JP2006185633A - Ceramic heater and its manufacturing method - Google Patents

Ceramic heater and its manufacturing method Download PDF

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JP2006185633A
JP2006185633A JP2004374977A JP2004374977A JP2006185633A JP 2006185633 A JP2006185633 A JP 2006185633A JP 2004374977 A JP2004374977 A JP 2004374977A JP 2004374977 A JP2004374977 A JP 2004374977A JP 2006185633 A JP2006185633 A JP 2006185633A
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ceramic
alumina
ceramic heater
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mass
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JP4938976B2 (en
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Kuniharu Tanaka
邦治 田中
Yoshihito Igai
良仁 猪飼
Kikuo Sakurai
喜久男 桜井
Shigehiro Otsuka
茂弘 大塚
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Niterra Co Ltd
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NGK Spark Plug Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a ceramic heater and a manufacturing method superior in electric durability and strength in a severe environment. <P>SOLUTION: The ceramic heater 1 is column-shaped, and a ceramic laminate 3 of which the main component is alumina is wound around a core material 2 of which similarly the main component is alumina. In this ceramic laminate 3, an exothermic body 6 of which the main component is tungsten (W) is pinched between a first ceramic layer 4 and a second ceramic layer 5. In the ceramic laminate 3, the ratio (a1/a2) of an intercept particle diameter (a1) measured from a surface direction and the intercept particle diameter (a2) measured from the cross-sectional direction is made to be 1.1 to 1.3. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、例えば、自動車用酸素センサ、グローシステム用ヒータ、半導体加熱用ヒータ、家庭用石油ファンヒータ、便座用ヒータ等に適用可能なセラミックヒータ及びその製造方法に関する。   The present invention relates to a ceramic heater applicable to, for example, an automobile oxygen sensor, a glow system heater, a semiconductor heating heater, a domestic petroleum fan heater, a toilet seat heater, and the like, and a manufacturing method thereof.

従来から、セラミックヒータとしては、板状や柱状のものが使用されている。このセラミックヒータは、シート成形、押し出し成形等により成形された平板、円筒等のセラミック基材に、白金、白金−ロジウム、モリブデン、タングステン等の高融点金属を含有するぺーストを用いて発熱パターンを厚膜印刷し、これを平板のまま、若しくは円筒状に巻いた後一体焼成して製造される。   Conventionally, as a ceramic heater, a plate-like or columnar one has been used. This ceramic heater uses a paste containing a refractory metal such as platinum, platinum-rhodium, molybdenum, tungsten, etc. on a ceramic substrate such as a flat plate or cylinder formed by sheet molding, extrusion molding, etc. Thick film printing is performed, and this is produced as a flat plate or rolled into a cylindrical shape and then integrally fired.

特に、セラミックとしてアルミナ（Ａｌ2 Ｏ3 ）、高融点金属としてタングステン（Ｗ）を用い、セラミック基材、発熱パターン、セラミックグリーンシートが順に積層され、ー体焼成されたセラミックヒータがその代表例であり、広範囲の分野で利用されている。 A typical example is a ceramic heater in which alumina (Al 2 O 3 ) is used as a ceramic, tungsten (W) is used as a refractory metal, a ceramic base material, a heat generation pattern, and a ceramic green sheet are laminated in order. Yes, it is used in a wide range of fields.

この種のセラミックヒータは、長時間高温に晒されることが多いため、特に耐久性及び強度が優れたものが必要とされる。耐久性及び強度を高める方法としては、セラミック基材に焼結助材を混合する方法が知られている。   Since this type of ceramic heater is often exposed to high temperatures for a long time, a ceramic heater having particularly excellent durability and strength is required. As a method for increasing durability and strength, a method of mixing a sintering aid with a ceramic base material is known.

しかしながら、焼結助剤を用いた場合、セラミックヒータを高温下で使用すると、添加物イオン等の低電位側への移動（マイグレーション）が発生してしまい、これが原因で断線が発生し、セラミックヒータの寿命の低下を引き起こすことがある。即ち、セラミック基材中のイオン化し易い成分が電界及び高熱によりイオン化し、陽イオン成分が発熱体の高電位側から遠ざかるとともに、発熱体の低電位側に集まる。その結果、発熱体の高電位側付近のセラミック基材は多孔質の状態となる。そして、この多孔質の領域が内部からセラミックヒータの表面に達したとき、その多孔質の領域に大気が進入して発熱体が酸化され、抵抗が増大し、断線が起こることがある（発熱体が、Ｗ等の酸化し易い材料の場合）。一方、発熱体の低電位側付近には、移動した陽イオン成分が凝集し、発熱体に陽イオンが進入することにより、この部分の抵抗が増大し、発熱量が増加して断線が起こることがある。   However, when a sintering aid is used, if the ceramic heater is used at a high temperature, the migration (migration) of additive ions and the like to the low potential side occurs, which causes disconnection, and the ceramic heater May cause a decrease in lifespan. That is, the easily ionized component in the ceramic substrate is ionized by the electric field and high heat, and the cation component moves away from the high potential side of the heating element and collects on the low potential side of the heating element. As a result, the ceramic substrate near the high potential side of the heating element becomes porous. When this porous region reaches the surface of the ceramic heater from the inside, the air enters the porous region, the heating element is oxidized, resistance increases, and disconnection may occur (heating element). However, in the case of a material that easily oxidizes such as W). On the other hand, the moved cation component aggregates near the low potential side of the heating element, and the cation enters the heating element, thereby increasing the resistance of this portion and increasing the amount of generated heat, resulting in disconnection. There is.

このため、セラミック基材のセラミック成分を改良することによってマイグレーションを抑制し、一定以上の耐久性を得る方法が知られている（例えば、特許文献１参照。）。また、発熱体の成分を改良することによって酸化を抑制し、一定以上の耐久性を得る方法が知られている（例えば、特許文献２参照。）。さらに、２つの異なった割掛率を有するセラミックシートを一体焼成させることによって板状セラミック焼結体の強度を強化する方法が知られている（例えば、特許文献３参照。）。さらにまた、ヒータ表面に圧縮残留応力を残して一定以上の強度及び耐久性を得る方法も知られている（例えば、特許文献４参照。）
特開平１−２２５０８７号公報 特開平６−１８８０６５号公報 特開昭６１−１４１８７号公報 特開平１１−８７０２１号公報 For this reason, a method is known in which migration is suppressed by improving the ceramic component of the ceramic substrate to obtain a certain durability or more (see, for example, Patent Document 1). Further, a method is known in which oxidation is suppressed by improving the components of the heating element to obtain a certain level of durability (for example, see Patent Document 2). Furthermore, a method is known in which the strength of a plate-shaped ceramic sintered body is strengthened by integrally firing ceramic sheets having two different crack rates (see, for example, Patent Document 3). Furthermore, a method of obtaining a certain level of strength and durability by leaving compressive residual stress on the heater surface is also known (see, for example, Patent Document 4).
Japanese Patent Laid-Open No. 1-225087 Japanese Patent Laid-Open No. 6-1888065 JP-A-61-14187 Japanese Patent Laid-Open No. 11-87021

上述したとおり、従来からセラミックヒータにおいては、苛酷な環境下における電気的耐久性及び強度の向上を図ることが行われている。しかしながら、上述した特許文献１〜４では十分でなく、更なるセラミックヒータにおける電気的耐久性及び強度の向上を図ることが求められている。   As described above, ceramic heaters have conventionally been improved in electrical durability and strength under harsh environments. However, Patent Documents 1 to 4 described above are not sufficient, and further improvements in electrical durability and strength in ceramic heaters are required.

本発明は、上記課題を解決するためになされたものである。本発明は、苛酷な環境下における電気的耐久性及び強度に優れたセラミックヒータ及びその製造方法を提供することを目的とする。   The present invention has been made to solve the above problems. An object of this invention is to provide the ceramic heater excellent in the electrical durability and intensity | strength in a severe environment, and its manufacturing method.

（請求項１）
上記目的を達成するために、本発明のセラミックヒータは、アルミナを主成分とする第１のセラミック層と、アルミナを主成分とする第２のセラミック層との間に、発熱体を挟持させたセラミック積層体を具備するセラミックヒータであって、前記セラミック積層体の表面方向から測定したインターセプト粒径（ａ1 ）と、断面方向から測定したインターセプト粒径（ａ2 ）の比（ａ1 ／ａ2 ）が、１．１〜１．３であることを特徴とする。 (Claim 1)
In order to achieve the above object, in the ceramic heater of the present invention, a heating element is sandwiched between a first ceramic layer mainly composed of alumina and a second ceramic layer mainly composed of alumina. A ceramic heater comprising a ceramic laminate, wherein the ratio (a1 / a2) of the intercept particle size (a1) measured from the surface direction of the ceramic laminate and the intercept particle size (a2) measured from the cross-sectional direction is 1.1 to 1.3.

（請求項３）
また、本発明のセラミックヒータは、アルミナを主成分とする芯材と、該芯材に巻回され、アルミナを主成分とする第３のセラミック層と該第３のセラミック層と前記芯材との間に挟持させた発熱体とを有するセラミック積層体と、を具備するセラミックヒータであって、前記セラミック積層体の表面方向から測定したインターセプト粒径（ａ1 ）と、断面方向から測定したインターセプト粒径（ａ2 ）の比（ａ1 ／ａ2 ）が、１．１〜１．３であることを特徴とする。 (Claim 3)
The ceramic heater of the present invention includes a core material mainly composed of alumina, a third ceramic layer wound around the core material and mainly composed of alumina, the third ceramic layer, and the core material. A ceramic laminate having a heating element sandwiched therebetween, wherein the intercept particle diameter (a1) measured from the surface direction of the ceramic laminate and the intercept grain measured from the cross-sectional direction The ratio (a1 / a2) of the diameter (a2) is 1.1 to 1.3.

ここで、インターセプト粒径とは、インターセプト法により測定した粒径（平均粒径）であり、具体的には、例えば、以下のようにして測定した粒径である。   Here, the intercept particle diameter is a particle diameter (average particle diameter) measured by the intercept method, and specifically, for example, a particle diameter measured as follows.

まず、ヒータ断面及び表面を切断または研削加工を用い平面を得る。その後ダイヤモンドディスク等を用いて鏡面研磨を行う。   First, a plane is obtained by cutting or grinding the heater cross section and surface. Thereafter, mirror polishing is performed using a diamond disk or the like.

その後、必要に応じて、サーマルエッチング、ケミカルエッチングを行ってもよい。   Thereafter, thermal etching and chemical etching may be performed as necessary.

次に、ＳＥＭ観察を所定倍率（例えば、３０００倍程度）で行い、組織面像を得る。この組織の面像上に合計長さが所定長さ（例えば、５００μｍ）相当になる直線を数本ランダムに引く。そして、直線が横切る粒子数を数えて、画像上での直線長さ（例えば、５００μｍ）を粒子数で除した値をインターセプト粒径とし、ａ1 ／ａ2 の値を求める。   Next, SEM observation is performed at a predetermined magnification (for example, about 3000 times) to obtain a tissue surface image. Several straight lines whose total length corresponds to a predetermined length (for example, 500 μm) are randomly drawn on the surface image of the tissue. Then, the number of particles traversed by the straight line is counted, and the value obtained by dividing the length of the straight line on the image (for example, 500 μm) by the number of particles is defined as the intercept particle diameter, and the value of a1 / a2 is obtained.

なお、図３は、倍率３０００倍で１本の線の長さが５０μｍの直線を引いてセラミック積層体の表面方向からインターセプト粒径を測定した組織面像（顕微鏡写真）の一例を示している。また図４は、同様にしてセラミック積層体の断面方向からインターセプト粒径を測定した組織面像（顕微鏡写真）の一例を示している。この例では、図３の場合、直線が横切る粒子数が２１個、図４の場合、直線が横切る粒子数が２７個となる。一例として図３，４に示されたそれぞれの１本の線のみからａ1 ／ａ2 を求めると、
ａ1 ／ａ2 ＝（５０／２１）／（５０／２７）＝１．２９
となる。実際には、上記のような線を複数（例えば、１０本）引いてこれらの結果からインターセプト粒径（ａ1 ，ａ2 ）及びその比（ａ1 ／ａ2 ）を求める。 FIG. 3 shows an example of a structure surface image (micrograph) obtained by measuring the intercept particle diameter from the surface direction of the ceramic laminate by drawing a straight line with a magnification of 3000 times and a length of one line of 50 μm. . FIG. 4 shows an example of a tissue surface image (micrograph) obtained by measuring the intercept particle diameter from the cross-sectional direction of the ceramic laminate in the same manner. In this example, in the case of FIG. 3, the number of particles crossed by the straight line is 21, and in the case of FIG. 4, the number of particles crossed by the straight line is 27. As an example, when a1 / a2 is obtained from only one line shown in FIGS.
a1 / a2 = (50/21) / (50/27) = 1.29
It becomes. Actually, a plurality of lines (for example, 10) as described above are drawn, and the intercept particle diameter (a1, a2) and the ratio (a1 / a2) are obtained from these results.

ａ1 ＞ａ2 （（ａ1 ／ａ2 ）＞１）の場合、アルミナ粒子はマイグレーションによりヒータ表面へ拡散する陽イオンの移動方向に対して垂直方向に大きく粒成長している状態となる。その結果、陽イオンの拡散時に、組織に異方性のない場合と比較して移動経路が長くなり、耐久寿命が向上する。１．１未満ではその効果が少なく、１．３より大きくなると粒径が大きくなりすぎ、強度が低下する。このため、（ａ1 ／ａ2 ）を１．１〜１．３の範囲内とすることが好ましい。   In the case of a1> a2 ((a1 / a2)> 1), the alumina particles are greatly grown in a direction perpendicular to the moving direction of the cation diffusing to the heater surface by migration. As a result, at the time of cation diffusion, the movement path becomes longer compared to the case where the tissue has no anisotropy, and the durability life is improved. If it is less than 1.1, the effect is small, and if it exceeds 1.3, the particle size becomes too large and the strength decreases. For this reason, it is preferable that (a1 / a2) be in the range of 1.1 to 1.3.

（請求項２，４，６）
また、本発明のセラミックヒータでは、第１のセラミック層及び第２のセラミック層 （第３のセラミック層及び第４のセラミック層）のアルミナの含有量が９５質量％以上であることを特徴とする。アルミナの含有量が多くなると、相対的にマイグレーションによって移動する助剤成分が少なくなり、マイグレーションに起因するヒータの抵抗の上昇を小さくすることができ、ヒータの局所加熱を抑制することができる。９５質量％未満ではその効果が少ない。 (Claims 2, 4, 6)
In the ceramic heater of the present invention, the alumina content of the first ceramic layer and the second ceramic layer (the third ceramic layer and the fourth ceramic layer) is 95% by mass or more. . When the content of alumina is increased, the amount of the auxiliary component that is relatively moved by migration is reduced, the increase in the resistance of the heater due to migration can be reduced, and local heating of the heater can be suppressed. If it is less than 95% by mass, the effect is small.

（請求項５）
また、本発明のセラミックヒータでは、芯材と発熱体との間に挟持させた第４のセラミック層を具備することを特徴とする。このように、セラミック積層体が、芯材と発熱体との間に挟持させた第４のセラミック層を具備するセラミックヒータであっても、インターセプト粒径の比（ａ1 ／ａ2 ）が、１．１〜１．３であることでセラミックヒータの耐久寿命が向上する。 (Claim 5)
The ceramic heater according to the present invention includes a fourth ceramic layer sandwiched between the core member and the heating element. Thus, even if the ceramic laminate is a ceramic heater including the fourth ceramic layer sandwiched between the core material and the heating element, the ratio of intercept particle diameters (a1 / a2) is 1. The durable life of a ceramic heater improves by being 1-1.3.

（請求項７）
また、本発明のセラミックヒータの製造方法は、請求項１又は２記載のセラミックヒータの製造方法であって、アルミナを主成分としＺｎＯが０．１〜２．０質量％添加された第１のグリーンシートと、アルミナを主成分としＺｎＯが０．１〜２．０質量％添加された第２のグリーンシートとの間に、発熱体材料を挟持させてシート成形体とし、アルミナを主成分とする支持基体成形体を１２５０〜１４００℃で予備焼成した後、当該支持基体成形体に前記シート成形体を積層し、水素を含有する雰囲気下で一体焼成することを特徴とする。 (Claim 7)
Moreover, the manufacturing method of the ceramic heater of this invention is a manufacturing method of the ceramic heater of Claim 1 or 2, Comprising: The alumina is a main component and ZnO is added 0.1 to 2.0 mass% 1st. A heating element material is sandwiched between the green sheet and a second green sheet containing alumina as a main component and containing 0.1 to 2.0% by mass of ZnO to form a sheet, and alumina as a main component. The support base molded body is pre-fired at 1250 to 1400 ° C., and then the sheet molded body is laminated on the support base base body and integrally fired in an atmosphere containing hydrogen.

（請求項８）
また、本発明のセラミックヒータの製造方法は、請求項３又は４記載のセラミックヒータの製造方法であって、アルミナを主成分としＺｎＯが０．１〜２．０質量％添加された第３のグリーンシートを、アルミナを主成分とする１２５０〜１４００℃で予備焼成した芯材成形体に発熱体材料を挟持させて巻回し、水素を含有する雰囲気下で一体焼成することを特徴とする。 (Claim 8)
Moreover, the manufacturing method of the ceramic heater of this invention is a manufacturing method of the ceramic heater of Claim 3 or 4, Comprising: 3rd with 0.1 to 2.0 mass% of ZnO which added alumina as a main component. A green sheet is wound by sandwiching a heating element material between core material compacts preliminarily fired at 1250 to 1400 ° C. containing alumina as a main component, and integrally fired in an atmosphere containing hydrogen.

（請求項９）
また、本発明のセラミックヒータの製造方法は、請求項５又は６記載のセラミックヒータの製造方法であって、アルミナを主成分とし、ＺｎＯが０．１〜２．０質量％添加された第３のグリーンシートと、アルミナを主成分とし、ＺｎＯが０．１〜２．０質量％添加された第４のグリーンシートとの間に発熱体材料を挟持させてシート成形体とし、アルミナを主成分とする芯材成形体を１２５０〜１４００℃で予備焼成した後前記シート成形体を巻回し、水素を含有する雰囲気下で一体焼成することを特徴とする。 (Claim 9)
Moreover, the manufacturing method of the ceramic heater of this invention is a manufacturing method of the ceramic heater of Claim 5 or 6, Comprising: The alumina is a main component and ZnO is added 0.1 to 2.0 mass% 3rd. The green sheet and a fourth green sheet containing alumina as a main component and 0.1 to 2.0% by mass of ZnO are sandwiched between the heating element materials to form a sheet, and the main component is alumina. The core molded body is pre-fired at 1250 to 1400 ° C., and then the sheet molded body is wound and integrally fired in an atmosphere containing hydrogen.

上記のセラミックヒータの製造方法において、ＺｎＯの効果に関して詳細は不明だが、焼成初期に他の焼結助剤と低融点ガラス相を形成して、異方性ある組織になりやすい状態にする効果があると推測される。そして、高温状態である焼結後期には、雰囲気中に含まれる水素によって金属Ｚｎに還元され、昇華し、焼結体中に残存しないために、他の焼結助剤成分と異なり、耐マイグレーション性能に悪影響を及ぼさない焼結助剤となる。尚その量が０．１％より少ないと効果が十分になく、多過ぎるとＺｎの昇華による焼成炉の汚染が懸念されるので、２％以下が適当と考えられる。また、支持基体成形体及び芯材成形体を予備焼成し、グリーンシートよりも収縮しない状態にしてからグリーンシートを取り付け、グリーンシートを焼成時に厚み方向に大きく収縮させることも同時に必要である。その予備焼成温度が１２５０℃よりも低いとＺｎＯを添加しても（ａ1 ／ａ2 ）が、１．１〜１．３になり難く、１．１よりも小さくなる傾向がある。一方、予備焼成温度が１４００℃を超えると（ａ1 ／ａ2 ）が１．３を超えてしまう傾向がある。   In the above ceramic heater manufacturing method, details regarding the effect of ZnO are unknown, but it has the effect of forming a low-melting glass phase with other sintering aids at the initial stage of firing, which tends to become an anisotropic structure. Presumed to be. And in the latter stage of sintering, which is a high temperature state, it is reduced to metal Zn by hydrogen contained in the atmosphere, sublimates, and does not remain in the sintered body. It becomes a sintering aid that does not adversely affect performance. If the amount is less than 0.1%, the effect is not sufficient, and if it is too much, contamination of the firing furnace due to Zn sublimation is concerned, so 2% or less is considered appropriate. In addition, it is also necessary to pre-fire the support base molded body and the core material molded body so that the green sheet is not shrunk in comparison with the green sheet, and then the green sheet is contracted greatly in the thickness direction during firing. When the pre-baking temperature is lower than 1250 ° C., even if ZnO is added, (a 1 / a 2) hardly becomes 1.1 to 1.3 and tends to be smaller than 1.1. On the other hand, when the pre-baking temperature exceeds 1400 ° C., (a1 / a2) tends to exceed 1.3.

本発明によれば、苛酷な環境下における電気的耐久性及び強度に優れたセラミックヒータ及びその製造方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the ceramic heater excellent in the electrical durability and intensity | strength in a severe environment, and its manufacturing method can be provided.

以下、本発明の実施の形態について図面を参照して説明する。図１は、本発明の一実施形態に係るセラミックヒータの概略構成を示すものである。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows a schematic configuration of a ceramic heater according to an embodiment of the present invention.

同図に示すように、本実施形態のセラミックヒータ１は、円柱状であり、アルミナを主成分とする芯材２の回りに、同様にアルミナを主成分とするセラミック積層体３を巻き付けたものである。このセラミック積層体３は、第１（第３）のセラミック層４と第２（第４）のセラミック層５との間に、タングステン（Ｗ）を主成分とする発熱体６を挟んだものである。また、発熱体６の基端側には、第１（第３）のセラミック層４に形成されたスルーホール１６（図２参照）を介して発熱体６と電気的に接続する一対の端子部７が設けられ、各端子部７には、それぞれリード線８が接続されている。   As shown in the figure, the ceramic heater 1 of the present embodiment has a cylindrical shape, and a ceramic laminate 3 mainly composed of alumina is wound around a core material 2 mainly composed of alumina. It is. This ceramic laminate 3 is obtained by sandwiching a heating element 6 containing tungsten (W) as a main component between a first (third) ceramic layer 4 and a second (fourth) ceramic layer 5. is there. Further, on the base end side of the heating element 6, a pair of terminal portions that are electrically connected to the heating element 6 through through holes 16 (see FIG. 2) formed in the first (third) ceramic layer 4. 7 is provided, and a lead wire 8 is connected to each terminal portion 7.

本実施形態において、セラミック積層体３は、表面方向から測定したインターセプト粒径（ａ1 ）と、断面方向から測定したインターセプト粒径（ａ2 ）の比（ａ1 ／ａ2 ）が、１．１〜１．３とされている。また、第１（第３）のセラミック層４及び第２（第４）のセラミック層５のアルミナ含有量は、９５質量％以上とされている。   In the present embodiment, the ceramic laminate 3 has a ratio (a1 / a2) of the intercept particle diameter (a1) measured from the surface direction to the intercept particle diameter (a2) measured from the cross-sectional direction of 1.1 to 1. It is set to 3. The alumina content of the first (third) ceramic layer 4 and the second (fourth) ceramic layer 5 is 95% by mass or more.

次に、このセラミックヒータ１の製造方法を、図２を参照して説明する。まず、φ２．４ｍｍ、長さ７４ｍｍのＭｇＯ−ＣａＯ−ＳｉＯ2 系のアルミナを主成分とする芯材の材料を、大気中で１２５０〜１４００℃で予備焼成し、芯材成形体１１とする。芯材成形体１１の形状としては、円柱状、円筒状、棒状、四角柱状、六角柱状等種々のものが使用できるが、熱の発散性、強度、及び成形のし易さの点から、円筒状であることが好ましい。芯材の材料は、例えば、粉末状としたアルミナを他の粉末とボールミル等で混合した後、スラリー状として所定の形状とする。 Next, a method for manufacturing the ceramic heater 1 will be described with reference to FIG. First, a core material composed mainly of MgO—CaO—SiO 2 -based alumina having a diameter of 2.4 mm and a length of 74 mm is pre-fired at 1250 to 1400 ° C. in the atmosphere to obtain a core material molded body 11. Various shapes such as a columnar shape, a cylindrical shape, a rod shape, a square columnar shape, and a hexagonal columnar shape can be used as the shape of the core material molded body 11, but in terms of heat diffusibility, strength, and ease of forming, it is a cylinder. It is preferable that it is a shape. The core material is, for example, powdered alumina mixed with other powders with a ball mill or the like, and then made into a predetermined shape as a slurry.

次に、該芯材成形体１１と同種の材質を有する第２のグリーンシート１２（８ｍｍ×６９ｍｍ，厚さ０．３ｍｍ）上に、発熱体材料である発熱パターン１３を印刷する。そして、この印刷面側に、同種の材質を有する第１のグリーンシート１４（８ｍｍ×６９ｍｍ，厚さ０．０７ｍｍ）を積層し、第１及び第２のグリーンシート１２，１４間に発熱パターン１３を挟んで圧着して、シート成形体１５とした。尚、第１のグリーンシート１４には、発熱パターン１３の基端側と端子部７とを電気的に接続するためのスルーホール１６が設けられている。上記第１のグリーンシート１２及び第２のグリーンシート１４は、例えば、粉末状としたアルミナにＺｎＯを０．１〜２．０質量％添加し、他の焼結助剤等の添加物を加えボールミル等で混合した後、スラリー状として、ドクターブレード法等で作成することができる。   Next, a heating pattern 13 as a heating element material is printed on a second green sheet 12 (8 mm × 69 mm, thickness 0.3 mm) having the same material as that of the core material molded body 11. Then, a first green sheet 14 (8 mm × 69 mm, thickness 0.07 mm) having the same kind of material is laminated on the printed surface side, and a heat generation pattern 13 is formed between the first and second green sheets 12 and 14. The sheet molded body 15 was formed by pressure bonding. Note that the first green sheet 14 is provided with a through hole 16 for electrically connecting the base end side of the heat generating pattern 13 and the terminal portion 7. In the first green sheet 12 and the second green sheet 14, for example, 0.1 to 2.0% by mass of ZnO is added to powdered alumina, and other additives such as a sintering aid are added. After mixing by a ball mill or the like, it can be prepared as a slurry by a doctor blade method or the like.

次に、シート成形体１５を芯材成形体１１に巻回し、Ｎ2 ＋Ｈ2 の雰囲気中で１５５０℃で一体焼成した。なお、水素含有量は、焼成炉中のＨ2 ／Ｈ2 Ｏが１以上となるようにしている。これにより、第１のグリーンシート１２、第２のグリーンシート１４、発熱パターン１３、シート成形体１５、芯材成形体１１は、それぞれ第１のセラミック層４、第２のセラミック層５、発熱体６、セラミック積層体３、芯材２となる。 Next, the sheet molding 15 was wound around the core molding 11 and integrally fired at 1550 ° C. in an atmosphere of N 2 + H 2 . The hydrogen content is set so that H 2 / H 2 O in the firing furnace is 1 or more. Accordingly, the first green sheet 12, the second green sheet 14, the heat generation pattern 13, the sheet molded body 15, and the core material molded body 11 are the first ceramic layer 4, the second ceramic layer 5, and the heat generating body, respectively. 6, the ceramic laminate 3 and the core material 2.

その後、発熱体６と電気的に通じるように、端子部７とリード線８とを接続し、セラミックヒータ１を完成した。   Then, the terminal part 7 and the lead wire 8 were connected so that it might be electrically connected with the heat generating body 6, and the ceramic heater 1 was completed.

表１は、アルミナ添加量及び助剤（ＳｉＯ2 −ＣａＯ−ＭｇＯ）添加量、ＺｎＯ添加量、予備焼成温度を変化させた場合に、ａ1 ／ａ2 の値、連続耐久寿命、クラック発生率がどのように変化するか調査した結果を示すものである。なお、連続耐久寿命の試験は、ヒータの芯材が１１５０℃になるようにヒータに通電し、発熱体の高電位側付近で発生する多孔質の領域のうち、最もセラミックヒータの表面に近い個所が発熱体とセラミックヒータの表面との中間の距離まで拡大する時間を調べることによって行った。また、クラック発生率は、セラミックヒータを酸素センサ素子に組み付け、酸素センサ素子表面が５秒で常温から４００℃まで昇温する条件でセラミックヒータに通電し、この通電を１００サイクル行った後にヒータのクラックの有無を確認して測定した。各実施例及び比較例において測定したサンプル数はそれぞれ１０個である。
Table 1 shows the values of a 1 / a 2, continuous durability life, and crack generation rate when the alumina addition amount, auxiliary (SiO 2 —CaO—MgO) addition amount, ZnO addition amount, and pre-baking temperature are changed. It shows the result of investigating whether it changes. In the continuous durability life test, the heater is energized so that the core material of the heater is 1150 ° C., and the portion of the porous region generated near the high potential side of the heating element is closest to the surface of the ceramic heater. Was performed by examining the time to expand to an intermediate distance between the heating element and the surface of the ceramic heater. In addition, the crack occurrence rate is determined by attaching the ceramic heater to the oxygen sensor element, energizing the ceramic heater under the condition that the surface of the oxygen sensor element is heated from room temperature to 400 ° C. in 5 seconds, and after conducting this energization for 100 cycles, The presence or absence of cracks was confirmed and measured. The number of samples measured in each example and comparative example is 10 each.

表１に示すように、比較例１ではＺｎＯの添加がないため、又比較例２では予備焼成温度が低いため、ａ1 ／ａ2 が１．１０に満たなかった。そして、この場合連続耐久寿命が１０時間未満となった。また、比較例３では予備焼成温度が高いため、ａ1 ／ａ2 が１．３０以上となった。そして、この場合連続耐久寿命が長くなるが、クラック発生率が高くなり強度の点で問題が生じた。   As shown in Table 1, in Comparative Example 1, ZnO was not added, and in Comparative Example 2, since the pre-calcination temperature was low, a1 / a2 was less than 1.10. In this case, the continuous durability life was less than 10 hours. In Comparative Example 3, since the pre-baking temperature was high, a1 / a2 was 1.30 or more. In this case, the continuous durability life becomes long, but the crack generation rate becomes high and a problem arises in terms of strength.

一方、実施例１〜４では、ＺｎＯを添加し、予備焼成温度を１２５０〜１４００℃の範囲内とすることにより、ａ1 ／ａ2 が１．１０〜１．３０の範囲となった。そして、この場合連続耐久寿命が１０時間以上であり、クラック発生率も０％となった。さらに、実施例１〜３では、アルミナ含有率を９５質量％以上とすることにより、連続耐久寿命を２０時間以上とすることができた。   On the other hand, in Examples 1 to 4, by adding ZnO and setting the pre-baking temperature within the range of 1250 to 1400 ° C., a1 / a2 was in the range of 1.10 to 1.30. In this case, the continuous durability life was 10 hours or more, and the crack generation rate was 0%. Furthermore, in Examples 1-3, the continuous durable life could be 20 hours or more by making alumina content rate 95 mass% or more.

なお、上記の実施形態では、本願発明を円柱状のセラミックヒータに適用した場合について説明したが、本願発明は円柱状のセラミックヒータに限らず、例えば板状のセラミックヒータ等他の形状のセラミックヒータについても同様にして適用することができる。また、本発明のセラミックヒータの製造方法としては、前述したの製造方法の他に、例えば次のような製造方法も使用可能と考えられる。すなわち、シート形成を強磁場中で行う方法、アスペクト比の大きな種結晶をグリーンシート成形時に添加し、押し出し成形やドクターブレード法で成形時に発生するせん断応力を利用してグリーンシート中に配向させる方法、粒成長促進効果のある焼結助剤（Ｎｂ酸化物、Ｔｉ酸化物等）を添加する方法等である。   In the above embodiment, the case where the present invention is applied to a columnar ceramic heater has been described. However, the present invention is not limited to a columnar ceramic heater, but may be other shapes such as a plate-shaped ceramic heater. The same applies to. Moreover, as a manufacturing method of the ceramic heater of this invention, it is thought that the following manufacturing methods can also be used other than the manufacturing method mentioned above, for example. That is, a method of forming a sheet in a strong magnetic field, a method of adding a seed crystal having a large aspect ratio at the time of green sheet molding, and orienting it in the green sheet using the shear stress generated at the time of molding by extrusion molding or doctor blade method And a method of adding a sintering aid (Nb oxide, Ti oxide, etc.) having an effect of promoting grain growth.

本発明の一実施形態に係るセラミックヒータの概略構成を示す斜視図。The perspective view which shows schematic structure of the ceramic heater which concerns on one Embodiment of this invention. 図１のセラミックヒータの製造方法を模式的に示す斜視図。The perspective view which shows typically the manufacturing method of the ceramic heater of FIG. セラミックヒータのインターセプト粒径の測定方法を説明するための顕微鏡写真。The microscope picture for demonstrating the measuring method of the intercept particle diameter of a ceramic heater. セラミックヒータのインターセプト粒径の測定方法を説明するための顕微鏡写真。The microscope picture for demonstrating the measuring method of the intercept particle diameter of a ceramic heater.

符号の説明Explanation of symbols

１……セラミックヒータ、２……芯材、３……セラミック積層体、４……第１のセラミック層、５……第２のセラミック層、６……発熱体、７……端子部、８……リード線。   DESCRIPTION OF SYMBOLS 1 ... Ceramic heater, 2 ... Core material, 3 ... Ceramic laminated body, 4 ... 1st ceramic layer, 5 ... 2nd ceramic layer, 6 ... Heat generating body, 7 ... Terminal part, 8 ……Lead.

Claims (9)

アルミナを主成分とする第１のセラミック層と、アルミナを主成分とする第２のセラミック層との間に、発熱体を挟持させたセラミック積層体を具備するセラミックヒータであって、
前記セラミック積層体の表面方向から測定したインターセプト粒径（ａ1 ）と、断面方向から測定したインターセプト粒径（ａ2 ）の比（ａ1 ／ａ2 ）が、１．１〜１．３であることを特徴とするセラミックヒータ。 A ceramic heater comprising a ceramic laminate in which a heating element is sandwiched between a first ceramic layer mainly composed of alumina and a second ceramic layer mainly composed of alumina,
The ratio (a1 / a2) of the intercept particle size (a1) measured from the surface direction of the ceramic laminate and the intercept particle size (a2) measured from the cross-sectional direction is 1.1 to 1.3. Ceramic heater. 請求項１記載のセラミックヒータにおいて、
前記第１のセラミック層及び前記第２のセラミック層のアルミナの含有量が９５質量％以上であることを特徴とするセラミックヒータ。 The ceramic heater according to claim 1, wherein
A ceramic heater, wherein the alumina content of the first ceramic layer and the second ceramic layer is 95% by mass or more. アルミナを主成分とする芯材と、
該芯材に巻回され、アルミナを主成分とする第３のセラミック層と該第３のセラミック層と前記芯材との間に挟持させた発熱体とを有するセラミック積層体と、を具備するセラミックヒータであって、
前記セラミック積層体の表面方向から測定したインターセプト粒径（ａ1 ）と、断面方向から測定したインターセプト粒径（ａ2 ）の比（ａ1 ／ａ2 ）が、１．１〜１．３であることを特徴とするセラミックヒータ。 A core mainly composed of alumina;
A ceramic laminated body wound around the core material and having a third ceramic layer mainly composed of alumina, and a heating element sandwiched between the third ceramic layer and the core material. A ceramic heater,
The ratio (a1 / a2) of the intercept particle size (a1) measured from the surface direction of the ceramic laminate and the intercept particle size (a2) measured from the cross-sectional direction is 1.1 to 1.3. Ceramic heater. 請求項３記載のセラミックヒータにおいて、
前記第３のセラミック層のアルミナの含有量が９５質量％以上であることを特徴とするセラミックヒータ。 The ceramic heater according to claim 3,
A ceramic heater, wherein the content of alumina in the third ceramic layer is 95% by mass or more. 請求項３又は４記載のセラミックヒータにおいて、
前記セラミック積層体には、前記芯材と前記発熱体との間に挟持させた第４のセラミック層を具備することを特徴とするセラミックヒータ。 The ceramic heater according to claim 3 or 4,
The ceramic laminated body includes a fourth ceramic layer sandwiched between the core member and the heating element. 請求項５記載のセラミックヒータにおいて、
前記第４のセラミック層のアルミナの含有量が９５質量％以上であることを特徴とするセラミックヒータ。 The ceramic heater according to claim 5, wherein
A ceramic heater, wherein the content of alumina in the fourth ceramic layer is 95% by mass or more. 請求項１又は２記載のセラミックヒータの製造方法であって、
アルミナを主成分としＺｎＯが０．１〜２．０質量％添加された第１のグリーンシートと、アルミナを主成分としＺｎＯが０．１〜２．０質量％添加された第２のグリーンシートとの間に、発熱体材料を挟持させてシート成形体とし、
アルミナを主成分とする支持基体成形体を１２５０〜１４００℃で予備焼成した後、当該支持基体成形体に前記シート成形体を積層し、水素を含有する雰囲気下で一体焼成することを特徴とするセラミックヒータの製造方法。 A method for producing a ceramic heater according to claim 1 or 2,
A first green sheet containing alumina as a main component and containing 0.1 to 2.0% by mass of ZnO; and a second green sheet containing alumina as a main component and containing 0.1 to 2.0% by mass of ZnO. In between, the heating element material is sandwiched to form a sheet molded body,
A support substrate molded body mainly composed of alumina is pre-fired at 1250 to 1400 ° C., and then the sheet molded body is laminated on the support substrate molded body and integrally fired in an atmosphere containing hydrogen. Manufacturing method of ceramic heater. 請求項３又は４記載のセラミックヒータの製造方法であって、
アルミナを主成分としＺｎＯが０．１〜２．０質量％添加された第３のグリーンシートを、アルミナを主成分とする１２５０〜１４００℃で予備焼成した芯材成形体に発熱体材料を挟持させて巻回し、水素を含有する雰囲気下で一体焼成することを特徴とするセラミックヒータの製造方法。 A method for producing a ceramic heater according to claim 3 or 4,
A heating element material is sandwiched between core materials formed by pre-firing a third green sheet containing alumina as a main component and containing 0.1 to 2.0% by mass of ZnO and pre-baking at 1250 to 1400 ° C. containing alumina as a main component. A method for manufacturing a ceramic heater, characterized by being wound and integrally fired in an atmosphere containing hydrogen. 請求項５又は６記載のセラミックヒータの製造方法であって、
アルミナを主成分とし、ＺｎＯが０．１〜２．０質量％添加された第３のグリーンシートと、アルミナを主成分とし、ＺｎＯが０．１〜２．０質量％添加された第４のグリーンシートとの間に発熱体材料を挟持させてシート成形体とし、
アルミナを主成分とする芯材成形体を１２５０〜１４００℃で予備焼成した後前記シート成形体を巻回し、水素を含有する雰囲気下で一体焼成することを特徴とするセラミックヒータの製造方法。 A method for producing a ceramic heater according to claim 5 or 6,
A third green sheet containing alumina as a main component and containing 0.1 to 2.0% by mass of ZnO, and a fourth green sheet containing alumina as a main component and containing 0.1 to 2.0% by mass of ZnO. A heating element material is sandwiched between the green sheet and a sheet molded body,
A method for producing a ceramic heater, comprising: pre-firing a core material compact comprising alumina as a main component at 1250 to 1400 ° C., winding the sheet compact, and firing integrally in an atmosphere containing hydrogen.
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CN104185320A (en) * 2014-08-14 2014-12-03 厦门格睿伟业电子科技有限公司 Heating rod for ceramic igniter and manufacturing technology thereof

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CN104185317B (en) * 2014-08-14 2016-09-07 厦门格睿伟业电子科技有限公司 A kind of double-deck bag pressure ceramic heating tube

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JPH01225087A (en) * 1988-03-03 1989-09-07 Ngk Spark Plug Co Ltd Ceramic heater
JPH1187021A (en) * 1997-09-02 1999-03-30 Ngk Spark Plug Co Ltd Ceramic heater and oxygen sensor
JP2000095557A (en) * 1998-07-23 2000-04-04 Ngk Spark Plug Co Ltd Alumina-base insulator for spark plug, its production and spark plug using the same

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CN104185320A (en) * 2014-08-14 2014-12-03 厦门格睿伟业电子科技有限公司 Heating rod for ceramic igniter and manufacturing technology thereof
CN104185320B (en) * 2014-08-14 2015-12-09 厦门格睿伟业电子科技有限公司 A kind of ceramic igniter heating rod used and manufacture craft thereof

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