JP2019021568A - Electric resistor, method for manufacturing the same, honeycomb structure, and electric heating type catalyst device - Google Patents
Electric resistor, method for manufacturing the same, honeycomb structure, and electric heating type catalyst device Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000005485 electric heating Methods 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 94
- 239000002344 surface layer Substances 0.000 claims abstract description 85
- 239000010410 layer Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000011856 silicon-based particle Substances 0.000 claims description 23
- 229910017082 Fe-Si Inorganic materials 0.000 claims description 3
- 229910017133 Fe—Si Inorganic materials 0.000 claims description 3
- 238000001039 wet etching Methods 0.000 claims description 3
- 229910018540 Si C Inorganic materials 0.000 claims description 2
- 229910008332 Si-Ti Inorganic materials 0.000 claims description 2
- 229910006295 Si—Mo Inorganic materials 0.000 claims description 2
- 229910006749 Si—Ti Inorganic materials 0.000 claims description 2
- 229910006774 Si—W Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 22
- 231100000572 poisoning Toxicity 0.000 abstract description 11
- 230000000607 poisoning effect Effects 0.000 abstract description 11
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- 150000001340 alkali metals Chemical group 0.000 description 5
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- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
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- 238000004891 communication Methods 0.000 description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
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- -1 MgCO 3 and MgSiO 3 Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、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に関する。 The present invention relates to an electric resistor, a manufacturing method thereof, a honeycomb structure, and an electrically heated catalyst device.
従来、様々な分野において、通電加熱に電気抵抗体が用いられている。例えば、車両分野では、排ガス浄化触媒を担持するハニカム構造体を電気抵抗体より構成し、通電加熱によってハニカム構造体を発熱させる電気加熱式触媒装置が公知である。 Conventionally, electric resistors are used for energization heating in various fields. For example, in the vehicle field, an electrically heated catalyst device is known in which a honeycomb structure carrying an exhaust gas purification catalyst is composed of an electrical resistor, and the honeycomb structure is heated by energization heating.
なお、先行する特許文献１には、金属Ｓｉ粉末２０〜３５ｗｔ％、石英粉末５〜１５ｗｔ％、ホウケイ酸ガラス２０〜３０ｗｔ％、粘土粉末３０〜４０ｗｔ％からなる混合粉末に、水を加え混練、成形した後、大気中にて１２００〜１３００℃の温度で熱処理して導電性セラミックスを得る点、得られた導電性セラミックスにおける電極形成部分を予め弗化水素酸にて化学エッチングして粗面化する点などが記載されている。 In addition, in the prior patent document 1, water is added to a mixed powder composed of metal Si powder 20 to 35 wt%, quartz powder 5 to 15 wt%, borosilicate glass 20 to 30 wt%, clay powder 30 to 40 wt%, and kneaded. After molding, heat treatment is performed in the atmosphere at a temperature of 1200 to 1300 ° C. to obtain conductive ceramics, and the electrode forming portion of the obtained conductive ceramics is roughened by chemical etching in advance with hydrofluoric acid. The points to do are described.
ところで、Ｓｉ粒子を含む電気抵抗体より構成されるハニカム構造体は、排ガス浄化触媒とＳｉ粒子とが接した状態で使用される。排ガス浄化触媒とＳｉ粒子とが接した状態で使用されると、Ｓｉによって排ガス浄化触媒が被毒されて劣化する。 By the way, the honeycomb structure comprised from the electrical resistor containing Si particle | grains is used in the state which the exhaust gas purification catalyst and Si particle | grains contact | connected. When the exhaust gas purification catalyst and Si particles are used in contact with each other, the exhaust gas purification catalyst is poisoned by Si and deteriorates.
本発明は、かかる課題に鑑みてなされたものであり、排ガス浄化触媒のＳｉ被毒を抑制可能な電気抵抗体およびその製造方法、上記電気抵抗体を用いたハニカム構造体、当該ハニカム構造体を用いた電気加熱式触媒装置を提供しようとするものである。 The present invention has been made in view of such problems, and an electric resistor capable of suppressing Si poisoning of an exhaust gas purification catalyst, a method for manufacturing the same, a honeycomb structure using the electric resistor, and the honeycomb structure. It is an object of the present invention to provide an electrically heated catalyst device used.
本発明の一態様は、ホウケイ酸塩（１０）とＳｉ含有粒子（１１）とを含む電気抵抗体（１）であって、
上記電気抵抗体は、上記電気抵抗体の表面を含む表層部（１００）と、上記表層部に接し、上記表層部の内側に配置された内層部（１０１）とを有しており、
上記表層部における上記Ｓｉ含有粒子の含有量は、上記内層部における上記Ｓｉ含有粒子の含有量よりも少ない、電気抵抗体（１）にある。
One aspect of the present invention is an electrical resistor (1) comprising borosilicate (10) and Si-containing particles (11),
The electrical resistor has a surface layer part (100) including the surface of the electrical resistor, and an inner layer part (101) disposed in contact with the surface layer part and disposed inside the surface layer part,
The content of the Si-containing particles in the surface layer portion is in the electric resistor (1), which is less than the content of the Si-containing particles in the inner layer portion.
本発明の他の態様は、上記電気抵抗体を含んで構成されている、ハニカム構造体（２）にある。 Another aspect of the present invention resides in a honeycomb structure (2) configured to include the electric resistor.
本発明のさらに他の態様は、上記ハニカム構造体を有する、電気加熱式触媒装置（３）にある。 Yet another embodiment of the present invention resides in an electrically heated catalyst device (3) having the above honeycomb structure.
本発明のさらに他の態様は、ホウケイ酸塩（１０）とＳｉ含有粒子（１１）とを含む複合材の表層部に含まれるＳｉ含有粒子（１１）を選択的に除去し、電気抵抗体（１）を得る、電気抵抗体の製造方法にある。 Still another embodiment of the present invention selectively removes the Si-containing particles (11) contained in the surface layer portion of the composite material including the borosilicate (10) and the Si-containing particles (11), 1) to obtain an electrical resistor manufacturing method.
上記電気抵抗体は、上記構成を有する。そのため、上記電気抵抗体は、表層部の表面に接触した排ガス浄化触媒と、上記電気抵抗体に含まれるＳｉ含有粒子とを隔絶しやすい。それ故、上記電気抵抗体によれば、Ｓｉ含有粒子に起因する排ガス浄化触媒のＳｉ被毒を抑制することができる。 The electric resistor has the above configuration. Therefore, the electric resistor is easy to isolate the exhaust gas purifying catalyst in contact with the surface of the surface layer portion and the Si-containing particles contained in the electric resistor. Therefore, according to the electrical resistor, Si poisoning of the exhaust gas purification catalyst due to the Si-containing particles can be suppressed.
上記ハニカム構造体は、上記電気抵抗体を含んで構成されている。そのため、上記ハニカム構造体は、排ガス浄化触媒を担持させた場合に、排ガス浄化触媒とＳｉ含有粒子とを隔絶しやすい。それ故、上記ハニカム構造体によれば、排ガス浄化触媒のＳｉ被毒を抑制することができる。 The honeycomb structure includes the electric resistor. Therefore, the honeycomb structure easily separates the exhaust gas purification catalyst from the Si-containing particles when the exhaust gas purification catalyst is supported. Therefore, according to the honeycomb structure, Si poisoning of the exhaust gas purification catalyst can be suppressed.
上記電気加熱式触媒装置は、上記ハニカム構造体を有している。そのため、上記電気加熱式触媒装置は、その使用時に、上記ハニカム構造体に担持された排ガス浄化触媒のＳｉ被毒を抑制することができる。 The electrically heated catalyst device has the honeycomb structure. Therefore, the electric heating catalyst device can suppress Si poisoning of the exhaust gas purifying catalyst carried on the honeycomb structure during use.
上記電気抵抗体の製造方法は、上記構成を有している。そのため、上記電気抵抗体の製造方法によれば、上記電気抵抗体を比較的簡単に製造することができる。 The method for manufacturing the electrical resistor has the above configuration. Therefore, according to the method for manufacturing the electric resistor, the electric resistor can be manufactured relatively easily.
なお、特許請求の範囲及び課題を解決する手段に記載した括弧内の符号は、後述する実施形態に記載の具体的手段との対応関係を示すものであり、本発明の技術的範囲を限定するものではない。 In addition, the code | symbol in the parenthesis described in the means to solve a claim and a subject shows the correspondence with the specific means as described in embodiment mentioned later, and limits the technical scope of this invention. It is not a thing.
（実施形態１）
実施形態１の電気抵抗体について、図１を用いて説明する。図１に例示されるように、本実施形態の電気抵抗体１は、ホウケイ酸塩１０とＳｉ含有粒子１１とを含んで構成されている。
(Embodiment 1)
The electrical resistor according to Embodiment 1 will be described with reference to FIG. As illustrated in FIG. 1, the electrical resistor 1 of the present embodiment includes a borosilicate 10 and Si-containing particles 11.
ホウケイ酸塩１０は、電気抵抗体１の母材となる部位であり、非晶質であってもよいし、結晶質であってもよい。ホウケイ酸塩１０は、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｌｉ、Ｂｅ、Ｒｂ、Ｓｒ、Ｃｓ、Ｂａ、Ｆｒ、および、Ｒａからなる群より選択される少なくとも１つのアルカリ金属原子・アルカリ土類金属原子を含むことができる。つまり、ホウケイ酸塩１０は、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｌｉ、Ｂｅ、Ｒｂ、Ｓｒ、Ｃｓ、Ｂａ、Ｆｒ、および、Ｒａからなる群より選択される少なくとも１つのアルカリ金属原子・アルカリ土類金属原子がドープされていてもよい。各アルカリ金属原子・アルカリ土類金属原子は、単独またはいずれの組み合わせでホウケイ酸塩１０に含まれていてもよい。つまり、ホウケイ酸塩１０は、アルカリ金属原子を１つまたは２つ以上含んでいてもよいし、アルカリ土類金属原子を１つまたは２つ以上含んでいてもよいし、これらの組み合わせを含んでいてもよい。ホウケイ酸塩１０は、電気抵抗体１の低電気抵抗化を図りやすいなどの観点から、好ましくは、Ｎａ、Ｍｇ、Ｋ、および、Ｃａからなる群より選択される少なくとも１つを含むことができる。より好ましくは、ホウケイ酸塩１０は、Ｎａ、Ｋ、または、ＮａおよびＫの双方を少なくとも含むことができる。なお、ホウケイ酸塩１０は、具体的には、アルミノホウケイ酸塩などとすることもできる。 The borosilicate 10 is a part that becomes a base material of the electrical resistor 1, and may be amorphous or crystalline. Borosilicate 10 is composed of at least one alkali metal atom / alkaline earth metal atom selected from the group consisting of Na, Mg, K, Ca, Li, Be, Rb, Sr, Cs, Ba, Fr, and Ra. Can be included. That is, the borosilicate 10 includes at least one alkali metal atom / alkaline earth selected from the group consisting of Na, Mg, K, Ca, Li, Be, Rb, Sr, Cs, Ba, Fr, and Ra. Metal atoms may be doped. Each alkali metal atom / alkaline earth metal atom may be contained in borosilicate 10 alone or in any combination. That is, the borosilicate 10 may contain one or more alkali metal atoms, one or more alkaline earth metal atoms, or a combination thereof. May be. The borosilicate 10 can preferably contain at least one selected from the group consisting of Na, Mg, K, and Ca from the viewpoint of easily reducing the electrical resistance of the electrical resistor 1. . More preferably, the borosilicate 10 can include at least Na, K, or both Na and K. The borosilicate 10 can be specifically an aluminoborosilicate.
Ｓｉ含有粒子１１は、Ｓｉ原子を含有する電子伝導性の粒子である。したがって、Ｓｉ含有粒子１１には、ＳｉＯ２粒子などは含まれない。Ｓｉ含有粒子としては、具体的には、Ｓｉ粒子、Ｆｅ−Ｓｉ系粒子、Ｓｉ−Ｗ系粒子、Ｓｉ−Ｃ系粒子、Ｓｉ−Ｍｏ系粒子、および、Ｓｉ−Ｔｉ系粒子などを例示することができる。これらは１種または２種以上含まれていてもよい。この構成によれば、Ｓｉ含有粒子１１の周囲のホウケイ酸塩１０にＳｉ含有粒子１１からＳｉ原子を拡散させてホウケイ酸塩１０の軟化点を上昇させやすくなる。また、この構成によれば、後述のエッチング処理によってＳｉ含有粒子１１を選択的に除去しやすいなどの利点もある。これらのうち、Ｓｉ原子のホウケイ酸塩１０への拡散性などの観点から、好ましくは、Ｓｉ粒子、Ｆｅ−Ｓｉ系粒子などであるとよい。 The Si-containing particles 11 are electron conductive particles containing Si atoms. Accordingly, the Si-containing particles 11 do not include SiO 2 particles. Specific examples of the Si-containing particles include Si particles, Fe—Si based particles, Si—W based particles, Si—C based particles, Si—Mo based particles, and Si—Ti based particles. Can do. One or more of these may be contained. According to this configuration, Si atoms are diffused from the Si-containing particles 11 to the borosilicate 10 around the Si-containing particles 11 and the softening point of the borosilicate 10 is easily increased. Moreover, according to this structure, there also exists an advantage that it is easy to selectively remove the Si-containing particles 11 by an etching process described later. Among these, from the viewpoint of diffusibility of Si atoms into the borosilicate 10, Si particles, Fe—Si based particles, and the like are preferable.
なお、電気抵抗体１は、Ｓｉ含有粒子１１以外にも、例えば、フィラー、熱膨張率を低下させる材料、熱伝導率を上昇させる材料、強度を向上させる材料、カオリンなどを必要に応じて１種または２種以上含むことができる。 In addition to the Si-containing particles 11, the electrical resistor 1 may include, for example, a filler, a material that lowers the coefficient of thermal expansion, a material that raises the thermal conductivity, a material that improves the strength, kaolin, etc. Species or two or more can be included.
電気抵抗体１は、図１に例示されるように、表層部１００と、内層部１０１とを有している。表層部１００は、電気抵抗体１の表面を含んでいる。したがって、表層部の表面が、電気抵抗体１の表面となる。本実施形態では、表層部１００は、具体的には、例えば、排ガス浄化触媒と接触する電気抵抗体１の表面全体を含むことができる。なお、表層部１００は、電気抵抗体１の表面から内方に向かって、電気抵抗体１の表面に垂直な断面のＥＰＭＡ像から特定されるＳｉ含有粒子１１の最大径まで、の深さ領域をいう。Ｓｉ含有粒子１１の最大径は、任意に選択した５か所のＥＰＭＡ像について、それぞれ外径が最大のＳｉ含有粒子を特定し、これら特定された５つのＳｉ含有粒子の外径の平均値である。内層部１０１は、表層部１００に接しており、表層部１００の内側に配置されている。なお、内層部１０１は、表層部１００に一体的（連続的）に繋がっている。 As illustrated in FIG. 1, the electrical resistor 1 has a surface layer portion 100 and an inner layer portion 101. The surface layer portion 100 includes the surface of the electrical resistor 1. Therefore, the surface of the surface layer portion becomes the surface of the electrical resistor 1. In the present embodiment, specifically, the surface layer portion 100 can include, for example, the entire surface of the electrical resistor 1 that is in contact with the exhaust gas purification catalyst. The surface layer portion 100 has a depth region from the surface of the electrical resistor 1 inward to the maximum diameter of the Si-containing particles 11 specified from the EPMA image of a cross section perpendicular to the surface of the electrical resistor 1. Say. The maximum diameter of the Si-containing particles 11 is determined by specifying the Si-containing particles having the maximum outer diameter for each of five arbitrarily selected EPMA images, and the average value of the outer diameters of the five specified Si-containing particles. is there. The inner layer portion 101 is in contact with the surface layer portion 100 and is disposed inside the surface layer portion 100. The inner layer portion 101 is connected to the surface layer portion 100 integrally (continuously).
電気抵抗体１において、表層部１００におけるＳｉ含有粒子１１の含有量は、内層部１０１におけるＳｉ含有粒子１１の含有量よりも少なくされている。表層部１００におけるＳｉ含有粒子１１の含有量は、次のようにして測定される。電気抵抗体１の表面に垂直な断面をＥＰＭＡ観察し、ＥＰＭＡ像上で、上述した表層部１００に相当する表層部領域を求める。次いで、求めた表層部領域について、元素マッピングを測定し、Ｓｉ含有粒子１１の存在箇所を特定する。次いで、測定した元素マッピングから、表層部領域に占めるＳｉ含有粒子１１の面積割合を算出する。なお、当該面積割合は、１００×（表層部領域に占めるＳｉ含有粒子１１の総面積）／（表層部領域の面積）によって求められる。算出された表層部領域に占めるＳｉ含有粒子１１の面積割合が、表層部１００におけるＳｉ含有粒子１１の含有量（％）とされる。
一方、内層部１０１におけるＳｉ含有粒子１１の含有量は、次のようにして測定される。電気抵抗体１の表面に垂直な断面をＥＰＭＡ観察し、ＥＰＭＡ像上で、上述した内層部１００に相当する内層部領域を求める。次いで、求めた内層部領域における内層部の厚み方向の中心部を含み、かつ、上記表層部領域と同じ面積となる内層部測定領域を求める。次いで、求めた内層部測定領域について、元素マッピングを測定し、Ｓｉ含有粒子１１の存在箇所を特定する。次いで、測定した元素マッピングから、内層部測定領域に占めるＳｉ含有粒子１１の面積割合を算出する。なお、当該面積割合は、１００×（内層部測定領域に占めるＳｉ含有粒子１１の総面積）／（内層部測定領域の面積）によって求められる。算出された内層部測定領域に占めるＳｉ含有粒子１１の面積割合が、内層部１０１におけるＳｉ含有粒子１１の含有量（％）とされる。
In the electrical resistor 1, the content of the Si-containing particles 11 in the surface layer portion 100 is less than the content of the Si-containing particles 11 in the inner layer portion 101. The content of the Si-containing particles 11 in the surface layer portion 100 is measured as follows. A cross section perpendicular to the surface of the electrical resistor 1 is observed by EPMA, and a surface layer portion region corresponding to the surface layer portion 100 described above is obtained on the EPMA image. Subsequently, element mapping is measured about the calculated | required surface layer part area | region, and the location where the Si containing particle | grains 11 exist is specified. Next, the area ratio of the Si-containing particles 11 in the surface layer region is calculated from the measured element mapping. In addition, the said area ratio is calculated | required by 100x (total area of the Si containing particle | grains 11 which occupies for a surface layer part area | region) / (area of a surface layer part area | region). The calculated area ratio of the Si-containing particles 11 in the surface layer portion region is the content (%) of the Si-containing particles 11 in the surface layer portion 100.
On the other hand, the content of the Si-containing particles 11 in the inner layer portion 101 is measured as follows. A cross section perpendicular to the surface of the electrical resistor 1 is observed with EPMA, and an inner layer portion region corresponding to the above-described inner layer portion 100 is obtained on the EPMA image. Next, an inner layer measurement region including the central portion in the thickness direction of the inner layer portion in the obtained inner layer portion region and having the same area as the surface layer portion region is obtained. Subsequently, element mapping is measured about the calculated | required inner layer part measurement area | region, and the location where the Si containing particle | grains 11 exist is specified. Next, the area ratio of the Si-containing particles 11 in the inner layer measurement region is calculated from the measured element mapping. In addition, the said area ratio is calculated | required by 100x (total area of the Si-containing particle | grains 11 which occupies for an inner layer part measurement area | region) / (area of an inner layer part measurement area | region). The calculated area ratio of the Si-containing particles 11 in the inner layer part measurement region is the content (%) of the Si-containing particles 11 in the inner layer part 101.
表層部１００におけるＳｉ含有粒子１１の含有量は、排ガス浄化触媒のＳｉ被毒の抑制効果を確実なものとするなどの観点から、好ましくは、５％以下、より好ましくは、３％以下、さらに好ましくは、１％以下とすることができる。なお、表層部１００は、内層部１０１に比べ、Ｓｉ含有粒子１１の割合が少なくされておれば、Ｓｉ含有粒子１１を含んでいてもよいし、Ｓｉ含有粒子１１を含んでいなくてもよい。電気抵抗体１の製造上、表層部１００からＳｉ含有粒子１１を完全に除去することは難しい。そのため、表層部１００は、Ｓｉ含有粒子１１を含んでいてもよい。もっとも、排ガス浄化触媒のＳｉ被毒の抑制効果を確実なものとするなどの観点から、図１に例示されるように、表層部１００の表面に、Ｓｉ含有粒子１１が露出していないことが好ましい。表層部１００におけるＳｉ含有粒子１１の含有量は、表層部１００の形成容易性などの観点から、例えば、０．１％以上とすることができる。 The content of the Si-containing particles 11 in the surface layer portion 100 is preferably 5% or less, more preferably 3% or less, from the viewpoint of ensuring the effect of suppressing the Si poisoning of the exhaust gas purification catalyst. Preferably, it may be 1% or less. Note that the surface layer portion 100 may include the Si-containing particles 11 or may not include the Si-containing particles 11 as long as the ratio of the Si-containing particles 11 is reduced as compared with the inner layer portion 101. . In manufacturing the electrical resistor 1, it is difficult to completely remove the Si-containing particles 11 from the surface layer portion 100. Therefore, the surface layer part 100 may include Si-containing particles 11. However, from the viewpoint of ensuring the effect of suppressing the Si poisoning of the exhaust gas purification catalyst, the Si-containing particles 11 may not be exposed on the surface of the surface layer portion 100 as illustrated in FIG. preferable. The content of the Si-containing particles 11 in the surface layer portion 100 can be set to, for example, 0.1% or more from the viewpoint of ease of formation of the surface layer portion 100.
内層部１０１におけるＳｉ含有粒子１１の含有量は、電気抵抗体１の導電性確保、強度確保などの観点から、好ましくは、１５％以上、より好ましくは、２０％以上、さらに好ましくは、２５％以上とすることができる。また、内層部１０１におけるＳｉ含有粒子１１の含有量は、電気抵抗体１がＰＴＣ特性を発現しやすくなるなどの観点から、好ましくは、４０％以下、より好ましくは、３５％以下、さらに好ましくは、３０％以下とすることができる。 The content of the Si-containing particles 11 in the inner layer portion 101 is preferably 15% or more, more preferably 20% or more, and still more preferably 25%, from the viewpoint of ensuring the conductivity of the electrical resistor 1 and ensuring the strength. This can be done. In addition, the content of the Si-containing particles 11 in the inner layer portion 101 is preferably 40% or less, more preferably 35% or less, and still more preferably, from the viewpoint that the electrical resistor 1 is likely to exhibit PTC characteristics. 30% or less.
電気抵抗体１において、表層部１００の気孔率は、内層部１０１の気孔率よりも大きい構成とすることができる。この構成によれば、表層部１００のＳｉ含有粒子１１の含有量＜内層部１０１のＳｉ含有粒子１１の含有量の関係を確実なものとしやすくなる。 In the electrical resistor 1, the porosity of the surface layer portion 100 can be configured to be larger than the porosity of the inner layer portion 101. According to this configuration, the relationship of the content of the Si-containing particles 11 in the surface layer portion 100 <the content of the Si-containing particles 11 in the inner layer portion 101 can be easily ensured.
表層部１００の気孔率は、次のようにして測定される。上述した要領で、表層部領域を求める。次いで、求めた表層部領域に占める気孔の面積割合を算出する。なお、当該面積割合は、１００×（表層部領域に占める気孔の総面積）／（表層部領域の面積）によって求められる。算出された表層部領域に占める気孔の面積割合が、表層部１００の気孔率（％）とされる。
一方、内層部１０１の気孔率は、次のようにして測定される。上述した要領で、内層部測定領域を求める。次いで、求めた内層部測定領域に占める気孔の面積割合を算出する。なお、当該面積割合は、１００×（内層部測定領域に占める気孔の総面積）／（内層部測定領域の面積）によって求められる。算出された内層部測定領域に占める気孔の面積割合が、内層部１０１における気孔率（％）とされる。
The porosity of the surface layer part 100 is measured as follows. The surface layer region is obtained in the manner described above. Subsequently, the area ratio of the pores in the obtained surface layer region is calculated. The area ratio is obtained by 100 × (total area of pores in the surface layer region) / (area of the surface layer region). The calculated area ratio of the pores in the surface layer region is the porosity (%) of the surface layer 100.
On the other hand, the porosity of the inner layer portion 101 is measured as follows. The inner layer measurement area is obtained in the manner described above. Next, the area ratio of the pores in the obtained inner layer measurement area is calculated. The area ratio is determined by 100 × (total area of pores in the inner layer measurement region) / (area of the inner layer measurement region). The calculated area ratio of the pores in the inner layer measurement area is the porosity (%) in the inner layer 101.
電気抵抗体１は、具体的には、図１に例示されるように、表層部１００に多数の気孔１００ａを有する構成とすることができる。この構成によれば、表層部１００の表面（電気抵抗体１の表面）に排ガス浄化触媒（不図示）を担持させやすくなる。また、アンカー効果により、担持させた排ガス浄化触媒の電気抵抗体１に対する密着性を向上させることができる。なお、内層部１０１は、気孔を含んでいてもよいし、気孔を含んでいなくてもよい。 Specifically, as illustrated in FIG. 1, the electrical resistor 1 can be configured to have a large number of pores 100 a in the surface layer portion 100. According to this configuration, an exhaust gas purification catalyst (not shown) can be easily carried on the surface of the surface layer portion 100 (the surface of the electrical resistor 1). In addition, due to the anchor effect, the adhesion of the supported exhaust gas purification catalyst to the electrical resistor 1 can be improved. Note that the inner layer portion 101 may include pores or may not include pores.
電気抵抗体１は、より具体的には、表層部１００におけるＳｉ含有粒子１１が選択的に除去された状態とされることにより、表層部１００に多数の気孔１００ａが導入されている構成とすることができる。この構成によれば、表層部１００の表面に接触した排ガス浄化触媒と、電気抵抗体１に含まれるＳｉ含有粒子１１との隔絶を確実なものとすることができる。さらに、かかる効果に加え、Ｓｉ含有粒子１１が選択的に除去されることにより、電気抵抗体１の熱容量の低減および重量の低減などの効果も得られる。ハニカム構造体は、一般に、表面積が大きな構造体である。そのため、上記構成による電気抵抗体１をハニカム構造体に用いれば、排ガス浄化触媒のＳｉ被毒を抑制しつつ、より少ない熱でハニカム構造体を温めることができるとともにハニカム構造体の軽量化も図ることが可能になる。なお、気孔１００ａは、表層部１００の表面に連通する連通孔を含むように構成することができる。連通孔は、具体的には、除去されたＳｉ含有粒子１１の跡より構成することができる。 More specifically, the electrical resistor 1 is configured such that a large number of pores 100a are introduced into the surface layer portion 100 by selectively removing the Si-containing particles 11 in the surface layer portion 100. be able to. According to this configuration, separation between the exhaust gas purifying catalyst in contact with the surface of the surface layer portion 100 and the Si-containing particles 11 included in the electric resistor 1 can be ensured. Furthermore, in addition to such an effect, by selectively removing the Si-containing particles 11, effects such as a reduction in the heat capacity and weight of the electrical resistor 1 can be obtained. A honeycomb structure is generally a structure having a large surface area. Therefore, if the electrical resistor 1 having the above-described configuration is used for the honeycomb structure, the honeycomb structure can be warmed with less heat while suppressing Si poisoning of the exhaust gas purification catalyst, and the honeycomb structure can be reduced in weight. It becomes possible. The pore 100a can be configured to include a communication hole communicating with the surface of the surface layer portion 100. Specifically, the communication hole can be constituted by a trace of the removed Si-containing particles 11.
本実施形態の電気抵抗体１は、表層部１００の表面に接触した排ガス浄化触媒と、電気抵抗体１に含まれるＳｉ含有粒子１１とを隔絶しやすい。それ故、本実施形態の電気抵抗体１によれば、Ｓｉ含有粒子１１に起因する排ガス浄化触媒のＳｉ被毒を抑制することができる。 The electric resistor 1 according to the present embodiment easily separates the exhaust gas purifying catalyst in contact with the surface of the surface layer portion 100 and the Si-containing particles 11 included in the electric resistor 1. Therefore, according to the electrical resistor 1 of the present embodiment, Si poisoning of the exhaust gas purification catalyst due to the Si-containing particles 11 can be suppressed.
（実施形態２）
実施形態２の電気抵抗体の製造方法について説明する。なお、実施形態２以降において用いられる符号のうち、既出の実施形態において用いた符号と同一のものは、特に示さない限り、既出の実施形態におけるものと同様の構成要素等を表す。
(Embodiment 2)
A method for manufacturing the electrical resistor according to the second embodiment will be described. Of the reference numerals used in the second and subsequent embodiments, the same reference numerals as those used in the above-described embodiments represent the same components as those in the above-described embodiments unless otherwise indicated.
本実施形態の電気抵抗体の製造方法は、ホウケイ酸塩１０とＳｉ含有粒子１１とを含む複合材の表層部１００に含まれるＳｉ含有粒子１１を選択的に除去し、本実施形態１の電気抵抗体１を得る方法である。 The manufacturing method of the electrical resistor according to the present embodiment selectively removes the Si-containing particles 11 contained in the surface layer portion 100 of the composite material including the borosilicate 10 and the Si-containing particles 11, thereby This is a method of obtaining the resistor 1.
複合材は、例えば、次のようにして準備することができる。ホウケイ酸塩１０と、Ｓｉ含有粒子１１と、必要に応じて、アルカリ金属原子および／またはアルカリ土類金属原子を含有するアルカリ原子含有物質、カオリン等を混合する。なお、アルカリ原子含有物質としては、例えば、Ｎａ２ＣＯ３、Ｎａ２ＳｉＯ３等のＮａ含有化合物、ＭｇＣＯ３、ＭｇＳｉＯ３等のＭｇ含有化合物、Ｋ２ＣＯ３、Ｋ２ＳｉＯ３等のＫ含有化合物、ＣａＣＯ３、ＣａＳｉＯ３等のＣａ含有化合物、Ｌｉ２ＣＯ３、Ｌｉ２ＳｉＯ３等のＬｉ含有化合物などを例示することができる。これらは１種または２種以上併用することができる。 The composite material can be prepared as follows, for example. The borosilicate 10, the Si-containing particles 11, and an alkali atom-containing substance containing alkali metal atoms and / or alkaline earth metal atoms, kaolin, or the like are mixed as necessary. Examples of the alkali atom-containing substance include Na-containing compounds such as Na 2 CO 3 and Na 2 SiO 3 , Mg-containing compounds such as MgCO 3 and MgSiO 3 , and K-containing substances such as K 2 CO 3 and K 2 SiO 3. Examples thereof include compounds, Ca-containing compounds such as CaCO 3 and CaSiO 3 , and Li-containing compounds such as Li 2 CO 3 and Li 2 SiO 3 . These can be used alone or in combination of two or more.
次いで、この混合物にバインダー、水を加える。バインダーとしては、例えば、メチルセルロール等の有機バインダーを用いることができる。また、バインダーの含有量は、例えば、２質量％程度とすることができる。 Next, a binder and water are added to the mixture. As the binder, for example, an organic binder such as methyl cellulose can be used. Moreover, content of a binder can be about 2 mass%, for example.
次いで、得られた成形体を焼成する。焼成条件は、具体的には、例えば、不活性ガス雰囲気下または大気雰囲気下、大気圧以下、焼成温度１１５０℃〜１３５０℃、焼成時間０．１〜５０時間とすることができる。なお、焼成雰囲気は、例えば、不活性ガス雰囲気、焼成時圧力は、常圧などとすることができる。電気抵抗体１の低電気抵抗化を図る場合には、酸化防止の観点から残存酸素の低減を図ることが好ましく、焼成時の雰囲気内を１．０×１０−４Ｐａ以上の高真空にした後に不活性ガスをパージして焼成するとよい。不活性ガス雰囲気としては、Ｎ２ガス雰囲気、ヘリウムガス雰囲気、アルゴンガス雰囲気などを例示することができる。また、上記焼成の前に、必要に応じて、上記成形体を仮焼することもできる。仮焼条件は、具体的には、大気雰囲気下または不活性ガス雰囲気下、仮焼温度５００℃〜７００℃、仮焼時間１〜５０時間とすることができる。以上により、ホウケイ酸塩１０とＳｉ含有粒子１１とを含む複合材を準備することができる。 Next, the obtained molded body is fired. Specifically, the firing conditions may be, for example, an inert gas atmosphere or an air atmosphere, atmospheric pressure or lower, a firing temperature of 1150 ° C. to 1350 ° C., and a firing time of 0.1 to 50 hours. The firing atmosphere can be, for example, an inert gas atmosphere, and the firing pressure can be normal pressure. When reducing the electrical resistance of the electrical resistor 1, it is preferable to reduce residual oxygen from the viewpoint of oxidation prevention, and the atmosphere during firing is set to a high vacuum of 1.0 × 10 −4 Pa or more. It is preferable to purge the inert gas later and fire. Examples of the inert gas atmosphere include an N 2 gas atmosphere, a helium gas atmosphere, and an argon gas atmosphere. Moreover, the said molded object can also be calcined before the said baking as needed. Specifically, the calcining conditions may be a calcining temperature of 500 ° C. to 700 ° C. and a calcining time of 1 to 50 hours in an air atmosphere or an inert gas atmosphere. As described above, a composite material including borosilicate 10 and Si-containing particles 11 can be prepared.
複合材の表層部１００に含まれるＳｉ含有粒子１１の選択的な除去方法としては、例えば、エッチングなどを好適な方法として例示することができる。エッチングは、ウェットエッチング、ドライエッチングのいずれを用いてもよい。ウェットエッチングを用いる場合には、複合材をエッチング液に浸漬することにより、エッチング液に触れた複合材の表面全体に、Ｓｉ含有粒子１１が選択的にエッチングされて形成された表層部を形成することができる。そのため、この場合には、上述した電気抵抗体１の量産性に優れる。エッチング液は、Ｓｉ含有粒子をエッチングすることができれば、アルカリ性であっても酸性であってもよい。なお、Ｓｉ含有粒子が、例えば、Ｓｉ粒子などの場合には、複合材を準備する際の真空焼成時に、複合材の表層部１００に含まれるＳｉ含有粒子１１を蒸気化して除去することも可能である。また、これらの組み合わせにより、表層部１００に含まれるＳｉ含有粒子１１を選択的に除去するようにしてもよい。 As a method for selectively removing the Si-containing particles 11 contained in the surface layer portion 100 of the composite material, for example, etching or the like can be exemplified as a suitable method. Etching may be either wet etching or dry etching. When wet etching is used, a surface layer portion formed by selectively etching the Si-containing particles 11 is formed on the entire surface of the composite material touched by the etchant by immersing the composite material in the etchant. be able to. Therefore, in this case, the above-described mass production of the electrical resistor 1 is excellent. The etching solution may be alkaline or acidic as long as it can etch Si-containing particles. When the Si-containing particles are, for example, Si particles, the Si-containing particles 11 included in the surface layer portion 100 of the composite material can be vaporized and removed during vacuum firing when preparing the composite material. It is. Moreover, you may make it selectively remove the Si containing particle | grains 11 contained in the surface layer part 100 by these combination.
得られる電気抵抗体１における表層部１００のＳｉ含有粒子１１の含有量は、例えば、エッチング液の種類、エッチング温度、エッチング時間等のエッチング条件を変えることによって変化させることができる。 The content of the Si-containing particles 11 in the surface layer portion 100 in the obtained electrical resistor 1 can be changed by changing the etching conditions such as the type of the etching solution, the etching temperature, and the etching time, for example.
本実施形態の電気抵抗体の製造方法は、上記構成を有している。そのため、本実施形態の電気抵抗体の製造方法によれば、本実施形態１の電気抵抗体１を比較的簡単に製造することができる。 The manufacturing method of the electrical resistor according to the present embodiment has the above configuration. Therefore, according to the manufacturing method of the electrical resistor of this embodiment, the electrical resistor 1 of this Embodiment 1 can be manufactured comparatively easily.
（実施形態３）
実施形態３のハニカム構造体について、図２を用いて説明する。図２に例示されるように、本実施形態のハニカム構造体２は、実施形態１の電気抵抗体を含んで構成されている。本実施形態では、具体的には、ハニカム構造体２は、実施形態１の電気抵抗体１より構成されている。図２では、具体的には、ハニカム構造体２の中心軸に垂直なハニカム断面視で、互いに隣接する複数のセル２０と、セル２０を形成するセル壁２１と、セル壁２１の外周部に設けられてセル壁２１を一体に保持する外周壁２２と、を有する構造が例示されている。なお、ハニカム構造体２には、公知の構造を適用することができ、図２の構造に限定されるものではない。図２は、セル２０を断面四角形状とした例である。
(Embodiment 3)
A honeycomb structure of Embodiment 3 will be described with reference to FIG. As illustrated in FIG. 2, the honeycomb structure 2 of the present embodiment includes the electric resistor of the first embodiment. In the present embodiment, specifically, the honeycomb structure 2 is constituted by the electric resistor 1 of the first embodiment. In FIG. 2, specifically, in a honeycomb cross-sectional view perpendicular to the central axis of the honeycomb structure 2, a plurality of cells 20 adjacent to each other, a cell wall 21 forming the cell 20, and an outer peripheral portion of the cell wall 21. The structure which has the outer peripheral wall 22 which is provided and hold | maintains the cell wall 21 integrally is illustrated. In addition, a well-known structure can be applied to the honeycomb structure 2, and it is not limited to the structure of FIG. FIG. 2 shows an example in which the cell 20 has a square cross section.
本実施形態のハニカム構造体２は、本実施形態の電気抵抗体１を含んで構成されている。そのため、本実施形態のハニカム構造体２は、排ガス浄化触媒を担持させた場合に、排ガス浄化触媒とＳｉ含有粒子とを隔絶しやすい。それ故、本実施形態のハニカム構造体２によれば、排ガス浄化触媒のＳｉ被毒を抑制することができる。 The honeycomb structure 2 of the present embodiment includes the electric resistor 1 of the present embodiment. Therefore, the honeycomb structure 2 of the present embodiment easily separates the exhaust gas purification catalyst and the Si-containing particles when the exhaust gas purification catalyst is supported. Therefore, according to the honeycomb structure 2 of the present embodiment, Si poisoning of the exhaust gas purification catalyst can be suppressed.
（実施形態４）
実施形態４の電気加熱式触媒装置について、図３を用いて説明する。図３に例示されるように、本実施形態の電気加熱式触媒装置３は、実施形態３のハニカム構造体２を有している。本実施形態では、具体的には、電気加熱式触媒装置３は、ハニカム構造体２と、ハニカム構造体２のセル壁２１に担持された排ガス浄化触媒（不図示）と、ハニカム構造体２の外周壁２２に対向配置された一対の電極３１、３２と、電極３１、３２に電圧を印加する電圧印加部３３とを有している。なお、電気加熱式触媒装置３には、公知の構造を適用することができ、図３の構造に限定されるものではない。
(Embodiment 4)
The electric heating type catalyst apparatus of Embodiment 4 is demonstrated using FIG. As illustrated in FIG. 3, the electrically heated catalyst device 3 of the present embodiment includes the honeycomb structure 2 of the third embodiment. In the present embodiment, specifically, the electrically heated catalyst device 3 includes a honeycomb structure 2, an exhaust gas purification catalyst (not shown) supported on the cell walls 21 of the honeycomb structure 2, and the honeycomb structure 2. A pair of electrodes 31, 32 disposed opposite to the outer peripheral wall 22, and a voltage application unit 33 that applies a voltage to the electrodes 31, 32 are provided. In addition, a well-known structure can be applied to the electrically heated catalyst device 3, and is not limited to the structure of FIG.
本実施形態の電気加熱式触媒装置３は、本実施形態のハニカム構造体２を有している。そのため、本実施形態の電気加熱式触媒装置３は、その使用時に、本実施形態のハニカム構造体２に担持された排ガス浄化触媒のＳｉ被毒を抑制することができる。 The electrically heated catalyst device 3 of the present embodiment has the honeycomb structure 2 of the present embodiment. Therefore, the electric heating catalyst device 3 of the present embodiment can suppress Si poisoning of the exhaust gas purification catalyst carried on the honeycomb structure 2 of the present embodiment during use.
（実験例）
＜実験例１＞
−試料１−
ホウケイ酸ガラスとＳｉ粒子とカオリンとを２９：３１：４０の質量比で混合した。次いで、この混合物にバインダーとしてメチルセルロースを２質量％添加し、水を加え、混練した。次いで、得られた混合物を押し出し成形機にてペレット状に成形し、焼成した。焼成条件は、Ｎ２ガス雰囲気下・常圧、焼成温度１３００℃、焼成時間３０分、昇温速度２００℃／時間とした。これにより、ホウケイ酸塩とＳｉ粒子とを含む複合材を準備した。なお、複合材の形状は、５ｍｍ×５ｍｍ×１８ｍｍとした。
(Experimental example)
<Experimental example 1>
-Sample 1-
Borosilicate glass, Si particles, and kaolin were mixed at a mass ratio of 29:31:40. Next, 2% by mass of methylcellulose as a binder was added to the mixture, and water was added and kneaded. Next, the obtained mixture was formed into pellets with an extrusion molding machine and baked. The firing conditions were an N 2 gas atmosphere and normal pressure, a firing temperature of 1300 ° C., a firing time of 30 minutes, and a temperature increase rate of 200 ° C./hour. Thus, a composite material containing borosilicate and Si particles was prepared. The shape of the composite material was 5 mm × 5 mm × 18 mm.
次に、準備した複合材をエッチング液（テトラメチルアンモニウムヒドロキシド２２％水溶液、関東化学社製、「ＴＭＡＨ２２」」）に浸漬し、複合材の表層部に含まれるＳｉ含有粒子を選択的に除去した。この際、エッチング温度は、９５℃、エッチング時間は４時間とした。これにより、試料１の電気抵抗体を得た。 Next, the prepared composite material is immersed in an etching solution (tetramethylammonium hydroxide 22% aqueous solution, “TMAH22” manufactured by Kanto Chemical Co., Inc.) to selectively remove Si-containing particles contained in the surface layer portion of the composite material. did. At this time, the etching temperature was 95 ° C. and the etching time was 4 hours. As a result, an electric resistor of Sample 1 was obtained.
−試料１Ｃ−
試料１におけるエッチング処理前の複合材を、試料１Ｃの電気抵抗体とした。
-Sample 1C-
The composite material before the etching treatment in Sample 1 was used as the electrical resistor of Sample 1C.
−電気抵抗体の表面観察−
各試料の電気抵抗体の表面を、走査型電子顕微鏡（ＳＥＭ）にて観察した。その結果を、図４に示す。図４（ａ）と図４（ｂ）との比較から示されるように、試料１の電気抵抗体は、表面をエッチング処理したことにより、表層部に多数の気孔１００ａが存在していることが確認された。エッチング処理に用いたエッチング液は、Ｓｉをエッチングできるものである。そのため、この結果から、試料１の電気抵抗体では、表層部のＳｉ粒子が選択的にエッチングされ、除去されたＳｉ粒子の跡より構成された気孔が表層部に多数存在しているといえる。また、試料１の電気抵抗体は、表層部の表面に連通する連通孔を多数含んでいることが確認された。なお、水銀ポロシメーターを用い、各試料の電気抵抗体の気孔分布も測定した。その結果、図５に示されるように、エッチング処理が施された試料１の電気抵抗体は、エッチング処理が施されていない試料１Ｃの電気抵抗体に比べ、表層部の気孔容積が明らかに増加していることが確認された。この結果からも、試料１の電気抵抗体では、表層部のＳｉ粒子が選択的にエッチングにされ、除去されたＳｉ粒子の跡より構成される気孔が表層部に形成されていることが確認された。
-Surface observation of electrical resistors-
The surface of the electrical resistor of each sample was observed with a scanning electron microscope (SEM). The result is shown in FIG. As shown from the comparison between FIG. 4A and FIG. 4B, the electrical resistor of sample 1 has a large number of pores 100a in the surface layer portion due to the etching process on the surface. confirmed. The etchant used for the etching process can etch Si. Therefore, from this result, it can be said that in the electrical resistor of Sample 1, the surface layer portion Si particles are selectively etched, and a large number of pores composed of traces of the removed Si particles exist in the surface layer portion. Moreover, it was confirmed that the electric resistor of Sample 1 includes a large number of communication holes communicating with the surface of the surface layer portion. In addition, the pore distribution of the electrical resistance body of each sample was also measured using the mercury porosimeter. As a result, as shown in FIG. 5, the electrical resistance body of the sample 1 subjected to the etching process clearly increases the pore volume of the surface layer portion as compared with the electrical resistance body of the sample 1C not subjected to the etching process. It was confirmed that Also from this result, it was confirmed that in the electric resistor of Sample 1, Si particles in the surface layer portion were selectively etched, and pores composed of traces of the removed Si particles were formed in the surface layer portion. It was.
−電気抵抗体の断面観察−
各試料の電気抵抗体の表面に垂直な断面について、Ｓｉ原子のマッピング像を測定した。その結果を図６に示す。図６（ｂ）に示されるように、本実験からも、試料１の電気抵抗体は、表層部のＳｉ粒子１１が選択的にエッチングにされ、除去されたＳｉ粒子１１の跡より構成される気孔１００ａが表層部に形成されたことが確認された。
-Cross-sectional observation of electrical resistor-
A mapping image of Si atoms was measured for a cross section perpendicular to the surface of the electric resistor of each sample. The result is shown in FIG. As shown in FIG. 6B, also from this experiment, the electric resistor of the sample 1 is composed of the traces of the Si particles 11 that are removed by selectively etching the Si particles 11 in the surface layer portion. It was confirmed that the pores 100a were formed in the surface layer portion.
−電気抵抗体の表層部および内層部におけるＳｉ含有粒子の含有量測定−
上述した測定方法により、試料１の電気抵抗体について、表層部におけるＳｉ含有粒子の含有量、および、内層部におけるＳｉ含有粒子の含有量を測定した。図７（ａ）に試料１の表層部領域１００ｂを含むＳＥＭ像、図７（ｂ）試料１の内層部測定領域１０１ｂを含むＳＥＭ像を示す。上記測定の結果、ＳＥＭ像から特定されるＳｉ粒子１１の最大径は１５μｍであった。したがって、本実験例では、電気抵抗体１の表面から内方に向かって１５μｍまでの深さ領域が表層部１００となる。当該表層部１００におけるＳｉ含有粒子１１の含有量は、２％であった。また、内層部１０１におけるＳｉ含有粒子１１の含有量は、３０％であった。本実験例によれば、試料１の電気抵抗体は、表層部に含まれていたＳｉ粒子がエッチング処理によって選択的にエッチングされることにより、表層部におけるＳｉ粒子の含有量＜内層部におけるＳｉ粒子の含有量の関係を満たしていることが確認された。
-Measurement of content of Si-containing particles in surface layer portion and inner layer portion of electric resistor-
With the measurement method described above, the content of the Si-containing particles in the surface layer part and the content of the Si-containing particles in the inner layer part of the electrical resistor of Sample 1 were measured. FIG. 7A shows an SEM image including the surface layer region 100b of the sample 1 and FIG. 7B shows an SEM image including the inner layer measurement region 101b of the sample 1. As a result of the measurement, the maximum diameter of the Si particles 11 specified from the SEM image was 15 μm. Therefore, in the present experimental example, the surface layer portion 100 is a depth region up to 15 μm from the surface of the electric resistor 1 inward. The content of the Si-containing particles 11 in the surface layer portion 100 was 2%. The content of the Si-containing particles 11 in the inner layer portion 101 was 30%. According to this experimental example, the electrical resistor of Sample 1 is such that the Si particles contained in the surface layer portion are selectively etched by the etching process, whereby the content of Si particles in the surface layer portion <Si in the inner layer portion. It was confirmed that the relationship of particle content was satisfied.
−電気抵抗体の電気抵抗率の測定−
各試料の電気抵抗体について、電気抵抗率を測定した。なお、電気抵抗率は、５ｍｍ×５ｍｍ×１８ｍｍの角柱サンプルについて、熱電特性評価装置（アルバック理工社製、「ＺＥＭ−２」）を用い、四端子法で測定した。図８に示されるように、表層部のＳｉ粒子を選択的にエッチングすることにより、電気抵抗率が１桁程度大きくなった。これは、エッチング処理によって導電性のＳｉ粒子が減少したためである。もっとも、図８に示されるように、試料１の電気抵抗体は、エッチング処理を施すことで電気抵抗率が大きくなったものの、電気加熱式触媒装置におけるハニカム構造体の材料として十分に適用可能な電気抵抗率を有していることが確認された。また、試料１の電気抵抗体は、電気抵抗率の温度依存性が小さく、電気抵抗率がＰＴＣ特性を示すことも確認された。
-Measurement of electrical resistivity of electrical resistor-
The electrical resistivity of each sample was measured. In addition, the electrical resistivity was measured by a four-terminal method using a thermoelectric property evaluation apparatus (“ZEM-2” manufactured by ULVAC-RIKO, Inc.) for a prism sample of 5 mm × 5 mm × 18 mm. As shown in FIG. 8, the electrical resistivity was increased by about one digit by selectively etching the Si particles in the surface layer portion. This is because the conductive Si particles are reduced by the etching process. However, as shown in FIG. 8, the electrical resistance of the sample 1 is sufficiently applicable as a material for the honeycomb structure in the electrically heated catalyst device, although the electrical resistivity is increased by performing the etching process. It was confirmed to have electrical resistivity. Moreover, it was also confirmed that the electrical resistor of Sample 1 has a small temperature dependency of electrical resistivity, and the electrical resistivity exhibits PTC characteristics.
本発明は、上記各実施形態、各実験例に限定されるものではなく、その要旨を逸脱しない範囲において種々の変更が可能である。また、各実施形態、各実験例に示される各構成は、それぞれ任意に組み合わせることができる。 The present invention is not limited to the above-described 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 be combined arbitrarily, respectively.
１ 電気抵抗体
１０ ホウケイ酸塩
１１ Ｓｉ含有粒子
１００ 表層部
１０１ 内層部
２ ハニカム構造体
３ 電気加熱式触媒装置
DESCRIPTION OF SYMBOLS 1 Electric resistor 10 Borosilicate 11 Si containing particle | grains 100 Surface layer part 101 Inner layer part 2 Honeycomb structure 3 Electric heating type catalyst apparatus
Claims (7)
上記電気抵抗体は、上記電気抵抗体の表面を含む表層部（１００）と、上記表層部に接し、上記表層部の内側に配置された内層部（１０１）とを有しており、
上記表層部における上記Ｓｉ含有粒子の含有量は、上記内層部における上記Ｓｉ含有粒子の含有量よりも少ない、電気抵抗体（１）。 An electrical resistor (1) comprising borosilicate (10) and Si-containing particles (11),
The electrical resistor has a surface layer part (100) including the surface of the electrical resistor, and an inner layer part (101) disposed in contact with the surface layer part and disposed inside the surface layer part,
The electric resistor (1) in which the content of the Si-containing particles in the surface layer portion is less than the content of the Si-containing particles in the inner layer portion.
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| WO2019124183A1 (en) * | 2017-12-19 | 2019-06-27 | 株式会社デンソー | Electrical resistor, honeycomb structure, and electrical heating-type ca- talytic device |
| JPWO2021182196A1 (en) * | 2020-03-13 | 2021-09-16 | ||
| CN113631266A (en) * | 2019-03-27 | 2021-11-09 | 株式会社电装 | Resistor, honeycomb structure, and electrically heated catalyst device |
| CN114846226A (en) * | 2020-01-07 | 2022-08-02 | 日本碍子株式会社 | Electric heating type carrier and exhaust gas purification device |
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| WO2019124183A1 (en) * | 2017-12-19 | 2019-06-27 | 株式会社デンソー | Electrical resistor, honeycomb structure, and electrical heating-type ca- talytic device |
| JP2019108863A (en) * | 2017-12-19 | 2019-07-04 | 株式会社デンソー | Electric resistor, honeycomb structure and electric heating type catalyst device |
| CN113631266A (en) * | 2019-03-27 | 2021-11-09 | 株式会社电装 | Resistor, honeycomb structure, and electrically heated catalyst device |
| CN114846226A (en) * | 2020-01-07 | 2022-08-02 | 日本碍子株式会社 | Electric heating type carrier and exhaust gas purification device |
| CN114846226B (en) * | 2020-01-07 | 2023-08-08 | 日本碍子株式会社 | Electric heating type carrier and exhaust gas purifying device |
| JPWO2021182196A1 (en) * | 2020-03-13 | 2021-09-16 | ||
| WO2021182196A1 (en) * | 2020-03-13 | 2021-09-16 | 日本碍子株式会社 | Honeycomb structure and electric heating-type carrier |
| JP7250996B2 (en) | 2020-03-13 | 2023-04-03 | 日本碍子株式会社 | Honeycomb structure and electrically heated carrier |
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