JP5194051B2 - Gas sensor element and gas sensor - Google Patents
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- 239000007789 gas Substances 0.000 claims description 99
- 238000001514 detection method Methods 0.000 claims description 21
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 18
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Description
本発明は、例えば燃焼器や内燃機関等の燃焼ガスや排気ガス中に含まれる特定ガスの測定に好適に用いられるガスセンサ素子及びガスセンサに関する。 The present invention relates to a gas sensor element and a gas sensor that are suitably used for measuring a specific gas contained in combustion gas or exhaust gas of, for example, a combustor or an internal combustion engine.
従来から、自動車等の内燃機関の燃費向上や燃焼制御を行うガスセンサとして、排気ガス中の酸素濃度を検出する酸素センサや全領域空燃比センサが知られている。これらガスセンサは、酸素イオン透過性のＺｒＯ２からなる固体電解質体の表面に検知電極と基準電極とを設けている。そして、検知電極を排気ガスに曝し、基準電極を基準ガスの雰囲気に曝したときに、排気ガス中の酸素濃度に応じて各電極間の起電力が変化することに基づき、酸素濃度を検出している。
ところで、自動車に搭載した内燃機関の排気系統から排出される排気ガスは未燃焼ガス成分を含むことが多く、近年では未燃焼ガス成分に対する濃度規制が厳しくなってきている。そのため、内燃機関の動作中に常に動作するよう、活性温度の低いガスセンサ、つまりは低温作動性がよく、ガス応答性に優れたガスセンサが求められている。
このようなことから、ＺｒＯ２にＳｃ２Ｏ３及びＹｂ２Ｏ３を添加し、インピーダンスを低減して電気伝導度を高めた固体電解質体が開発されている（特許文献１，２）。
2. Description of the Related Art Conventionally, oxygen sensors that detect oxygen concentration in exhaust gas and full-range air-fuel ratio sensors are known as gas sensors that improve fuel consumption and control combustion in internal combustion engines such as automobiles. These gas sensors are provided with a detection electrode and a reference electrode on the surface of a solid electrolyte body made of oxygen ion permeable ZrO 2 . Then, when the sensing electrode is exposed to the exhaust gas and the reference electrode is exposed to the atmosphere of the reference gas, the oxygen concentration is detected based on the fact that the electromotive force between the electrodes changes according to the oxygen concentration in the exhaust gas. ing.
By the way, exhaust gas discharged from an exhaust system of an internal combustion engine mounted on an automobile often contains unburned gas components, and in recent years, concentration regulations on unburned gas components have become stricter. Therefore, there is a demand for a gas sensor having a low activation temperature, that is, a gas sensor with good low temperature operability and excellent gas responsiveness so that it always operates during the operation of the internal combustion engine.
For this reason, a solid electrolyte body in which Sc 2 O 3 and Yb 2 O 3 are added to ZrO 2 to reduce impedance and increase electric conductivity has been developed (Patent Documents 1 and 2).
しかしながら、内燃機関の動作中にガスセンサを常に動作させるためには、固体電解質体のインピーダンスを低減して低温作動性を向上させるだけでなく、ヒータによる固体電解質体の急熱に対する強度向上が求められる。
従って、本発明は、活性温度が低く低温作動性に優れており、且つヒータによる急熱に耐え得る強度を有する、早期活性を実現したガスセンサ素子及びガスセンサを提供することを目的とする。
However, in order to always operate the gas sensor during the operation of the internal combustion engine, not only the impedance of the solid electrolyte body is reduced to improve the low-temperature operability, but also the strength against the rapid heating of the solid electrolyte body by the heater is required. .
Accordingly, an object of the present invention is to provide a gas sensor element and a gas sensor that realize an early activation that has a low activation temperature and excellent low-temperature operability and has a strength that can withstand rapid heating by a heater.
本発明のガスセンサ素子は、酸素イオン伝導性の固体電解質体と、該固体電解質体の表面に設けられて被測定ガスに曝される検知電極と、前記固体電解質体を介して前記検知電極に対向する基準電極とを有するガスセンサ素子であって、前記固体電解質体はＺｒＯ２を８０質量％以上含み、前記ＺｒＯ２は、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２とを含有し、かつ前記固体電解質体のＸ線回折において、回折角２θ＝７３．２〜７３．６度のピーク強度（Ｉａ）と、回折角２θ＝７３．９〜７４．３度のピーク強度（Ｉｂ）との比（Ｉａ／Ｉｂ）が０．７１〜０．８６である。
Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２の影響により固体電解質体のインピーダンスを低減させる事ができ、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２の影響により強度を向上させることができる。Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２とを、ビーク強度比が０．７１〜０．８６となるように混合し固体電解質体を形成することにより、固体電解質体のインピーダンスを低減させつつ、強度をも向上させることが出来る。
The gas sensor element of the present invention includes an oxygen ion conductive solid electrolyte body, a detection electrode provided on the surface of the solid electrolyte body and exposed to a gas to be measured, and opposed to the detection electrode through the solid electrolyte body the gas sensor element and a reference electrode for the solid electrolyte body comprises ZrO 2 80% by mass or more, the ZrO 2 has a cubic ZrO 2 of most solid solution Yb 2 O 3, Sc 2 O 3 contains a tetragonal ZrO 2 to the most solid solution, and in X-ray diffraction of the solid electrolyte body, and the diffraction angle 2 [Theta] = 73.2-73.6 ° peak intensity (Ia), the diffraction angle 2 [Theta] The ratio (Ia / Ib) to the peak intensity (Ib) of 73.9 to 74.3 degrees is 0.71 to 0.86.
The impedance of the solid electrolyte can be reduced by the effect of cubic ZrO 2 that dissolves the most Yb 2 O 3, and the strength is improved by the effect of tetragonal ZrO 2 that dissolves Sc 2 O 3 most. be able to. Cubic ZrO 2 of most solid solution Yb 2 O 3, a tetragonal ZrO 2 to the most solid solution Sc 2 O 3, beaks intensity ratio were mixed such that 0.71 to 0.86 By forming the solid electrolyte body, it is possible to improve the strength while reducing the impedance of the solid electrolyte body.
前記ガスセンサ素子に一体に積層されたヒータをさらに備え、前記ヒータはヒータ素子をアルミナで囲んでなり、前記固体電解質体は、単斜晶ＺｒＯ２を１０〜２０質量％含むことが好ましい。
このような構成により、固体電解質体とＡｌ２Ｏ３からなる層とを同時焼成して形成した際、両者の熱膨張係数の値が近くなるので、ガスセンサ素子１００が割れたり、反りが発生することを防止することができる。
It is preferable that the heater further includes a heater integrally laminated on the gas sensor element. The heater surrounds the heater element with alumina, and the solid electrolyte body includes 10 to 20% by mass of monoclinic ZrO 2 .
With such a configuration, when the solid electrolyte body and the layer made of Al 2 O 3 are formed by simultaneous firing, since the values of the thermal expansion coefficients of both are close, the gas sensor element 100 is cracked or warped. This can be prevented.
前記検知電極は、単斜晶ＺｒＯ２を含むことが好ましい。このような構成により、特に低温域でのガスセンサの応答時間を短くすることができ、応答性に優れたガスセンサにできる。 The detection electrode preferably includes monoclinic ZrO 2 . With such a configuration, it is possible to shorten the response time of the gas sensor particularly in a low temperature region, and to make the gas sensor excellent in responsiveness.
本発明のガスセンサは、前記ガスセンサ素子を有する。 The gas sensor of the present invention has the gas sensor element.
この発明によれば、活性温度が低く低温作動性に優れており、且つヒータによる急熱に耐え得る強度を有する、早期活性を実現したガスセンサ素子及びガスセンサが得られる。 According to the present invention, it is possible to obtain a gas sensor element and a gas sensor that have low activation temperature, excellent low-temperature operability, and have strength that can withstand rapid heating by a heater and realize early activation.
以下、本発明の実施形態について説明する。
図１は、本発明の実施形態に係るガスセンサ３００の長手方向に沿った断面図を示す。このガスセンサ３００は、自動車の排気管（図示しない）に取り付けられ、排気ガス中の酸素濃度を検知するものであり、図１の下方（プロテクタ２４側）をガスセンサ３００の先端側とし、上方を基端側とする。
ガスセンサ３００は、ガスセンサ素子１００、ガスセンサ素子１００を内側に保持する筒状の主体金具３０、主体金具３０の先端側の所定部位に装着されたプロテクタ２４、主体金具３０の基端側の所定部位に接続された筒状の外筒２５等から構成されている。
Hereinafter, embodiments of the present invention will be described.
FIG. 1 shows a cross-sectional view along the longitudinal direction of a gas sensor 300 according to an embodiment of the present invention. The gas sensor 300 is attached to an exhaust pipe (not shown) of an automobile and detects the oxygen concentration in the exhaust gas. The lower side (the protector 24 side) in FIG. End side.
The gas sensor 300 includes a gas sensor element 100, a cylindrical metal shell 30 that holds the gas sensor element 100 inside, a protector 24 attached to a predetermined site on the distal end side of the metal shell 30, and a predetermined site on the base end side of the metal shell 30. It is composed of a connected cylindrical outer cylinder 25 and the like.
ガスセンサ素子１００は、後述するセラミック絶縁層と固体電解質体（固体電解質層）とを積層してなる長尺板状の積層型素子であり、検出部を先端側に備えている。
主体金具３０は、ＳＵＳ４３０等のステンレスからなり、ガスセンサ１００を排気管に取り付けるための雄ネジ部３１と、取り付け時に工具を係合させる六角係合部３２とを外側に有する。また、主体金具３０の内側には、径方向内側に向かって突出する内側段部３３が設けられ、内側段部３３は、ガスセンサ素子１００を保持する有底円筒状の金属ホルダ３４を外側から支持している。
そして、この金属ホルダ３４の内側には、ガスセンサ素子１００を金属ホルダ３４内に保持するためのセラミックホルダ３５及び第１滑石充填層３７とが先端側から順に配置されている。さらに主体金具３０の内側のうち、第１滑石充填層３７の基端側には、主体金具３０とガスセンサ素子１００との間の気密性（シール性）を確保するための第２滑石充填層３８が配置されている。第２滑石充填層３８の基端側には、アルミナ製の多段円筒状のスリーブ３９が配置されている。そして、セラミックホルダ３５、第１滑石充填層３７、第２滑石充填層３８及びスリーブ３９の軸孔３９１にガスセンサ素子１００が内挿されている。主体金具３０の基端には、スリーブ３９の基端に被さるように加締部３０１が延びており、加締部３０１を内側に折り曲げることにより、ステンレス製のリング部材４０を介して、スリーブ３９が主体金具３０の先端側に押圧され、セラミックホルダ３５や第２滑石充填層３８等によってガスセンサ素子１００が主体金具３０内に保持されるようになっている。
The gas sensor element 100 is a long plate-shaped laminated element formed by laminating a ceramic insulating layer and a solid electrolyte body (solid electrolyte layer), which will be described later, and includes a detection unit on the distal end side.
The metal shell 30 is made of stainless steel such as SUS430, and has an external thread portion 31 for attaching the gas sensor 100 to the exhaust pipe and a hexagonal engagement portion 32 for engaging a tool when attached. Further, an inner step portion 33 that protrudes radially inward is provided inside the metal shell 30, and the inner step portion 33 supports a bottomed cylindrical metal holder 34 that holds the gas sensor element 100 from the outside. doing.
Inside the metal holder 34, a ceramic holder 35 and a first talc filling layer 37 for holding the gas sensor element 100 in the metal holder 34 are arranged in this order from the front end side. Further, a second talc filling layer 38 for securing an airtightness (sealing property) between the metal shell 30 and the gas sensor element 100 on the proximal end side of the first talc filling layer 37 in the inside of the metal shell 30. Is arranged. A multi-stage cylindrical sleeve 39 made of alumina is disposed on the base end side of the second talc filling layer 38. The gas sensor element 100 is inserted into the shaft hole 391 of the ceramic holder 35, the first talc filling layer 37, the second talc filling layer 38, and the sleeve 39. A caulking portion 301 extends at the base end of the metal shell 30 so as to cover the base end of the sleeve 39, and the sleeve 39 is bent via the stainless steel ring member 40 by bending the caulking portion 301 inward. Is pressed to the front end side of the metal shell 30, and the gas sensor element 100 is held in the metal shell 30 by the ceramic holder 35, the second talc filling layer 38, and the like.
一方、主体金具３０の先端外周には、主体金具３０の先端から突出するガスセンサ素子１００の先端部を覆うようにして、金属製のプロテクタ２４が溶接されている。プロテクタ２４は、有底円筒状で外側に位置する外側プロテクタ４１と、有底円筒状で内側に位置する内側プロテクタ４２とからなる二重構造をなし、外側プロテクタ４１及び内側プロテクタ４２には、それぞれ排気ガスを内側に取り入れるためのガス取入穴２４１が複数設けられている。
なお、図１において、ガスセンサ素子１００はセラミックホルダ３５より先端側がプロテクタ２４内に突出し、プロテクタ２４に導入された被測定ガスに曝される。従って、ガスセンサ素子１００のうち、金属ホルダ３４の先端面Ｓより先端側が被測定ガスに曝されることになる。
On the other hand, a metal protector 24 is welded to the outer periphery of the front end of the metal shell 30 so as to cover the front end of the gas sensor element 100 protruding from the front end of the metal shell 30. The protector 24 has a double structure consisting of an outer protector 41 that is cylindrical and has a bottomed outer shape and an inner protector 42 that is cylindrically shaped and has a bottomed shape, and each of the outer protector 41 and the inner protector 42 has a double structure. A plurality of gas intake holes 241 for taking the exhaust gas inside are provided.
In FIG. 1, the gas sensor element 100 protrudes into the protector 24 from the ceramic holder 35 and is exposed to the gas to be measured introduced into the protector 24. Therefore, the tip side of the gas sensor element 100 with respect to the tip surface S of the metal holder 34 is exposed to the gas to be measured.
主体金具３０の基端側外周には、金属製の筒状の外筒２５が溶接され、外筒２５の内側には、円筒状のセパレータ５０が配置されている。セパレータ５０は、５本のリード線１１１〜１１３（図１では、５本のうちの３本が図示されている）をそれぞれ分離して保持する挿通孔を有すると共に、セパレータ５０先端側にガスセンサ素子１００の基端側を収容する中心孔５０２を有する。セパレータ５０の中心孔５０２を囲むように複数の接続端子金具１１６が配置され、接続端子金具１１６はガスセンサ素子１００の基端側表面に形成された後述する電極パッドと接触するようになっている。又、各接続端子金具１１６から延びる５本のリード線１１１〜１１３（リード線のうちの２本はリード線１１１の紙面奥に配置される関係から図示されていない）がガスセンサ１００の基端側外部に取出されている。なお、セパレータ５０先端の外周には、バネ状の保持部材５１が配置され、保持部材５１が拡開して外筒２５内面に当接すると共に、セパレータ５０の突出部５０１を基端側に押圧することにより、この保持部材５１と後述するゴムキャップ５２の先端面との間でセパレータ５０が挟持固定されている。 A metallic cylindrical outer cylinder 25 is welded to the base end side outer periphery of the metal shell 30, and a cylindrical separator 50 is disposed inside the outer cylinder 25. The separator 50 has insertion holes for separating and holding the five lead wires 111 to 113 (three of the five wires are shown in FIG. 1), and a gas sensor element on the leading end side of the separator 50. It has a central hole 502 that accommodates 100 base ends. A plurality of connection terminal fittings 116 are disposed so as to surround the center hole 502 of the separator 50, and the connection terminal fittings 116 come into contact with electrode pads (described later) formed on the base end side surface of the gas sensor element 100. In addition, five lead wires 111 to 113 (two of the lead wires are not shown in the figure because they are arranged at the back of the drawing surface of the lead wire 111) extending from each connection terminal fitting 116 are on the base end side of the gas sensor 100. It has been taken out to the outside. A spring-like holding member 51 is disposed on the outer periphery of the front end of the separator 50. The holding member 51 expands and contacts the inner surface of the outer cylinder 25, and presses the protruding portion 501 of the separator 50 toward the base end side. Thus, the separator 50 is sandwiched and fixed between the holding member 51 and a front end surface of a rubber cap 52 described later.
セパレータ５０の基端には、外筒２５の基端側開口２５２を閉塞する円柱状のゴムキャップ５２が配置され、ゴムキャップ５２が外筒２５に装着された状態で外筒２５の外周を径方向内側に加締めることにより、外筒２５にゴムキャップ５２が固定されている。ゴムキャップ５２には、５本のリード線１１１〜１１３を挿通するための複数の挿通孔５２１が設けられている。 A columnar rubber cap 52 that closes the base-end opening 252 of the outer cylinder 25 is disposed at the base end of the separator 50, and the outer periphery of the outer cylinder 25 is formed in a diameter with the rubber cap 52 attached to the outer cylinder 25. The rubber cap 52 is fixed to the outer cylinder 25 by caulking inward in the direction. The rubber cap 52 is provided with a plurality of insertion holes 521 for inserting the five lead wires 111 to 113.
次に、図２、図３を参照してガスセンサ素子１００の構成について説明する。
図２は、ガスセンサ素子１００の長手方向に直交する断面図を示す。ガスセンサ素子１００は、酸素濃度を検知可能なセル（酸素濃淡電池素子）１と、セル１を加熱するヒータ２とを備える。
セル１は、後述する酸素イオン伝導性の固体電解質体１１と、固体電解質体１１の表面（図２の上方を便宜上、表面とする）に形成された検知電極１３１と、固体電解質体１１の裏面に形成された基準電極１３２とを有する。
一方、ヒータ２は、抵抗発熱体（特許請求の範囲の「ヒータ素子」に相当）２１と、抵抗発熱体２１を挟持する１対のセラミック絶縁層２２、２３とを有し、セラミック絶縁層２２側が固体電解質体１１の裏面に積層されている。
そして、検知電極１３１の表面を覆うように多孔質からなる電極保護層５が形成されている。電極保護層５は、検知電極１３１の被毒を防止し、外部と酸素を出入させる。さらに、これらの積層体の排気ガスに晒されることになる先端側の露出部分をすべて覆う多孔質保護層４が形成されている。この多孔質保護層４は、排気ガス中に含まれる凝縮水等の水滴が、積層体の表面に直に接触するのを防止するための機能を果たすものである。
なお、この実施形態では、セラミック絶縁層２２、２３はアルミナ（Ａｌ２Ｏ３）からなる。
Next, the configuration of the gas sensor element 100 will be described with reference to FIGS. 2 and 3.
FIG. 2 is a cross-sectional view orthogonal to the longitudinal direction of the gas sensor element 100. The gas sensor element 100 includes a cell (oxygen concentration battery element) 1 capable of detecting an oxygen concentration and a heater 2 that heats the cell 1.
The cell 1 includes an oxygen ion conductive solid electrolyte body 11 which will be described later, a detection electrode 131 formed on the surface of the solid electrolyte body 11 (the upper side in FIG. 2 is referred to as the surface for convenience), and the back surface of the solid electrolyte body 11. And a reference electrode 132 formed on the substrate.
On the other hand, the heater 2 includes a resistance heating element (corresponding to a “heater element” in the claims) 21 and a pair of ceramic insulating layers 22 and 23 sandwiching the resistance heating element 21. The side is laminated on the back surface of the solid electrolyte body 11.
A porous electrode protective layer 5 is formed so as to cover the surface of the detection electrode 131. The electrode protective layer 5 prevents poisoning of the detection electrode 131 and allows oxygen to enter and exit from the outside. Furthermore, a porous protective layer 4 is formed to cover all exposed portions on the tip end side that are exposed to the exhaust gas of these laminates. The porous protective layer 4 functions to prevent water droplets such as condensed water contained in the exhaust gas from coming into direct contact with the surface of the laminate.
In this embodiment, the ceramic insulating layers 22 and 23 are made of alumina (Al 2 O 3 ).
ここで、検知電極１３１、基準電極１３２は、多孔質状の電極からなり、例えば金、白金、ロジウム、パラジウム、ルテニウム又はこれらの合金を用いることができ、さらに、固体電解質体を構成する主成分材料を共材として混合してもよい。抵抗発熱体２１は、例えば、白金、ロジウム、タングステン、レニウム又はこれらの合金を用いることができ、さらに、セラミック絶縁層を構成する主成分材料を共材として混合してもよい。
なお、後述する理由により検知電極１３１が単斜晶ＺｒＯ２を含むと好ましい。
又、多孔質保護層４、電極保護層５としては、ジルコニア、アルミナ、スピネル等の多孔質体を用いることができる。なお、多孔質保護層４及び電極保護層５は、本発明において必須の構成ではない。
Here, the detection electrode 131 and the reference electrode 132 are made of porous electrodes, and for example, gold, platinum, rhodium, palladium, ruthenium or an alloy thereof can be used, and the main component constituting the solid electrolyte body. You may mix a material as a co-material. For example, platinum, rhodium, tungsten, rhenium, or an alloy thereof can be used for the resistance heating element 21, and a main component material constituting the ceramic insulating layer may be mixed as a co-material.
Note that the detection electrode 131 preferably contains monoclinic ZrO 2 for the reason described later.
As the porous protective layer 4 and the electrode protective layer 5, porous bodies such as zirconia, alumina, and spinel can be used. The porous protective layer 4 and the electrode protective layer 5 are not essential components in the present invention.
図３は、ガスセンサ素子１００の分解斜視図である。矩形状をなす検知電極１３１、基準電極１３２は、それぞれ固体電解質体１１の先端側に対向して配置されている。そして、検知電極１３１、基準電極１３２から基端に向いたガスセンサ素子１００の長手方向に、それぞれリード部１３３、１３４が一体に形成されている。リード部１３３の基端は接続端子金具１１６と接続される電極パッド１８となる。又、リード部１３４の基端は、固体電解質体１１を貫通するスルーホール導体１５を介して、電極パッド１５１ｃに接続されている。
一方、抵抗発熱体２１は、検知電極１３１及び基準電極１３２の直下に配置され蛇行状に延びる発熱部２１２と、発熱部２１２の端部にそれぞれ接続され、ガスセンサ素子１００の長手方向に延びるヒータリード部２１３とを有している。ヒータリード部２１３の各基端２１１は、セラミック絶縁層２３を貫通する２個のスルーホール導体２３１を介して、２個の電極パッド２３２にそれぞれ接続されている。
なお、矩形状の電極保護層５は検知電極１３１の周囲を覆い、固体電解質体１１の表面（リード部１３３を含む）のうち、電極保護層５で覆われていない部分は強化保護層５２で覆われている。但し、電極パッド１８、１５１ｃは強化保護層５２で覆われずに露出している。
FIG. 3 is an exploded perspective view of the gas sensor element 100. The detection electrode 131 and the reference electrode 132 having a rectangular shape are respectively arranged to face the front end side of the solid electrolyte body 11. Lead parts 133 and 134 are integrally formed in the longitudinal direction of the gas sensor element 100 from the detection electrode 131 and the reference electrode 132 toward the base end. The base end of the lead part 133 becomes an electrode pad 18 connected to the connection terminal fitting 116. The base end of the lead portion 134 is connected to the electrode pad 151 c through the through-hole conductor 15 that penetrates the solid electrolyte body 11.
On the other hand, the resistance heating element 21 is disposed immediately below the detection electrode 131 and the reference electrode 132 and extends in a meandering manner. The heater lead is connected to the end of the heating part 212 and extends in the longitudinal direction of the gas sensor element 100. Part 213. Each base end 211 of the heater lead part 213 is connected to two electrode pads 232 via two through-hole conductors 231 penetrating the ceramic insulating layer 23.
The rectangular electrode protection layer 5 covers the periphery of the detection electrode 131, and a portion of the surface of the solid electrolyte body 11 (including the lead portion 133) that is not covered with the electrode protection layer 5 is a reinforced protection layer 52. Covered. However, the electrode pads 18 and 151 c are exposed without being covered with the reinforced protective layer 52.
次に、固体電解質体１１の組成について説明する。固体電解質体１１はＺｒＯ２を８０質量％以上含み、ＺｒＯ２は、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２とを含有し、かつ固体電解質体１１のＸ線回折において、回折角２θ＝７３．２〜７３．６のピーク強度（Ｉａ）と、回折角２θ＝７３．９〜７４．３のピーク強度（Ｉｂ）との比（Ｉａ／Ｉｂ）が０．７１〜０．８６である。
固体電解質体１１は、ＺｒＯ２を主成分とし、その安定化成分としてＹｂ２Ｏ３及びＳｃ２Ｏ３を含む。
Next, the composition of the solid electrolyte body 11 will be described. The solid electrolyte body 11 includes a ZrO 2 80 wt% or more, ZrO 2 has a cubic ZrO 2 of most solid solution Yb 2 O 3, a tetragonal ZrO 2 to the most solid solution Sc 2 O 3 In addition, in the X-ray diffraction of the solid electrolyte body 11, the peak intensity (Ia) at a diffraction angle 2θ = 73.2 to 73.6 and the peak intensity (Ib) at a diffraction angle 2θ = 73.9 to 74.3 (Ia / Ib) is 0.71 to 0.86.
The solid electrolyte body 11 contains ZrO 2 as a main component and includes Yb 2 O 3 and Sc 2 O 3 as stabilizing components.
本発明者らは固体電解質体の組成について検討した結果、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２とを所定の割合で含有すると、固体電解質体のインピーダンスを低減し、強度をも向上させることができることを見出した。
ここで、Ｙｂ２Ｏ３で完全安定化されたＺｒＯ２は、８ｍｏｌ％Ｙｂ２Ｏ３−９２ｍｏｌ％ＺｒＯ２（２２ｗｔ％Ｙｂ２Ｏ３−７８ｗｔ％ＺｒＯ２；以下、必要に応じて「８ＹｂＳＺ」と表記する）であって立方晶を示すが、このＹｂＳＺ中にもＳｃ２Ｏ３が若干固溶するので、固体電解質体１１の組成を８ＹｂＳＺで規定することはできない。そのため、ＹｂＳＺ中にＳｃ２Ｏ３が固溶した組成を「Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２」と称する。
同様に、Ｓｃ２Ｏ３で部分安定化されたＺｒＯ２は、６ｍｏｌ％Ｙｂ２Ｏ３−９４ｍｏｌ％ＺｒＯ２（７ｗｔ％Ｓｃ２Ｏ３−９３ｗｔ％ＺｒＯ２；以下、必要に応じて「６ＳｃＳＺ」と表記する）であって正方晶を示すが、この６ＳｃＳＺ中にもＹｂ２Ｏ３が若干固溶するので、固体電解質体１１の組成を６ＳｃＳＺで規定することはできない。そのため、６ＳｃＳＺ中にＹｂ２Ｏ３が固溶した組成を「Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２」と称する。
As a result of studying the composition of the solid electrolyte body, the present inventors have determined that a predetermined ratio of cubic ZrO 2 that dissolves most Yb 2 O 3 and tetragonal ZrO 2 that dissolves Sc 2 O 3 most. It has been found that the content of can reduce the impedance of the solid electrolyte body and improve the strength.
Here, ZrO 2 completely stabilized with Yb 2 O 3 is 8 mol% Yb 2 O 3 -92 mol% ZrO 2 (22 wt% Yb 2 O 3 -78 wt% ZrO 2 ; hereinafter referred to as “8YbSZ” as necessary. In this YbSZ, Sc 2 O 3 is slightly dissolved, so the composition of the solid electrolyte body 11 cannot be defined by 8YbSZ. Therefore, the composition in which Sc 2 O 3 is dissolved in YbSZ is referred to as “cubic ZrO 2 in which Yb 2 O 3 is most dissolved.
Similarly, ZrO 2 partially stabilized with Sc 2 O 3 is 6 mol% Yb 2 O 3 -94 mol% ZrO 2 (7 wt% Sc 2 O 3 -93 wt% ZrO 2 ; hereinafter referred to as “6ScSZ” as necessary. In this 6ScSZ, Yb 2 O 3 is slightly dissolved, so the composition of the solid electrolyte body 11 cannot be defined by 6ScSZ. Therefore, the composition in which Yb 2 O 3 is solid-solved in 6ScSZ is referred to as “tetragonal ZrO 2 in which Sc 2 O 3 is most dissolved.”
なお、固体電解質体１１の各領域を透過型電子顕微鏡(TEM)で観察し、エネルギー分散型X線分析装置(EDS；通常、TEMに付随するEDS装置)による元素分析を行うと、ＺｒＯ２中の固溶種(安定化剤、Ｙｂ２Ｏ３、Ｓｃ２Ｏ３等)を知ることができる。この方法により、固体電解質体１１の各領域において、ＺｒＯ２中に最も多く固溶している安定化剤を同定可能である。 Note that each region of the solid electrolyte body 11 was observed by a transmission electron microscope (TEM), energy dispersive X-ray spectrometer (EDS; typically, EDS associated apparatus TEM) performed elemental analysis, ZrO 2 in The solid solution species (stabilizer, Yb 2 O 3 , Sc 2 O 3 etc.) can be known. By this method, it is possible to identify the stabilizer that is most dissolved in ZrO 2 in each region of the solid electrolyte body 11.
ここで、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２は、固体電解質体１１のＸ線回折において、回折角２θ＝７３．２〜７３．６度のピーク強度（Ｉａ）に対応すると考えられる。又、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２は、固体電解質体１１のＸ線回折において、回折角２θ＝７３．９〜７４．３度のピーク強度（Ｉｂ）に対応すると考えられる。
従って、固体電解質体１１中において、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２との含有割合を、比（Ｉａ／Ｉｂ）によって求めることができる。そして、（Ｉａ／Ｉｂ）を０．７１〜０．８６の範囲内に管理することにより、固体電解質体のインピーダンスを低減し、強度をも向上させることができる。
図４は、後述する実施例１の固体電解質体の焼結体のＸ線回折チャートを示す。回折角２θ＝７０〜７７度の範囲に、ピーク強度Ｉａ、Ｉｂが存在することがわかる。
Here, the tetragonal ZrO 2 that dissolves most Sc 2 O 3 in the X-ray diffraction of the solid electrolyte body 11 corresponds to the peak intensity (Ia) of diffraction angle 2θ = 73.2 to 73.6 degrees. Conceivable. Further, the cubic ZrO 2 in which Yb 2 O 3 is dissolved in the largest amount is considered to correspond to the peak intensity (Ib) of the diffraction angle 2θ = 73.9 to 74.3 degrees in the X-ray diffraction of the solid electrolyte body 11. It is done.
Therefore, in the solid electrolyte body 11, the content ratio of cubic ZrO 2 that dissolves most of Yb 2 O 3 and tetragonal ZrO 2 that dissolves most of Sc 2 O 3 is expressed as a ratio (Ia / Ib ). And by managing (Ia / Ib) within the range of 0.71-0.86, the impedance of a solid electrolyte body can be reduced and intensity | strength can also be improved.
FIG. 4 shows an X-ray diffraction chart of a sintered body of the solid electrolyte body of Example 1 described later. It can be seen that the peak intensities Ia and Ib exist in the range of the diffraction angle 2θ = 70 to 77 degrees.
（Ｉａ／Ｉｂ）が０．７１未満であると、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２の割合が少なくなり、固体電解質体１１の強度が低下する。このとき、ヒータによる急加熱を行うと固体電解質体にクラックが発生する可能性がある。そのため、ヒータによる急加熱が出来ないためライトオフ特性も劣化する。一方、（Ｉａ／Ｉｂ）が０．８６を超えると、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２の割合が少なくなる。Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２のほうがＹｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２よりもインピーダンスが高い為、固体電解質体１１全体としてはインピーダンスが増大する。
なお、ライトオフ時間は、ガスセンサのヒータの通電を開始してから、特性が安定し測定可能となるまでに要する時間であり、ライトオフ時間が短いほどガスセンサの早期活性が優れている。
When (Ia / Ib) is less than 0.71, the proportion of tetragonal ZrO 2 that dissolves Sc 2 O 3 most often decreases, and the strength of the solid electrolyte body 11 decreases. At this time, if rapid heating with a heater is performed, cracks may occur in the solid electrolyte body. For this reason, since the heater cannot be heated rapidly, the light-off characteristics are also deteriorated. On the other hand, when (Ia / Ib) exceeds 0.86, the proportion of cubic ZrO 2 that dissolves Yb 2 O 3 most often decreases. Sc 2 O 3 most towards the tetragonal ZrO 2 to solid solution because the impedance is higher than the cubic ZrO 2 of most solid solution Yb 2 O 3 and the impedance is increased as a whole solid electrolyte layer 11.
The light-off time is the time required from the start of energization of the heater of the gas sensor until the characteristics become stable and measurement is possible. The shorter the light-off time, the better the early activation of the gas sensor.
固体電解質体１１の製造方法としては、８ＹｂＳＺ、６ＳｃＳＺ、及び単斜晶ＺｒＯ２の各粉末を所定割合で混合し、さらに必要に応じてバインダーおよび可塑剤等を加え、スラリーを調製する。そして、得られたスラリーをドクターブレード法等により成形し、グリーンシートを作製した後、脱脂および焼成する方法が挙げられる。予め８ＹｂＳＺ及び６ＳｃＳＺになっている粉末を混合することで、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２とが共に固体電解質体１１中に存在するようになる。
これに対し、Ｙｂ２Ｏ３、Ｓｃ２Ｏ３、及び単斜晶ＺｒＯ２の各粉末を混合して焼成した場合では、固体電解質中のＺｒＯ２には、Ｙｂ２Ｏ３及びＳｃ２Ｏ３が粉末の混合比と略同じ割合のままで固溶している。つまり、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２との両者が共に存在するような、各ＺｒＯ２に固溶するＹｂ２Ｏ３及びＳｃ２Ｏ３の割合が異なる固体電解質体を得ることは出来ない。
As a manufacturing method of the solid electrolyte body 11, each powder of 8YbSZ, 6ScSZ, and monoclinic ZrO 2 is mixed in a predetermined ratio, and a binder, a plasticizer, and the like are further added as necessary to prepare a slurry. And the method of degreasing and baking after forming the obtained slurry by a doctor blade method etc. and producing a green sheet is mentioned. By mixing powders that are preliminarily 8YbSZ and 6ScSZ, cubic ZrO 2 that dissolves most of Yb 2 O 3 and tetragonal ZrO 2 that dissolves most of Sc 2 O 3 together are solid electrolytes. It exists in the body 11.
In contrast, when Yb 2 O 3 , Sc 2 O 3 , and monoclinic ZrO 2 powders are mixed and fired, ZbO 2 in the solid electrolyte includes Yb 2 O 3 and Sc 2 O 3. However, the solid solution remains in the same proportion as the mixing ratio of the powder. That is, Yb that dissolves in each ZrO 2 such that both cubic ZrO 2 that dissolves most of Yb 2 O 3 and tetragonal ZrO 2 that dissolves most of Sc 2 O 3 exist together. Solid electrolyte bodies having different ratios of 2 O 3 and Sc 2 O 3 cannot be obtained.
（Ｉａ／Ｉｂ）を０．７１〜０．８６の範囲内に管理する方法としては、８ＹｂＳＺ、６ＳｃＳＺ、及び単斜晶ＺｒＯ２の各粉末を混合する際、単斜晶ＺｒＯ２の配合割合をほぼ一定にし、８ＹｂＳＺと６ＳｃＳＺの配合割合を変えることが挙げられる。この場合、８ＹｂＳＺの配合割合を多くするほど（Ｉａ／Ｉｂ）が小さくなり、６ＳｃＳＺの配合割合を多くするほど（Ｉａ／Ｉｂ）が大きくなるので、（Ｉａ／Ｉｂ）が０．７１〜０．８６となる範囲内で８ＹｂＳＺと６ＳｃＳＺの配合割合を調整すればよい。
例えば、表１においては、単斜晶ＺｒＯ２の配合割合が２４〜３０質量％の間で一定であり、この場合に８ＹｂＳＺの配合割合を多くするほど（Ｉａ／Ｉｂ）が小さくなる傾向が見られる。なお、固体電解質体１１の原料である８ＹｂＳＺ、６ＳｃＳＺ、及び単斜晶ＺｒＯ２の合計量に対し、単斜晶ＺｒＯ２の配合割合を２０〜３２質量％とするのが好ましい。又、この単斜晶ＺｒＯ２の配合割合は、固体電解質体１１の原料としての単斜晶ＺｒＯ２の割合であり、焼成後の固体電解質体１１中の単斜晶ＺｒＯ２の割合と同一ではない。
(Ia / Ib) as a method of managing the range of 0.71 to 0.86 is, 8YbSZ, 6ScSZ, and when mixing the powder of monoclinic ZrO 2, the proportion of monoclinic ZrO 2 For example, the mixing ratio of 8YbSZ and 6ScSZ can be changed. In this case, (Ia / Ib) decreases as the blending ratio of 8YbSZ increases, and (Ia / Ib) increases as the blending ratio of 6ScSZ increases. The blending ratio of 8YbSZ and 6ScSZ may be adjusted within the range of 86.
For example, in Table 1, the blending ratio of monoclinic ZrO 2 is constant between 24 and 30% by mass, and in this case, the tendency that (Ia / Ib) decreases as the blending ratio of 8YbSZ increases. It is done. In addition, it is preferable that the compounding ratio of monoclinic ZrO 2 is 20 to 32 mass% with respect to the total amount of 8YbSZ, 6ScSZ, and monoclinic ZrO 2 which are raw materials of the solid electrolyte body 11. The mixing ratio of the monoclinic ZrO 2 is the ratio of monoclinic ZrO 2 as a raw material of the solid electrolyte body 11, the same as the proportion of monoclinic ZrO 2 in the solid electrolyte body 11 after firing Absent.
なお、この実施形態では、ガスセンサ素子１００（つまり、固体電解質体１１）にヒータ２が一体に積層されている。又、ヒータ２はヒータ素子２１をアルミナ（Ａｌ２Ｏ３）製のセラミック絶縁層２２、２３で囲んでなる。従って、ガスセンサ素子１００とヒータ２との積層界面において、固体電解質体１１とセラミック絶縁層２２とが接しており、これらは同時焼成して形成される。そのため、固体電解質体１１とセラミック絶縁層２２の熱膨張係数の値が近いほど、焼成時の膨張の度合いに差が生じてガスセンサ素子１００が割れたり、反りが発生することを防止する。
このようなことから、固体電解質体１１に含まれる全ＺｒＯ２に対して、固体電解質体１１が単斜晶ＺｒＯ２を１０〜２０質量％含むと、アルミナ製のセラミック絶縁層２２と熱膨張係数の値が近くなるので好ましい。
固体電解質体１１中の単斜晶ＺｒＯ２の含有割合が１０質量％未満であると、固体電解質体１１の熱膨張係数がセラミック絶縁層２２の熱膨張係数と大きく変わり、これらを同時焼成した際にガスセンサ素子１００が割れたり、反りが発生することがある。固体電解質体１１中の単斜晶ＺｒＯ２の含有割合が２０質量％を超えると、上記したＹｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２とＳｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２が固体電解質体１１中に占める割合が少なくなり、固体電解質体のインピーダンスを低減し、強度を向上させることが困難になる場合がある。
In this embodiment, the heater 2 is integrally laminated on the gas sensor element 100 (that is, the solid electrolyte body 11). The heater 2 includes a heater element 21 surrounded by ceramic insulating layers 22 and 23 made of alumina (Al 2 O 3 ). Therefore, the solid electrolyte body 11 and the ceramic insulating layer 22 are in contact with each other at the laminated interface between the gas sensor element 100 and the heater 2, and these are formed by simultaneous firing. Therefore, the closer the values of the thermal expansion coefficients of the solid electrolyte body 11 and the ceramic insulating layer 22 are, the more the difference in the degree of expansion at the time of firing occurs, thereby preventing the gas sensor element 100 from cracking or warping.
Therefore, when the solid electrolyte body 11 contains 10 to 20% by mass of monoclinic ZrO 2 with respect to all ZrO 2 contained in the solid electrolyte body 11, the ceramic insulating layer 22 made of alumina and the thermal expansion coefficient are obtained. Since the value of becomes close, it is preferable.
When the content ratio of monoclinic ZrO 2 in the solid electrolyte body 11 is less than 10% by mass, the thermal expansion coefficient of the solid electrolyte body 11 is greatly changed from the thermal expansion coefficient of the ceramic insulating layer 22, and when these are fired simultaneously In addition, the gas sensor element 100 may be cracked or warped. When the content ratio of monoclinic ZrO 2 in the solid electrolyte body 11 exceeds 20% by mass, the above-described cubic ZrO 2 and Sc 2 O 3 that are the most solid solution of Yb 2 O 3 are the most solid solution. The proportion of the crystalline ZrO 2 in the solid electrolyte body 11 decreases, and it may be difficult to reduce the impedance of the solid electrolyte body and improve the strength.
検知電極１３１が単斜晶ＺｒＯ２を含むと、特に低温域でのガスセンサの応答時間が短くなり、応答性が優れるので好ましい。例えば、検知電極１３１として、Ｐｔ１００質量部に対して５質量部以上の単斜晶ＺｒＯ２を含む組成とすることができる。 It is preferable that the detection electrode 131 contains monoclinic ZrO 2 because the response time of the gas sensor particularly in a low temperature range is shortened and the response is excellent. For example, the detection electrode 131 may have a composition containing monoclinic ZrO 2 in an amount of 5 parts by mass or more with respect to 100 parts by mass of Pt.
次に、ガスセンサ素子１００の製造方法の一例を説明する。
まず、セルを構成することになる固体電解質体１１のグリーンシートを作製し、このグリーンシートの両面に、検知電極、基準電極、素子配線部、それらのリード、電極パッド、スルーホール導体などを、導体ペーストをスクリーン印刷して形成し、セル１の未焼成体を作製する。
同様に、ヒータ２を構成するセラミック絶縁層２３のグリーンシートを作製し、このグリーンシート表面に、抵抗発熱体及びリードなどを、導体ペーストをスクリーン印刷して形成する。同様にセラミック絶縁層２２のグリーンシートを作製し、セラミック絶縁層２２，２３となる各グリーンシートを積層して、ヒータ２の積層体を作製する。
そして、セル１の未焼成体とヒータ２の積層体を圧着し、両者を一体に積層した後、全体を焼成（同時焼成）する。焼成条件は、例えば、大気中（または不活性ガス雰囲気中）、焼成温度１３００〜１７００℃、焼成時間１〜１０時間とすることができる。これにより、ガスセンサ素子１００が得られる。
Next, an example of a method for manufacturing the gas sensor element 100 will be described.
First, a green sheet of the solid electrolyte body 11 that constitutes the cell is produced, and a detection electrode, a reference electrode, an element wiring part, their leads, an electrode pad, a through-hole conductor, and the like are formed on both sides of the green sheet. A conductor paste is formed by screen printing to produce an unfired body of the cell 1.
Similarly, a green sheet of the ceramic insulating layer 23 constituting the heater 2 is manufactured, and a resistance heating element, a lead, and the like are formed on the surface of the green sheet by screen printing a conductor paste. Similarly, a green sheet of the ceramic insulating layer 22 is produced, and the green sheets to be the ceramic insulating layers 22 and 23 are laminated to produce a laminate of the heater 2.
Then, the unfired body of the cell 1 and the laminated body of the heater 2 are pressure-bonded and laminated together, and then the whole is fired (simultaneously fired). The firing conditions can be, for example, in the air (or in an inert gas atmosphere), a firing temperature of 1300 to 1700 ° C., and a firing time of 1 to 10 hours. Thereby, the gas sensor element 100 is obtained.
本発明は上記した実施形態に限定されず、本発明の思想と範囲に含まれる様々な変形及び均等物に及ぶことはいうまでもない。例えば、本発明のガスセンサとしては酸素センサ、酸素濃度に応じてリニアに出力が変化する全領域空燃比センサ、ＮＯxセンサ、ＣＯセンサなどが挙げられる。 It goes without saying that the present invention is not limited to the above-described embodiments, and extends to various modifications and equivalents included in the spirit and scope of the present invention. For example, examples of the gas sensor of the present invention include an oxygen sensor, a full-range air-fuel ratio sensor whose output changes linearly according to the oxygen concentration, a NOx sensor, and a CO sensor.
以下、実施例を挙げて、本発明を具体的に説明するが、本発明は勿論これらの例に限定されるものではない。
８ＹｂＳＺ、６ＳｃＳＺ、及び単斜晶ＺｒＯ２の各粉末を表１に示す割合で混合し、さらにバインダーおよび可塑剤等を加え、スラリーを調製した。得られたスラリーをドクターブレード法により厚み２００μｍのグリーンシートに成形した。このグリーンシートを４２０℃で４時間脱脂した後、１５２５℃で１時間焼成して厚み１６０μｍの固体電解質体を得た。
比較例１として、８ＹｂＳＺ粉末の配合割合を多くし、同様に固体電解質体を得た。
比較例２として、８ＹｂＳＺ粉末の配合割合を少なくし、同様に固体電解質体を得た。
比較例３として、６ＳｃＳＺ粉末の代わりにＡｌ２Ｏ３粉末を配合し、また８ＹｂＳＺ粉末の代わりに８ＹＳＺ（８ｍｏｌ％Ｙｂ２Ｏ３−９２ｍｏｌ％ＺｒＯ２）粉末を配合して、固体電解質体を得た。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these examples of course.
Each powder of 8YbSZ, 6ScSZ, and monoclinic ZrO 2 was mixed at a ratio shown in Table 1, and a binder, a plasticizer, and the like were further added to prepare a slurry. The obtained slurry was formed into a green sheet having a thickness of 200 μm by a doctor blade method. The green sheet was degreased at 420 ° C. for 4 hours and then fired at 1525 ° C. for 1 hour to obtain a solid electrolyte body having a thickness of 160 μm.
As Comparative Example 1, the blending ratio of 8YbSZ powder was increased to obtain a solid electrolyte body in the same manner.
As Comparative Example 2, the blending ratio of 8YbSZ powder was decreased, and a solid electrolyte body was obtained in the same manner.
As Comparative Example 3, Al 2 O 3 powder was blended instead of 6ScSZ powder, and 8YSZ (8 mol% Yb 2 O 3 -92 mol% ZrO 2 ) powder was blended instead of 8YbSZ powder to obtain a solid electrolyte body. It was.
得られた固体電解質体について、以下の測定及び評価を行った。
得られた固体電解質体のＸ線回折を行い、回折角２θ＝７３．２〜７３．６のピーク強度（Ｉａ）と、回折角２θ＝７３．９〜７４．３のピーク強度（Ｉｂ）との比（Ｉａ／Ｉｂ）を求めた。
又、得られた固体電解質体のＸ線回折を行い、次式
なお、比較例３の固体電解質体中のＡｌ２Ｏ３の割合は、固体電解質体用の各粉末の配合割合と同じとみなした。
The following measurement and evaluation were performed on the obtained solid electrolyte body.
The obtained solid electrolyte body was subjected to X-ray diffraction, and the peak intensity (Ia) at a diffraction angle 2θ = 73.2 to 73.6 and the peak intensity (Ib) at a diffraction angle 2θ = 73.9 to 74.3 The ratio (Ia / Ib) was determined.
Further, X-ray diffraction of the obtained solid electrolyte body was performed, and the following formula
The ratio of Al 2 O 3 solid electrolyte body of Comparative Example 3 was regarded as the same as the proportions of the powder for the solid electrolyte body.
又、得られた固体電解質体の両面にＰｔペーストをスクリーン印刷し、１２００℃で１時間熱処理し、面積３ｍｍ２のＰｔ電極の焼付を行った。交流インピーダンス法により、各Ｐｔ電極間の固体電解質体の内部抵抗を測定した。測定条件は、試験温度５００℃、振幅電圧１０ｍＶとした。
又、上記した固体電解質体用のグリーンシートと、所定のアルミナグリーンシートとをアルミナペーストを用いて貼り合わせ、４２０℃で４時間脱脂した後、１５２５℃で１時間焼成した。焼成体のレッドチェックを行い、固体電解質体のクラック（キレ）の有無を調査した。レッドチェックは染色浸透探傷法とも称され、肉眼で見えないような傷の発見に用いられる。対象部位に着色した浸透剤を吹き付けた後、浸透剤を洗浄し、現像液を吹き付けると、クラックが生じた部分が着色されて浮き出る。
Moreover, Pt paste was screen-printed on both surfaces of the obtained solid electrolyte body, heat-treated at 1200 ° C. for 1 hour, and a Pt electrode having an area of 3 mm 2 was baked. The internal resistance of the solid electrolyte body between each Pt electrode was measured by the AC impedance method. The measurement conditions were a test temperature of 500 ° C. and an amplitude voltage of 10 mV.
Further, the above-described green sheet for a solid electrolyte body and a predetermined alumina green sheet were bonded together using an alumina paste, degreased at 420 ° C. for 4 hours, and then fired at 1525 ° C. for 1 hour. A red check was performed on the fired body, and the presence or absence of cracks in the solid electrolyte body was investigated. Red check is also called a dye penetrant flaw detection method, and is used to find scratches that cannot be seen with the naked eye. After the colored penetrant is sprayed on the target site, the penetrant is washed and then the developer is sprayed, so that the cracked portion is colored and floated.
次に、上記した各実施例及び比較例１〜３の固体電解質体の製造に用いたのと同じ混合粉末をボールミルで２０時間混合、湯煎乾燥した。この混合粉末を一軸加圧により仮成形した後、１５０ＭＰａの静水圧プレスで成形し、大気中、１５２５℃で１時間焼成した。得られた焼結体を研磨加工後、ＪＩＳ−Ｒ−１６０１の３点曲げ強度試験を行った。 Next, the same mixed powder used in the production of the solid electrolyte bodies of each of the above Examples and Comparative Examples 1 to 3 was mixed with a ball mill for 20 hours and dried in a hot water bath. This mixed powder was temporarily formed by uniaxial pressing, then formed by a 150 MPa hydrostatic press, and fired at 1525 ° C. for 1 hour in the air. After the obtained sintered body was polished, a three-point bending strength test of JIS-R-1601 was performed.
さらに、上記した各実施例及び比較例１〜３の固体電解質体を用いて図１〜図３のガスセンサ（λセンサ）を製造し、以下のライトオフ特性（時間）の評価を行った。ライトオフ時間は、ガスセンサのヒータの通電を開始してから、特性が安定し測定可能となるまでに要する時間であり、ライトオフ時間が短いほどガスセンサの早期活性が優れている。
ここで、λセンサでは、リッチ側からリーン側に排気ガスの空燃比が変化する場合と、リーン側からリッチ側に排気ガスの空燃比が変化する場合とでそれぞれセンサ出力が変化する。そのため、これら２つの状態を共に再現するよう、空燃比を一定の周期でリッチ側およびリーン側に交番させて排気ガスを検出した。具体的には、エンジンの排気管にガスセンサを取付け、ヒータに通電すると共に、エンジンのＥＣＵを制御して排気ガスの空燃比をリッチ側（空燃比0.97）とリーン側（空燃比1.03）との間で周波数１Ｈｚで交番させた。そして、ヒータに通電してからセンサ出力が８００ｍＶに到達するまでの時間を活性時間（ライトオフ時間）とした。
なお、エンジン制御用ＰＣをＥＣＵに接続し、ＥＣＵが燃料噴射量と吸気通路への空気の吸入量とを調整することで、空燃比を上記周波数毎にリッチ側とリーン側とに交番させた。又、排気ガス温度を３５０℃とし、ヒータ（抵抗９Ω）に直流１４Ｖの電圧を印加して通電を行った。
Furthermore, the gas sensor ((lambda) sensor) of FIGS. 1-3 was manufactured using the solid electrolyte body of each above-mentioned Example and Comparative Examples 1-3, and the following light-off characteristics (time) were evaluated. The light-off time is the time required from the start of energization of the heater of the gas sensor until the characteristics become stable and measurement is possible. The shorter the light-off time, the better the early activation of the gas sensor.
Here, in the λ sensor, the sensor output changes when the air-fuel ratio of the exhaust gas changes from the rich side to the lean side and when the air-fuel ratio of the exhaust gas changes from the lean side to the rich side. Therefore, the exhaust gas is detected by alternating the air-fuel ratio between the rich side and the lean side at a constant cycle so as to reproduce both of these two states. Specifically, a gas sensor is attached to the exhaust pipe of the engine, the heater is energized, and the ECU of the engine is controlled to control the exhaust gas air-fuel ratio between the rich side (air-fuel ratio 0.97) and the lean side (air-fuel ratio 1.03). Alternating at a frequency of 1 Hz. The time from when the heater was energized until the sensor output reached 800 mV was defined as the active time (light-off time).
The engine control PC is connected to the ECU, and the ECU adjusts the fuel injection amount and the intake amount of air into the intake passage so that the air-fuel ratio is alternated between the rich side and the lean side for each frequency. . Further, the exhaust gas temperature was set to 350 ° C., and a voltage of DC 14 V was applied to the heater (resistance 9Ω) to conduct electricity.
得られた結果を表１及び図４〜図６に示す。 The obtained results are shown in Table 1 and FIGS.
表１及び図４〜図６から明らかなように、ガスセンサ素子の固体電解質体のＸ線回折において、（Ｉａ／Ｉｂ）が０．７１〜０．８６である各実施例の場合、固体電解質体のインピーダンス（内部抵抗）が低減し、強度も向上した。又、各実施例の場合、固体電解質体をアルミナ層と同時焼成しても固体電解質体にクラックが発生しなかった。これより、固体電解質体中の単斜晶ＺｒＯ２の含有割合を１０〜２０質量％とするのが好ましいことがわかる。 As is apparent from Table 1 and FIGS. 4 to 6, in each example where (Ia / Ib) is 0.71 to 0.86 in the X-ray diffraction of the solid electrolyte body of the gas sensor element, the solid electrolyte body Impedance (internal resistance) was reduced and strength was improved. In each example, no cracks occurred in the solid electrolyte body even when the solid electrolyte body was co-fired with the alumina layer. From this, it can be seen that the content ratio of monoclinic ZrO 2 in the solid electrolyte body is preferably 10 to 20% by mass.
一方、ガスセンサ素子の固体電解質体のＸ線回折において、（Ｉａ／Ｉｂ）が０．７１未満である比較例１の場合、固体電解質体の強度が低下した。
ガスセンサ素子の固体電解質体のＸ線回折において、（Ｉａ／Ｉｂ）が０．８６を超えた比較例２の場合、固体電解質体の内部抵抗が増大した。
又、ガスセンサ素子の固体電解質体のＸ線回折において、（Ｉａ／Ｉｂ）が０．７１未満である比較例３の場合、実施例１に比べてライトオフ時間が約２倍長くなった。なお、強度が向上すれば、ヒータによる昇温速度も上げることができ、活性化温度まで素早く上げることが出来るので、ライトオフ時間が短くなる。
On the other hand, in the X-ray diffraction of the solid electrolyte body of the gas sensor element, in the case of Comparative Example 1 where (Ia / Ib) is less than 0.71, the strength of the solid electrolyte body was lowered.
In the X-ray diffraction of the solid electrolyte body of the gas sensor element, in the case of Comparative Example 2 where (Ia / Ib) exceeded 0.86, the internal resistance of the solid electrolyte body increased.
Further, in the X-ray diffraction of the solid electrolyte body of the gas sensor element, in the case of Comparative Example 3 where (Ia / Ib) is less than 0.71, the light-off time is about twice as long as that in Example 1. In addition, if intensity | strength improves, the temperature increase rate by a heater can also be raised and it can raise to activation temperature quickly, Therefore Light-off time becomes short.
なお、図４は、実施例１の固体電解質体の焼結体のＸ線回折チャートを示す。回折角２θ＝７０〜７７度の範囲に、ピーク強度Ｉａ、Ｉｂが存在することがわかる。
又、図５は、実施例１及び比較例３の固体電解質体を用いたガスセンサのライトオフ時間を示す。
図６は、実施例１の固体電解質体の組織のＳＥＭ像である。大径の粒子がＹｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２であり、それより小径の粒子がＳｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２及び単斜晶ＺｒＯ２である。正方晶ＺｒＯ２は一般に粒成長しにくい材料であるため、微細結晶となりやすく、高強度の固体電解質体を形成しやすい。一方、立方晶ＺｒＯ２は一般に粒成長しやすいため、粗大結晶粒となりやすく、固体電解質体の強度を低下させやすい。つまり、実施例１の固体電解質体では、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２自身が高強度であることに加えて、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２の存在により、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２の粒成長を抑制することが出来る。このため、固体電解質体中のＺｒＯ２を比較的微細な結晶粒構造とすることができ、固体電解質体の強度を向上させることが出来る。
FIG. 4 shows an X-ray diffraction chart of the sintered body of the solid electrolyte body of Example 1. It can be seen that the peak intensities Ia and Ib exist in the range of the diffraction angle 2θ = 70 to 77 degrees.
FIG. 5 shows the light-off time of the gas sensor using the solid electrolyte bodies of Example 1 and Comparative Example 3.
6 is an SEM image of the structure of the solid electrolyte body of Example 1. FIG. Large-diameter particles are cubic ZrO 2 in which Yb 2 O 3 is most dissolved, and smaller-diameter particles are tetragonal ZrO 2 and monoclinic ZrO 2 in which Sc 2 O 3 is most dissolved. . Since tetragonal ZrO 2 is a material that is generally difficult to grow grains, it tends to be a fine crystal and easily forms a high-strength solid electrolyte. On the other hand, since cubic ZrO 2 generally tends to grow, it tends to be coarse crystal grains and tends to reduce the strength of the solid electrolyte body. That is, the solid electrolyte of Example 1, Sc 2 O 3 in addition to the most tetragonal ZrO 2 itself to solid solution is a high strength, Sc 2 O 3 tetragonal ZrO 2 to the most solid solution Therefore, it is possible to suppress the grain growth of cubic ZrO 2 in which Yb 2 O 3 is most dissolved. For this reason, ZrO 2 in the solid electrolyte body can have a relatively fine crystal grain structure, and the strength of the solid electrolyte body can be improved.
１ セル
２ ヒータ
１１ 固体電解質体
２１ ヒータ素子
２２ Ａｌ２Ｏ３からなる層
１００ ガスセンサ素子
１３１ 検知電極
１３２ 基準電極
３００ ガスセンサ
1 cell 2 heater 11 solid electrolytic substrate 21 heater elements 22 Al 2 O 3 consists of a layer 100 the gas sensor element 131 sensing electrode 132 reference electrode 300 gas sensor
Claims (4)
前記固体電解質体はＺｒＯ２を８０質量％以上含み、
前記ＺｒＯ２は、Ｙｂ２Ｏ３を最も多く固溶する立方晶ＺｒＯ２と、Ｓｃ２Ｏ３を最も多く固溶する正方晶ＺｒＯ２とを含有し、
かつ前記固体電解質体のＸ線回折において、回折角２θ＝７３．２〜７３．６度のピーク強度（Ｉａ）と、回折角２θ＝７３．９〜７４．３度のピーク強度（Ｉｂ）との比（Ｉａ／Ｉｂ）が０．７１〜０．８６であるガスセンサ素子。 A gas sensor having an oxygen ion conductive solid electrolyte body, a detection electrode provided on a surface of the solid electrolyte body and exposed to a gas to be measured, and a reference electrode facing the detection electrode through the solid electrolyte body An element,
The solid electrolyte body contains 80% by mass or more of ZrO 2 ,
The ZrO 2 contains cubic ZrO 2 that dissolves most Yb 2 O 3 and tetragonal ZrO 2 that dissolves Sc 2 O 3 most,
In the X-ray diffraction of the solid electrolyte body, the peak intensity (Ia) at a diffraction angle 2θ = 73.2 to 73.6 degrees and the peak intensity (Ib) at a diffraction angle 2θ = 73.9 to 74.3 degrees Gas sensor element having a ratio (Ia / Ib) of 0.71 to 0.86.
前記固体電解質体は、単斜晶ＺｒＯ２を１０〜２０質量％含む請求項１記載のガスセンサ素子。 The heater further comprises a heater integrally laminated on the gas sensor element, and the heater surrounds the heater element with a layer made of Al 2 O 3 .
The gas sensor element according to claim 1, wherein the solid electrolyte body contains 10 to 20 mass% of monoclinic ZrO 2 .
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