramic-metal joined body in which a ceramic member and the metal member are joined via the brazing material, wherein the ceramic material constituting the ceramic member comprises silicon carbide particles as an aggregate and the carbonized material; It contains silicon as a bonding material for bonding silicon particles, and a brazing material mixed with a reducing agent having a reducing property is used as the brazing material, and the brazing material uses the brazing material to form the first ceramic member. A method for manufacturing a ceramic-metal assembly (hereinafter referred to as “second manufacturing method”) in which the bonding surface is reduced to reduce and remove the oxide film on the first bonding surface. is there).

[3] The reducing agent is selected from the group consisting of chromium, silicon, boron, potassium, sodium, manganese, tantalum, niobium, vanadium, titanium, lithium, aluminum, magnesium, zirconium, barium, calcium, beryllium, and fluorine. The method for producing a ceramic-metal joined body according to the above [1] or [2], which is a compound containing at least one element.

[4] A brazing material further mixed with a diffusion inhibitor containing at least one element selected from the group consisting of zirconium, titanium, tantalum, niobium, vanadium, tungsten, molybdenum, chromium, and manganese. The method for producing a ceramic-metal joined body according to any one of [1] to [3], wherein

[5] The ceramic-metal bonded body according to any one of [1] to [4], wherein the ceramic material and the metal material are bonded while allowing at least a part of the brazing material to penetrate into the metal material. Manufacturing method.

[6] to the sum of the respective masses of the silicon and the silicon carbide particles contained in the ceramic material, the ratio of the mass of the silicon contained in the ceramic material, the 20 to 40 wt% [1 ] The manufacturing method of the ceramic-metal joined body in any one of [5] .

[ 7 ] A cylindrical honeycomb having, as the ceramic member, a porous partition wall defining a plurality of cells extending from one end surface to the other end surface serving as a fluid flow path, and an outer peripheral wall located at the outermost periphery. Using a honeycomb structure including a structure portion, a pair of electrode portions disposed on a side surface of the honeycomb structure portion, and an electrode terminal protrusion disposed on each surface of the pair of electrode portions, The method for producing a ceramic-metal assembly according to any one of [1] to [ 6 ], wherein a metal terminal portion or metal wiring made of a metal material that is electrically connected to the electrode terminal protrusion is used as the metal material. .

[ 8 ] A ceramic member made of a ceramic material having conductivity and a metal member, wherein the ceramic member contains silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles. The ceramic member is formed of the ceramic material, and the ceramic member and the metal member are formed by reducing at least a joint surface of the ceramic member with the metal member by a reducing agent having a reducing property. A ceramic-metal joined body joined via a brazing material in a state in which the oxide film on the joining surface is reduced and removed.

[ 9 ] The brazing material is selected from the group consisting of chromium, silicon, boron, potassium, sodium, manganese, tantalum, niobium, vanadium, titanium, lithium, aluminum, magnesium, zirconium, barium, calcium, beryllium, and fluorine. The ceramic-metal bonded body according to [ 8 ], including a compound containing at least one element.

[10] to the sum of the respective mass of the silicon carbide particles and the silicon contained in the ceramic material, the ratio of the mass of the silicon contained in the ceramic material, the 20 to 40 wt% [8 ] Or the ceramic-metal joined body according to [9] .

  The method for producing a ceramic-metal joined body according to the present invention is good in a state in which high conductivity between members is secured by brazing a conductive ceramic material and a metal material, that is, with low electrical resistance. Can be joined. More specifically, the oxide on the surface of the ceramic member can be reduced with a reducing agent and bonded with a brazing material, and the ceramic member made of a conductive ceramic material and the metal member made of a metal material However, it is possible to easily manufacture a ceramic-metal bonded body bonded in a state where high conductivity is ensured.

  Moreover, the ceramic-metal joined body of the present invention is obtained by joining a ceramic member made of a ceramic material having conductivity and a metal member made of a metal material while ensuring high conductivity. The ceramic member having the property is a ceramic electrode terminal or the like connected to a resistor such as a heater or a resistor as another ceramic member, and the metal member applies voltage to the resistor described above. In the case of a metal electrode terminal or electrode wiring, the electrical resistance at the bonding interface between the ceramic member and the metal member can be reduced.

It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member. It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member. It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member. It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member. It is a schematic diagram which shows the cross section orthogonal to the joining surface of a ceramic member and a metal member, showing the ceramic-metal bonded body manufactured by other embodiment of the manufacturing method of the ceramic-metal bonded body of the present invention. It is a perspective view which shows typically the honeycomb structure with an electrode manufactured by further another embodiment of the manufacturing method of the ceramic-metal joined body of this invention. FIG. 4 is a schematic diagram showing a cross section of the honeycomb structure with an electrode shown in FIG. 3 parallel to the cell extending direction. Fig. 4 is a side view showing a honeycomb structure of the honeycomb structure with an electrode shown in Fig. 3. FIG. 6 is a schematic view showing an A-A ′ cross section of the honeycomb structure shown in FIG. 5. FIG. 5 is an enlarged cross-sectional view illustrating an electrode terminal protrusion and a metal terminal portion of the honeycomb structure with an electrode illustrated in FIG. 4 in an enlarged manner. The electrode terminal protrusion part and the metal terminal part in the cross section orthogonal to the cell extending direction of the honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention are enlarged. FIG. The electrode terminal protrusion part and the metal terminal part in the cross section orthogonal to the cell extending direction of the honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention are enlarged. FIG. The state in which the electrode portion is disposed on the outer peripheral wall in the cross section perpendicular to the cell extending direction of the honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is a schematic diagram shown. The state in which the electrode portion is disposed on the outer peripheral wall in the cross section perpendicular to the cell extending direction of the honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is a schematic diagram shown. The state in which the electrode portion is disposed on the outer peripheral wall in the cross section perpendicular to the cell extending direction of the honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is a schematic diagram shown. The state in which the electrode portion is disposed on the outer peripheral wall in the cross section perpendicular to the cell extending direction of the honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is a schematic diagram shown. It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member. It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member. It is a schematic diagram which shows the manufacturing process of the ceramic-metal joined body in one Embodiment of the manufacturing method of the ceramic-metal joined body of this invention, and shows the cross section orthogonal to the joining surface of a ceramic member and a metal member.

  DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments for carrying out the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and those skilled in the art do not depart from the spirit of the present invention. It should be understood that design changes, improvements, and the like can be made as appropriate based on ordinary knowledge.

(1) Manufacturing method of ceramic-metal joined body (first manufacturing method):
First, as a method for producing a ceramic-metal joined body (hereinafter sometimes referred to as “first production method”), an embodiment of a method for producing a ceramic-metal joined body of the present invention will be described.

  As shown in FIGS. 1A to 1D, the method for manufacturing a ceramic-metal joined body according to the present embodiment is made of a ceramic material having conductivity, a ceramic member 131 having a first joining surface 131a, and a metal material. The ceramic-metal joined body 100 in which the metal member 132 having the second joining surface 132a is joined via the brazing material, and the ceramic member 131 and the metal member 132 are joined via the brazing material 133. It is a manufacturing method of the ceramic-metal joined body provided with the process to manufacture. For example, the ceramic-metal laminate 140 is obtained by laminating the first joint surface 131a and the second joint surface 132a so as to face each other across the brazing material 133, and the obtained ceramic-metal laminate is obtained. By heating 140, the ceramic-metal joined body 100 in which the ceramic member 131 and the metal member 132 are joined via the brazing material 133 can be manufactured.

  In addition, as a joining method using the brazing material, the surfaces for joining the ceramic member and the metal member are brought into contact with each other, and the brazing material is arranged in contact with at least one surface of the ceramic member and the metal member. Do. At this time, as a method for arranging the brazing material, a method in which the brazing material is sandwiched in advance between the ceramic member and the metal member (for example, see FIG. 1C), and the ceramic member and the metal member are overlapped and laminated. The brazing material is placed in contact with the gap between the ceramic member and the metal member, and the brazing material is melted, so that the melted braze (brazing material) is separated from the ceramic member and the metal member by utilizing the capillary phenomenon. Two methods, i.e., a method of pouring into the solution, can be given as preferred examples.

  Note that the “gap” into which the melted wax is poured using the capillary phenomenon described above is used when the two members (ceramic member and metal member) are overlapped, and the surface roughness and processing accuracy of the joint surfaces of both members are reduced. For example, there may be a gap at a bonding interface that exists due to (for example, an unavoidable existence), or a gap that occurs due to a difference in thermal expansion coefficient between members to be bonded due to, for example, an increase in temperature. It is also possible to form a gap for intentionally pouring wax.

  And in the manufacturing method of the ceramic-metal joined body of this embodiment, as shown to FIG. 1B and FIG. 1C, the reducing agent 134 which has a reducing property was applied to the 1st joining surface 131a of the ceramic member 131. FIG. Later, the first bonding surface 131 a of the ceramic member 131 and the second bonding surface 132 a of the metal member 132 are bonded via the brazing material 133.

  Here, FIG. 1A to FIG. 1D show a manufacturing process of the ceramic-metal joined body in one embodiment of the method for producing a ceramic-metal joined body of the present invention, and are orthogonal to the joint surface between the ceramic member and the metal member. It is a schematic diagram which shows the cross section to perform. 1A shows a state before the ceramic member 131 and the metal member 132 are laminated, and FIG. 1B shows that a reducing agent 134 having a reducing property is applied to the first joint surface 132a of the ceramic member 132. FIG. 1C shows a state in which the first joining surface 131a and the second joining surface 132a are arranged so as to face each other with the brazing material 133 therebetween, and FIG. 1D shows the ceramic member 131 and the metal member 132. The process of manufacturing the ceramic-metal joined body 100 joined through the brazing filler metal 133 is shown. In addition, if the manufacturing method of the ceramic-metal joined body of this embodiment is equipped with the process of reducing the 1st joining surface of a ceramic member with the reducing agent which has a reducing property, about the arrangement | positioning method of a brazing material, The method shown in FIGS. 1A to 1D is not limited. That is, as described above, a method of pouring molten wax into the gap between the ceramic member and the metal member using the capillary phenomenon may be used.

  By comprising in this way, the ceramic material and metal material which have electroconductivity can be favorably joined in the state which ensured the high electroconductivity between each member by brazing, ie, low electrical resistance. . Thereby, a ceramic-metal joined body in which a ceramic member made of a ceramic material having conductivity and a metal member made of a metal material are joined in a state where high conductivity is ensured can be easily produced.

  That is, in the conventional joining method by brazing, for example, conductive ceramics as a ceramic material, for example, conductive ceramics containing silicon carbide particles and silicon (hereinafter referred to as “Si-SiC ceramics” or “Si-SiC”). In some cases, the electrical resistance between the members increases at the bonding interface between the ceramic member and the metal member.

  For example, the above-described Si-SiC ceramics may form a protective film (oxide film) made of silicon oxide on the surface of the ceramic member in order to improve durability such as mechanical strength and corrosion resistance. Since such an oxide film is an insulating substance, in a joined body in which a conductive ceramic member and a metal member are joined, the electrical resistance at the joint interface increases. In addition, in the firing step when producing the ceramic member and the cooling step after firing, the surface may be oxidized to form an oxide film.

  In the method for manufacturing a ceramic-metal bonded body according to the present embodiment, as shown in FIGS. 1A and 1B, a reducing agent 134 having a reducing property is added before the brazing material bonding between the ceramic member 131 and the metal member 132. The ceramic material was oxidized (or deliberately oxidized) by coating the first bonding surface 131a of the ceramic member 131 and reducing the first bonding surface 131a of the ceramic member 131. Since the low conductivity or insulating oxide film 131x is removed, the electrical resistance between the two members can be reduced.

  As the reducing agent, for example, a flux containing a reducing agent (hereinafter, a flux containing such a reducing agent may be referred to as “specific flux”) can be used.

  When the oxide film is removed by the reducing agent, the reducing agent acts only on the surface to be bonded by the brazing material, that is, only the surface that is actually bonded to the second bonding surface (that is, the bonding surface of the metal material). It is preferable to remove the oxide film. For example, if the oxide film on the surface other than the first bonding surface is removed, durability such as mechanical strength and corrosion resistance of the ceramic member may be lowered. That is, since the oxide film can be a protective film that improves the durability of the ceramic member, the oxide film other than the surface on which the brazing material is joined does not have to be particularly reduced and removed. Of course, when another electrical connection is made to the other surface of the ceramic member, the oxide film on the surface of the part to be electrically connected may be removed by a reducing agent.

The reducing agent for reducing the first bonding surface of the ceramic member is a conductive component contained in the conductive ceramic, more specifically, an oxide in which a metal component contained in the conductive ceramic is oxidized, If it is a compound which can reduce | restore, there will be no restriction | limiting in particular. For example, at least one element selected from the group consisting of chromium, silicon, boron, potassium, sodium, manganese, tantalum, niobium, vanadium, titanium, lithium, aluminum, magnesium, zirconium, barium, calcium, beryllium, and fluorine. It is preferable that it is a compound to contain .

Further, such a reducing agent is preferably used as a paste or particle state by forming a boron compound, fluoride, chloride or the like having a melting point of 370 to 1100 ° C. More specific reducing agents include, for example, H ₃ BO ₃ , KHF ₂ , KBF _{4 and the} like. Such a compound may be in the form of a paste (liquid) in advance, or in the case of a solid, it can be used as a slurry (paste) after being powdered and mixed with a solvent or a binder. For example, the reducing agent in a paste or particle state can be used by being contained in the above-described flux. The flux that may contain a reducing agent is mainly used as a flux that is added to facilitate melting of the substance.

  When the oxide film formed on the first bonding surface of the ceramic member is reduced and removed, for example, a paste-like specific flux containing a reducing agent is covered with the first bonding surface of the ceramic member. It is preferable to apply to.

  In addition, by applying the reducing agent described so far to the first joint surface of the ceramic member, the oxide film on the first joint surface can be reduced and removed. The reduction of the reducing agent is promoted by heating and reducing atmosphere (such as vacuum). When the temperature at which the reducing agent becomes active is known, it is preferable that the temperature schedule at the time of joining with the brazing material is maintained for about 30 to 120 minutes in the temperature range where the reducing agent becomes active. In addition, although it does not specifically limit, It is preferable to select and use the thing whose activation temperature of a reducing agent is 50-350 degreeC lower than melting | fusing point of a brazing material.

  The reducing component in the reducing agent is reduced and removed from the oxide film on the first bonding surface, and is then discharged out of the molten brazing material or uniformly mixed with the molten brazing material. The second joint surface of the metal member and the second joint surface of the metal member are joined together in a state of being electrically well connected via the brazing material.

Although there is no restriction | limiting in particular about the coating amount of a reducing agent, It is preferable that the coating amount of a reducing agent is 3-500 g / m < ² >, and it is still more preferable that it is 15-150 g / m < ² >. By comprising in this way, the oxide film of a 1st joining surface can be removed favorably, and it suppresses effectively the joint strength fall by a reducing agent, and the mechanical strength and corrosion resistance fall in a joining surface. Can do. For example, if the coating amount of the reducing agent is less than 3 g / m ² , the reducing component may not be sufficiently obtained, and the oxide film may not be sufficiently removed. Is more than 500 g / m ² , there are too many reducing agents, which obstructs the joining by the brazing material, or the layer by the reducing agent remains in the resulting ceramic-metal joint, resulting in mechanical strength. And corrosion resistance may be reduced.

  As a method for applying the reducing agent to the first joint surface of the ceramic member, for example, in the case of a liquid reducing agent, a spray method, a dip method, or the like can be used. By using such a method, for example, even in the case of a porous ceramic member, the reducing agent can be satisfactorily applied to the first joint surface and formed on the first joint surface. The oxide film can be removed efficiently.

  “Removing the oxide film” not only completely removes all the oxide film formed on the first bonding surface of the ceramic member, but also at least part of the oxide film formed on the first bonding surface. Removing. For example, in the case of removing the oxide film, the conductive ceramic will be exposed because at least a part of the oxide film is removed, thereby exposing the conductive ceramic to at least a part of the first bonding surface. It is possible to satisfactorily join the ceramic member and the metal member through the material in a state in which electrical connection is ensured. In addition, although not particularly limited, the oxide film of the ceramic member is removed in the range of 50% or more (that is, 50 to 100%) in the area of the first joint surface, and the conductive ceramic is obtained. It is preferable that it is exposed. By removing the oxide film in this way, the electrical resistance at the joint interface between the ceramic member and the metal member can be reduced.

Ceramic of the present embodiment - ceramic member used in the method for producing a metal conjugate, der made of a ceramic material having conductivity is, as a binding material which binds the silicon carbide particles and silicon carbide particles as an aggregate Ru have use a conductive ceramics containing silicon. In such Si-SiC ceramics, silicon (metal silicon) as a binder has conductivity, so that the entire ceramic member has conductivity.

  In Si-SiC ceramics, silicon (metal silicon) is oxidized to form an oxide film, so that an insulating oxide film made of silicon oxide may be formed on the surface thereof. Moreover, in this embodiment, as a ceramic member using such Si-SiC ceramics, in order to improve durability, such as mechanical strength and corrosion resistance, it produces from the ceramic raw material containing an aggregate and a binder. After firing the molded body, it is also possible to use one that has been subjected to an oxidation treatment for about 1 to 24 hours at a temperature of 1200 to 1350 ° C. By comprising in this way, the oxide film used as a protective film is favorably formed on the surface of the ceramic member, the durability of the ceramic member can be improved, and the first bonding surface of the ceramic member Since the oxide film (protective film) can be reduced and removed by the reducing agent, the electrically conductive ceramic member and the metal member can be joined well together with the brazing material while ensuring electrical connection. Can do.

  The ceramic member used for the manufacturing method of the ceramic-metal joined body of this embodiment can be manufactured as follows, for example. First, metal silicon (metal silicon powder), a binder, a surfactant, water and the like are added to silicon carbide powder (silicon carbide) to produce a forming raw material. It is preferable that the mass of the metal silicon is 30 to 80% by mass with respect to the total of the mass of the silicon carbide powder and the mass of the metal silicon. The average particle diameter of the silicon carbide particles in the silicon carbide powder is preferably 30 to 100 μm, and more preferably 30 to 60 μm. The average particle diameter of metal silicon (metal silicon powder) is preferably 0.1 to 50 μm. The average particle diameter of silicon carbide particles and metal silicon (metal silicon particles) is a value measured by a laser diffraction method. The silicon carbide particles are silicon carbide fine particles constituting the silicon carbide powder, and the metal silicon particles are metal silicon fine particles constituting the metal silicon powder.

  Further, a porous ceramic member may be formed by adding a pore former to the above-described forming raw material. In this way, when a porous ceramic member is formed by adding a pore former, the reduction effect when a reducing agent is used can be made higher.

  Examples of the binder include methyl cellulose, hydroxypropyl methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. Among these, it is preferable to use methyl cellulose and hydroxypropoxyl cellulose in combination. The content of the binder is preferably 1 to 15% by mass with respect to the entire forming raw material.

  The water content is preferably 10 to 45 mass% with respect to the entire forming raw material.

  As the surfactant, ethylene glycol, dextrin, fatty acid soap, polyalcohol and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type. The content of the surfactant is preferably 2% by mass or less with respect to the whole forming raw material.

  The pore former used when forming the porous ceramic member is not particularly limited as long as it becomes pores after firing. For example, graphite powder, starch, foamed resin, water absorbent resin, A silica gel etc. can be mentioned. The pore former content is preferably 10% by mass or less based on the entire forming raw material. The average particle diameter of the pore former is preferably 5 to 50 μm. If it is smaller than 5 μm, pores may not be formed sufficiently. When it is larger than 50 μm, the die may be clogged when the forming raw material is extruded. The average particle diameter of the pore former is a value measured by a laser diffraction method.

  Moreover, it is preferable that a shaping | molding raw material contains strontium carbonate as a sintering auxiliary agent. The content of the sintering aid is preferably 0.1 to 3% by mass with respect to the entire forming raw material.

  Next, the forming raw material is kneaded to form a clay. There is no restriction | limiting in particular as a method of kneading | mixing a shaping | molding raw material and forming a clay, For example, the method of using a kneader, a vacuum clay kneader, etc. can be mentioned.

  Next, the clay is formed into a predetermined shape to produce an unfired ceramic member. There is no restriction | limiting in particular about a shaping | molding method, What is necessary is just a method which can produce the ceramic member used for a ceramic-metal joined body. For example, conventionally known molding methods such as extrusion molding, injection molding, press molding, and sheet molding can be used. Further, after molding, processing may be performed so that a predetermined shape is obtained.

  The green ceramic member thus obtained is dried and then fired to produce a ceramic member. In addition, it is preferable that drying conditions shall be 50-100 degreeC.

  Moreover, in order to remove a binder etc. before baking, it is preferable to perform temporary baking. Pre-baking is preferably performed, for example, in an air atmosphere at 400 to 500 ° C. for 0.5 to 20 hours. The method of temporary baking and baking is not particularly limited, and baking can be performed using an electric furnace, a gas furnace, or the like. The firing conditions are preferably 1400 to 1500 ° C. for 1 to 20 hours in an inert atmosphere such as nitrogen or argon.

  Moreover, it is preferable to oxidize a ceramic member for 1 to 10 hours, for example at 1200-1350 degreeC after baking, in order to improve durability. By performing such oxidation treatment, an oxide film (protective film) in which metallic silicon is oxidized can be formed on the surface of the ceramic member. However, since such an oxide film is made of insulating silicon oxide, when a ceramic member and a metal member are simply joined using a brazing material, the conductive ceramic constituting the ceramic member is used. The insulating oxide film is disposed between the material and the metal material constituting the metal member, and the electrical resistance between the ceramic member and the metal member is increased. Thus, improving the durability by forming an oxide film and suppressing the increase in the electrical resistance of the ceramic-metal joint are in a trade-off relationship, and both members are simply joined by a brazing material. In the manufacturing method, it is extremely difficult to make both compatible.

  In the method for producing a ceramic-metal joined body according to the present embodiment, the oxide film formed on the joining surface is oxidized and removed using a reducing agent. The brazing material can be joined in a state in which

  There is no restriction | limiting in particular as a metal material which comprises the metal member which joins a ceramic member, According to the use application etc. of a ceramic-metal joined body, it can select suitably. For example, metal materials such as Fe-base heat-resistant alloys (including stainless steel), Ni-base heat-resistant alloys, Co-base heat-resistant alloys, Ni-base low expansion alloys, and the like can be suitably used. Among such metal materials, SUS430, SUS310S, Inconel 600, Inconel 718, Incoloy 909, S816, Kovar, and the like are given as preferred examples of metal materials having excellent heat resistance and corrosion resistance and low electrical resistance. be able to. By using such a metal material, the ceramic-metal joined body of the present embodiment can be applied to apparatus parts such as an exhaust gas treatment apparatus installed in an automobile exhaust system, for example.

  Further, the metal material constituting the metal member includes a metal body that can cause at least one of the four phase transformations of ferrite transformation, martensite transformation, bainite transformation, and pearlite transformation by cooling of the austenite phase. It is preferable that By using such a metal material containing a metal body, the thermal stress between the ceramic and the metal generated in the cooling process during brazing can be relaxed, and damage to the brazed portion can be prevented.

  Such a metal body is selected from the group consisting of Fe (iron), Ni (nickel), Ti (titanium), Co (cobalt), Cu (copper), Zn (zinc), and Al (aluminum). It is a metal body containing at least one kind. For example, a known ferritic stainless steel, martensitic stainless steel, precipitation hardening stainless steel, Ni-base heat resistant alloy, etc. is used as a metal material having excellent heat resistance and low electrical resistance. be able to. More specifically, SUS430, SUS630, Inconel 600, Incoloy 909, etc. can be mentioned.

  There is no restriction | limiting in particular about the shape of a ceramic member and a metal member, According to the use application of a ceramic-metal joined body, it can select suitably. In the ceramic-metal joined body of the present embodiment, both the ceramic member and the metal member have conductivity. For example, the ceramic member can be used as a resistor such as a heater or another ceramic member. A ceramic electrode terminal connected to the resistor can be used, and the metal member can be an electrode terminal or an electrode wiring for applying a voltage to the ceramic member.

  Regarding the production of the metal member, a metal member having a desired shape can be produced by conventionally known metal processing.

  Moreover, there is no restriction | limiting in particular as a brazing material used in order to join a ceramic member and a metal member, A conventionally well-known brazing material can be used. For example, a brazing material containing nickel (Ni), iron (Fu), copper (Cu), silver (Ag), aluminum (Al), titanium (Ti), and the like can be given. In particular, since the strength of the joint portion is high and a joint excellent in heat resistance, corrosion resistance, impact resistance and the like can be realized, for example, BNi-2 (Japanese Industrial Standard), BNi-5 (Japanese Industrial Standard), As a suitable example, FP-613 (trade name) manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. can be mentioned.

  The brazing material described above is, for example, chromium (Cr), silicon (Si), phosphorus (P), boron (B), manganese (Mn), molybdenum (Mo), aluminum (Al), magnesium (Mg), At least one additive selected from the group consisting of calcium (Ca), sodium (Na), zirconium (Zr), beryllium (Be), barium (Ba), titanium (Ti), and lithium (Li) It may be included. What further contains such an additive can improve bonding reliability.

  Although there is no restriction | limiting in particular about the content rate of such an additive, For example, it is preferable that it is contained (added) in the ratio of 0.1-50 mass% in the brazing material, 5-40 mass% More preferably, it is a ratio.

  The brazing material is a mixture of a diffusion inhibitor containing at least one element selected from the group consisting of zirconium, titanium, tantalum, niobium, vanadium, tungsten, molybdenum, chromium, and manganese. May be.

  For example, if the Si-SiC ceramic and the metal are in a state of being brazed well, the components of the ceramic may flow from the ceramic into the brazing material and the metal material, and deteriorate the brazing material and the metal material. is there. Examples of the deterioration of the brazing filler metal and the metal material due to the diffusion component from the ceramic include a decrease in oxidation resistance, a decrease in heat resistance (melting point), and a decrease in strength. For this reason, as described above, it is preferable to further mix (contain) a diffusion inhibitor containing a specific element in the brazing material to prevent the diffusion component from flowing out of the ceramic.

  By constituting in this way, the diffusion component from the ceramics can form a compound with the component of the diffusion inhibitor contained in the brazing filler metal, and block (block) the diffusion component to the brazing filler metal or metal material. .

Moreover, as a characteristic of the diffusion inhibitor containing a specific element, the linear expansion coefficient α is preferably 10 × 10 ⁻⁶ or less, and more preferably 5 × 10 ⁻⁶ or less. By comprising in this way, the linear expansion coefficient of a brazing material can be lowered | hung and the thermal stress between ceramics and a metal can be relieve | moderated.

  Although there is no restriction | limiting in particular about the content rate of a spreading | diffusion prevention agent, For example, it is preferable to contain in the ratio of 0.1-50 mass% in a brazing material, and it is the ratio of 1-20 mass%. Further preferred.

  Although not particularly limited, the brazing material described above is preferably in the form of a paste, a wire, or a foil in which a small amount of binder is mixed with a particulate brazing material, and more preferably in the form of a paste. . Although there is no restriction | limiting in particular about the magnitude | size of particle | grains, it is preferable that it is 0.1-500 micrometers, and it is still more preferable that it is 5-150 micrometers. Although there is no restriction | limiting in particular about the wire diameter of a wire, It is preferable that it is 0.05-3 mm, and it is still more preferable that it is 0.1-1 mm. In the case of the foil shape, the thickness is not particularly limited, but is preferably 0.1 to 200 μm, and more preferably 5 to 150 μm, for example. By comprising in this way, it becomes possible to perform favorable brazing material joining.

  Further, although not particularly limited, in the method for manufacturing a ceramic-metal joined body of the present embodiment, as shown in FIG. 2, at least a part of the brazing material 333 (the brazing material 333a) is at least a metal member. The ceramic-metal joined body 300 may be manufactured by joining the ceramic material 331 and the metal material 332 while infiltrating the inside of the 332. Here, FIG. 2 shows a ceramic-metal joined body produced by another embodiment of the method for producing a ceramic-metal joined body of the present invention, and shows a cross section orthogonal to the joint surface between the ceramic member and the metal member. It is a schematic diagram.

  That is, in the method for manufacturing a ceramic-metal joined body according to this embodiment, it is preferable to use a brazing material made of a material that can penetrate into the metal member as the brazing material for joining the ceramic member and the metal member. By using such a brazing material, the brazing material does not exist as a layer (brazing material layer) on the joint surface between the ceramic member and the metal member, and the ceramic-metal joined body by the brazing material layer. It is possible to effectively prevent a decrease in mechanical strength, heat resistance and corrosion resistance.

  The method for joining the ceramic member and the metal member is not particularly limited. As described above, for example, the first joining surface (more specifically, the surface coated with the reducing agent) of the ceramic member and the metal member. A method of joining a ceramic member and a metal member in a state in which a brazing material is sandwiched by laminating the brazing material between the second joining surfaces of the ceramic member and heating the laminated body; For example, a method of pouring molten solder (brazing material) into the gap between the member and the metal member can be used.

  The atmosphere, temperature conditions, pressure applied to the joined body, etc. at the time of joining are appropriately set according to the type of brazing material used, the material of the metal member, the shape of the ceramic member and the metal member, the size of the joining surface, etc. be able to. In particular, it is preferable to perform bonding with a favorable degree of vacuum, a temperature below the melting point of the metal member, and a pressure below the breaking strength of the ceramic member. As specific conditions, for example, the degree of vacuum is preferably 1 Pa or less, more preferably 0.1 Pa or less, and particularly preferably 0.01 Pa or less. About temperature, the temperature of 580-1140 degreeC is preferable, It is more preferable that it is 780-1090 degreeC, It is especially preferable that it is 890-1050 degreeC. The pressure is preferably 2 MPa or less, more preferably 0.5 MPa or less, and particularly preferably no load.

  In the method of manufacturing the ceramic-metal joined body according to the present embodiment, the ceramic member has a plurality of ceramic members extending from one end surface 11 serving as a fluid flow path to the other end surface 12 as shown in FIGS. A cylindrical honeycomb structure portion 4 having a porous partition wall 1 for defining cells 2 and an outer peripheral wall 3 located at the outermost periphery (disposed so as to surround the outer periphery of the entire partition wall 1); Honeycomb structure including a pair of electrode portions 21 and 21 disposed on the side surface of the structure portion 4 and electrode terminal protrusions 22 and 22 disposed on the respective surfaces of the pair of electrode portions 21 and 21 20 and the metal member is a metal terminal portion or metal wiring made of a metal material that is electrically connected to the electrode terminal protrusions 22, 22 (in FIG. 3 and FIG. 4, the metal terminal portions 23, 23, Electrode terminal protrusions 22, 22 Can also be applied to a method of manufacturing a metal bonded body) - electrode with honeycomb structure 100A that is a showing a connected state) (ceramics.

  This honeycomb structure with electrode 100A is made of the above-described honeycomb structure 20 made of a conductive ceramic material containing silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles. The electrode terminal protrusions 22 and 22 as ceramic members and the metal terminal portions 23 and 23 as metal members are joined via a brazing material. Here, FIG. 3 is a perspective view schematically showing a honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention, and FIG. It is a schematic diagram which shows the cross section parallel to the cell extending direction of the honeycomb structure with an electrode shown. FIG. 5 is a side view showing the honeycomb structure of the honeycomb structure with an electrode shown in FIG. 3, and FIG. 6 is a schematic diagram showing an A-A ′ cross section of the honeycomb structure shown in FIG. FIG. 7 is an enlarged cross-sectional view showing the electrode terminal protrusion and the metal terminal portion of the honeycomb structure with an electrode shown in FIG.

  In such a honeycomb structure with electrode 100A, the honeycomb structure 20 is made of a ceramic material containing silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles. When a current is passed between the pair of electrode portions 21 and 21 disposed on the side surfaces of the honeycomb structure, the honeycomb structure portion 4 generates heat and can be suitably used as a heater. In the honeycomb structure 20, a plurality of silicon carbide particles are bonded by silicon so as to form pores between the silicon carbide particles.

  And the honeycomb structure with electrode 100A is coated with the reducing agent on the surface (that is, the first bonding surface) of the electrode terminal protrusion 22 to which the brazing material is bonded, whereby the electrode terminal protrusion 22 is formed. The oxide film on the surface is removed by reduction. For this reason, the metal terminal parts 23 and 23 and the electrode terminal protrusion part 22 are favorably joined in a state in which high conductivity is ensured, that is, with low electrical resistance.

  Further, since the honeycomb structure part 4, the electrode part 21, and the electrode terminal protrusion part 22 are both made of a ceramic material containing silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles, Since the thermal expansion coefficients of the constituent members are close to each other and the bonding strength is high, the electrode portion 21 can be disposed on the side surface of the honeycomb structure portion 4 very simply. For example, it is not possible to obtain sufficient bonding strength by directly disposing a metal electrode portion on the honeycomb structure portion 4 made of a ceramic material. For example, when a honeycomb structure part with a thin partition wall and a low strength is joined to a metal, the honeycomb structure part may be damaged by thermal stress generated due to a difference in thermal expansion coefficient. That is, in such a honeycomb structure with electrodes, up to the electrode terminal protrusions constituting a part of the honeycomb structure is formed of a conductive ceramic material, and the electrode terminal protrusions made of the ceramic material are formed. Then, the metal terminal portion or the metal wiring made of a metal material is bonded by brazing material bonding by applying the bonding method in the ceramic-metal bonded body of the present embodiment described so far.

  In the honeycomb structured body 100A with an electrode, when a voltage is applied between the metal terminal portions 23 and 23, a current flows through the electrode terminal protruding portion 22 and the electrode portion 21 to the honeycomb structured portion 4, and the honeycomb structured portion 4 becomes a resistor. It generates heat.

  Conventionally, when exhaust gas is treated with a catalyst supported on a honeycomb structure, it is necessary to raise the temperature of the catalyst to a predetermined temperature. For example, when starting an engine, the catalyst temperature is low and the exhaust gas is not sufficiently purified. However, in such a honeycomb structure with an electrode, a voltage can be applied to the honeycomb structure portion to generate heat, so that the honeycomb structure is appropriately determined as necessary regardless of the operating state of the engine. The temperature can be raised to

  The electrode terminal protrusion described above is a terminal on the honeycomb structure side for ensuring electrical connection with an electrical wiring or the like for applying a voltage to the honeycomb structure, and the electrode terminal protrusion is electrically connected to the electric power from the power source. The metal terminal part to which wiring etc. were connected is electrically connected. In a conventional honeycomb structure, for example, when bonding a ceramic material and a metal material, extremely complicated bonding such as physical vapor deposition or chemical vapor deposition has been required. Since the electrode terminal protrusion made of the material and the metal terminal made of the metal material are joined in a state of being electrically connected via the brazing material, excellent heat resistance and high resistance are achieved by a simple method. Bonding with impact resistance has been realized.

  The voltage applied between the pair of electrode parts (in other words, the respective metal terminal parts joined to the electrode terminal protrusions) is appropriately selected depending on the temperature at which the honeycomb structure is heated, the material of the honeycomb structure part, and the like. For example, 50 to 300V is preferable, and 100 to 200V is more preferable. For example, when a power supply with a voltage of 200 V is used in an electric system of an automobile, it is preferable to apply the voltage of 200 V.

  In such a honeycomb structure with an electrode, the electrode terminal protrusion is formed in a convex shape or a concave shape, and the shape of the metal terminal portion at the joint portion with the electrode terminal protrusion is a complementary shape. It is preferably formed in a concave shape or a convex shape. 3 to 7 show an example in which the electrode terminal protrusion 22 is formed in a convex shape and the metal terminal portion is formed in a concave shape. In addition, as shown in FIG. 8, the pole terminal projection part 22 may be formed in a concave shape, and the metal terminal part may be formed in a convex shape. Here, FIG. 8 shows electrode terminal protrusions in a cross section perpendicular to the cell extending direction of a honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is an expanded sectional view which expands and shows a metal terminal part.

  For example, as shown in FIG. 7, when the electrode terminal protrusion 22 is formed in a convex shape and the metal terminal portion 23 is formed in a concave shape, the metal terminal portion 23 is The thickness of the wall portion forming the concave shape is preferably 0.05 to 5 mm, more preferably 0.1 to 2 mm, and particularly preferably 0.2 to 1 mm. By configuring in this way, the apparent strength of the metal terminal portion is reduced, and stress (specifically, thermal stress generated by the difference in thermal expansion) on the convex electrode terminal protrusion is reduced, and heat It is possible to effectively prevent breakage of the electrode terminal protrusion and the metal terminal due to the cycle, and peeling of the joint portion due to the brazing material. In addition, since the thickness of the wall part which forms above-mentioned concave shape changes with the magnitude | sizes of an electrode terminal protrusion part and a metal terminal part, it is not limited to an above-described range.

  Further, for example, as shown in FIG. 9, the honeycomb structure has the electrode terminal protrusion 22 formed in a convex shape and the metal terminal portion 23 formed in a concave shape. The end surface shape of the wall portion forming the concave shape is preferably a tapered shape such that the inner peripheral side of the concave shape protrudes. By comprising in this way, the compressive and tensile stress in the end surface of the wall part which forms the concave shape of the metal terminal part 23 can be made small. Here, FIG. 9 shows electrode terminal protrusions in a cross section orthogonal to the cell extending direction of a honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is an expanded sectional view which expands and shows a metal terminal part.

  In addition, in the honeycomb structure with electrodes described so far, an example in which the electrode terminal protrusion and the metal terminal are joined via the brazing material is shown. Alternatively, a honeycomb structure with an electrode in which metal wiring is directly joined with a brazing material may be used. In other words, the oxide film on the surface of the electrode terminal protrusion is oxidized and removed by the reducing agent described so far, so that any shape of metal material can be bonded with good brazing material in a state where high conductivity is ensured. The shape on the metal member side is not particularly limited.

  The electrode portion and the electrode terminal protrusion may be made of a conductive ceramic material having the same ratio of silicon carbide particles to silicon, or made of a conductive ceramic material having a different ratio. Also good. In addition, when the component of an electrode part and the component of an electrode terminal protrusion part are the same (or close) component, since the thermal expansion coefficient of an electrode part and an electrode terminal protrusion part becomes the same (or close) value, it is preferable. Further, since the materials are the same (or close), the bonding strength between the electrode portion and the electrode terminal protrusion is also increased. Therefore, even when a thermal stress is applied to the honeycomb structure, it is possible to satisfactorily prevent the electrode terminal protrusion from being peeled off from the electrode part or the joint between the electrode terminal protrusion and the electrode part being damaged. .

  As shown in FIGS. 3 to 7, the electrode terminal protrusion 22 is preferably composed of a square plate-like substrate 22 a and a columnar protrusion 22 b (convex portion). By adopting such a shape, the electrode terminal protrusion 22 can be firmly bonded to the electrode portion 21 by the substrate 22a, and the electric wiring can be reliably bonded by the protrusion 22b.

  In the electrode terminal protrusion 22, the thickness of the substrate 22a is preferably 1 to 5 mm. By setting it as such thickness, the electrode terminal protrusion part 22 can be joined to the electrode part 21 reliably. If it is thinner than 1 mm, the substrate 22a becomes weak, and the protrusion 22b may be easily detached from the substrate 22a. If it is thicker than 5 mm, the space for arranging the honeycomb structure may become larger than necessary.

  In the electrode terminal protrusion 22, the length (width) of the substrate 22a in the “circumferential direction R of the honeycomb structure 4” is 20 times the length of the electrode 21 in the “circumferential direction R of the honeycomb structure 4”. It is preferably -100%, and more preferably 30-100%. By setting it as such a range, the electrode terminal protrusion part 22 becomes difficult to remove | deviate from the electrode part 21. FIG. If it is shorter than 20%, the electrode terminal protrusion 22 may be easily detached from the electrode portion 21. In the electrode terminal protrusion 22, the length of the substrate 22 a in the “cell 2 extending direction” is preferably 5 to 30% of the length of the honeycomb structure 4 in the cell extending direction. By setting the length of the substrate 22a in the “direction in which the cells 2 extend” within such a range, sufficient bonding strength can be obtained. If the length of the substrate 22 a in the “cell 2 extending direction” is shorter than 5% of the length of the honeycomb structure portion 4 in the cell extending direction, the substrate 22 a may be easily detached from the electrode portion 21. And if it is longer than 30%, the mass may increase.

  In the electrode terminal protrusion 22, the thickness of the protrusion 22b is preferably 3 to 20 mm. By setting it as such thickness, the projection part 22b and the metal terminal part 23 can be joined more firmly. If it is thinner than 3 mm, the protrusion 22b may be easily broken. If it is thicker than 20 mm, it may be difficult to connect to the metal terminal portion 23. Further, the length of the protrusion 22b is preferably 3 to 20 mm. With such a length, the metal terminal portion 23 can be satisfactorily bonded to the protruding portion 22b. If it is shorter than 3 mm, it may be difficult to join the metal terminal portion 23. If it is longer than 20 mm, the protrusion 22b may be easily broken.

  As shown in FIG. 4, the electrode terminal protrusion 22 is preferably arranged at the center of the electrode portion 21 in the “direction in which the cell 2 extends”. Thereby, it becomes easy to heat the whole honeycomb structure part 4 uniformly.

  The volume electrical resistance of the electrode terminal protrusion 22 at 400 ° C. is preferably 0.01 to 2.0 Ωcm, and more preferably 0.01 to 1.0 Ωcm. By setting the volume electrical resistance of the electrode terminal protrusion 22 at 400 ° C. in such a range, current can be efficiently supplied from the electrode terminal protrusion 22 to the electrode section 21 in a pipe through which high-temperature exhaust gas flows. Can do. If the volume electrical resistance at 400 ° C. of the electrode terminal protrusion 22 is smaller than 0.01 Ωcm, it may be deformed during manufacturing. If the volume electrical resistance at 400 ° C. of the electrode terminal protrusion 22 is larger than 2.0 Ωcm, it may be difficult to supply a current to the electrode portion 21 because the current hardly flows.

  The electrode terminal protrusion 22 preferably has an average pore diameter of 5 to 50 μm, and more preferably 10 to 35 μm. When the average pore diameter of the electrode terminal protrusion 22 is within such a range, an appropriate volume electric resistance can be obtained. If the average pore diameter of the electrode terminal protrusion 22 is smaller than 5 μm, it may be deformed during manufacture. When the average pore diameter of the electrode terminal protrusion 22 is larger than 50 μm, the strength of the electrode terminal protrusion 22 may be reduced. In particular, when the strength of the protrusion 22b is reduced, the protrusion 22b may be easily broken. The average pore diameter is a value measured with a mercury porosimeter.

  In addition, the electrical resistance at 400 ° C. of the honeycomb structure with electrode 100A measured at “between the electrode terminal protrusions disposed on each of the pair of electrode portions 21 and 21” is preferably 1 to 20Ω. More preferably, it is 3 to 10Ω. If the electrical resistance at 400 ° C. is smaller than 1Ω, it is not preferable because an excessive current flows when the honeycomb structure 20 is energized by a 200 V power source. When the electrical resistance at 400 ° C. is greater than 20Ω, it is not preferable because current hardly flows when the honeycomb structure 20 is energized by a 200 V power source. The electrical resistance at 400 ° C. of the honeycomb structure is a value measured by the two-terminal method.

  Moreover, there is no restriction | limiting in particular about the kind of metal material which comprises a metal terminal part, For example, it is preferable that a low thermal expansion metal is used and it can reduce the thermal stress at the time of a heat cycle (heating cooling). Specific examples of the metal material include Kovar, SUS430, Incoloy 909, and the like.

  With respect to the total of “mass of silicon carbide particles as an aggregate” contained in the honeycomb structure part 4 constituting the honeycomb structure 20 and “mass of silicon as a binder” contained in the honeycomb structure part 4, The ratio of “mass of silicon as a binder” contained in the honeycomb structure part 4 is preferably 10 to 40% by mass, and more preferably 25 to 35% by mass. If it is lower than 10% by mass, the strength of the honeycomb structure may be lowered. If it is higher than 40% by mass, the shape may not be maintained during firing.

  The partition wall thickness constituting the honeycomb structure part 4 is preferably 50 to 150 μm, and more preferably 70 to 100 μm. By setting the partition wall thickness in such a range, even when the honeycomb structure 20 is used as a catalyst carrier and a catalyst is supported, it is possible to suppress an excessive increase in pressure loss when exhaust gas flows. When the partition wall thickness is less than 50 μm, the strength of the honeycomb structure may be reduced. When the partition wall thickness is greater than 150 μm, the exhaust gas is not emitted when the honeycomb structure 20 is used as a catalyst carrier and a catalyst is supported. The pressure loss when flowing may become too large.

The honeycomb structure portion 4 preferably has a cell density of 40 to 200 cells / cm ² , and more preferably 70 to 100 cells / cm ² . By setting the cell density in such a range, the purification performance of the catalyst can be enhanced while reducing the pressure loss when the exhaust gas is flowed. When the cell density is lower than 40 cells / cm ² , the catalyst supporting area may be reduced. When the cell density is higher than 200 cells / cm ² , the honeycomb structure 20 is used as a catalyst carrier to support the catalyst. In addition, the pressure loss when the exhaust gas flows may become too large.

  The average particle diameter of the silicon carbide particles (aggregate) constituting the honeycomb structure part 4 is preferably 3 to 30 μm, and more preferably 5 to 20 μm. By setting the average particle diameter of the silicon carbide particles constituting the honeycomb structure portion 4 in such a range, the volume electrical resistance of the honeycomb structure 20 at 400 ° C. can be 1 to 20 Ωcm. When the average particle diameter of the silicon carbide particles is smaller than 3 μm, the volume electrical resistance at 400 ° C. of the honeycomb structure 20 may increase. If the average particle diameter of the silicon carbide particles is larger than 30 μm, the volume electrical resistance at 400 ° C. of the honeycomb structure 20 may be reduced. If the average particle diameter of the silicon carbide particles is larger than 30 μm, the extrusion forming die may be clogged with the forming raw material when the honeycomb formed body is extruded. The average particle diameter of the silicon carbide particles is a value measured by a laser diffraction method.

  Moreover, the volume electrical resistance at 400 ° C. of the honeycomb structure part 4 is preferably 1 to 20 Ωcm, and more preferably 3 to 10 Ωcm. If the volume electrical resistance at 400 ° C. is less than 1 Ωcm, an excessive current flows when the honeycomb structure 20 is energized by a 200 V power source (the voltage is not limited to 200 V), which is not preferable. When the volume electrical resistance at 400 ° C. is greater than 20 Ωcm, it is preferable that current does not flow easily when the honeycomb structure 20 is energized by a 200 V power source (the voltage is not limited to 200 V), and may not generate sufficient heat. Absent. The volume electrical resistance at 400 ° C. of the honeycomb structure is a value measured by the two-terminal method.

  Moreover, the electrical resistance of the honeycomb structure 20 at 400 ° C. is preferably 1 to 20Ω, and more preferably 3 to 10Ω. If the electrical resistance at 400 ° C. is less than 1Ω, for example, when the honeycomb structure 20 is energized by a 200 V power source (the voltage is not limited to 200 V), an excessive current flows, which is not preferable. If the electrical resistance at 400 ° C. is greater than 20Ω, for example, when the honeycomb structure 20 is energized by a 200 V power source (the voltage is not limited to 200 V), it is not preferable because the current hardly flows. The electrical resistance at 400 ° C. of the honeycomb structure is a value measured by the two-terminal method.

  The volume electrical resistance at 400 ° C. of the electrode part 21 is preferably lower than the volume electrical resistance at 400 ° C. of the honeycomb structure part 4. Further, the volume electrical resistance at 400 ° C. of the electrode part 21 is more preferably 20% or less of the volume electrical resistance of the honeycomb structure part 4 at 400 ° C., particularly preferably 1 to 10%. By setting the volume electrical resistance of the electrode portion 21 at 400 ° C. to 20% or less of the volume electrical resistance of the honeycomb structure portion 4 at 400 ° C., the electrode portion 21 functions more effectively as an electrode.

  The porosity of the partition wall 1 is preferably 35 to 60%, more preferably 45 to 55%. A porosity of less than 35% is not preferable because deformation during firing increases. If the porosity exceeds 60%, the strength of the honeycomb structure decreases, which is not preferable. The porosity is a value measured with a mercury porosimeter.

  The average pore diameter of the partition wall 1 is preferably 2 to 15 μm, and more preferably 4 to 8 μm. If the average pore diameter is smaller than 2 μm, the volume electric resistance becomes too large, which is not preferable. If the average pore diameter is larger than 15 μm, the volume electric resistance becomes too small, which is not preferable. The average pore diameter is a value measured with a mercury porosimeter.

  Moreover, it is preferable that the partition wall 1 and the outer peripheral wall 3 constituting the honeycomb structure portion 4 are mainly composed of silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles. It may be formed only from. Even when the partition wall 1 and the outer peripheral wall 3 are formed only of silicon carbide and silicon, a trace amount of impurities of 10% by mass or less may be contained. When the partition wall 1 and the outer peripheral wall 3 contain a substance (a trace amount of impurities) other than “silicon carbide and silicon”, examples of other substances contained in the partition wall 1 and the outer peripheral wall 3 include silicon oxide and strontium. be able to. Here, when “the partition wall 1 and the outer peripheral wall 3 are mainly composed of silicon carbide particles and silicon”, the partition wall 1 and the outer peripheral wall 3 contain 90% by mass or more of silicon carbide particles and silicon. Means that

  As shown in FIGS. 3 to 6, each of the pair of electrode portions 21 and 21 extends in the cell 2 extension direction of the honeycomb structure portion 4 and extends between both end portions (between both end surfaces 11 and 12). It is preferable to be formed. And in the cross section orthogonal to the extending direction of the cell 2, one electrode portion 21 in the pair of electrode portions 21, 21 is formed of the honeycomb structure portion 4 with respect to the other electrode portion 21 in the pair of electrode portions 21, 21. It is preferable that the central portion O be disposed on the opposite side. Thus, the electrode portion 21 is formed in a strip shape, the longitudinal direction of the strip-shaped electrode portion 21 extends in the direction in which the cells 2 of the honeycomb structure portion 4 extend, and the electrode portion 21 further includes the honeycomb structure portion 4. Since it extends between both end portions (between both end surfaces 11 and 12), the entire honeycomb structure portion 4 can be heated more uniformly. In addition, in the cross section orthogonal to the extending direction of the cell 2, one electrode portion 21 in the pair of electrode portions 21, 21 is formed of the honeycomb structure portion 4 with respect to the other electrode portion 21 in the pair of electrode portions 21, 21. By arranging the central portion O on the opposite side across the center portion O, the entire honeycomb structure portion 4 can be heated more evenly.

  The length (width) of the electrode portion 21 in the “circumferential direction R of the honeycomb structure portion 4” is 1/30 to the length of the side surface 5 of the honeycomb structure portion 4 in the circumferential direction R (length of the outer periphery). It is preferably 1/4, and more preferably 1/30 to 1/10. By setting it as such a range, the whole honeycomb structure part 4 can be heated more uniformly. If the length (width) of the electrode portion 21 in the circumferential direction R of the honeycomb structure portion 4 is shorter than 1/30 of the length of the side surface 5 of the honeycomb structure portion 4 in the circumferential direction R, heat cannot be generated uniformly. There is. If it is longer than ¼, the vicinity of the center portion of the honeycomb structure portion 4 may be difficult to be heated.

  The thickness of the electrode portion 21 is preferably 0.2 to 2.0 mm, and more preferably 0.5 to 1.5 mm. By setting it within such a range, heat can be generated uniformly. If the thickness of the electrode part 21 is less than 0.2 mm, the electrical resistance may increase and heat may not be generated uniformly. If it is thicker than 2.0 mm, it may be damaged during canning.

  The electrode part 21 is preferably disposed on the surface of the outer peripheral wall 3 as shown in FIG. 10A. Moreover, the electrode part 21 may be arrange | positioned so that it may be embedded inside the outer peripheral wall 3, as shown to FIG. 10B. Further, as shown in FIGS. 10C and 10D, the electrode portion 21 is partially embedded (in the side in contact with the outer peripheral wall) inside the outer peripheral wall 3, and the remaining part (on the front surface side). It is also a preferable aspect that a part) is out of the outer peripheral wall 3 (to the surface side). FIG. 10C shows an aspect in which the thickness of the portion embedded in the outer peripheral wall 3 of the electrode 21 is thinner than the thickness of the outer peripheral wall 3. FIG. 10D shows a mode in which the thickness of the portion embedded in the outer peripheral wall 3 of the electrode 21 is the same as the thickness of the outer peripheral wall 3.

  Here, FIGS. 10A to 10D are outer peripheral walls in a cross section orthogonal to the cell extending direction of a honeycomb structure with an electrode manufactured by still another embodiment of the method for manufacturing a ceramic-metal joined body of the present invention. It is a schematic diagram which shows the state by which the electrode part was arrange | positioned. 10A to 10D, only a part of the outer peripheral wall 3 and one electrode portion 21 are shown, and the partition walls and the like are not shown.

  The electrode part 21 is composed mainly of silicon carbide particles and silicon, and the component of the electrode part 21 and the component of the honeycomb structure part 4 are the same (or close) components. The thermal expansion coefficient of 4 is the same (or close). Further, since the materials are the same (or close), the bonding strength between the electrode portion 21 and the honeycomb structure portion 4 is also increased. For this reason, even if thermal stress is applied to the honeycomb structure, it is possible to prevent the electrode portion 21 from peeling off from the honeycomb structure portion 4 and the joint portion between the electrode portion 21 and the honeycomb structure portion 4 from being damaged. be able to. The electrode terminal protrusion 22 is also composed mainly of silicon carbide particles and silicon, and can be manufactured using the same conductive ceramic material as the electrode portion 21.

  The volume electric resistance of the electrode portion 21 at 400 ° C. is preferably 0.1 to 2.0 Ωcm, and more preferably 0.1 to 1.0 Ωcm. By setting the volume electrical resistance of the electrode portion 21 at 400 ° C. in such a range, the pair of electrode portions 21 and 21 effectively serve as electrodes in the pipe through which high-temperature exhaust gas flows. If the volume electrical resistance at 400 ° C. of the electrode portion 21 is smaller than 0.1 Ωcm, it may be deformed during manufacturing. If the volume electrical resistance of the electrode portion 21 at 400 ° C. is larger than 2.0 Ωcm, it may be difficult to play a role as an electrode because current hardly flows.

  The electrode part 21 preferably has a porosity of 30 to 45%, more preferably 30 to 40%. When the porosity of the electrode portion 21 is within such a range, a suitable volume electric resistance can be obtained. If the porosity of the electrode portion 21 is lower than 30%, it may be deformed during manufacturing. When the porosity of the electrode part 21 is higher than 45%, the volume electrical resistance may become too high. The porosity is a value measured with a mercury porosimeter.

  The electrode portion 21 preferably has an average pore diameter of 5 to 20 μm, and more preferably 7 to 15 μm. When the average pore diameter of the electrode portion 21 is in such a range, a suitable volume electric resistance can be obtained. When the average pore diameter of the electrode part 21 is smaller than 5 μm, the volume electric resistance may become too high. When the average pore diameter of the electrode part 21 is larger than 20 μm, the strength is weak and the electrode part 21 may be damaged. The average pore diameter is a value measured with a mercury porosimeter.

  It is preferable that the average particle diameter of the silicon carbide particle contained in the electrode part 21 is 10-60 micrometers, and it is still more preferable that it is 20-60 micrometers. When the average particle diameter of the silicon carbide particles contained in the electrode part 21 is in such a range, the volume electrical resistance of the electrode part 21 at 400 ° C. can be 0.1 to 2.0 Ωcm. When the average pore diameter of the silicon carbide particles contained in the electrode part 21 is smaller than 10 μm, the volume electric resistance at 400 ° C. of the electrode part 21 may become too large. If the average pore diameter of the silicon carbide particles contained in the electrode portion 21 is larger than 60 μm, the strength of the electrode portion 21 may be weak and may be damaged. The average particle diameter of the silicon carbide particles contained in the electrode part 21 is a value measured by a laser diffraction method.

  The ratio of the mass of silicon contained in the electrode portion 21 with respect to the “total mass of silicon carbide particles and silicon” contained in the electrode portion 21 is preferably 20 to 40% by mass. More preferably, it is mass%. When the ratio of the mass of silicon to the total mass of silicon carbide particles and silicon contained in the electrode portion 21 is in such a range, an appropriate volume electric resistance can be obtained. When the ratio of the mass of silicon to the total mass of silicon carbide particles and silicon contained in the electrode portion 21 is smaller than 20 mass%, the volume electrical resistance may be excessively increased. And when larger than 40 mass%, it may become easy to deform | transform at the time of manufacture.

  In such a honeycomb structure with electrode 100A, the porosity of the electrode portion 21 is 30 to 45%, the average pore diameter of the electrode portion is 5 to 20 μm, and the “silicon carbide particles contained in the electrode portion 21” The ratio of the “mass of silicon” contained in the electrode part 21 to the “total of the respective masses of silicon and silicon” is 20 to 40% by mass, and the average particle diameter of the silicon carbide particles contained in the electrode part 21 is It is 10-60 micrometers, and it is preferable that the volume electrical resistance of the electrode part 21 is 0.1-2.0 ohm-cm. Thereby, especially the honeycomb structure can generate heat uniformly during energization.

  In such a honeycomb structure with an electrode, when a tangent line that is in contact with the outer periphery of the honeycomb structure portion is drawn at the central portion in the circumferential direction of the honeycomb structure portion in a cross section orthogonal to the cell extending direction. The tangent line is preferably parallel to any partition wall. This makes it difficult to break during canning.

  Moreover, it is preferable that the thickness of the outer peripheral wall 3 which comprises the outermost periphery of the honeycomb structure 20 is 0.1-2 mm. If it is thinner than 0.1 mm, the strength of the honeycomb structure 20 may be lowered. If it is thicker than 2 mm, the area of the partition wall supporting the catalyst may be small.

  In the honeycomb structure 20, the shape of the cell 2 in a cross section orthogonal to the extending direction of the cell 2 is preferably a square or a hexagon. By making the cell shape in this way, the pressure loss when exhaust gas flows through the honeycomb structure 20 is reduced, and the purification performance of the catalyst is excellent.

The shape of the honeycomb structure 20 is not particularly limited. For example, the bottom surface is a circular cylinder (cylindrical shape), the bottom surface is an oval cylinder, the bottom surface is a polygon (square, pentagon, hexagon, heptagon, An octagonal shape or the like can be used. The honeycomb structure preferably has a bottom area of 2000 to 20000 mm ² , and more preferably 4000 to 10000 mm ² . The length of the honeycomb structure in the central axis direction is preferably 50 to 200 mm, and more preferably 75 to 150 mm.

  The isostatic strength of the honeycomb structure 20 is preferably 1 MPa or more. When the isostatic strength is less than 1 MPa, the honeycomb structure may be easily damaged when used as a catalyst carrier or the like. Isostatic strength is a value measured by applying hydrostatic pressure in water.

(2) Manufacturing method of ceramic-metal joined body (second manufacturing method):
Next, one embodiment of a second method for producing a ceramic-metal bonded body (hereinafter, “second production method”) will be described.

  As shown in FIGS. 11A to 11C, the method for manufacturing a ceramic-metal joined body according to the present embodiment is made of a ceramic material having conductivity, a ceramic member 231 having a first joint surface 231 a, and a metal material. The ceramic-metal joined body 200 formed by joining the metal member 232 having the second joining surface 232a through the brazing material 233 and joining the ceramic member 231 and the metal member 232 through the brazing material 233. It is a manufacturing method of the ceramic-metal joined body provided with the process of manufacturing. In addition, about the joining method by a brazing material, the method similar to the 1st manufacturing method demonstrated so far can be used suitably. For example, in FIGS. 11A to 11C, the first bonding surface 231a and the second bonding surface 232a are stacked in a state where the first bonding surface 231a and the second bonding surface 232a are disposed so as to face each other with the brazing material 233 interposed therebetween, thereby obtaining the ceramic-metal laminate 240. The process of manufacturing the ceramic-metal joined body 200 in which the ceramic member 231 and the metal member 232 are joined through the brazing material 233 by heating the obtained ceramic-metal laminate 240 is shown.

  In the embodiment of the second manufacturing method, for example, a paste-like brazing material 233 mixed with a reducing agent having a reducing property is used as the brazing material 233, and the brazing material 233 is used to form a ceramic member. The first joint surface 231a of 231 is reduced.

  That is, in the first manufacturing method described so far, the oxide film on the first joint surface is reduced and removed by applying a reducing agent having a reducing property to the first joint surface of the ceramic member. However, in the method for manufacturing a ceramic-metal joined body according to this embodiment, as shown in FIGS. 11A to 11C, a brazing material 233 mixed with a reducing agent having a reducing property is used as the brazing material 233. Thus, the oxide film 231x formed on the first bonding surface 231a of the ceramic member 231 can be reduced and removed at the time of bonding with the brazing material 233.

  By comprising in this way, the effect similar to the 1st manufacturing method of this invention demonstrated until now can be acquired. That is, the ceramic material and the metal material having conductivity can be satisfactorily joined by brazing in a state in which high conductivity is secured between the members, that is, with low electrical resistance.

  Furthermore, in the method for manufacturing a ceramic-metal bonded body according to the present embodiment, since the brazing material contains a reducing agent, for example, the second bonded surface of the metal member is oxidized to form an oxide film. Even in this case, the oxide film formed on the metal member side can be removed, and an extremely good electrical connection can be achieved. Originally, the surface of the metal member is rarely oxidized, but an oxide film may be formed by, for example, natural oxidation. According to the method for manufacturing a ceramic-metal joined body of this embodiment, Such oxide films can also be reduced.

  Further, in this embodiment, the step of applying the reducing agent is omitted as compared with the first manufacturing method, and the manufacturing process is extremely simple. In other words, the conductive ceramic material and the metal material are joined together in a state in which high conductivity is ensured between the members, that is, with low electrical resistance, by the same procedure as in the conventional manufacturing method using brazing filler metal. can do.

  In addition, as a ceramic member and a metal member used for the manufacturing method of the ceramic-metal joined body of this embodiment, it is the same as that of the ceramic member and metal member demonstrated in embodiment of the 1st manufacturing method demonstrated so far. What was comprised in can be used.

  The brazing material used in the method for producing a ceramic-metal joined body of the present embodiment can reduce and remove the oxide film formed on the first joining surface of the ceramic member in the brazing material component. A reducing agent mixed (contained).

  The reducing agent is selected from the group consisting of, for example, chromium, silicon, boron, potassium, sodium, manganese, tantalum, niobium, vanadium, titanium, lithium, aluminum, magnesium, zirconium, barium, calcium, beryllium, and fluorine. It is preferable that it contains at least one element. As such a reducing agent, the same reducing agent used in the first production method can be used.

  Moreover, there is no restriction | limiting in particular as a brazing material with which such a reducing agent is mixed, A conventionally well-known paste-like brazing material can be used. For example, a paste-like brazing material mainly composed of nickel (Ni), iron (Fu), copper (Cu), silver (Ag), aluminum (Al), titanium (Ti), and the like can be given. In particular, since the strength of the joint portion is high and a joint excellent in heat resistance, corrosion resistance, impact resistance, and the like can be realized, for example, Ni solder such as “BNi-2” of Japanese Industrial Standard can be mentioned. .

  In addition, there is no restriction | limiting in particular about the quantity of the reducing agent mixed (contained) in a brazing material, For example, it is preferable that a reducing agent is 0.1-30 mass parts with respect to 100 mass parts of brazing materials. More preferably, it is 5 to 15 parts by mass. When the content of the reducing agent is less than 1 part by mass, the amount of the reducing agent that acts on the first bonding surface of the ceramic member is too small when the brazing material is bonded, and the reducing agent is formed on the first bonding surface. In some cases, the oxide film cannot be sufficiently removed. On the other hand, if the content of the reducing agent is more than 30 parts by mass, brazing failure may be caused.

  In addition, the method for joining the ceramic member and the metal member using the brazing material containing such a reducing agent is the same method as the joining method of the ceramic member and the metal member in the first manufacturing method. Can be done by.

  The brazing material described above is, for example, chromium (Cr), silicon (Si), phosphorus (P), boron (B), manganese (Mn), molybdenum (Mo), aluminum (Al), magnesium (Mg), At least one additive selected from the group consisting of calcium (Ca), sodium (Na), zirconium (Zr), beryllium (Be), barium (Ba), titanium (Ti), and lithium (Li) It may be included. What further contains such an additive can improve bonding reliability. In addition, the preferable range of the content rate of an additive is the same as that of a 1st manufacturing method.

  The brazing material is a mixture of a diffusion inhibitor containing at least one element selected from the group consisting of zirconium, titanium, tantalum, niobium, vanadium, tungsten, molybdenum, chromium, and manganese. May be.

  Although not particularly limited, the brazing material described above is preferably in the form of a paste in which a small amount of binder is mixed with particulate brazing material. Although there is no restriction | limiting in acquisition about the magnitude | size of particle | grains, it is preferable that it is 0.1-500 micrometers, and it is still more preferable that it is 5-150 micrometers. By comprising in this way, it becomes possible to perform favorable brazing material joining.

  Although not particularly limited, in the method for manufacturing a ceramic-metal joined body according to the present embodiment, as shown in FIG. 2, at least a part of the brazing material 333 (the brazing material 333a) is at least a metal member. The ceramic-metal joined body 300 may be manufactured by joining the ceramic material 331 and the metal material 332 while infiltrating the inside of the 332.

  Also in this second manufacturing method, as in the first manufacturing method, the ceramic member is formed from one end surface 11 serving as a fluid flow path to the other end surface 12 as shown in FIGS. A tubular honeycomb structure portion 4 having a porous partition wall 1 defining a plurality of extending cells 2 and an outer peripheral wall 3 located at the outermost periphery (disposed so as to surround the outer periphery of the entire partition wall 1); And a pair of electrode portions 21 and 21 disposed on the side surface of the honeycomb structure portion 4, and electrode terminal protrusions 22 and 22 disposed on the respective surfaces of the pair of electrode portions 21 and 21. In the honeycomb structure 20, the metal member is a metal terminal portion or metal wiring made of a metal material electrically connected to the electrode terminal protrusions 22 and 22 (in FIGS. 3 and 4, the metal terminal portion 23, 23 with an electrode) It can also be applied to a method of manufacturing a - (metal bonded ceramics) cam structure 100A.

(3) Ceramics-metal joint:
Next, an embodiment of the ceramic-metal bonded body of the present invention will be described. The ceramic-metal joined body of the present embodiment includes a ceramic member made of a ceramic material having conductivity and a metal member, and the ceramic member and the metal member are at least a joining surface (hereinafter referred to as a metal member) of the ceramic member. The ceramic-metal joined body is joined through the brazing material in a state where the “first joining surface” is also reduced with a reducing agent having reducing properties.

  Such a ceramic-metal joined body of this embodiment can be manufactured by the first manufacturing method and the second manufacturing method described so far. That is, the ceramic-metal bonded body according to the present embodiment, for example, after applying a reducing agent 134 having a reducing property to the first bonding surface 131a of the ceramic member 131 as shown in FIGS. 1A to 1D, A ceramic-metal bonded body 100 (a ceramic-metal bonded body manufactured by the first manufacturing method) in which the ceramic member 131 and the metal member 132 are bonded via the brazing material 133 can be given.

  Moreover, as shown in FIGS. 11A to 11C, a brazing material in which a ceramic member 231 having a first joint surface 231a and a metal member 232 having a second joint surface 232a are mixed with a reducing agent having a reducing property. The ceramic-metal joined body 200 (ceramic-metal joined body manufactured by the second manufacturing method) bonded via 233 may be used.

  Further, in the ceramic-metal joined body of the present embodiment, the ceramic member partitions a plurality of cells 2 extending from one end surface 11 serving as a fluid flow path to the other end surface 12 as shown in FIGS. A cylindrical honeycomb structure portion 4 having a porous partition wall 1 to be formed and an outer peripheral wall 3 located at the outermost periphery (disposed so as to surround the outer periphery of the entire partition wall 1); A honeycomb structure 20 including a pair of electrode portions 21 and 21 disposed on a side surface and electrode terminal protrusions 22 and 22 disposed on respective surfaces of the pair of electrode portions 21 and 21; The metal member is a metal terminal portion or metal wiring made of a metal material electrically connected to the electrode terminal protrusions 22 and 22 (FIGS. 3 and 4 show the case of the metal terminal portions 23 and 23). Honeycomb structure 1 with electrode A 0A may be.

  As described above, the ceramic-metal bonded body according to the present embodiment includes the ceramic member and the metal member via the brazing material in a state in which the first bonding surface of the ceramic member is reduced by the reducing agent having reducing properties. Is a ceramic-metal bonded body formed by bonding, so that a ceramic member made of a ceramic material having conductivity and a metal member made of a metal material are bonded in a state in which high conductivity is ensured. The conductive ceramic member is a resistor such as a heater or a ceramic electrode terminal connected to a resistor as another ceramic member, and the metal member applies a voltage to the resistor. Therefore, the electrical resistance at the bonding interface between the ceramic member and the metal member can be reduced It can be.

  In addition, about each component of the ceramic member, metal member, and brazing material which comprise the ceramic-metal joined body of this embodiment, it is the manufacturing method (the 1st manufacturing method and the 2nd of the ceramic-metal joined body of this invention). It is preferable that the ceramic member, the metal member, and the brazing material described in the manufacturing method) are configured in the same manner.

  Next, the manufacturing method of the honeycomb structure with an electrode shown in FIGS. 3-7 as an example of the ceramic-metal joined body of this embodiment is demonstrated.

  First, metal silicon (metal silicon powder), a binder, a surfactant, a pore former, water, and the like are added to silicon carbide powder (silicon carbide) to produce a forming raw material. It is preferable that the mass of the metal silicon is 10 to 30% by mass with respect to the total of the mass of the silicon carbide powder and the mass of the metal silicon. The average particle diameter of the silicon carbide particles in the silicon carbide powder is preferably 3 to 30 μm, and more preferably 5 to 20 μm. The average particle diameter of metal silicon (metal silicon powder) is preferably 2 to 20 μm. If it is smaller than 2 μm, the volume electric resistance may become too small. If it is larger than 20 μm, the volume electric resistance may become too large. The average particle diameter of silicon carbide particles and metal silicon (metal silicon particles) is a value measured by a laser diffraction method. The silicon carbide particles are silicon carbide fine particles constituting the silicon carbide powder, and the metal silicon particles are metal silicon fine particles constituting the metal silicon powder. The total mass of the silicon carbide particles and the metal silicon is preferably 30 to 78 mass% with respect to the mass of the entire forming raw material.

  Examples of the binder include methyl cellulose, hydroxypropyl methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. Among these, it is preferable to use methyl cellulose and hydroxypropoxyl cellulose in combination. The content of the binder is preferably 2 to 10% by mass with respect to the entire forming raw material.

  The water content is preferably 20 to 60% by mass with respect to the entire forming raw material.

  As the surfactant, ethylene glycol, dextrin, fatty acid soap, polyalcohol and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type. The content of the surfactant is preferably 2% by mass or less with respect to the whole forming raw material.

  The pore former is not particularly limited as long as it becomes pores after firing, and examples thereof include graphite powder, starch, foamed resin, water absorbent resin, and silica gel. The pore former content is preferably 10% by mass or less based on the entire forming raw material. The average particle diameter of the pore former is preferably 10 to 30 μm. If it is smaller than 10 μm, pores may not be formed sufficiently. If it is larger than 30 μm, the die may be clogged during molding. The average particle diameter of the pore former is a value measured by a laser diffraction method.

  Moreover, it is preferable that a shaping | molding raw material contains strontium carbonate as a sintering auxiliary agent. The content of the sintering aid is preferably 0.1 to 3% by mass with respect to the entire forming raw material.

  Next, the forming raw material is kneaded to form a clay. There is no restriction | limiting in particular as a method of kneading | mixing a shaping | molding raw material and forming a clay, For example, the method of using a kneader, a vacuum clay kneader, etc. can be mentioned.

  Next, the kneaded material is extruded to form a honeycomb formed body. In extrusion molding, it is preferable to use a die having a desired overall shape, cell shape, partition wall thickness, cell density and the like. As the material of the die, a cemented carbide which does not easily wear is preferable. The honeycomb formed body has a structure having porous partition walls that define and form a plurality of cells serving as fluid flow paths and an outer peripheral wall located at the outermost periphery.

  The partition wall thickness, cell density, outer peripheral wall thickness, and the like of the honeycomb formed body can be appropriately determined according to the structure of the honeycomb structure of the present invention to be manufactured in consideration of shrinkage during drying and firing.

  It is preferable to dry the obtained honeycomb formed body. The drying method is not particularly limited, and examples thereof include an electromagnetic heating method such as microwave heating drying and high-frequency dielectric heating drying, and an external heating method such as hot air drying and superheated steam drying. Among these, the entire molded body can be dried quickly and uniformly without cracks, and after drying a certain amount of moisture with an electromagnetic heating method, the remaining moisture is dried with an external heating method. It is preferable to make it. As drying conditions, it is preferable to remove moisture of 30 to 99% by mass with respect to the amount of moisture before drying by an electromagnetic heating method, and then to make the moisture to 3% by mass or less by an external heating method. As the electromagnetic heating method, dielectric heating drying is preferable, and as the external heating method, hot air drying is preferable.

  When the length in the central axis direction of the honeycomb formed body is not a desired length, it is preferable that both end faces (both end portions) are cut to a desired length. The cutting method is not particularly limited, and examples thereof include a method using a circular saw cutting machine.

  Next, an electrode part forming raw material for forming the electrode part is prepared. When the main components of the electrode part are silicon carbide and silicon, the electrode part forming raw material is preferably formed by adding a predetermined additive to silicon carbide powder and silicon powder and kneading.

  Specifically, metal silicon (metal silicon powder), a binder, a surfactant, a pore former, water, and the like are added to silicon carbide powder (silicon carbide) and kneaded to prepare an electrode part forming raw material. It is preferable that the mass of the metal silicon is 20 to 40% by mass with respect to the total of the mass of the silicon carbide powder and the mass of the metal silicon. The average particle diameter of the silicon carbide particles in the silicon carbide powder is preferably 10 to 60 μm. The average particle diameter of metal silicon (metal silicon powder) is preferably 2 to 20 μm. If it is smaller than 2 μm, the volume electric resistance may become too small. If it is larger than 20 μm, the volume electric resistance may become too large. The average particle diameter of silicon carbide particles and metal silicon (metal silicon particles) is a value measured by a laser diffraction method. The silicon carbide particles are silicon carbide fine particles constituting the silicon carbide powder, and the metal silicon particles are metal silicon fine particles constituting the metal silicon powder. The total mass of the silicon carbide particles and the metal silicon is preferably 40 to 80% by mass with respect to the mass of the entire electrode part forming raw material.

  Examples of the binder include methyl cellulose, hydroxypropyl methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. Among these, it is preferable to use methyl cellulose and hydroxypropoxyl cellulose in combination. The content of the binder is preferably 0.1 to 15% by mass with respect to the entire electrode part forming raw material.

  The water content is preferably 10 to 45 mass% with respect to the entire electrode part forming raw material.

  As the surfactant, ethylene glycol, dextrin, fatty acid soap, polyalcohol and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type. The content of the surfactant is preferably 2% by mass or less with respect to the entire electrode part forming raw material.

  The pore former is not particularly limited as long as it becomes pores after firing, and examples thereof include graphite powder, starch, foamed resin, water absorbent resin, and silica gel. The pore former content is preferably 10% by mass or less based on the entire electrode part forming raw material. The average particle diameter of the pore former is preferably 5 to 50 μm. If it is smaller than 5 μm, pores may not be formed sufficiently. If it is larger than 50 μm, the die may be clogged during molding. The average particle diameter of the pore former is a value measured by a laser diffraction method.

  Moreover, it is preferable that an electrode part formation raw material contains strontium carbonate as a sintering aid. The content of the sintering aid is preferably 0.1 to 3% by mass with respect to the entire electrode part forming raw material.

  Next, a paste-like electrode part is formed by kneading a mixture obtained by mixing silicon carbide powder (silicon carbide), metal silicon (metal silicon powder), a binder, a surfactant, a pore former, water, and the like. It is preferable to use it as a raw material. The method of kneading is not particularly limited, and for example, a vertical stirrer can be used.

  Next, it is preferable to apply the obtained electrode part forming raw material to the side surface of the dried honeycomb formed body. The method for applying the electrode part forming raw material to the side surface of the honeycomb formed body is not particularly limited, and for example, a printing method can be used. The electrode part forming raw material is preferably applied to the side surface of the honeycomb formed body so as to have the shape of the electrode part in the honeycomb structure of the present invention. The thickness of an electrode part can be made into desired thickness by adjusting the thickness when apply | coating an electrode part formation raw material. Thus, since the electrode part can be formed simply by applying the electrode part forming raw material to the side surface of the honeycomb formed body, drying and firing, the electrode part can be formed very easily.

  Next, it is preferable to dry the electrode part forming raw material applied to the side surface of the honeycomb formed body. The drying conditions are preferably 50 to 100 ° C.

  Next, it is preferable to produce a member for forming an electrode terminal protrusion. The electrode terminal protrusion forming member is attached to the honeycomb formed body to become an electrode terminal protrusion. The shape of the electrode terminal protrusion forming member can be formed in various shapes described in the embodiment of the honeycomb structure. And it is preferable to affix the obtained electrode terminal protrusion part forming member to the part by which the electrode part formation raw material was apply | coated of the honeycomb molded object to which the electrode part formation raw material was apply | coated. In addition, the order of preparation of the honeycomb formed body, preparation of the electrode part forming raw material, and preparation of the electrode terminal protrusion part forming member may be any order.

  The electrode terminal protrusion forming member is preferably obtained by molding and drying an electrode terminal protrusion forming raw material (raw material for forming the electrode terminal protrusion forming member). The electrode terminal protrusion forming raw material is preferably formed by adding predetermined additives to silicon carbide powder and silicon powder and kneading them.

  Specifically, metal silicon (metal silicon powder), a binder, a surfactant, a pore former, water, etc. are added to silicon carbide powder (silicon carbide) and kneaded to produce an electrode terminal protrusion forming raw material. To do. It is preferable that the mass of the metal silicon is 30 to 80% by mass with respect to the total of the mass of the silicon carbide powder and the mass of the metal silicon. The average particle diameter of the silicon carbide particles in the silicon carbide powder is preferably 30 to 100 μm. The average particle diameter of metal silicon (metal silicon powder) is preferably 0.1 to 50 μm. If it is smaller than 0.1 μm, handling may become difficult and the cost may increase. If it is larger than 50 μm, the volume electric resistance may become too large. The average particle diameter of silicon carbide particles and metal silicon (metal silicon particles) is a value measured by a laser diffraction method. The silicon carbide particles are silicon carbide fine particles constituting the silicon carbide powder, and the metal silicon particles are metal silicon fine particles constituting the metal silicon powder. The total mass of the silicon carbide particles and the metal silicon is preferably 50 to 85 mass% with respect to the mass of the entire electrode terminal protrusion forming raw material.

  Examples of the binder include methyl cellulose, hydroxypropyl methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. Among these, it is preferable to use methyl cellulose and hydroxypropoxyl cellulose in combination. The binder content is preferably 1 to 15 mass% with respect to the entire electrode terminal protrusion forming raw material.

  The water content is preferably 10 to 45 mass% with respect to the entire electrode terminal protrusion forming raw material.

  As the surfactant, ethylene glycol, dextrin, fatty acid soap, polyalcohol and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type. The content of the surfactant is preferably 2% by mass or less based on the entire electrode terminal protrusion forming raw material.

  The pore former is not particularly limited as long as it becomes pores after firing, and examples thereof include graphite powder, starch, foamed resin, water absorbent resin, and silica gel. The pore former content is preferably 10% by mass or less based on the entire electrode terminal protrusion forming raw material. The average particle diameter of the pore former is preferably 5 to 50 μm. If it is smaller than 5 μm, pores may not be formed sufficiently. If it is larger than 50 μm, the die may be clogged during molding. The average particle diameter of the pore former is a value measured by a laser diffraction method.

  A method of mixing and kneading silicon carbide powder (silicon carbide), metal silicon (metal silicon powder), a binder, a surfactant, a pore former, water and the like is not particularly limited, and for example, a kneader is used. it can.

  Moreover, the method of shape | molding the obtained electrode terminal protrusion part forming raw material and making it the shape of the member for electrode terminal protrusion part formation is not specifically limited, The method of processing after extrusion molding can be mentioned.

  It is preferable that the electrode terminal protrusion forming raw material is formed into the shape of the electrode terminal protrusion forming member and then dried to obtain the electrode terminal protrusion forming member. The drying conditions are preferably 50 to 100 ° C.

  Next, the electrode terminal protrusion forming member is preferably attached to the honeycomb formed body to which the electrode portion forming raw material is applied. The method for attaching the electrode terminal protrusion forming member to the honeycomb formed body (the portion where the electrode part forming raw material of the honeycomb formed body is applied) is not particularly limited, but the electrode terminal protrusion is formed using the electrode part forming raw material. It is preferable to attach the member for use to the honeycomb formed body. For example, an electrode part forming raw material is applied to the “surface that adheres to the honeycomb formed body (surface that contacts the honeycomb formed body)” of the electrode terminal protrusion forming member, and the “surface on which the electrode part forming raw material is applied” is the honeycomb surface. The electrode terminal protrusion forming member is preferably attached to the honeycomb molded body so as to be in contact with the molded body.

  Then, the honeycomb formed body to which the electrode part forming raw material is applied and the electrode terminal protrusion forming member is attached is dried and fired, and the honeycomb structure part and a pair of the honeycomb structure part disposed on the side surface of the honeycomb structure part are disposed. And electrode terminal protrusions disposed on the respective surfaces of the pair of electrode portions.

  The drying conditions at this time are preferably 50 to 100 ° C.

  Moreover, in order to remove a binder etc. before baking, it is preferable to perform temporary baking. Pre-baking is preferably performed at 400 to 500 ° C. for 0.5 to 20 hours in an air atmosphere. The method of temporary baking and baking is not particularly limited, and baking can be performed using an electric furnace, a gas furnace, or the like. The firing conditions are preferably 1400 to 1500 ° C. for 1 to 20 hours in an inert atmosphere such as nitrogen or argon. Moreover, after baking, it is preferable to perform an oxidation process at 1200-1350 degreeC for 1 to 10 hours for durability improvement.

  The electrode terminal protrusion forming member may be attached before firing the honeycomb formed body, or may be attached after firing. When the electrode terminal protrusion forming member is attached after the honeycomb formed body is fired, it is preferably fired again under the above conditions.

  Next, a metal terminal portion made of a metal material is produced. The metal terminal portion may be manufactured before the honeycomb structure portion is manufactured.

  In addition, it is preferable to form the shape of a metal terminal part in the concave shape or convex shape from which the shape in a junction part with an electrode terminal protrusion part becomes a complementary shape. As a metal material for forming the metal terminal portion, Kovar can be suitably used.

  Next, the obtained metal terminal part and the electrode terminal protrusion part arrange | positioned at the surface of a pair of electrode part arrange | positioned at the side surface of a honeycomb structure part are joined through a brazing material. At this time, a reducing agent having a reducing property is applied to the surface (that is, the first bonding surface) of the electrode terminal protruding portion that is bonded to the metal member, and the first bonding surface of the electrode terminal protruding portion is coated. The oxide film on the first joint surface of the electrode terminal protrusion is reduced and removed at the time of joining by reducing and removing the oxide film or by joining the brazing material using a brazing material mixed with a reducing agent having reducing properties. It is preferable.

For example, when a reducing agent having reducing properties is applied, a flux containing a reducing agent containing H ₃ BO ₄ as a main component as a reducing component is applied to the first joint surface of the electrode terminal protrusion in the flux. Coating is performed so that the amount of the reducing agent applied is 22 g / m ² . Although there is no restriction | limiting in particular about the coating method, For example, it can carry out by dipping. Thereafter, the metal terminal portion and the electrode terminal protrusion portions disposed on the surfaces of the pair of electrode portions disposed on the side surfaces of the honeycomb structure portion are joined to each other through a brazing material by a conventionally known method.

On the other hand, when joining a brazing material using a brazing material containing a reducing agent having reducibility, H ₃ BO ₃ is mainly used as a reducing component in a brazing material mainly composed of BNi-2 (Japanese Industrial Standard). A brazing material containing a reducing agent is prepared by containing a reducing agent as a component at a ratio (mass ratio) of 20: 1. Thereafter, the brazing material is disposed between the metal terminal portion and the electrode terminal protrusion portion disposed on the surface of the pair of electrode portions disposed on the side surface of the honeycomb structure portion, and 10 ⁻¹ Pa or less. In a vacuum furnace, the electrode terminal protrusion and the metal terminal are joined to each other while being electrically connected via a brazing material by heating to 1000 ° C. or higher. In this way, a honeycomb structure with an electrode as shown in FIGS. 3 to 7 can be manufactured.

  About the kind of brazing material, the brazing material explained so far in the embodiment of the method for producing a ceramic-metal joined body can be appropriately selected and used, and the reducing agent (reducing component) has also been used so far. The elements used in the reducing agent described in 1 can be appropriately selected and used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1
Silicon carbide (SiC) powder and metal silicon (Si) powder are mixed at a mass ratio of 70:30, and strontium carbonate as a sintering aid, hydroxypropylmethylcellulose as a binder, and a water absorbent resin as a pore former. At the same time, water was added to form a forming raw material, and the forming raw material was kneaded with a vacuum kneader to prepare a clay.

  The obtained clay was molded using an extrusion molding machine to obtain a round bar-shaped unfired ceramic member. The obtained unfired ceramic member was dried and then fired to prepare a ceramic member having an end face diameter of 8.3 mm and a length of 20 mm. Thereafter, in order to improve the durability of the ceramic member, oxidation treatment was performed at 1200 ° C. for 24 hours to form a protective film (oxide film) made of silicon oxide on the surface of the ceramic member.

  On the other hand, as a metal member, two cap-shaped metal terminals having an inner diameter of 8.4 mm and an inner dimension of 8 mm (depth of the cap-shaped recess) were produced by cutting. In addition, the thickness of a recessed part is 0.5 mm.

When joining the ceramic member and the metal member obtained in this way via a brazing material, a reducing agent containing H ₃ BO ₃ as a reducing component is applied to the surface (first joining surface) of the ceramic member. The protective film (oxide film) on the first bonding surface was reduced and removed.

  Thereafter, the ceramic member and the metal member are joined to the brazing material using a paste-like Ni-based brazing material containing 5% of a diffusion inhibitor containing tungsten (W) in a state where the reducing agent is applied. Thus, a ceramic-metal joined body was produced.

The conditions for joining with the brazing material were a vacuum atmosphere of 10 ⁻² Pa or less and a temperature of 1000 ° C. or more.

  The ceramic-metal joined body thus obtained was subjected to the measurement of the electrical resistance between the ceramic member and the metal member and the evaluation of the thermal endurance test by the following method. The results are shown in Table 1.

(Electrical resistance)
The obtained ceramic-metal bonded body was measured for electric resistance (Ω) using a four-probe method.

(Cooling durability test)
The obtained ceramic-metal bonded body was repeatedly heated and lowered in an atmospheric furnace at 800 ° C. and 650 ° C., and then the appearance and the brazed part were evaluated every 100 cycles. The number of cycles in which damage was found in the brazing metal or ceramic member was evaluated as the durability of this sample.

(Example 2)
As shown in Table 1, a ceramic-metal joined body was produced in the same manner as in Example 1 except that a brazing material containing no diffusion inhibitor was used. The obtained ceramic-metal bonded body was subjected to measurement of electric resistance and evaluation of a thermal endurance test. The results are shown in Table 1.

(Comparative Example 1)
A ceramic-metal joined body was produced in the same manner as in Example 1 except that the step of applying the reducing agent was not performed. The obtained ceramic-metal bonded body was subjected to measurement of electric resistance and evaluation of a thermal endurance test. The results are shown in Table 1.

(Comparative Example 2)
A ceramic-metal joined body was produced in the same manner as in Example 2 except that the step of applying the reducing agent was not performed. The obtained ceramic-metal bonded body was subjected to measurement of electric resistance and evaluation of a thermal endurance test. The results are shown in Table 1.

(result)
As shown in Table 1, the ceramic-metal joined bodies obtained in Examples 1 and 2 had low electrical resistance, and Example 1 was also excellent in durability. On the other hand, the ceramic-metal joined bodies obtained in Comparative Examples 1 and 2 had extremely high electrical resistance compared to the Examples. That is, the ceramic-metal bonded body obtained in Comparative Examples 1 and 2 has an oxide film as a protective film on the bonded surface of the ceramic member, and this oxide film causes an electrical connection between the ceramic member and the metal member. It is presumed that the resistance has increased. Further, it was confirmed that a joined body having a low electrical resistance was obtained in the same manner as in Examples 1 and 2 when a reducing agent was mixed in the brazing material to produce a ceramic-metal joined body.

  The method for producing a ceramic-metal joined body of the present invention is suitable as a method for producing a joined body of dissimilar materials in which a conductive ceramic material and a metal material are joined together while securing high electrical conductivity by brazing. Can be used.

  Moreover, the ceramic-metal joined body of the present invention can be used as a joined body in which a conductive ceramic material and a metal material are electrically connected and joined. For example, a ceramic member can be used as a heater or the like. Use a resistor or a ceramic electrode terminal connected to a resistor as another ceramic member, and use a metal member as a joined body as an electrode terminal or electrode wiring for applying a voltage to the ceramic member. Can do.

1: partition wall, 2: cell, 3: outer peripheral wall, 4: honeycomb structure part, 5: side face, 11: one end face, 12: other end face, 20: honeycomb structure, 21: electrode part, 22: electrode terminal Projection, 22a: substrate, 22b: projection, 23: metal terminal, 24: brazing material, 25: gap, 26: crystallized glass, 27: metal coating, 31, 131, 231, 331: ceramic member, 131a , 231a: first bonding surface, 131x: oxide film, 32, 132, 232, 332: metal member, 132a, 232a: second bonding surface, 33, 133, 233, 333: brazing material, 333a: brazing material (Brazing material permeating into the metal member), 134: reducing agent, 100, 200, 300: ceramic-metal joined body, 100A: ceramic-metal joined body (honeycomb structure with electrode), 140, 40: ceramic - metal laminate, O: center, R: circumferential direction.

Claims (10)

A ceramic member made of a ceramic material having electrical conductivity and having a first joint surface and a metal member made of a metal material and having a second joint surface are joined via a brazing material, Comprising a step of producing a ceramic-metal joined body in which the metal member is joined via the brazing material,
The ceramic material constituting the ceramic member contains silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles.
The reducing member having a reducing property is applied to the first bonding surface of the ceramic member to reduce and remove the oxide film on the first bonding surface, and then the oxide member is reduced and removed. A method for producing a ceramic-metal joined body, wherein the first joining surface and the second joining surface of the metal member are joined via the brazing material. A ceramic member made of a ceramic material having electrical conductivity and having a first joint surface and a metal member made of a metal material and having a second joint surface are joined via a brazing material, Comprising a step of producing a ceramic-metal joined body in which the metal member is joined via the brazing material,
The ceramic material constituting the ceramic member contains silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles.
A brazing material mixed with a reducing agent having a reducing property is used as the brazing material, and the brazing material reduces the first joint surface of the ceramic member to reduce the oxide film on the first joint surface. A method for producing a ceramic-metal joined body to be removed.   The reducing agent is at least one selected from the group consisting of chromium, silicon, boron, potassium, sodium, manganese, tantalum, niobium, vanadium, titanium, lithium, aluminum, magnesium, zirconium, barium, calcium, beryllium, and fluorine. The method for producing a ceramic-metal bonded body according to claim 1 or 2, wherein the compound contains any of the above elements.   As the brazing material, a brazing material further mixed with a diffusion inhibitor containing at least one element selected from the group consisting of zirconium, titanium, tantalum, niobium, vanadium, tungsten, molybdenum, chromium, and manganese is used. The method for producing a ceramic-metal joined body according to any one of claims 1 to 3.   The method for producing a ceramic-metal bonded body according to any one of claims 1 to 4, wherein the ceramic material and the metal material are bonded while allowing at least a part of the brazing material to penetrate into the metal material. The ratio of the mass of the silicon contained in the ceramic material to the total mass of the silicon carbide particles and the silicon contained in the ceramic material is 20 to 40% by mass . The method for producing a ceramic-metal joined body according to any one of the above. As the ceramic member, a cylindrical honeycomb structure portion having a porous partition wall defining a plurality of cells extending from one end surface to the other end surface serving as a fluid flow path, and an outer peripheral wall located at the outermost periphery; A honeycomb structure including a pair of electrode portions disposed on a side surface of the honeycomb structure portion, and electrode terminal protrusions disposed on respective surfaces of the pair of electrode portions,
The method for producing a ceramic-metal bonded body according to any one of claims 1 to 6 , wherein a metal terminal portion or a metal wiring made of a metal material electrically connected to the electrode terminal protrusion is used as the metal material. A ceramic member made of a ceramic material having conductivity, and a metal member;
The ceramic member is a ceramic member formed of the ceramic material containing silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles;
The ceramic member and the metal member are formed in a state in which at least the joint surface of the ceramic member with the metal member is reduced by a reducing agent having a reducing property, so that the oxide film on the joint surface is reduced and removed. A ceramic-metal joined body joined through a brazing material. In the brazing material, at least one selected from the group consisting of chromium, silicon, boron, potassium, sodium, manganese, tantalum, niobium, vanadium, titanium, aluminum, magnesium, zirconium, barium, calcium, beryllium, and fluorine. The ceramic-metal joined body according to claim 8 , comprising a compound containing an element. To the sum of the respective mass of the silicon carbide particles and the silicon contained in the ceramic material, the ratio of the mass of the silicon contained in the ceramic material, to claim 8 or 9, which is 20 to 40 wt% The ceramic-metal bonded body described.

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