WO2019003984A1 - Résistance électrique, structure en nid d'abeilles et dispositif catalyseur chauffé électriquement - Google Patents

Résistance électrique, structure en nid d'abeilles et dispositif catalyseur chauffé électriquement Download PDF

Info

Publication number
WO2019003984A1
WO2019003984A1 PCT/JP2018/023137 JP2018023137W WO2019003984A1 WO 2019003984 A1 WO2019003984 A1 WO 2019003984A1 JP 2018023137 W JP2018023137 W JP 2018023137W WO 2019003984 A1 WO2019003984 A1 WO 2019003984A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
electric
sample
matrix
electrical
Prior art date
Application number
PCT/JP2018/023137
Other languages
English (en)
Japanese (ja)
Inventor
剛大 徳野
淳一 成瀬
平田　和希
美香 川北
泰史 ▲高▼山
Original Assignee
株式会社デンソー
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017243080A external-priority patent/JP6740995B2/ja
Application filed by 株式会社デンソー filed Critical 株式会社デンソー
Priority to CN201880042219.4A priority Critical patent/CN110786075A/zh
Priority to DE112018003319.8T priority patent/DE112018003319T5/de
Publication of WO2019003984A1 publication Critical patent/WO2019003984A1/fr
Priority to US16/728,261 priority patent/US20200154524A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material

Definitions

  • the present disclosure relates to an electric resistor, a honeycomb structure, and an electrically heated catalyst device.
  • electric resistors are used for electric heating.
  • an electrically heated catalyst device in which a honeycomb structure supporting a catalyst is formed of an electric resistor such as SiC and the honeycomb structure is heated by electric heating.
  • water is added to a mixed powder consisting of 20 to 35 wt% of metal Si powder, 5 to 15 wt% of quartz powder, 20 to 30 wt% of borosilicate glass, and 30 to 40 wt% of clay powder and kneaded.
  • a conductive ceramic is described which is formed and heat treated at a temperature of 1200 to 1300 ° C. in the atmosphere.
  • the electrical resistivity of the electrical resistor changes significantly with temperature, for example, in a constant voltage control electrical circuit, the fluctuation range of the current flowing through the electrical resistor becomes large. Therefore, the electric circuit becomes complicated to avoid this, and the cost of the electric circuit increases.
  • an electrical resistor that exhibits NTC characteristics such as SiC
  • the temperature change of the electrical resistivity is large and the electrical resistivity decreases as the temperature rises
  • the current is concentrated in a short distance between electrodes during current heating. Flow locally and generate heat locally. Therefore, an electrical resistor exhibiting NTC characteristics is likely to cause temperature distribution.
  • a thermal expansion difference is generated inside the electric resistor, and the electric resistor is easily broken.
  • the characteristic that the electrical resistivity increases as the temperature rises is called a PTC characteristic.
  • the present disclosure is an electric resistor having a small temperature dependence of the electric resistivity and exhibiting an PTC characteristic of the electric resistivity, or having little temperature dependence of the electric resistivity, and a honeycomb structure using the electric resistor.
  • An object of the present invention is to provide an electrically heated catalyst device using a body and the honeycomb structure.
  • One aspect of the present disclosure is a borosilicate including at least one alkali-based atom selected from the group consisting of Na, Mg, K, Ca, Li, Be, Rb, Sr, Cs, Ba, Fr, and Ra.
  • the electric resistor has a matrix composed of:
  • Another aspect of the present disclosure is a honeycomb structure configured to include the electric resistor.
  • Yet another aspect of the present disclosure is an electrically heated catalyst device having the above honeycomb structure.
  • the electric resistor is made of borosilicate containing at least one alkali-based atom selected from the group consisting of Na, Mg, K, Ca, Li, Be, Rb, Sr, Cs, Ba, Fr, and Ra. It has a matrix that is configured.
  • the region that governs the electrical resistance at the time of electric current heating is the matrix that is the base material.
  • the matrix has a smaller temperature dependency of the electrical resistivity than SiC, and the electrical resistivity exhibits a PTC characteristic. Therefore, when the electrical resistivity of another substance different from the matrix that can be included in the electrical resistor exhibits PTC characteristics, the electrical resistivity of the electrical resistor has a small temperature dependency, and the PTC is It can show the characteristics.
  • the electric resistivity of the other substance shows NTC characteristics
  • the electric resistance of the matrix showing the PTC characteristic and the electric resistivity of the other substance showing the NTC characteristic gives the electric resistance.
  • the electrical resistivity of the body can be designed to have low temperature dependence and to exhibit PTC properties or to have little temperature dependence.
  • the electric resistor by adopting the matrix, the temperature dependency of the electric resistivity is small, and the electric resistivity exhibits the PTC characteristic, or the temperature dependency of the electric resistivity is almost the same. No electrical resistor is obtained.
  • the electric resistor can be configured such that the electric resistivity does not have the NTC characteristic, it becomes possible to avoid current concentration at the time of current heating. Therefore, in the electric resistor, temperature distribution is hard to occur inside, and cracking due to the thermal expansion difference is hard to occur. In addition, although it is possible to prevent generation of a crack due to a thermal expansion coefficient difference by electrically heating SiC with a small current, it takes time to sufficiently heat it.
  • the said electrical resistor can achieve the low electrical resistance of a matrix by employ
  • the honeycomb structure includes the electric resistor. Therefore, in the above-mentioned honeycomb structure, temperature distribution does not easily occur inside the structure at the time of electric current heating, and cracking due to the difference in thermal expansion hardly occurs. In addition, since the above-mentioned electric resistor is used in the above-mentioned honeycomb structure, heat can be generated earlier at a lower temperature at the time of electric heating.
  • the electrically heated catalyst device has the honeycomb structure. Therefore, in the electrically heated catalyst device, the honeycomb structure is less likely to be broken during electric heating, and the reliability can be improved. Further, since the electrically heated catalyst device uses the honeycomb structure, the honeycomb structure can generate heat earlier at a lower temperature during electric heating, which is advantageous for early activation of the catalyst.
  • FIG. 1 is an explanatory view schematically showing a fine structure of the electric resistor according to the first embodiment
  • FIG. 2 is an explanatory view schematically showing a fine structure of the electric resistor according to the second embodiment
  • FIG. 3 is an explanatory view schematically showing a honeycomb structure of Embodiment 3.
  • FIG. 4 is an explanatory view schematically showing an electrically heated catalyst device of Embodiment 4.
  • FIG. 5 is a graph showing the relationship between the temperature and the electrical resistivity of Sample 1 and Sample 2 in Experimental Example 1, FIG.
  • FIG. 6 is a graph showing the relationship between the temperature and the electrical resistivity of Sample 2 and Sample 1C in Experimental Example 1
  • FIG. 7 is a graph showing the relationship between the addition ratio of sodium carbonate and the electrical resistivity of the sample in Experimental Example 2
  • FIG. 8 shows (a) an atomic mapping image of aluminum of sample 2 and (b) an optical microscope image of the periphery of the emission portion in Experimental Example 3
  • FIG. 9 is an atomic mapping image of aluminum in the vicinity of the emission part of Sample 2 in Experimental Example 4
  • FIG. 10 shows the result of analysis of the composition of Sample 2 by SEM-EDX in Experimental Example 5
  • 11 is a graph showing the relationship between the temperature and the electrical resistivity of Sample 6 and Sample 7 in Experimental Example 6, FIG.
  • FIG. 12 is an atomic mapping image of a cross section of a material of Sample 6 in Experimental Example 6
  • FIG. 13 is an atomic mapping image of a cross section of a material of sample 7 in Experimental Example 6
  • FIG. 14 is a line profile of Ca in the depth direction from the material surface of sample 6 in Experimental Example 6
  • FIG. 15 is a line profile of Ca in the depth direction from the material surface of sample 7 in Experimental Example 6
  • FIG. 16 is a graph showing the relationship between the temperature and the electrical resistivity of Samples 8 and 9 (baked product at 1250 ° C.) in Experimental Example 7
  • FIG. 17 is a graph showing the relationship between the temperature and the electrical resistivity of Samples 10 to 12 (baked article at 1300 ° C.) in Experimental Example 7.
  • the electric resistor 1 of the present embodiment has a matrix 10.
  • the matrix 10 is a portion to be a base material of the electric resistor 1.
  • the matrix 10 may be amorphous or crystalline.
  • the matrix 10 is made of Na (sodium), Mg (magnesium), K (potassium), Ca (calcium), Li (lithium), Be (beryllium), Rb (rubidium), Sr (strontium), Cs (cesium), Ba. It is comprised from the borosilicate containing at least 1 sort (s) of alkali-type atom selected from the group which consists of (barium), Fr (francium), and Ra (radium). Each alkali-based atom may be contained in the borosilicate singly or in any combination. That is, the borosilicate may contain one or more alkali metal atoms, one or more alkaline earth metal atoms, or a combination of these. It is also good.
  • the borosilicate preferably contains at least one selected from the group consisting of Na, Mg, K, and Ca as an alkali atom, from the viewpoint of facilitating reduction of the electrical resistance of the matrix 10 and the like.
  • the borosilicate can include at least Na, K, or both Na and K.
  • the total content of alkali-based atoms can be 10% by mass or less. According to this configuration, the reduction of the electrical resistance of the matrix 10 can be facilitated. Moreover, according to this configuration, the temperature dependence of the electrical resistivity is smaller than that of SiC, and the matrix 10 in which the electrical resistivity exhibits the PTC characteristic can be made reliable.
  • total content of an alkali type atom means the mass% of one type of alkali type atom, when borosilicate contains 1 type of alkali type atoms. Moreover, when borosilicate contains multiple types of alkali-type atoms, the total content (mass%) which added each content (mass%) of each of these several alkali-type atoms is meant.
  • the total content of alkali-based atoms is preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, from the viewpoint of suppression of shape change due to softening point reduction of matrix 10 It can be done.
  • the total content of alkali atoms is more preferably 2 in view of suppression of formation of insulating glass film by segregation of alkali atoms to the surface side of electric resistor 1 at the time of firing in an oxidizing atmosphere.
  • the content may be less than or equal to mass%, more preferably less than or equal to 1.5 mass%, still more preferably less than or equal to 1.2 mass%, and most preferably less than or equal to 1 mass%.
  • the borosilicate specifically includes at least one selected from the group consisting of Na, Mg, K, and Ca as alkali atoms, and the total content of the alkali atoms is 2 It can be set as the mass% or less. According to this configuration, even if the gas barrier film for blocking the oxygen gas is not formed at the time of firing in the atmosphere containing the oxygen gas, the oxygen in the atmosphere is an alkali-based atom eluted and segregated to the surface side of the electric resistor 1 It is easy to suppress the formation of an insulating glass film by reacting with In addition, when using the electric resistor 1 as a material of the conductive honeycomb structure, it is not necessary to remove the insulating glass film in advance when forming the electrode on the surface of the honeycomb structure, and the productivity of the honeycomb structure There is also an advantage that The total content of alkali atoms in this case is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, from the viewpoint of suppression of formation of insulating glass film
  • alkali atoms may be intentionally added. Therefore, it is important to appropriately select the total content of the alkali-based atoms described above depending on the manufacturing conditions, the method of use, and the like.
  • an alkali-based atom is an element which is relatively easy to be mixed from the raw material of the electric resistor 1.
  • the total content of alkali-based atoms is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0. It can be 2% by mass or more.
  • the electric resistance body 1 it becomes possible to aim at reduction of an alkali type atom by using a boric acid as a raw material, without using the borosilicate glass containing an alkali type atom. The details will be described later in experimental examples.
  • the borosilicate can contain B (boron) atoms of 0.1% by mass or more and 5% by mass or less. According to this configuration, there is an advantage that the PTC characteristics can be easily expressed.
  • the content of B atoms is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass from the viewpoint of facilitating reduction of the electrical resistance of the matrix 10 and the like. % Or more, still more preferably 1.2% by mass or more, still more preferably 1.5% by mass or more, still more preferably the temperature dependence of the electrical resistivity is small, and the electrical resistivity is PTC From the viewpoint of easily showing characteristics, etc., it can be more than 2% by mass.
  • the content of B atoms is limited in the amount of doping to the silicate, and when not doped, it is unevenly distributed in the material as B 2 O 3 which is an insulator, which causes a decrease in conductivity, etc. From this, preferably, it can be 4% by mass or less, more preferably, 3.5% by mass or less, and still more preferably, 3% by mass or less.
  • the borosilicate can contain 5 mass% or more and 40 mass% or less of Si (silicon) atoms. According to this configuration, the electrical resistivity of the borosilicate tends to exhibit PTC characteristics.
  • the content of the Si atom is preferably 7% by mass or more, more preferably 10% by mass or more, and still more preferably 15 from the viewpoint of ensuring the above effects and raising the softening point of the matrix. It can be made to be% by mass or more.
  • the content of Si atoms is preferably 30% by mass or less, more preferably 26% by mass or less, and still more preferably 24% by mass or less from the viewpoint of ensuring the above effects and the like. Can.
  • the borosilicate can contain 40% by mass or more and 85% by mass or less of O (oxygen) atoms. According to this configuration, there is an advantage that the PTC characteristics can be easily expressed.
  • the content of O atom is preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and still more preferably, from the viewpoint of ensuring the above effects and the like. , 60 mass% or more.
  • the content of O atom is preferably 82% by mass or less, more preferably 80% by mass or less, and still more preferably 78% by mass or less from the viewpoint of ensuring the above effects and the like. Can.
  • the borosilicate can be specifically an aluminoborosilicate or the like. According to this configuration, the temperature dependency of the electrical resistivity is small, and the electrical resistivity exhibits PTC characteristics, or the temperature resistance of the electrical resistivity has almost no temperature dependency. Can.
  • the aluminoborosilicate can contain an Al atom content of 0.5% by mass or more and 10% by mass or less.
  • the content of Al (aluminum) atom is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more from the viewpoint of ensuring the above effects and the like. be able to.
  • the content of Al atoms is preferably 8% by mass or less, more preferably 6% by mass or less, and still more preferably 5% by mass or less from the viewpoint of ensuring the above effects and the like. Can.
  • content of each atom in the borosilicate mentioned above can be selected from the range mentioned above so that it may be 100 mass% in total.
  • the electric resistor 1 can be made sure that the temperature dependence of the electric resistivity is small and the electric resistivity exhibits a PTC characteristic or the temperature dependence of the electric resistivity is hardly present.
  • an atom which may be contained in the borosilicate which comprises the matrix 10 Fe, C, etc. can be illustrated in addition to the above.
  • each content of an alkali type atom, Si, O, and Al among each atom mentioned above it measures using an electron beam micro analyzer (EPMA) analyzer.
  • EPMA electron beam micro analyzer
  • the content of B is measured using an inductively coupled plasma (ICP) analyzer.
  • ICP inductively coupled plasma
  • the electric resistor 1 may have only the matrix 10 or may have one or more other substances besides the matrix 10.
  • other substances include fillers, materials that lower the coefficient of thermal expansion, materials that increase the thermal conductivity, and materials that improve the strength.
  • the electric resistor 1 further includes a conductive filler 11 as illustrated in FIG. 1.
  • the electric resistivity of the entire electric resistor 1 is determined by the addition of the electric resistivity of the matrix 10 and the electric resistivity of the conductive filler 11. Be done. Therefore, according to this configuration, by adjusting the conductivity of the conductive filler 11 and the content of the conductive filler 11, control of the electric resistivity of the electric resistor 1 becomes possible.
  • the electrical resistivity of the conductive filler 11 may show any of a PTC characteristic and an NTC characteristic, and there may be no temperature dependency of the electrical resistivity.
  • the electric resistor 1 can have the microstructure of the sea-island structure which makes the matrix 10 the sea-like part, and makes the conductive filler 11 an island-like part, as illustrated in FIG.
  • the conductive filler 11 preferably contains Si atoms.
  • the Si atoms of the conductive filler 11 diffuse into the borosilicate, and the borosilicate
  • the silicon enrichment of the salt is promoted, and the softening point of the matrix 10 can be improved. Therefore, according to this configuration, it is possible to improve the shape retentivity of the electric resistor 1, and the electric resistor 1 useful as a material of the structure can be obtained.
  • the honeycomb structure is a structure having thin cell walls. Therefore, the electric resistor 1 according to the above configuration is useful as a material of a conductive honeycomb structure having high structural reliability.
  • Si particles, Fe-Si based particles, Si-W based particles, Si-C based particles, Si- Examples include Mo-based particles and Si-Ti-based particles. These can be used alone or in combination of two or more.
  • the electric resistor 1 When the electric resistor 1 has the matrix 10 and the conductive filler 11, specifically, the electric resistor 1 can be configured to contain the matrix 10 and the conductive filler 11 in a total of 50 vol% or more. .
  • the electric resistor 1 since the matrix 10 composed of the borosilicate described above is adopted, the electric resistance of the matrix 10 can be reduced, and the matrix 10 can also transmit electrons. According to the above configuration, although it depends on the shape of the electric resistor 1, the conductivity of the electric resistor 1 can be reliably ensured by the known percolation theory.
  • the total content of the matrix 10 and the conductive filler 11 is preferably 52 vol% or more, more preferably 55 vol% or more, still more preferably 57 vol% or more, further preferably from the viewpoint of conductivity by formation of percolation, etc. Preferably, it can be 60 vol% or more.
  • the electric resistor 1 has the matrix 10 and the conductive filler 11, electrons flow while traveling through the conductive filler 11 and the matrix 10.
  • the reason why the electric resistor 1 exhibits the PTC characteristic is presumed to be that the electrons moving in the electric resistor 1 are affected by lattice vibration. Specifically, it is presumed that the large polaron reported for Na x WO 3 substances and the like is also generated in the electric resistor 1.
  • the electric resistor 1 can be configured such that a glass film containing an alkali-based atom is not substantially formed on the surface. According to this configuration, when the electric resistor 1 is used as a material of the conductive honeycomb structure, it is not necessary to remove the insulating glass film in advance when forming the electrode on the surface of the honeycomb structure, and the honeycomb structure The improvement of the manufacturability of the body can be ensured.
  • the glass film containing an alkali type atom is not substantially formed on the surface has the following meaning. Even if the glass coating is slightly formed on the surface of the electric resistor 1, the electric heating generates heat in the electric resistor 1 even if the glass coating is not removed when forming the electrode on the surface of the electric resistor 1. In the case where there is no problem in causing the glass coating, it can be assumed that the glass coating is not substantially formed on the surface.
  • the electric resistor 1 In the temperature range from 25 ° C. to 500 ° C., the electric resistor 1 has an electrical resistivity of 0.0001 ⁇ ⁇ m or more and 1 ⁇ ⁇ m or less, and an electric resistance increase rate of 0.01 ⁇ 10 ⁇ 6 / K or more 5
  • the configuration can be in the range of not more than 0 ⁇ 10 ⁇ 4 / K.
  • the electric resistor 1 In the temperature range of 25 ° C. to 500 ° C., the electric resistor 1 has an electric resistivity of 0.0001 ⁇ ⁇ m or more and 1 ⁇ ⁇ m or less, and an electric resistance increase rate of 0 or more and 0.01 ⁇ 10 ⁇ 6. It can be configured to be in the range of less than / K.
  • the electric resistor 1 in which the temperature distribution is not easily generated at the time of electric current heating and the crack due to the thermal expansion difference is not easily generated. Moreover, according to the above configuration, since the electric resistor 1 can generate heat earlier at a lower temperature during electric heating, the material of the honeycomb structure is required to be heated early for early activation of the catalyst. Useful as. When the rate of increase in electrical resistance is in the range of 0 or more and less than 0.01 ⁇ 10 ⁇ 6 / K, it can be considered that the temperature dependence of the electrical resistivity is almost nonexistent.
  • the electrical resistivity of the electrical resistor 1 varies depending on the required specification of the system using the electrical resistor 1 and the like, but from the viewpoint of reducing the electrical resistance of the electrical resistor 1, for example, preferably 0.5 ⁇ ⁇ m or less , More preferably 0.3 ⁇ ⁇ m or less, still more preferably 0.1 ⁇ ⁇ m or less, still more preferably 0.05 ⁇ ⁇ m or less, still more preferably 0.01 ⁇ ⁇ m or less, still more still Preferably, it may be less than 0.01 ⁇ ⁇ m, most preferably 0.005 ⁇ ⁇ m or less.
  • the electrical resistivity of the electrical resistor 1 is preferably 0.0002 ⁇ ⁇ m or more, more preferably 0.0005 ⁇ ⁇ m or more, still more preferably 0.001 ⁇ , from the viewpoint of increase in calorific value at the time of electric current heating. It can be m or more. According to this configuration, the electric resistor 1 suitable for the material of the honeycomb structure used for the electrically heated catalyst device can be obtained.
  • the electrical resistance increase rate of the electric resistor 1 is preferably 0.001 ⁇ 10 ⁇ 6 / K or more, more preferably 0.01 ⁇ 10 6 from the viewpoint of facilitating suppression of the temperature distribution by electric heating. It can be made ⁇ 6 / K or more, more preferably 0.1 ⁇ 10 ⁇ 6 / K or more. It is ideal that the rate of increase in electrical resistance of the electrical resistor 1 does not change from the viewpoint of the presence of an electrical resistance value that is optimal for current heating in an electrical circuit. From this point of view, the rate of increase in electrical resistance of the electrical resistor 1 is preferably 100 ⁇ 10 ⁇ 6 / K or less, more preferably 10 ⁇ 10 ⁇ 6 / K or less, still more preferably 1 ⁇ 10 ⁇ 6 / K. It can be less than or equal to K.
  • the electrical resistor 1 can be manufactured, for example, as follows, but is not limited thereto.
  • a boric acid, a Si atom containing substance, and kaolin are mixed. Or you may mix the borosilicate containing an alkali type atom, Si atom containing substance, and kaolin.
  • the shape of the borosilicate may be fibrous, particulate or the like.
  • the shape of the borosilicate is preferably fibrous from the viewpoint of improving the extrudability of the mixture and the like.
  • the electroconductive filler etc. which contain the Si atom mentioned above can be illustrated.
  • the mass ratio of boric acid can be, for example, 4 or more and 8 or less.
  • the mass ratio of boric acid is within the above range, it becomes easy to obtain the electric resistor 1 having a small temperature dependency of the electric resistivity.
  • content of the boron contained in borosilicate becomes easy to raise by raising the calcination temperature mentioned later.
  • the amount of boron doped in the silicate increases, it is advantageous for reducing the electrical resistance of the electrical resistor 1.
  • binder water
  • binder organic binders, such as a methyl cellulose, can be used, for example.
  • content of a binder can be about 2 mass%, for example.
  • the resulting mixture is then shaped into a predetermined shape.
  • the obtained molded body is fired.
  • the firing conditions can be, for example, under an inert gas atmosphere or in the air, under atmospheric pressure, a firing temperature of 1150 ° C. to 1350 ° C., and a firing time of 0.1 to 50 hours.
  • the firing atmosphere may be, for example, an inert gas atmosphere, and the pressure during firing may be normal pressure or the like.
  • the atmosphere at the time of firing is set to a high vacuum of 1.0 ⁇ 10 ⁇ 4 Pa or more. It is good to purge and bake an inert gas later.
  • the inert gas atmosphere an N 2 gas atmosphere, a helium gas atmosphere, an argon gas atmosphere, and the like can be exemplified.
  • the said molded object can also be calcined as needed.
  • the calcination conditions can be a calcination temperature of 500 ° C. to 700 ° C. and an calcination time of 1 to 50 hours in an air atmosphere or an inert gas atmosphere.
  • the electric resistor 1 can be obtained.
  • the temperature dependence of the electric resistivity is small, and the electric resistivity exhibits PTC characteristics, or the electric resistivity 1 has almost no temperature dependence of the electric resistivity. It can be realized.
  • the electrical resistor 1 of the present embodiment can be configured such that the electrical resistivity does not have NTC characteristics, it becomes possible to avoid current concentration at the time of current heating. Therefore, in the electric resistor 1 of the present embodiment, temperature distribution is hard to occur inside, and cracking due to thermal expansion difference is hard to occur.
  • the electrical resistor 1 of the present embodiment has an advantage that the temperature dependency of the electrical resistivity can be reduced with a lower electrical resistance than the resistor or SiC or the like in which the entire bulk is made of the matrix 10 described above. is there.
  • the electrical resistor 1 of the present embodiment contains another substance in addition to the matrix 10, and the other substance is the nonconductive filler 12 in that the embodiment is implemented. It is different from Form 1. According to this configuration, by combining the matrix 10 and the nonconductive filler 12, the electric resistivity of the entire electric resistor 1 is obtained by the addition of the electric resistivity of the matrix 10 and the electric resistivity of the nonconductive filler 12. Is determined. Therefore, according to this configuration, it is possible to control the electrical resistivity of the electrical resistor 1 by adjusting the content of the nonconductive filler 12 or the like.
  • the nonconductive filler 12 preferably contains Si atoms. According to this configuration, when manufacturing the electric resistor 1 by sintering the raw material containing the borosilicate and the nonconductive filler 12, Si atoms of the nonconductive filler 12 diffuse into the borosilicate, The silicon enrichment of the borosilicate is promoted and the softening point of the matrix 10 can be improved. Therefore, according to this configuration, it is possible to improve the shape retentivity of the electric resistor 1, and the electric resistor 1 useful as a material of the structure can be obtained.
  • the nonconductive filler 12 containing Si atoms is not particularly limited as long as Si atoms can be diffused into the borosilicate, and for example, SiO 2 particles, Si 3 N 4 particles, etc. may be exemplified. it can. These can be used alone or in combination of two or more. Moreover, specifically, the electric resistor 1 can be configured to contain 50 vol% or more of the matrix 10 and the nonconductive filler 12 in total.
  • the honeycomb structure 2 of the present embodiment is configured to include the electric resistor 1 of the first embodiment.
  • the honeycomb structure 2 is configured of the electric resistor 1 of the first embodiment.
  • a well-known structure can be applied to the honeycomb structure 1, and it is not limited to the structure of FIG.
  • FIG. 3 shows an example in which the cell 20 has a rectangular shape in cross section, the cell 20 may also have a hexagonal shape in cross section.
  • the honeycomb structure 2 of the present embodiment is configured to include the electric resistor 1 of the present embodiment. Therefore, in the honeycomb structure 2 of the present embodiment, temperature distribution is less likely to occur inside the structure at the time of electric heating, and cracking due to the thermal expansion difference is less likely to occur. In addition, since the honeycomb structure 2 of the present embodiment uses the electric resistor 1 of the present embodiment, it can generate heat earlier at a lower temperature at the time of electric heating.
  • the electrically heated catalyst device 3 of the present embodiment includes the honeycomb structure 2 of the third embodiment.
  • the electrically heated catalyst device 3 includes the honeycomb structure 2, a three-way catalyst (not shown) supported on the cell walls 21 of the honeycomb structure 2, and the honeycomb structure 2.
  • a pair of electrodes 31 and 32 disposed opposite to the outer peripheral wall 22 and a voltage application unit 33 for applying a voltage to the electrodes 31 and 32 are provided.
  • a well-known structure can be applied to the electrically heated catalyst device 3, and it is not limited to the structure of FIG.
  • the electrically heated catalyst device 3 of the present embodiment has the honeycomb structure 2 of the present embodiment. Therefore, in the electrically heated catalyst device 3 of the present embodiment, the honeycomb structure 2 is not easily broken at the time of electric current heating, and the reliability can be improved. Further, since the electrically heated catalyst device 3 of the present embodiment uses the honeycomb structure 2 of the present embodiment, the honeycomb structure 2 can generate heat earlier at a lower temperature during electric heating, which is a catalyst It is advantageous for the early activation of
  • the matrix in sample 1 is 2.9 mass% in total of alkali type atoms (Na, Mg, K and Ca), Si: 24.7 mass%, O: 69.5 mass% , Al: contained 1.1% by mass. Further, according to ICP measurement, the matrix in Sample 1 contained B: 0.8% by mass.
  • the EPMA analyzer "JXA-8500F” manufactured by Nippon Denshi Co., Ltd. was used.
  • ICP analyzer "SPS-3520 UV” manufactured by Hitachi High-Tech Science Co., Ltd. was used. The same applies below.
  • Sample 2 was obtained in the same manner as in sample 1 except that borosilicate glass particles, Si particles and kaolin were mixed at a mass ratio of 29:31:40. Note that according to EPMA measurement, the matrix in sample 2 has a total of 2.4 mass% of alkali type atoms (Na, Mg, K and Ca), Si: 22.7 mass%, O: 68.1 % By mass and Al: 5.4% by mass. Further, according to ICP measurement, the matrix in Sample 2 contained B: 0.6% by mass.
  • sample 1C was used as sample 1C.
  • the electrical resistivity was measured for each of the obtained samples.
  • the electrical resistivity was measured by a four-terminal method using a thermoelectric characteristic evaluation apparatus (“ZEM-2” manufactured by ULVAC-RIKO, Inc.) on a 5 mm ⁇ 5 mm ⁇ 18 mm prism sample.
  • ZEM-2 thermoelectric characteristic evaluation apparatus manufactured by ULVAC-RIKO, Inc.
  • both sample 1 and sample 2 have significantly smaller temperature dependence of electrical resistivity than SiC of sample 1C, and the electrical resistivity exhibits PTC characteristics. Recognize.
  • the sample 1 and the sample 2 have smaller electric resistivity in the measurement temperature range as compared to the SiC of the sample 1C.
  • the electrical resistivity exhibits PTC characteristics without using kaolin.
  • Samples 1 and 2 have an electrical resistivity of 0.0001 ⁇ ⁇ m or more and 1 ⁇ ⁇ m or less and an electric resistance increase rate of 0.01 ⁇ 10 ⁇ 6 / K or more in a temperature range of 25 ° C. to 500 ° C. It turns out that it exists in the range below 5.0 * 10 ⁇ -4 > / K.
  • Example 3- Borosilicate glass particles containing Na, Mg, K, Ca, Si particles and kaolin were mixed in a mass ratio of 29:31:40. Next, 0.4 mass% of sodium carbonate (Na 2 CO 3 ) and 2 mass% of methyl cellulose as a binder were added to this mixture, water was added, and the mixture was kneaded. Next, the obtained mixture was formed into pellets by an extruder and fired. The firing conditions were as follows: atmosphere pressure: atmospheric pressure, firing temperature 1300 ° C., firing time 30 minutes, heating rate 200 ° C./hour under argon gas atmosphere. This obtained sample 3 which has a shape of 5 mm x 5 mm x 18 mm.
  • the matrix in the sample 3 is 3.1 mass% in total of alkali-based atoms (Na, Mg, K and Ca), Si: 22.3 mass%, O: 67.7 % By mass, and Al: 5.3% by mass. Further, according to ICP measurement, the matrix in Sample 3 contained B: 0.6% by mass.
  • sample 4 was obtained in the same manner as in the preparation of the sample 3, except that the addition amount of sodium carbonate was 0.8 mass%.
  • the matrix in the sample 4 contains 3.5 mass% in total of alkali atoms (Na, Mg, K and Ca), Si: 22.4 mass%, O: 66.7 % By mass, and Al: 5.5% by mass.
  • the matrix in sample 4 contained B: 0.6% by mass.
  • sample 5 was obtained in the same manner as in the preparation of the sample 3, except that sodium carbonate was not added.
  • the matrix in the sample 5 has a total of 2.4 mass% of alkali type atoms (Na, Mg, K and Ca), Si: 22.7 mass%, O: 68.1 % By mass, and Al: 5.7% by mass.
  • the matrix in Sample 5 contained B: 0.6% by mass.
  • the electrical resistivity at room temperature was measured for each of the obtained samples. As shown in FIG. 7, the electrical resistivity of the sample decreased by adding an alkali-based atom-containing compound such as sodium carbonate. It is considered that the electrical resistivity of the sample is lowered by the addition of the alkali-based atom-containing compound because the oxidation of the Si particles is suppressed. In addition, it was confirmed that the total content of alkali-based atoms is increased in the samples 3 and 4 to which sodium carbonate is added as compared with the sample 5 to which sodium carbonate is not added. This is because the borosilicate glass used as the raw material is doped with Na by the addition of sodium carbonate, and the total content of alkali atoms is increased.
  • an alkali-based atom-containing compound such as sodium carbonate.
  • FIG. 8 (a) shows an atomic mapping image of aluminum around the Au electrode pads 9 with an emission microscope ("PHEMOS-1000" manufactured by Hamamatsu Photonics Co., Ltd.)
  • FIG. 8 (b) shows an optical microscope image of the periphery of the emission part E in the sample 2.
  • reference numeral 101 denotes a matrix
  • reference numeral 111 denotes Si particles.
  • the arrow Y indicates the estimated conductive path.
  • FIG. 8 it can be seen that electrons flow while traveling through Si and the matrix. Further, it can be seen that the Si site does not generate heat, but generates heat in the portion of the matrix made of borosilicate glass. From this result, it was confirmed that the region that governs the electric resistance at the time of electric current heating is a matrix which is a base material.
  • FIG. 9 shows an atomic mapping image of aluminum in the vicinity of the emission part of sample 2.
  • the circled part is an emission part.
  • the chemical composition at each site of the symbols a to l in FIG. 9 was measured. The results are shown in Table 1.
  • symbol a is an electrode.
  • the part i and the part j corresponding to the emission part were aluminosilicates.
  • the site b, the site e, the site f, the site k, and the site 1 were also aluminosilicates.
  • the part c and the part d were borosilicate glass.
  • the site g and the site h were silicon.
  • B is contained in the part i and the part j corresponding to the emission part. Therefore, the part i and the part j corresponding to the emission part are presumed to be aluminoborosilicate.
  • boron may not be detected due to low detection sensitivity.
  • the reason why a large amount of Fe was detected at the part a was because the point at which Fe was segregated was measured.
  • FIG. 10 (a) shows a base site to be subjected to composition analysis.
  • FIG. 10 (b) shows the composition ratio of Phase 1 shown in Table 2 or a region having the composition ratio.
  • FIG. 10C shows a composition ratio of Phase 2 shown in Table 2 or a region having the composition ratio.
  • FIG. 10D shows the composition ratio of Phase 5 shown in Table 2 or a region having the composition ratio.
  • FIG. 10E shows a composition ratio of Phase 6 shown in Table 2 or a region having the composition ratio. It can be seen that Phase 2 is a Si portion, and Phases 1, 5 and 6 are matrix portions.
  • the matrix part is composed of an aluminoborosilicate containing at least one selected from the group consisting of Na, Mg, K, and Ca, and this aluminoborosilicate is alkaline-based.
  • Total 0.01 to 10 mass% of atoms, 0.1 to 5 mass% of B atoms, 5 to 40 mass% of Si atoms, 40 to 85 mass of O atoms
  • the Al atom is contained in an amount of 0.5% by mass or more and 10% by mass or less.
  • kaolin was used for the raw material that the matrix part became an alumino borosilicate containing an alkali-type atom. Therefore, when kaolin is not used as the raw material, it can be said that the matrix part is a borosilicate containing an alkali atom.
  • the conditions for the primary firing were a firing temperature of 700 ° C., a temperature raising time of 100 ° C./hour, a holding time of 1 hour, and an atmospheric pressure / atmospheric pressure.
  • the primarily fired fired body was secondarily fired.
  • Conditions of the secondary firing N 2 gas atmosphere and pressure, the firing temperature 1300 ° C., firing time 30 min, and the heating rate 200 ° C. / hour.
  • This obtained sample 6 which has a shape of 5 mm x 5 mm x 18 mm.
  • the matrix in the sample 6 has a total of 6.4 mass% of alkali atoms (Na, Mg, K and Ca), Si: 21.4 mass%, O: 65.4 mass% , Al: contained 5.1% by mass.
  • the matrix in Sample 6 contained B: 0.8 mass%.
  • Example 7 The boric acid, the Si particles and the kaolin were mixed in a mass ratio of 4:42:54. Subsequently, 2 mass% of methylcellulose was added to this mixture as a binder, water was added, and it knead
  • the conditions for the primary firing were a firing temperature of 700 ° C., a temperature raising time of 100 ° C./hour, a holding time of 1 hour, and an atmospheric pressure / atmospheric pressure. Next, the primarily fired fired body was secondarily fired.
  • the matrix in sample 7 is 0.5 mass% in total of alkali type atoms (Na, Mg, K and Ca), Si: 22.7 mass%, O: 68.1 mass% , Al: contained 5.7% by mass. Further, according to ICP measurement, the matrix in Sample 7 contained B: 0.9% by mass.
  • the electrical resistivity of each of the obtained samples was measured in the same manner as in Experimental Example 1. As shown in FIG. 11, the temperature dependence of the electrical resistivity of each of the samples 6 and 7 is significantly smaller than that of the SiC of the sample 1C described in the experimental example 1, and the electrical resistivity has PTC characteristics. It can be seen that Samples 6 and 7 have an electrical resistivity of 0.0001 ⁇ ⁇ m or more and 1 ⁇ ⁇ m or less and an electric resistance increase rate of 0.01 ⁇ 10 ⁇ 6 / K or more in a temperature range of 25 ° C. to 500 ° C. It turns out that it exists in the range below 5.0 * 10 ⁇ -4 > / K. Although the sample 7 is fired at a lower temperature than the sample 6, predetermined characteristics are obtained.
  • Experimental Example 7 -Sample 8- A sample 8 was obtained in the same manner as the sample 7 of Experimental Example 6 except that the boric acid, the Si particles, and the kaolin were mixed at a mass ratio of 6:41:53, and the firing temperature was 1250 ° C.
  • the matrix in sample 8 contains 0.5 mass% of alkali-based atoms in total, 23.6 mass% of Si, 66.8 mass% of O, and 5.8 mass% of Al. It was. Further, according to ICP measurement, the matrix in Sample 8 contained B: 1.3% by mass.
  • sample 9 was obtained in the same manner as the sample 7 of Experimental Example 6 except that the boric acid, the Si particles, and the kaolin were mixed at a mass ratio of 8:40:52, and the baking temperature was 1250 ° C.
  • the matrix in sample 9 contains 0.4 mass% of alkali-based atoms in total, 23.9 mass% of Si, 66.1 mass% of O, and 5.6 mass% of Al. It was. Further, according to ICP measurement, the matrix in Sample 9 contained B: 2.1% by mass.
  • sample 10 was obtained in the same manner as the sample 7 of Experimental Example 6 except that the boric acid, the Si particles, and the kaolin were mixed at a mass ratio of 4:42:54, and the firing temperature was 1300.degree.
  • the matrix in the sample 10 contains 0.4 mass% of alkali-based atoms in total, 24.1 mass% of Si, 65.9 mass% of O, and 5.9 mass% of Al. It was. Further, according to ICP measurement, the matrix in sample 10 contained B: 0.9% by mass.
  • sample 11 was obtained in the same manner as the sample 7 of the experimental example 6, except that the boric acid, the Si particles, and the kaolin were mixed at a mass ratio of 6:41:53, and the firing temperature was 1300.degree.
  • the matrix in the sample 11 contains 0.4 mass% in total of alkali-based atoms, 23.0 mass% of Si, 67.1 mass% of O, and 5.5 mass% of Al. It was. Further, according to ICP measurement, the matrix in the sample 11 contained B: 1.4% by mass.
  • sample 12 was obtained in the same manner as the sample 7 of Experimental Example 6 except that the boric acid, the Si particles, and the kaolin were mixed at a mass ratio of 8:40:52, and the baking temperature was 1300 ° C.
  • the matrix in the sample 12 contains 0.4 mass% of alkali-based atoms in total, 22.8 mass% of Si, 68.2 mass% of O, and 5.4 mass% of Al. It was. Further, according to ICP measurement, the matrix in the sample 12 contained B: 2.0% by mass.
  • the electrical resistivity of each of the obtained samples was measured in the same manner as in Experimental Example 1. The results are shown in FIG. 16 and FIG. As shown in FIG. 16 and FIG. 17, it was confirmed that, as the baking temperature is higher and the preparation amount of boric acid is larger, boron doping to the aluminosilicate is promoted and the electrical resistivity is lowered.
  • the following can be said by using a borosilicate containing at least one or more alkali atoms such as Na, Mg, K and Ca as a matrix of the electric resistor.
  • the region that governs the electrical resistance at the time of electric current heating is the matrix that is the base material.
  • the matrix has a smaller temperature dependency of the electrical resistivity than SiC, and the electrical resistivity exhibits a PTC characteristic. Therefore, when the electrical resistivity of another substance different from the matrix that can be included in the electrical resistor shows PTC characteristics, the temperature dependence of the electrical resistivity of the electrical resistor is small, and the PTC characteristics are It can be configured as shown.
  • the electrical resistivity of the other substance when the electrical resistivity of the other substance exhibits NTC characteristics, the electrical resistivity of the matrix exhibiting the PTC characteristic and the electrical resistivity of the other substance exhibiting the NTC characteristic add up to the electrical resistance of the electrical resistor.
  • the resistivity can be designed to have a small temperature dependence and to exhibit PTC characteristics or to have little temperature dependence. Therefore, by employing the above matrix, it is possible to obtain an electric resistor having a small temperature dependency of the electrical resistivity and exhibiting a PTC characteristic of the electrical resistivity or having little temperature dependency of the electrical resistivity. It will be possible.
  • the electric resistor can be configured such that the electric resistivity does not have the NTC characteristic, it becomes possible to avoid current concentration at the time of current heating.
  • the electric resistor in which a temperature distribution does not easily occur inside and a crack due to a thermal expansion difference is not easily produced. Furthermore, by adopting the matrix, the electric resistor can achieve low electric resistance of the matrix, and obtains an electric resistor with low electric resistance and small temperature dependency of electric resistivity. It becomes possible.
  • the present disclosure is not limited to the above embodiments and experimental examples, and various modifications can be made without departing from the scope of the invention. Moreover, each structure shown by each embodiment and each experiment example can each be combined arbitrarily. That is, although the present disclosure has been described based on the embodiments, it is understood that the present disclosure is not limited to the embodiments, structures, and the like. The present disclosure includes various modifications and variations within the equivalent range. In addition, various combinations and forms, and further, other combinations and forms including only one element, or more or less than these elements are also within the scope and the scope of the present disclosure.
  • the honeycomb structure is formed of the electrical resistor of the first embodiment is described. However, the honeycomb structure may be formed of the electrical resistor of the second embodiment.
  • the electrically heated catalyst device can also apply the honeycomb structure configured of the electric resistor of the second embodiment. It is.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention concerne une résistance électrique (1), comprenant une matrice (10) constituée d'un borosilicate contenant au moins un atome alcalin choisi dans le groupe constitué par le Na, le Mg, le K, le Ca, le Li, le Be, le Rb, le Sr, le Cs, le Ba, le Fr et le Ra. De préférence, la résistance électrique (1) comprend une charge électriquement conductrice (11). Une structure en nid d'abeilles (2) est conçue de manière à comporter la résistance électrique (1). Un dispositif catalyseur chauffé électriquement (3) comprend la structure en nid d'abeilles (2). De préférence, la résistance électrique (1) présente une résistivité électrique allant de 0,0001 à 1 Ω∙m et une vitesse d'augmentation de résistivité électrique allant de 0,01×10-6 à5,0×10-4/K dans une plage de températures de 25 à 500°C.
PCT/JP2018/023137 2017-06-30 2018-06-18 Résistance électrique, structure en nid d'abeilles et dispositif catalyseur chauffé électriquement WO2019003984A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880042219.4A CN110786075A (zh) 2017-06-30 2018-06-18 电阻体、蜂窝结构体及电加热式催化剂装置
DE112018003319.8T DE112018003319T5 (de) 2017-06-30 2018-06-18 Elektrischer Widerstand, Wabenstruktur und elektrisch beheizte Katalysatorvorrichtung
US16/728,261 US20200154524A1 (en) 2017-06-30 2019-12-27 Electrical resistor, honeycomb structure and electrically heated catalyst device

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017-129229 2017-06-30
JP2017129229 2017-06-30
JP2017243080A JP6740995B2 (ja) 2017-06-30 2017-12-19 電気抵抗体、ハニカム構造体、および、電気加熱式触媒装置
JP2017-243080 2017-12-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/728,261 Continuation US20200154524A1 (en) 2017-06-30 2019-12-27 Electrical resistor, honeycomb structure and electrically heated catalyst device

Publications (1)

Publication Number Publication Date
WO2019003984A1 true WO2019003984A1 (fr) 2019-01-03

Family

ID=64741443

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/023137 WO2019003984A1 (fr) 2017-06-30 2018-06-18 Résistance électrique, structure en nid d'abeilles et dispositif catalyseur chauffé électriquement

Country Status (1)

Country Link
WO (1) WO2019003984A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019124183A1 (fr) * 2017-12-19 2019-06-27 株式会社デンソー Résistance électrique, structure en nid d'abeilles et dispositif catalytique chauffé électriquement
JPWO2021049075A1 (fr) * 2019-09-11 2021-03-18
JPWO2021176757A1 (fr) * 2020-03-04 2021-09-10
CN113631266A (zh) * 2019-03-27 2021-11-09 株式会社电装 电阻体、蜂窝结构体及电加热式催化剂装置
CN114846226A (zh) * 2020-01-07 2022-08-02 日本碍子株式会社 电加热式载体及废气净化装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4380750A (en) * 1981-07-06 1983-04-19 Rca Corporation Indium oxide resistor inks
JP2000311805A (ja) * 1999-04-27 2000-11-07 Tokai Konetsu Kogyo Co Ltd セラミック抵抗体の製造方法
JP2009534479A (ja) * 2006-04-21 2009-09-24 オレックス オーストラリア ピーティワイ リミテッド 耐火性組成物
JP2012106223A (ja) * 2010-04-09 2012-06-07 Ibiden Co Ltd ハニカム構造体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4380750A (en) * 1981-07-06 1983-04-19 Rca Corporation Indium oxide resistor inks
JP2000311805A (ja) * 1999-04-27 2000-11-07 Tokai Konetsu Kogyo Co Ltd セラミック抵抗体の製造方法
JP2009534479A (ja) * 2006-04-21 2009-09-24 オレックス オーストラリア ピーティワイ リミテッド 耐火性組成物
JP2012106223A (ja) * 2010-04-09 2012-06-07 Ibiden Co Ltd ハニカム構造体

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019124183A1 (fr) * 2017-12-19 2019-06-27 株式会社デンソー Résistance électrique, structure en nid d'abeilles et dispositif catalytique chauffé électriquement
JP2019108863A (ja) * 2017-12-19 2019-07-04 株式会社デンソー 電気抵抗体、ハニカム構造体、および、電気加熱式触媒装置
CN113631266A (zh) * 2019-03-27 2021-11-09 株式会社电装 电阻体、蜂窝结构体及电加热式催化剂装置
JPWO2021049075A1 (fr) * 2019-09-11 2021-03-18
CN114846226A (zh) * 2020-01-07 2022-08-02 日本碍子株式会社 电加热式载体及废气净化装置
CN114846226B (zh) * 2020-01-07 2023-08-08 日本碍子株式会社 电加热式载体及废气净化装置
JPWO2021176757A1 (fr) * 2020-03-04 2021-09-10
WO2021176757A1 (fr) * 2020-03-04 2021-09-10 日本碍子株式会社 Support chauffé électriquement et dispositif d'épuration de gaz d'échappement
JP7261934B2 (ja) 2020-03-04 2023-04-20 日本碍子株式会社 電気加熱式担体及び排気ガス浄化装置

Similar Documents

Publication Publication Date Title
WO2019003984A1 (fr) Résistance électrique, structure en nid d'abeilles et dispositif catalyseur chauffé électriquement
JP6740995B2 (ja) 電気抵抗体、ハニカム構造体、および、電気加熱式触媒装置
WO2019187711A1 (fr) Résistance électrique, structure en nid d'abeilles, et dispositif catalyseur à chauffage électrique
JP2000077167A (ja) 面状発熱体
CN111163864A (zh) 电加热式催化剂
WO2020195063A1 (fr) Résistance électrique, structure en nid d'abeilles et dispositif catalytique chauffé électriquement
JP2019021568A (ja) 電気抵抗体およびその製造方法、ハニカム構造体、電気加熱式触媒装置
US20200323040A1 (en) Electrical resistor, honeycomb structure, and electric heating catalytic device
JP5780620B2 (ja) Ｐｔｃサーミスタ部材
WO2020021898A1 (fr) Résistance électrique, structure en nid d'abeilles et dispositif catalytique à chauffage électrique
JP7182732B2 (ja) 電気加熱式担体及び排気ガス浄化装置
WO2021111869A1 (fr) Résistance électrique, structure en nid d'abeilles et dispositif catalyseur chauffé électriquement
JP6621170B2 (ja) Ｐｔｃサーミスタ部材およびｐｔｃサーミスタ素子
JP2014099431A (ja) コンポジットｐｔｃサーミスタ部材
WO2021111870A1 (fr) Corps de résistance électrique, structure en nid d'abeilles, et dispositif catalytique chauffé électriquement
JP7095544B2 (ja) 電気抵抗体、ハニカム構造体、および、電気加熱式触媒装置
JPH09245946A (ja) セラミックヒータ
JP2004342622A (ja) セラミックヒータ
JP5723429B2 (ja) 導電性炭化珪素質焼結体
JP2018166045A (ja) セラミックヒーター及びセラミックヒーターの製造方法
RU2559802C2 (ru) Резистивный композиционный корунд-углеродный материал
JP2023078994A (ja) アルミナセラミックス、及びアルミナセラミックスの製造方法
JP2019186100A (ja) 電気抵抗体、ハニカム構造体、および、電気加熱式触媒装置
JPH0824004B2 (ja) 電気絶縁充填材料及びその製造方法
JP2016039276A (ja) サーミスタ素子、その製造方法、及び、それを用いた温度センサ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18823643

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 18823643

Country of ref document: EP

Kind code of ref document: A1