JP2010185891A - Method of manufacturing gas sensor element, and method of manufacturing the gas sensor - Google Patents
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この発明は、内燃機関の燃焼制御等に用いられるガスセンサ素子及びガスセンサ並びにそれらの製造方法に関する。更に詳しくは、被毒による空燃比の検出の低下を防止することができるガスセンサ素子及びガスセンサ並びにそれらの製造方法に関する。 The present invention relates to a gas sensor element and a gas sensor used for combustion control or the like of an internal combustion engine, and a manufacturing method thereof. More specifically, the present invention relates to a gas sensor element and a gas sensor that can prevent a decrease in detection of an air-fuel ratio due to poisoning, and methods for manufacturing the same.
従来、内燃機関の排気系に設置し、排気ガス中の酸素濃度を検出して内燃機関の燃焼制御に利用されるガスセンサとして、酸素センサが知られている。この酸素センサは、例えば、筒状の主体金具と、その主体金具に保持された板状のガスセンサ素子を有している。ガスセンサ素子は、長手方向に延びる固体電解質層、及び固体電解質層のうち測定対象気体に晒される先端側の表裏面に対向する電極を有するセルと、セルに積層される多孔質部と、該多孔質部を介してセルと積層される遮蔽体を有しており、多孔質部、セル及び遮蔽体により測定室が形成されている。なお、この測定室には、セルの一方の電極が配置されている。また、多孔質部は、測定室内に導入される測定対象気体の拡散律速を行うために設けられている。 2. Description of the Related Art Conventionally, an oxygen sensor is known as a gas sensor that is installed in an exhaust system of an internal combustion engine, detects oxygen concentration in exhaust gas, and is used for combustion control of the internal combustion engine. This oxygen sensor has, for example, a cylindrical metal shell and a plate-shaped gas sensor element held by the metal shell. The gas sensor element includes a solid electrolyte layer extending in the longitudinal direction, a cell having electrodes facing the front and back surfaces of the solid electrolyte layer exposed to the measurement target gas, a porous portion stacked on the cell, and the porous The measurement chamber is formed by the porous portion, the cell, and the shield. In this measurement chamber, one electrode of the cell is arranged. Moreover, the porous part is provided in order to carry out the diffusion control of the measurement object gas introduced into the measurement chamber.
ところで、一般に自動車エンジン等の内燃機関に使用される燃料やエンジンオイ中にはリンやシリコンを含むものが存在している。この燃料やエンジンオイルを使用すると、このリンやシリコンが多孔質部の表面に付着し、多孔質の孔を塞いでしまうことで多孔質部が目詰まりを起こしてしまう問題がある。その結果、多孔質部の拡散抵抗が変化してしまい、ガスセンサの空燃比の検出の精度が低下する虞がある。 By the way, in general, some fuels and engine oils used for internal combustion engines such as automobile engines contain phosphorus and silicon. When this fuel or engine oil is used, there is a problem that the porous part is clogged because the phosphorus or silicon adheres to the surface of the porous part and blocks the porous hole. As a result, the diffusion resistance of the porous portion changes, and there is a possibility that the accuracy of detection of the air-fuel ratio of the gas sensor is lowered.
そこで、この多孔質部の目詰まりの発生や電極の異常に対しては、例えば多孔質部と外部との間にリンやシリコンからの被毒を防止する第２多孔質部を有することが知られている。（特許文献１、２参照）この第２多孔質部でリンやシリコンを吸着し、多孔質部での目詰まりの発生を抑制することができる。よって、多孔質部の拡散抵抗の変化を抑制し、ガスセンサの空燃比の検出の精度が低下するのを抑制することができる。 In view of this, the occurrence of clogging of the porous portion and the abnormality of the electrode are known to have, for example, a second porous portion that prevents poisoning from phosphorus and silicon between the porous portion and the outside. It has been. (See Patent Documents 1 and 2) Phosphorus and silicon are adsorbed by the second porous portion, and the occurrence of clogging in the porous portion can be suppressed. Therefore, it is possible to suppress a change in the diffusion resistance of the porous portion and to suppress a decrease in the accuracy of detection of the air-fuel ratio of the gas sensor.
この第２多孔質部は、特許文献１によれば以下のように作製される。焼成後に酸素濃淡電池素子、酸素ポンプ素子（セルに相当）や拡散律速部（多孔質部に相当）となる未焼成酸素濃淡電池素子、未焼成酸素ポンプ素子や未焼成拡散律速部を積層する際に、さらに焼成後に被毒防止部（第２多孔質部に相当）となる未焼成被毒防止部を同様に積層し、その後、未焼成被毒防止部を未焼成酸素ポンプ素子や未焼成拡散律速部と同時に焼成すること作製されている。 According to Patent Document 1, the second porous portion is produced as follows. When stacking an oxygen concentration cell element, an oxygen pump element (corresponding to a cell) or a diffusion rate controlling part (corresponding to a porous part) after firing, an unsintered oxygen concentration cell element, an unsintered oxygen pump element or an unsintered diffusion rate controlling part In addition, an unfired poisoning prevention part that becomes a poisoning prevention part (corresponding to the second porous part) after firing is similarly laminated, and then the unfired poisoning prevention part is used as an unfired oxygen pump element or unfired diffusion It is made by firing at the same time as the rate-limiting part.
しかしながら、近年、ガスセンサの高性能化、高精度化が求められており、そのためには第２多孔質部にてリンやシリコンをより多く吸着して、多孔質部での発生する目詰まりをさらに抑制することが重要視されている。しかしながら、特許文献１の第２多孔質部では、ガスセンサの高性能化、高精度化に必要となるリンやシリコンの十分な吸着を行うことができない。その結果、多孔質部に発生する目詰まりの抑制が十分でなく、ガスセンサの高性能化、高精度化に適用した多孔質部とすることができない虞がある。 However, in recent years, there has been a demand for higher performance and higher accuracy of gas sensors. For this purpose, more phosphorus and silicon are adsorbed in the second porous portion, and clogging that occurs in the porous portion is further increased. It is important to suppress. However, in the second porous portion of Patent Document 1, it is not possible to sufficiently adsorb phosphorus and silicon necessary for high performance and high accuracy of the gas sensor. As a result, clogging that occurs in the porous portion is not sufficiently suppressed, and there is a possibility that the porous portion is not applicable to high performance and high accuracy of the gas sensor.
本発明は、かかる従来の問題点を鑑みてなされたもので、第２多孔質部でリンやシリコンを十分に吸着することができ、その結果、多孔質部の目詰まりの発生をさらに抑制して、ガスセンサの高性能化、高精度化に対応した多孔質部とし、空燃比の検出の精度をさらに向上させるガスセンサ素子及びガスセンサ並びにそれらの製造方法を提供するものである。 The present invention has been made in view of such conventional problems, and can sufficiently adsorb phosphorus and silicon in the second porous portion, thereby further suppressing the occurrence of clogging of the porous portion. Thus, the present invention provides a gas sensor element, a gas sensor, and a method for manufacturing the same, which are made of a porous portion corresponding to high performance and high accuracy of a gas sensor, and further improve the accuracy of air-fuel ratio detection.
そこで本発明のガスセンサ素子は、長手方向に延びる固体電解質層、及び該固体電解質層の表裏面に対向する電極を有する第１セルと、該第１セルに積層される第１多孔質部と、該第１多孔質部を介して前記第１セルと積層される遮蔽体と、前記第１多孔質部、前記第１セル及び前記遮蔽体で区画され、前記電極の一方が配置された測定室と、を有する板状のガスセンサ素子であって、
前記第１多孔質部を介して前記測定室とは反対側に配置され、前記第１多孔質部よりも拡散抵抗が小さい多孔質状をなすとともに、ＢＥＴ比表面積が１．０ｍ２／ｇ以上である第２多孔質部を有することを特徴とする。
Therefore, the gas sensor element of the present invention includes a first cell having a solid electrolyte layer extending in the longitudinal direction, electrodes facing the front and back surfaces of the solid electrolyte layer, and a first porous portion laminated on the first cell, A measurement chamber in which one of the electrodes is disposed, which is partitioned by the shield laminated with the first cell via the first porous portion, the first porous portion, the first cell, and the shield. A plate-like gas sensor element having
It is disposed on the opposite side of the measurement chamber through the first porous portion, has a porous shape having a diffusion resistance smaller than that of the first porous portion, and has a BET specific surface area of 1.0 m 2 / g or more. It has the 2nd porous part which is these.
このように、第２多孔質部のＢＥＴ比表面積が１．０ｍ２／ｇ以上とすることで、第２多孔質部を形成する粒の粒径が細かくなり、第２多孔質部でリンやシリコンがより多く吸着することができる。よって、第１多孔質部の目詰まりの発生をさらに抑制して、測定対象気体の拡散抵抗の変化による空燃比の検出の精度を向上させることができる。第２多孔質部のＢＥＴ比表面積が１．０ｍ２／ｇ未満では、上記効果を得ることが難しい。なお、ＢＥＴ比表面積は、ＢＥＴ式を用いて測定することができる。 As described above, when the BET specific surface area of the second porous portion is 1.0 m 2 / g or more, the particle diameter of the particles forming the second porous portion becomes finer. More silicon can be adsorbed. Therefore, generation | occurrence | production of the clogging of a 1st porous part can further be suppressed, and the precision of the detection of the air fuel ratio by the change of the diffusion resistance of measurement object gas can be improved. When the BET specific surface area of the second porous portion is less than 1.0 m 2 / g, it is difficult to obtain the above effect. The BET specific surface area can be measured using the BET formula.
また、第２多孔質部の拡散抵抗が第１多孔質部の拡散抵抗よりも小さい。これにより、リンやシリコンを吸着するのための第２多孔質部で測定対象気体が拡散律速することを防止し、空燃比の検出の精度が低下することを防止する。 Further, the diffusion resistance of the second porous portion is smaller than the diffusion resistance of the first porous portion. This prevents the measurement target gas from being diffusion-controlled in the second porous part for adsorbing phosphorus and silicon, and prevents the accuracy of air-fuel ratio detection from being reduced.
さらに、第２多孔質部は、少なくとも一部が第１セルと遮蔽体との間に配置されることが好ましい。第２多孔質部がリンやシリコンをより多く吸着するためには、測定対象気体が第２多孔質部を通過する距離（以下、第２多孔質部の幅という）を長くすることが効果的である。しかし、第２多孔質部の幅を長くすればするほど、第２多孔質部が大きくなり、その結果、ガスセンサ素子が巨大化してしまう。ガスセンサ素子は、ヒータにより加熱されて、ガスセンサ素子が活性することで空燃比の検出することができる。しかし、ガスセンサ素子が巨大化すると、ガスセンサ素子が活性するまでの時間（以下、活性時間とも言う）が遅くなる。その結果、ガスセンサ素子が早期に空燃比の検出することができない虞がある。そこで、第２多孔質部の一部を第１セルと遮蔽体との間に位置させることで、第２多孔質部の幅を長くしつつ、ガスセンサ素子の巨大化を防ぐことができる。これにより、ガスセンサ素子の活性時間が遅くなるのを防ぎつつ、第２多孔質部によるリンやシリコンの吸着を効果的に行うことができる。なお、第２多孔質部は、その一部が第１セルと遮蔽体との間に配置されていても良いし、第２多孔質部全部が第１セルと遮蔽体との間に配置されていても良い。 Furthermore, it is preferable that at least a part of the second porous portion is disposed between the first cell and the shield. In order for the second porous portion to adsorb more phosphorus and silicon, it is effective to increase the distance that the measurement target gas passes through the second porous portion (hereinafter referred to as the width of the second porous portion). It is. However, the longer the width of the second porous portion is, the larger the second porous portion is, and as a result, the gas sensor element is enlarged. The gas sensor element is heated by the heater, and the air sensor can be detected by activating the gas sensor element. However, when the gas sensor element is enlarged, the time until the gas sensor element is activated (hereinafter also referred to as activation time) is delayed. As a result, the gas sensor element may not be able to detect the air-fuel ratio at an early stage. Therefore, by positioning a part of the second porous portion between the first cell and the shield, it is possible to prevent the gas sensor element from becoming enormous while increasing the width of the second porous portion. Thereby, adsorption | suction of phosphorus and a silicon | silicone by a 2nd porous part can be performed effectively, preventing that the active time of a gas sensor element becomes late. A part of the second porous part may be disposed between the first cell and the shield, or the entire second porous part is disposed between the first cell and the shield. May be.
また、本発明のガスセンサは、円筒状の主体金具と、該主体金具に保持されるガスセンサ素子と、を有するガスセンサであって、
前記ガスセンサ素子は、請求項１または２に記載のガスセンサ素子であることを特徴とする。
The gas sensor of the present invention is a gas sensor having a cylindrical metal shell and a gas sensor element held by the metal shell,
The gas sensor element is the gas sensor element according to claim 1 or 2.
本発明のガスセンサに、上述のガスセンサ素子を用いることで、測定対象気体の拡散抵抗の変化による精度の良い空燃比の検出ができる。 By using the gas sensor element described above for the gas sensor of the present invention, it is possible to detect the air-fuel ratio with high accuracy by changing the diffusion resistance of the measurement target gas.
また、本発明のガスセンサの製造方法は、長手方向に延びる固体電解質層、及び該固体電解質層の表裏面に対向する電極を有する第１セルと、該第１セルに積層される第１多孔質部と、該第１多孔質部を介して前記第１セルと積層される遮蔽体と、前記第１多孔質部、前記第１セル及び前記遮蔽体で区画され、前記電極の一方が配置された測定室と、を有する板状のガスセンサ素子の製造方法であって、
前記ガスセンサ素子は、前記第１多孔質部を介して前記測定室とは反対側に配置され、前記第１多孔質部よりも拡散抵抗が小さい多孔質状をなす第２多孔質部を有し、
焼成後に前記第１セルとなる未焼成第１セルと、焼成後に前記第１多孔質部となる未焼成第１多孔質部と、焼成後に遮蔽体となる未焼成遮蔽体とを積層し、焼成後に積層体となる未焼成積層体を作成する積層工程と、前記未焼成積層体を焼成する焼成工程と、前記焼成工程後に、熱処理後に第２多孔質部となる未処理第２多孔質部を前記積層体上に配置し、前記焼成工程よりも低温度で熱処理を行って、第２多孔質部を形成する熱処理工程と、を有することを特徴とする。
In addition, the gas sensor manufacturing method of the present invention includes a first cell having a solid electrolyte layer extending in the longitudinal direction, electrodes facing the front and back surfaces of the solid electrolyte layer, and a first porous layer laminated on the first cell. And a shield laminated with the first cell via the first porous part, the first porous part, the first cell, and the shield, and one of the electrodes is disposed. A plate-shaped gas sensor element having a measurement chamber,
The gas sensor element has a second porous portion that is disposed on the opposite side of the measurement chamber via the first porous portion and has a porous shape having a diffusion resistance smaller than that of the first porous portion. ,
An unfired first cell that becomes the first cell after firing, an unfired first porous portion that becomes the first porous portion after firing, and an unfired shield that becomes a shield after firing are laminated and fired A laminating step of creating an unfired laminated body to be a laminated body later, a firing step of firing the unfired laminated body, and an untreated second porous portion that becomes a second porous portion after the heat treatment after the firing step. And a heat treatment step of forming the second porous portion by performing heat treatment at a temperature lower than that of the firing step.
このように、未焼成積層体を焼成した後、積層体上に未焼成第２多孔質部を配置して、焼成温度よりも低温で熱処理を行うことで、粒の粒径が細かい第２多孔質部を作製することができ、リンやシリコンがより多く吸着することができる第２多孔質部を形成することができる。よって、作製されたガスセンサ素子は、第１多孔質部の目詰まりの発生を抑制して、測定対象気体の拡散抵抗の変化による空燃比の検出の精度を向上させることができる。 Thus, after baking an unbaked laminated body, by arrange | positioning an unbaked 2nd porous part on a laminated body, and performing heat processing at low temperature rather than baking temperature, the 2nd porous with a fine particle diameter A mass part can be produced, and a second porous part capable of adsorbing more phosphorus and silicon can be formed. Therefore, the produced gas sensor element can suppress the occurrence of clogging of the first porous portion and improve the accuracy of detection of the air-fuel ratio by the change in the diffusion resistance of the measurement target gas.
また、作製された第２多孔質部の拡散抵抗は第１多孔質部の拡散抵抗よりも小さくなり、リンやシリコンを吸着するのための第２多孔質部で測定対象気体が拡散律速することを防止して、空燃比の検出の精度が低下することを防止するガスセンサ素子を作製することができる。 In addition, the diffusion resistance of the produced second porous part is smaller than that of the first porous part, and the measurement target gas is diffusion-controlled in the second porous part for adsorbing phosphorus and silicon. Thus, it is possible to manufacture a gas sensor element that prevents a decrease in the accuracy of air-fuel ratio detection.
また、本発明のガスセンサの製造方法は、円筒状の主体金具と、該主体金具に保持されるガスセンサ素子と、を有するガスセンサの製造方法であって、
前記ガスセンサ素子は、請求項６に記載のガスセンサ素子を用いて形成されることを特徴とする。
The gas sensor manufacturing method of the present invention is a gas sensor manufacturing method having a cylindrical metal shell and a gas sensor element held by the metal shell,
The gas sensor element is formed using the gas sensor element according to claim 6.
本発明のガスセンサとして、上述のガスセンサ素子を用いて作製されることで、作製されたガスセンサを測定対象気体の拡散抵抗の変化による精度の良い空燃比の検出ができるガスセンサとすることができる。 As the gas sensor of the present invention, the gas sensor manufactured using the gas sensor element described above can be used as a gas sensor that can accurately detect the air-fuel ratio by changing the diffusion resistance of the measurement target gas.
以下に、本発明を適用した実施形態であるガスセンサを図面と共に説明する。本実施形態では、自動車や各種内燃機関における空燃比フィードバック制御に使用するために、測定対象気体となる排ガス中の特定ガスを検出するガスセンサ素子が組みつけられるとともに、内燃機関の排気管に装着される全領域空燃比センサ２について説明する。 Hereinafter, a gas sensor as an embodiment to which the present invention is applied will be described with reference to the drawings. In the present embodiment, a gas sensor element for detecting a specific gas in the exhaust gas that is the measurement target gas is assembled for use in air-fuel ratio feedback control in automobiles and various internal combustion engines, and is mounted on the exhaust pipe of the internal combustion engine. The full-range air-fuel ratio sensor 2 will be described.
図１は、実施形態の空燃比センサ２の全体構成を示す断面図である。空燃比センサ２は、排気管に固定するためのネジ部３９が外表面に形成された筒状の主体金具３８と、軸線方向(空燃比センサ２の長手方向：図中上下方向)に延びる板状形状をなすガスセンサ素子４と、ガスセンサ素子４の径方向周囲を取り囲むように配置される筒状のセラミックスリーブ６と、軸線方向に貫通するコンタクト挿通孔６８の内壁面がガスセンサ素子４の後端部の周囲を取り囲む状態で配置される絶縁コンタクト部材６６と、ガスセンサ素子４と絶縁コンタクト部材６６との間に配置される５個の接続端子１０（図１では２個図示）と、を備えている。 FIG. 1 is a cross-sectional view showing the overall configuration of the air-fuel ratio sensor 2 of the embodiment. The air-fuel ratio sensor 2 includes a cylindrical metal shell 38 having a screw portion 39 formed on the outer surface for fixing to an exhaust pipe, and a plate extending in the axial direction (longitudinal direction of the air-fuel ratio sensor 2: vertical direction in the figure). The gas sensor element 4 having a shape, the cylindrical ceramic sleeve 6 disposed so as to surround the circumference of the gas sensor element 4, and the inner wall surface of the contact insertion hole 68 penetrating in the axial direction are the rear end of the gas sensor element 4 Insulating contact member 66 arranged so as to surround the periphery of the unit, and five connection terminals 10 (two shown in FIG. 1) arranged between gas sensor element 4 and insulating contact member 66 are provided. Yes.
主体金具３８は、軸線方向に貫通する貫通孔５４を有し、貫通孔５４の径方向内側に突出する棚部５２を有する略筒状形状に構成されている。また、主体金具３８は、先端側（後述する検出部８）を貫通孔５４の先端側外部に配置し、電極端子部１２０、１２１を貫通孔５４の後端側外部に配置する状態で貫通孔５４に押通されたガスセンサ素子４を保持するよう構成されている。さらに、棚部５２は、軸線方向に垂直な平面に対して傾きを有する内向きのテーパ面として形成されている。 The metal shell 38 has a through-hole 54 that penetrates in the axial direction, and has a substantially cylindrical shape that has a shelf 52 that protrudes radially inward of the through-hole 54. Further, the metal shell 38 has a front end side (detection unit 8 to be described later) disposed outside the front end side of the through hole 54, and the electrode terminal portions 120 and 121 are disposed outside the rear end side of the through hole 54. The gas sensor element 4 pushed through 54 is held. Further, the shelf 52 is formed as an inwardly tapered surface having an inclination with respect to a plane perpendicular to the axial direction.
なお、主体金具３８の貫通孔５４の内部には、ガスセンサ素子４の径方向周囲を取り囲む状態で、環状形状のセラミックホルダ５１、粉末充填層５３、５６(以下、滑石リング５３、５６ともいう)、および上述のセラミックスリーブ６が、この順に先端側から後端側にかけて積層されている。また、セラミックスリーブ６と主体金具３８の後端部４０との間には、加締パッキン５７が配置されており、セラミックホルダ５１と主体金具３８の棚部５２との間には、滑石リング５３やセラミックホルダ５１を保持し、気密性を維持するための金属ホルダ５８が配置されている。なお、主体金具３８の後端部４０は、加締パッキン５７を介してセラミックスリーブ６を先端側に押し付けるように、加締められている。 In addition, inside the through hole 54 of the metal shell 38, an annular ceramic holder 51 and powder filling layers 53 and 56 (hereinafter also referred to as talc rings 53 and 56) in a state of surrounding the periphery of the gas sensor element 4 in the radial direction. The ceramic sleeve 6 is laminated in this order from the front end side to the rear end side. Further, a caulking packing 57 is disposed between the ceramic sleeve 6 and the rear end portion 40 of the metal shell 38, and a talc ring 53 is provided between the ceramic holder 51 and the shelf 52 of the metal shell 38. In addition, a metal holder 58 for holding the ceramic holder 51 and maintaining hermeticity is disposed. Note that the rear end portion 40 of the metal shell 38 is crimped so as to press the ceramic sleeve 6 toward the distal end side via the crimping packing 57.
一方、図１に示すように、主体金具３８の先端側(図１における下方)外周には、ガスセンサ素子４の突出部分を覆うと共に、複数の孔部を有する金属製(例えば、ステンレスなど)の二重の外部プロテクタ４２および内部プロテクタ４３が、溶接等によって取り付けられている。 On the other hand, as shown in FIG. 1, a metal (for example, stainless steel) having a plurality of holes and covering the protruding portion of the gas sensor element 4 on the outer periphery of the front end side (lower side in FIG. 1) of the metal shell 38. A double external protector 42 and an internal protector 43 are attached by welding or the like.
そして、主体金具３８の後端側外周には、外筒４４が固定されている。また、外筒４４の後端側(図１における上方)の開口部には、ガスセンサ素子４の電極端子部１２０、１２１とそれぞれ電気的に接続される５本のリード線４６(図１では３本図示)が押通されるリード線押通孔６１が形成されたグロメット５０が配置されている。 An outer cylinder 44 is fixed to the outer periphery of the rear end side of the metal shell 38. Further, five lead wires 46 (3 in FIG. 1) electrically connected to the electrode terminal portions 120 and 121 of the gas sensor element 4 are respectively provided in the opening on the rear end side (upper side in FIG. 1) of the outer cylinder 44. A grommet 50 in which a lead wire pushing hole 61 through which this figure is pushed is formed is disposed.
また、主体金具３８の後端部４０より突出されたガスセンサ素子４の後端側(図１における上方)には、絶縁コンタクト部材６６が配置される。なお、この絶縁コンタクト部材６６は、ガスセンサ素子４の後端側の表面に形成される電極端子部１２０、１２１の周囲に配置される。この絶縁コンタクト部材６６は、軸線方向に貫通するコンタクト挿通孔６８を有する筒状形状に形成されると共に、外表面から径方向外側に突出する鍔部６７が備えられている。絶縁コンタクト部材６６は、鍔部６７が保持部材６９を介して外筒４４に当接することで、外筒４４の内部に配置される。 An insulating contact member 66 is disposed on the rear end side (upper side in FIG. 1) of the gas sensor element 4 protruding from the rear end portion 40 of the metal shell 38. The insulating contact member 66 is disposed around the electrode terminal portions 120 and 121 formed on the rear end surface of the gas sensor element 4. The insulating contact member 66 is formed in a cylindrical shape having a contact insertion hole 68 penetrating in the axial direction, and is provided with a flange portion 67 protruding radially outward from the outer surface. The insulating contact member 66 is disposed inside the outer cylinder 44 by the flange 67 contacting the outer cylinder 44 via the holding member 69.
次に、本発明の主要部であるガスセンサ素子４について説明する。
ガスセンサ素子４は、軸線方向に延びる板状形状をなし、測定対象となるガスに向けられる先端側(図中下方)に検出部８が形成され、後端側(図中上方)の外表面のうち表裏面に電極端子部１２０、１２１が形成されている。なお、検出部８には、多孔質部３０（図１、図４参照）が形成されている。接続端子１０は、ガスセンサ素子４と絶縁コンタクト部材６６との間に配置されることで、ガスセンサ素子４の電極端子部１２０、１２１にそれぞれ電気的に接続される。また、接続端子１０は、外部からセンサの内部に配設されるリード線４６にも電気的に接続されており、リード線４６が接続される外部機器と電極端子部１２０、１２１との間に流れる電流の電流経路を形成する。
Next, the gas sensor element 4 which is a main part of the present invention will be described.
The gas sensor element 4 has a plate-like shape extending in the axial direction, and a detection portion 8 is formed on the front end side (lower side in the figure) directed toward the gas to be measured, and on the outer surface on the rear end side (upper side in the figure). Of these, electrode terminal portions 120 and 121 are formed on the front and back surfaces. Note that a porous portion 30 (see FIGS. 1 and 4) is formed in the detection portion 8. The connection terminal 10 is electrically connected to the electrode terminal portions 120 and 121 of the gas sensor element 4 by being disposed between the gas sensor element 4 and the insulating contact member 66. The connection terminal 10 is also electrically connected from the outside to a lead wire 46 disposed inside the sensor, and between the external device to which the lead wire 46 is connected and the electrode terminal portions 120 and 121. A current path for the flowing current is formed.
図２はガスセンサ素子４の展開図であり、図３はガスセンサ素子の斜視図である。なお、図２、図３には、多孔質部３０は、図示していない。
ガスセンサ素子４は、図２に示すように、検出素子３００とヒータ２００が積層されており、さらに検出素子３００は、酸素濃度検出セル１３０と酸素ポンプセル１４０とが積層されている。
FIG. 2 is a development view of the gas sensor element 4, and FIG. 3 is a perspective view of the gas sensor element. 2 and 3, the porous portion 30 is not shown.
As shown in FIG. 2, the gas sensor element 4 includes a detection element 300 and a heater 200 that are stacked, and the detection element 300 includes an oxygen concentration detection cell 130 and an oxygen pump cell 140 that are stacked.
ヒータ２００は、アルミナを主体とする第１基体１０１及び第２基体１０３と、第１基体１０１と第２基体１０３とに挟まれ、白金を主体とする発熱体１０２を有している。発熱体１０２は、先端側に位置する発熱部１０２ａと、発熱部１０２ａから第１基体１０１の長手方向に沿って延びる一対のヒータリード部１０２ｂとを有している。そして、ヒータリード部１０２ｂの端末は、第１基体１０１に設けられるヒータ側スルーホール１０１ａを介して電極端子部１２０と電気的に接続している。 The heater 200 includes a first base 101 and a second base 103 mainly composed of alumina, and a heating element 102 mainly composed of platinum sandwiched between the first base 101 and the second base 103. The heating element 102 has a heating part 102a located on the tip side and a pair of heater lead parts 102b extending from the heating part 102a along the longitudinal direction of the first base 101. The terminal of the heater lead portion 102b is electrically connected to the electrode terminal portion 120 through the heater side through hole 101a provided in the first base 101.
酸素濃度検出セル１３０は、第１固体電解質体１０５と、その第１固体電解質１０５の両面に形成された第１電極１０４及び第２電極１０６とから形成されている。第１電極１０４は、第１電極部１０４ａと、第１電極部１０４ａから第１固体電解質体１０５の長手方向に沿って延びる第１リード部１０４ｂとから形成されている。第２電極１０６は、第２電極部１０６ａと、第２電極部１０６ａから第１固体電解質体１０５の長手方向に沿って延びる第２リード部１０６ｂとから形成されている。 The oxygen concentration detection cell 130 is formed of a first solid electrolyte body 105 and a first electrode 104 and a second electrode 106 formed on both surfaces of the first solid electrolyte 105. The first electrode 104 is formed of a first electrode portion 104 a and a first lead portion 104 b extending from the first electrode portion 104 a along the longitudinal direction of the first solid electrolyte body 105. The second electrode 106 is formed of a second electrode portion 106 a and a second lead portion 106 b extending from the second electrode portion 106 a along the longitudinal direction of the first solid electrolyte body 105.
そして、第１リード部１０４ｂの端末は、第１固体電解質体１０５に設けられる第１スルーホール１０５ａ、後述する絶縁層１０７に設けられる第２スルーホール１０７ａ、第２固体電解質体１０９に設けられる第４スルーホール１０９ａ及び保護層１１１に設けられる第６スルーホール１１１ａを介して電極端子部１２１と電気的に接続する。一方、第２リード部１０６ｂの端末は、後述する絶縁層１０７に設けられる第３スルーホール１０７ｂ、第２固体電解質体１０９に設けられる第５スルーホール１０９ｂ及び保護層１１１に設けられる第７スルーホール１１１ｂを介して電極端子部１２１と電気的に接続する。 The terminals of the first lead portion 104b are first through holes 105a provided in the first solid electrolyte body 105, second through holes 107a provided in the insulating layer 107 described later, and second terminals provided in the second solid electrolyte body 109. The electrode terminal portion 121 is electrically connected through the fourth through hole 109 a and the sixth through hole 111 a provided in the protective layer 111. On the other hand, the end of the second lead portion 106b is a third through hole 107b provided in the insulating layer 107 described later, a fifth through hole 109b provided in the second solid electrolyte body 109, and a seventh through hole provided in the protective layer 111. It is electrically connected to the electrode terminal portion 121 through 111b.
一方、酸素ポンプセル１４０は、第２固体電解質体１０９と、その第２固体電解質体１０９の両面に形成された第３電極１０８、第４電極１１０とから形成されている。第３電極１０８は、第３電極部１０８ａと、この第３電極部１０８ａから第２固体電解質体１０９の長手方向に沿って延びる第３リード部１０８ｂとから形成されている。第４電極１１０は、第４電極部１１０ａと、この第４電極部１１０ａから第２固体電解質体１０９の長手方向に沿って延びる第４リード部１１０ｂとから形成されている。 On the other hand, the oxygen pump cell 140 is formed of the second solid electrolyte body 109 and the third electrode 108 and the fourth electrode 110 formed on both surfaces of the second solid electrolyte body 109. The third electrode 108 is formed of a third electrode portion 108 a and a third lead portion 108 b extending from the third electrode portion 108 a along the longitudinal direction of the second solid electrolyte body 109. The fourth electrode 110 is formed of a fourth electrode portion 110 a and a fourth lead portion 110 b extending from the fourth electrode portion 110 a along the longitudinal direction of the second solid electrolyte body 109.
そして、第３リード部１０８ｂの端末は、第２固体電解質体１０９に設けられる第５スルーホール１０９ｂ及び保護層１１１に設けられる第７スルーホール１１１ｂを介して電極端子部１２１と電気的に接続する。一方、第４リード部１１０ｂの端末は、後述する保護層１１１に設けられる第８スルーホール１１１ｃを介して電極端子部１２１と電気的に接続する。なお、第２リード部１０６ｂと第３リード部１０８ｂは第３スルーホール１０７ｂを介して同電位となっている。 The terminal of the third lead portion 108b is electrically connected to the electrode terminal portion 121 via the fifth through hole 109b provided in the second solid electrolyte body 109 and the seventh through hole 111b provided in the protective layer 111. . On the other hand, the terminal of the fourth lead portion 110b is electrically connected to the electrode terminal portion 121 through an eighth through hole 111c provided in the protective layer 111 described later. The second lead portion 106b and the third lead portion 108b are at the same potential through the third through hole 107b.
これら第１固体電解質体１０５、第２固体電解質体１０９は、ジルコニア（ＺｒＯ２）に安定化剤としてイットリア（Ｙ２Ｏ３）又はカルシア（ＣａＯ）を添加してなる部分安定化ジルコニア焼結体から構成されている。 The first solid electrolyte body 105 and the second solid electrolyte body 109 are composed of a partially stabilized zirconia sintered body obtained by adding yttria (Y2O3) or calcia (CaO) as a stabilizer to zirconia (ZrO2). Yes.
発熱体１０２、第１電極１０４、第２電極１０６、第３電極１０８、第４電極１１０、電極端子部１２０及び電極端子部１２１は、白金族元素で形成することができる。これらを形成する好適な白金族元素としては、Ｐｔ、Ｒｈ、Ｐｄ等を挙げることができ、これらはその一種を単独で使用することもできるし、又二種以上を併用することもできる。 The heating element 102, the first electrode 104, the second electrode 106, the third electrode 108, the fourth electrode 110, the electrode terminal portion 120, and the electrode terminal portion 121 can be formed of a platinum group element. Pt, Rh, Pd etc. can be mentioned as a suitable platinum group element which forms these, These can also be used individually by 1 type, and can also use 2 or more types together.
もっとも、発熱体１０２、第１電極１０４、第２電極１０６、第３電極１０８、第４電極１１０、電極端子部１２０及び電極端子部１２１は、耐熱性及び耐酸化性を考慮するとＰｔを主体にして形成することがより一層好ましい。さらに、発熱体１０２、第１電極１０４、第２電極１０６、第３電極１０８、第４電極１１０、電極端子部１２０及び電極端子部１２１は、主体となる白金族元素の他にセラミック成分を含有することが好ましい。このセラミック成分は、固着という観点から、積層される側の主体となる材料（例えば、第１固体電解質体１０５、第２固体電解質体１０９の主体となる成分）と同様の成分であることが好ましい。 However, the heating element 102, the first electrode 104, the second electrode 106, the third electrode 108, the fourth electrode 110, the electrode terminal portion 120, and the electrode terminal portion 121 are mainly composed of Pt in consideration of heat resistance and oxidation resistance. It is even more preferable to form them. Furthermore, the heating element 102, the first electrode 104, the second electrode 106, the third electrode 108, the fourth electrode 110, the electrode terminal portion 120, and the electrode terminal portion 121 contain a ceramic component in addition to the main platinum group element. It is preferable to do. This ceramic component is preferably the same component as the main material on the side to be laminated (for example, the main component of the first solid electrolyte body 105 and the second solid electrolyte body 109) from the viewpoint of fixation. .
そして、上記酸素ポンプセル１４０と酸素濃度検出セル１３０との間に、絶縁層１０７が形成されている。絶縁層１０７は、絶縁部１１４と拡散律速部１１５とからなる。この絶縁層１０７の絶縁部１１４には、第２電極部１０６ａ及び第３電極部１０８ａに対応する位置にガス検出室１０７ｃが形成されている。このガス検出室１０７ｃは、絶縁層１０７の幅方向で外部と連通しており、該連通部分には、外部とガス検出室１０７ｃとの間のガス拡散を所定の律速条件下で実現する拡散律速部１１５が配置されている。 An insulating layer 107 is formed between the oxygen pump cell 140 and the oxygen concentration detection cell 130. The insulating layer 107 includes an insulating portion 114 and a diffusion rate controlling portion 115. In the insulating portion 114 of the insulating layer 107, a gas detection chamber 107c is formed at a position corresponding to the second electrode portion 106a and the third electrode portion 108a. The gas detection chamber 107c communicates with the outside in the width direction of the insulating layer 107, and the communication portion has a diffusion rate-determining method that realizes gas diffusion between the outside and the gas detection chamber 107c under a predetermined rate-limiting condition. Part 115 is arranged.
絶縁部１１４は、絶縁性を有するセラミック焼結体であれば特に限定されなく、例えば、アルミナやムライト等の酸化物系セラミックを挙げることができる。 The insulating part 114 is not particularly limited as long as it is an insulating ceramic sintered body, and examples thereof include oxide ceramics such as alumina and mullite.
拡散律速部１１５は、アルミナからなる多孔質体である。この拡散律速部１１５によって検出ガスがガス検出室１０７ｃへ流入する際の律速が行われる。 The diffusion control part 115 is a porous body made of alumina. The diffusion rate-determining unit 115 performs rate-limiting when the detection gas flows into the gas detection chamber 107c.
また、第２固体電解質体１０９の表面には、第４電極１１０を挟み込むようにして、保護層１１１が形成されている。この保護層１１１は、第４電極部１１０ａを挟み込む多孔質の電極保護部１１３ａが、第４リード部１１０ｂを挟み込む補強部１１２に形成された貫通孔１１２ａに挿入されている。 A protective layer 111 is formed on the surface of the second solid electrolyte body 109 so as to sandwich the fourth electrode 110. In this protective layer 111, a porous electrode protective part 113a sandwiching the fourth electrode part 110a is inserted into a through hole 112a formed in a reinforcing part 112 sandwiching the fourth lead part 110b.
図４は図３のＡ−Ａ´にて切断した切断面である。なお、図４には、多孔質部３０が形成されている。図４に示すように、拡散律速部１１５を介してガス検出室１０７ｃとは反対側に、多孔室部３０が形成されている。この多孔室部３０は、拡散律速部１１５よりも拡散抵抗が小さく、かつＢＥＴ比表面積が１．６ｍ２／ｇである。このように、多孔質部３０のＢＥＴ比表面積が１．０ｍ２／ｇ以上とすることで、多孔質部３０を形成する粒の粒径が細かくなり、多孔質部３０でリンやシリコンがよく多く吸着することができる。よって、拡散律速部１１５の目詰まりの発生をさらに抑制して、測定対象気体の拡散抵抗の変化による空燃比の検出の精度を向上させることができる。 FIG. 4 is a cut surface cut along AA ′ in FIG. In FIG. 4, a porous portion 30 is formed. As shown in FIG. 4, a porous chamber portion 30 is formed on the opposite side of the gas detection chamber 107c through the diffusion rate controlling portion 115. The porous chamber portion 30 has a diffusion resistance smaller than that of the diffusion rate controlling portion 115 and a BET specific surface area of 1.6 m 2 / g. Thus, when the BET specific surface area of the porous part 30 is 1.0 m 2 / g or more, the particle diameter of the particles forming the porous part 30 becomes fine, and phosphorus and silicon are good in the porous part 30. Many can be adsorbed. Therefore, the occurrence of clogging of the diffusion rate controlling unit 115 can be further suppressed, and the accuracy of air-fuel ratio detection based on the change in the diffusion resistance of the measurement target gas can be improved.
さらに、この多孔室部３０は、一部が酸素ポンプセル１４０と第１固体電解質体１０５との間に配置されている。これにより、ガスセンサ素４の巨大化を防ぎつつ、多孔質部３０の幅を長くすることができる。よって、ガスセンサ素子４の活性時間の遅れを防ぎつつ、多孔質部３０によるリンやシリコンの吸着を効果的に行うことができる。 Further, a part of the porous chamber portion 30 is disposed between the oxygen pump cell 140 and the first solid electrolyte body 105. Thereby, the width of the porous portion 30 can be increased while preventing the gas sensor element 4 from becoming enormous. Therefore, adsorption of phosphorus and silicon by the porous portion 30 can be effectively performed while preventing a delay in the activation time of the gas sensor element 4.
さらに、多孔室部３０は、ガスセンサ素子４の検出部８の全周を覆っている。その結果、検出部８が被水したとき、ガスセンサ素子４にクラックが発生することを抑制することができる。 Further, the porous chamber portion 30 covers the entire circumference of the detection portion 8 of the gas sensor element 4. As a result, when the detection part 8 gets wet, it can suppress that a crack generate | occur | produces in the gas sensor element 4. FIG.
なお、本実施形態の酸素ポンプセル１４０が特許請求の範囲における「第１セル」に相当し、拡散律速部１１５が特許請求の範囲における「第１多孔質部」に相当し、第１固体電解質１０５が特許請求の範囲における「遮蔽体」に相当し、多孔質部３０が特許請求の範囲の「第２多孔質部」に相当する。 The oxygen pump cell 140 of this embodiment corresponds to the “first cell” in the claims, the diffusion-controlling portion 115 corresponds to the “first porous portion” in the claims, and the first solid electrolyte 105. Corresponds to the “shielding body” in the claims, and the porous portion 30 corresponds to the “second porous portion” in the claims.
次に、このガスセンサ素子４の製造方法について説明する。
なお、焼成前の部位と焼成後の部位とは同符号を用いて説明している。例えば、焼成後に第１固体電解質体１０５となる未焼成第１固体電解質体１０５として説明している。
Next, a method for manufacturing the gas sensor element 4 will be described.
In addition, the site | part before baking and the site | part after baking are demonstrated using the same code | symbol. For example, the non-fired first solid electrolyte body 105 that becomes the first solid electrolyte body 105 after firing is described.
まず、第１原料粉末と可塑剤とを湿式混合により分散したスラリーを用意した。第１原料粉末は、例えば、アルミナ粉末９７質量％と、焼結調整剤としてのシリカ３質量％とからなる。可塑剤はブチラール樹脂及びジブチルフタレート（ＤＢＰ）からなる。ドクターブレード装置を使用したシート成形法により、このスラリーを厚さ０．４ｍｍのシート状物に成形した後、１４０ｍｍ×１４０ｍｍに切断し、未焼成補強部１１２、第１未焼成基体１０１、第２未焼成基体１０３、未焼成絶縁層１０７の未焼成絶縁部１１４を得た。そして、未焼成補強部１１２に貫通孔１１２ａを形成した。また、未焼成絶縁部１１４に、ガス検出室１０７ｃを形成した。 First, a slurry in which a first raw material powder and a plasticizer were dispersed by wet mixing was prepared. The first raw material powder is composed of, for example, 97% by mass of alumina powder and 3% by mass of silica as a sintering regulator. The plasticizer consists of butyral resin and dibutyl phthalate (DBP). This slurry is formed into a sheet-like material having a thickness of 0.4 mm by a sheet forming method using a doctor blade device, and then cut into 140 mm × 140 mm, and the unfired reinforcing portion 112, the first unfired substrate 101, the second An unsintered insulating portion 114 of the unsintered substrate 103 and the unsintered insulating layer 107 was obtained. And the through-hole 112a was formed in the unbaking reinforcement part 112. FIG. Further, the gas detection chamber 107 c is formed in the unfired insulating portion 114.
一方、第２原料粉末と可塑剤とを湿式混合により分散したスラリーを用意した。第２原料粉末は、例えば、アルミナ粉末６３質量％と、焼結調整剤としてのシリカ３質量％と、カーボン粉末３４質量％とからなる。可塑剤はブチラール樹脂及びＤＢＰからなる。そして、このスラリーを用い、未焼成電極保護部１１３を得た。 On the other hand, a slurry in which the second raw material powder and the plasticizer were dispersed by wet mixing was prepared. The second raw material powder includes, for example, 63% by mass of alumina powder, 3% by mass of silica as a sintering regulator, and 34% by mass of carbon powder. The plasticizer consists of butyral resin and DBP. And the unsintered electrode protection part 113 was obtained using this slurry.
また、第３原料粉末と可塑剤とを湿式混合により分散したスラリーを用意した。第３原料粉末は、例えば、ジルコニア粉末９７質量％と、焼結調整剤としてシリカ（ＳｉＯ２粉末及びアルミナ粉末合計３質量％とからなる。可塑剤はブチラール樹脂及びＤＢＰからなる。このスラリーを用い、第１固体電解質体１０５及び第２固体電解質体１０９を得た。 Moreover, the slurry which disperse | distributed the 3rd raw material powder and the plasticizer by wet mixing was prepared. The third raw material powder is composed of, for example, 97% by mass of zirconia powder and silica (SiO 2 powder and alumina powder in total 3% by mass as a sintering adjusting agent. The plasticizer is composed of butyral resin and DBP. This slurry is used. First solid electrolyte body 105 and second solid electrolyte body 109 were obtained.
さらに、例えば、アルミナ粉末１００質量％及び可塑剤を湿式混合により分散したスラリーを用意した。可塑剤はブチラール樹脂及びＤＢＰからなる。このスラリーを用い、未焼成絶縁層１０７の未焼成拡散律速部１１５を得た。 Furthermore, for example, a slurry in which 100% by mass of alumina powder and a plasticizer are dispersed by wet mixing was prepared. The plasticizer consists of butyral resin and DBP. Using this slurry, an unsintered diffusion rate controlling portion 115 of the unsintered insulating layer 107 was obtained.
そして、下方から順に第１未焼成基体１０１、未焼成発熱体１０２、第２未焼成基体１０３、第１未焼成電極１０４、第１未焼成固体電解質体１０５、第２未焼成電極１０６、未焼成絶縁層１０７、第３未焼成電極１０８、第２未焼成固体電解質体１０９、第４未焼成電極１１０、未焼成保護層１１１等が積層される（特許請求の範囲の積層工程）。 Then, in order from the bottom, the first unfired substrate 101, the unfired heating element 102, the second unfired substrate 103, the first unfired electrode 104, the first unfired solid electrolyte body 105, the second unfired electrode 106, the unfired The insulating layer 107, the third unsintered electrode 108, the second unsintered solid electrolyte body 109, the fourth unsintered electrode 110, the unsintered protective layer 111, and the like are stacked (lamination step in the claims).
具体的には、第１未焼成基体１０１上に、白金を主体とするペーストを用い、スクリーン印刷により未焼成発熱体１０２を成形した。そして、未焼成発熱部１０２を挟み込むようにして第２未焼成基体１０３を積層する。 Specifically, an unfired heating element 102 was formed on the first unfired substrate 101 by screen printing using a paste mainly composed of platinum. Then, the second unfired substrate 103 is laminated so as to sandwich the unfired heat generating portion 102.
そして、第１未焼成固体電解質体１０５上に、第１未焼成電極１０４を成形した。なお、第１未焼成電極１０４は白金９０質量％及びジルコニア粉末１０質量％の白金ペーストからなる。この白金ペーストを用いたスクリーン印刷法により、第１未焼成電極１０４を成形した。 Then, the first green electrode 104 was formed on the first green solid electrolyte body 105. The first unsintered electrode 104 is made of a platinum paste of 90% by mass of platinum and 10% by mass of zirconia powder. The first green electrode 104 was formed by a screen printing method using this platinum paste.
さらに、第１未焼成電極１０４を挟み込むようにして、第２未焼成基体１０３に積層し、さらに、その第１未焼成固体電解質体１０５上に第２未焼成電極１０６を印刷して形成した。なお、第２未焼成電極１０６は第１未焼成電極１０４と同様の材料である。 Further, the first unsintered electrode 104 was sandwiched between the second unsintered substrates 103, and the second unsintered electrode 106 was printed on the first unsintered solid electrolyte body 105. The second green electrode 106 is the same material as the first green electrode 104.
そして、第２未焼成電極１０６上に未焼成絶縁層１０７を形成した。具体的には、未焼成絶縁部１１４、未焼成拡散律速部１１５を形成した。なお、焼成後、ガス検出室１０７ｃとなる部位、及び焼成後、多孔質部３０が配置される第１固体電解質体と第２固体電解質体との間には、カーボンを主体とするペーストを印刷している。 Then, an unfired insulating layer 107 was formed on the second unfired electrode 106. Specifically, the unsintered insulating part 114 and the unsintered diffusion rate controlling part 115 were formed. A paste mainly composed of carbon is printed between the portion that becomes the gas detection chamber 107c after firing and the first solid electrolyte body and the second solid electrolyte body where the porous portion 30 is disposed after firing. is doing.
さらに、第２未焼成固体電解質体１０９上に、第３未焼成電極１０８を印刷し、第３未焼成電極１０８を挟み込むようにして、未焼成絶縁層１０７に積層した。そして、第２未焼成固体電解質体１０９上に第４未焼成電極１１０を印刷した。なお、第３未焼成電極１０８、第４未焼成電極１１０は、第１未焼成電極１０４と同様の材料を用いている。そして、第４未焼成電極１１０上に、未焼成保護層１１１を積層した。未焼成保護層１１１は、すでに未焼成電極保護部１１３を未焼成補強部１１２の貫通孔１１２ａに挿入されている。 Further, the third green electrode 108 was printed on the second green solid electrolyte body 109 and laminated on the green insulating layer 107 so as to sandwich the third green electrode 108. Then, a fourth green electrode 110 was printed on the second green solid electrolyte body 109. The third green electrode 108 and the fourth green electrode 110 are made of the same material as that of the first green electrode 104. Then, an unfired protective layer 111 was laminated on the fourth unfired electrode 110. In the unsintered protective layer 111, the unsintered electrode protection part 113 has already been inserted into the through hole 112 a of the unsintered reinforcing part 112.
そして、これらを１ＭＰａで加圧して圧着後、所定の大きさで切断し、１成形型から１０個の未焼成積層体を得た。 And after pressurizing these by 1 MPa and crimping | bonding, it cut | disconnected by the predetermined magnitude | size and obtained 10 unbaking laminated bodies from 1 shaping | molding die.
その後、未焼成ガスセンサ素子を樹脂抜きし、さらに焼成温度１５００℃で１時間保持し、本焼成を行って排気ガス中の酸素濃度を検出する積層体を得た（特許請求の範囲の焼成工程）。 Thereafter, the unsintered gas sensor element was removed from the resin, and was further held at a firing temperature of 1500 ° C. for 1 hour, followed by firing to obtain a laminate for detecting the oxygen concentration in the exhaust gas (the firing step of the claims) .
焼成工程により、第１未焼成電極１０４は、第１電極部１０４ａと第１リード部１０４ｂとからなる第１電極１０４となる。第１未焼成固体電解質体１０５は第１固体電解質体１０５となる。第２未焼成電極１０６は、第２電極部１０６ａと第２リード部１０６ｂとからなる第２電極１０６となる。未焼成絶縁層１０７の未焼成絶縁部１１４は絶縁部１１４となり、未焼成絶縁層１０７の未焼成拡散律速部１１５は多孔質の拡散律速部１１５となる。未焼成絶縁層１０７は絶縁層１０７となる。絶縁層１０７のガス検出室１０７ｃは絶縁部１１４の幅方向両側で拡散律速部１１５を介して外部と連通している。拡散律速部１１５は外部とガス検出室１０７ｃとの間のガス拡散を所定の律速条件下で実現する。第３未焼成電極１０８は、第３電極部１０８ａと第３リード部１０８ｂとからなる第３電極１０８となる。第２未焼成固体電解質体１０９は第２固体電解質体１０９となる。第４未焼成電極１１０は、第４電極部１１０ａと第４リード部１１０ｂとからなる第４電極１１０となる。未焼成保護層１１１の未焼成補強部１１２は第２固体電解質体１０９を保護するための補強部１１２となり、未焼成保護層１１１の未焼成電極保護部１１３ａは第４電極１１０を被毒から防御するための多孔質の電極保護部１１３ａとなる。 By the firing step, the first unsintered electrode 104 becomes the first electrode 104 including the first electrode portion 104a and the first lead portion 104b. The first unsintered solid electrolyte body 105 becomes the first solid electrolyte body 105. The second green electrode 106 becomes the second electrode 106 composed of the second electrode portion 106a and the second lead portion 106b. The unsintered insulating part 114 of the unsintered insulating layer 107 becomes the insulating part 114, and the unsintered diffusion rate controlling part 115 of the unsintered insulating layer 107 becomes the porous diffusion controlling part 115. The unsintered insulating layer 107 becomes the insulating layer 107. The gas detection chamber 107 c of the insulating layer 107 communicates with the outside through the diffusion rate controlling portion 115 on both sides in the width direction of the insulating portion 114. The diffusion rate control unit 115 realizes gas diffusion between the outside and the gas detection chamber 107c under a predetermined rate control condition. The third unfired electrode 108 becomes the third electrode 108 including the third electrode portion 108a and the third lead portion 108b. The second unsintered solid electrolyte body 109 becomes the second solid electrolyte body 109. The fourth unfired electrode 110 becomes the fourth electrode 110 including the fourth electrode portion 110a and the fourth lead portion 110b. The unfired reinforcing portion 112 of the unfired protective layer 111 becomes the reinforcing portion 112 for protecting the second solid electrolyte body 109, and the unfired electrode protecting portion 113a of the unfired protective layer 111 protects the fourth electrode 110 from poisoning. Therefore, a porous electrode protection part 113a is obtained.
その後、この積層体の先端側の周囲に未焼成多孔質部３０を形成する。具体的には、スピネル粉末とチタニアと残部がアルミナゾルで作成されたのスラリーを作製し、そのスラリーを用いて、未焼成多孔質部３０を積層体の先端側に全周に渡って形成した。なお、形成手段としては、スプレーや塗布等により形成することができる。その後、この未焼成多孔質部３０が形成された積層体を、焼成温度１０００℃、焼成時間３時間で熱処理を行い、多孔質部３０が形成されたガスセンサ素子４を得た（特許請求の範囲の熱処理工程）。 Thereafter, an unfired porous portion 30 is formed around the front end side of the laminate. Specifically, a slurry of spinel powder, titania and the balance made of alumina sol was prepared, and the unfired porous portion 30 was formed over the entire circumference on the tip side of the laminate using the slurry. The forming means can be formed by spraying or coating. Thereafter, the laminate in which the unfired porous portion 30 was formed was heat-treated at a firing temperature of 1000 ° C. and a firing time of 3 hours, thereby obtaining a gas sensor element 4 in which the porous portion 30 was formed (claims). Heat treatment step).
このように、焼成後の積層体に未焼成多孔質部３０を形成し、焼成温度よりも低温で熱処理を行うことで、粒の粒径が細かい多孔質部３０を作製することができる。これにより、多孔室部３０は、リンやシリコンが効率よく吸着することができ、作製されたガスセンサ素子４は、拡散律速部１１５の目詰まりの発生をさらに抑制して、測定対象気体の拡散抵抗の変化による空燃比の検出の精度を向上させることができる Thus, the non-baked porous part 30 is formed in the laminated body after baking, and the porous part 30 with a fine particle diameter can be produced by performing heat processing at a temperature lower than the baking temperature. Thereby, the porous chamber part 30 can adsorb | suck phosphorus and silicon efficiently, and the produced gas sensor element 4 further suppresses generation | occurrence | production of the clogging of the diffusion control part 115, and the diffusion resistance of measurement object gas It is possible to improve the accuracy of air-fuel ratio detection due to changes in
また、作製された第２多孔質部の拡散抵抗が第１多孔質部の拡散抵抗よりも小さくなり、リンやシリコンを吸着するのための第２多孔質部で測定対象気体が拡散律速することを防止して、空燃比の検出の精度が低下することを防止するガスセンサ素子を作製することができる。 Further, the diffusion resistance of the produced second porous portion is smaller than that of the first porous portion, and the measurement target gas is diffusion-controlled in the second porous portion for adsorbing phosphorus and silicon. Thus, it is possible to manufacture a gas sensor element that prevents a decrease in the accuracy of air-fuel ratio detection.
そして、上記製造方法で作製されたガスセンサ素子４を金属ホルダ５８に挿入し、さらにセラミックホルダ５１、滑石リング５３で固定し、組み立て体を作製する。その後、この組み立て体を主体金具３８に固定し、滑石リング５６、セパレータ６を挿入し、主体金具３８の後端側４０にて加締め、下部組立体を作製する。なお、下部組立体には、あらかじめ外部プロテクタ４２、内部プロテクタ４３が取付けられている。一方、外筒４４、絶縁コンタクト部材６６、グロメット５０等を組みつけ、上部組立体を作製する。そして、下部組立体と上部組立体と接合し、ガスセンサ２を得る。 And the gas sensor element 4 produced with the said manufacturing method is inserted in the metal holder 58, and also it fixes with the ceramic holder 51 and the talc ring 53, and produces an assembly. Thereafter, this assembly is fixed to the metal shell 38, the talc ring 56 and the separator 6 are inserted, and crimped at the rear end side 40 of the metal shell 38, thereby producing a lower assembly. Note that an external protector 42 and an internal protector 43 are attached to the lower assembly in advance. On the other hand, the outer cylinder 44, the insulating contact member 66, the grommet 50, etc. are assembled to produce an upper assembly. Then, the lower assembly and the upper assembly are joined to obtain the gas sensor 2.
次に、本発明の効果を確認した。
まず、実施例は上記製造方法により作製されたガスセンサ素子４とする。一方、比較例としては、未焼成補強部１１２、第１未焼成基体１０１、第２未焼成基体１０３、未焼成絶縁部１１４、未焼成電極保護部１１３、第１固体電解質体１０５、第２固体電解質体１０９、未焼成拡散律速部１１５用のシートをそれぞれ準備する。さらに、水酸アパタイト７７質量％、ジルコニア粉末２３質量％からなるスラリーを作成し、このスラリーを用い、未焼成多孔質部３０のシートを得た。そして、下方から順に第１未焼成基体１０１、未焼成発熱体１０２、第２未焼成基体１０３、第１未焼成電極１０４、第１未焼成固体電解質体１０５、第２未焼成電極１０６、未焼成絶縁層１０７、第３未焼成電極１０８、第２未焼成固体電解質体１０９、第４未焼成電極１１０、未焼成保護層１１１等が積層される。なお、積層工程は、未焼成多孔質部３０の積層方法以外は、上記方法と略同一であり、未焼成多孔質部３０の積層方法を中心に説明する。第１未焼成基体１０１、未焼成発熱体１０２、第２未焼成基体１０３、未焼成電極１０４、第１未焼成固体電解質体１０５、第２未焼成電極１０６が積層された後、第２未焼成電極１０６上に未焼成絶縁層１０７を形成した。具体的には、未焼成絶縁部１１４、未焼成拡散律速部１１５及び未焼成多孔質部３０を形成した。なお、焼成後、ガス検出室１０７ｃとなる部位には、カーボンを主体とするペーストを印刷している。その後、第３未焼成電極１０８、第２未焼成固体電解質体１０９、第４未焼成電極１１０、未焼成保護層１１１を積層した。
Next, the effect of the present invention was confirmed.
First, the embodiment is assumed to be the gas sensor element 4 manufactured by the above manufacturing method. On the other hand, as a comparative example, the unfired reinforcing portion 112, the first unfired substrate 101, the second unfired substrate 103, the unfired insulating portion 114, the unfired electrode protection portion 113, the first solid electrolyte body 105, and the second solid Sheets for the electrolyte body 109 and the unsintered diffusion rate controlling part 115 are prepared. Furthermore, a slurry composed of 77% by mass of hydroxyapatite and 23% by mass of zirconia powder was prepared, and a sheet of the unfired porous portion 30 was obtained using this slurry. Then, in order from the bottom, the first unfired substrate 101, the unfired heating element 102, the second unfired substrate 103, the first unfired electrode 104, the first unfired solid electrolyte body 105, the second unfired electrode 106, the unfired The insulating layer 107, the third green electrode 108, the second green solid electrolyte body 109, the fourth green electrode 110, the green protective layer 111, and the like are stacked. The lamination process is substantially the same as the above method except for the method for laminating the unfired porous part 30 and will be described focusing on the method for laminating the unfired porous part 30. After the first green substrate 101, the green heating element 102, the second green substrate 103, the green electrode 104, the first green solid electrolyte body 105, and the second green electrode 106 are stacked, the second green substrate An unsintered insulating layer 107 was formed over the electrode 106. Specifically, the unsintered insulating part 114, the unsintered diffusion control part 115, and the unsintered porous part 30 were formed. Note that a paste mainly composed of carbon is printed on a portion that becomes the gas detection chamber 107c after firing. Thereafter, the third unfired electrode 108, the second unfired solid electrolyte body 109, the fourth unfired electrode 110, and the unfired protective layer 111 were laminated.
そして、これらを１ＭＰａで加圧して圧着後、所定の大きさで切断し、１成形型から１０個の未焼成積層体を得た。その後、未焼成ガスセンサ素子を樹脂抜きし、さらに焼成温度１５００℃で１時間保持し、本焼成を行って比較例のガスセンサ素子４を得た。 And after pressurizing these by 1 MPa and crimping | bonding, it cut | disconnected by the predetermined magnitude | size and obtained 10 unbaking laminated bodies from 1 shaping | molding die. Thereafter, the unfired gas sensor element was removed from the resin, and further held at a firing temperature of 1500 ° C. for 1 hour, followed by firing to obtain a gas sensor element 4 of a comparative example.
そして、この実施例と比較例とのＢＥＴ比表面積を測定した。この比表面積の測定は、ＢＥＴ式を用いて行う。その結果、実施例のガスセンサ素子４の多孔質部３０は、ＢＥＴ比表面積が１．６ｍ２／ｇであるのに対し、比較例のガスセンサ素子４の多孔質部３０は、ＢＥＴ比表面積が０．６ｍ２／ｇであった。 And the BET specific surface area of this Example and a comparative example was measured. The specific surface area is measured using the BET equation. As a result, the porous part 30 of the gas sensor element 4 of the example has a BET specific surface area of 1.6 m 2 / g, whereas the porous part 30 of the gas sensor element 4 of the comparative example has a BET specific surface area of 0. 0.6 m 2 / g.
次に、この実施例のガスセンサ素子４と比較例のガスセンサ素子４とをそれぞれ主体金具３８、外筒４４等に組付け、ガスセンサ２を作製する。そして、それぞれのガスセンサ２に対して被毒耐久試験を行った。 Next, the gas sensor element 4 of this embodiment and the gas sensor element 4 of the comparative example are assembled to the metal shell 38, the outer cylinder 44, etc., respectively, and the gas sensor 2 is manufactured. A poisoning durability test was performed on each gas sensor 2.
具体的に、この被毒耐久試験は１．６Ｌの直列４気筒エンジンを用い、エンジン回転数３０００ｒｐｍ（空燃費λ＝１）排ガス温度５００℃、Ｐ被毒成分（ＺｎＤＴＰ：１．３ｃｃ／Ｌ、Ｃａスルホネート：１．０ｃｃ／Ｌ）、素子温８３０℃制御という条件下にガスセンサをさらして、１５時間、３０時間、４５時間、６０時間でそれぞれ抜き取り、ＩＰ値を測定した。結果を図５に示す。 Specifically, this poisoning endurance test uses a 1.6 L in-line four-cylinder engine, engine speed 3000 rpm (air fuel consumption λ = 1), exhaust gas temperature 500 ° C., P poisoning component (ZnDTP: 1.3 cc / L, (Ca sulfonate: 1.0 cc / L) and the temperature of the element was controlled at 830 ° C., the gas sensor was exposed and extracted at 15 hours, 30 hours, 45 hours, and 60 hours, and the IP value was measured. The results are shown in FIG.
比較例のガスセンサ２は、時間が進むにつれてＩＰ変化率が大きくなり、６０時間後には、ＩＰ変化率が−０．１８％となる。それに対し、実施例のガスセンサ２は、６０時間後もＩＰ変化率が−０．０５％未満と空燃比の検出の精度が良いことが分かる。つまり、実施例のガスセンサは、多孔質部３０でリンやシリコンがよく多く吸着できており、拡散律速部１１５の目詰まりの発生を抑制していることが分かる。 In the gas sensor 2 of the comparative example, the IP change rate increases with time, and the IP change rate becomes −0.18% after 60 hours. On the other hand, it can be seen that the gas sensor 2 of the example has a high accuracy in detecting the air-fuel ratio with an IP change rate of less than -0.05% even after 60 hours. That is, it can be seen that in the gas sensor of the example, a large amount of phosphorus and silicon can be adsorbed in the porous portion 30 and the occurrence of clogging of the diffusion rate controlling portion 115 is suppressed.
以上、この発明の実施形態について説明したが、この発明は実施形態に限定されることはなく、この発明の目的を達成することのできる範囲で、様々に設計変更することができる。
例えば、本実施形態では、拡散律速部１１５と多孔質部３０とが当接していたが、これに限られず、離間していてもよい。
The embodiment of the present invention has been described above. However, the present invention is not limited to the embodiment, and various design changes can be made within a range in which the object of the present invention can be achieved.
For example, in this embodiment, the diffusion rate controlling part 115 and the porous part 30 are in contact with each other. However, the present invention is not limited to this and may be separated from each other.
１０７ｃ・・ガス検出室
１１５・・・拡散律速部
１３０・・・酸素濃度検地セル
１４０・・・酸素ポンプセル
２・・・・・ガスセンサ
２００・・・ヒータ
３０・・・・多孔質部
３００・・・検出素子
４・・・・・ガスセンサ素子
４４・・・・外筒
６・・・・・主体金具
107c ... Gas detection chamber 115 ... Diffusion limiting part 130 ... Oxygen concentration detection cell 140 ... Oxygen pump cell 2 ... Gas sensor 200 ... Heater 30 ... Porous part 300 ...・ Detecting element 4 ... Gas sensor element 44 ... External cylinder 6 ... Metal fitting
Claims (5)
該第１セルに積層される第１多孔質部と、
該第１多孔質部を介して前記第１セルと積層される遮蔽体と、
前記第１多孔質部、前記第１セル及び前記遮蔽体で区画され、前記電極の一方が配置された測定室と、
を有する板状のガスセンサ素子であって、
前記第１多孔質部を介して前記測定室とは反対側に配置され、前記第１多孔質部よりも拡散抵抗が小さい多孔質状をなすとともに、ＢＥＴ比表面積が１．０ｍ２／ｇ以上である第２多孔質部を有することを特徴とするガスセンサ素子。 A first cell having a solid electrolyte layer extending in the longitudinal direction and electrodes facing the front and back surfaces of the solid electrolyte layer;
A first porous portion laminated in the first cell;
A shield laminated with the first cell via the first porous portion;
A measurement chamber defined by the first porous portion, the first cell, and the shield, in which one of the electrodes is disposed;
A plate-shaped gas sensor element having
It is disposed on the opposite side of the measurement chamber through the first porous portion, has a porous shape having a diffusion resistance smaller than that of the first porous portion, and has a BET specific surface area of 1.0 m 2 / g or more. A gas sensor element having a second porous portion.
前記第２多孔質部は、少なくとも一部が前記第１セルと前記遮蔽体との間に配置されることを特徴とするガスセンサ素子。 The gas sensor element according to claim 1, wherein
The gas sensor element according to claim 1, wherein at least a part of the second porous portion is disposed between the first cell and the shield.
該主体金具に保持されるガスセンサ素子と、
を有するガスセンサであって、
前記ガスセンサ素子は、請求項１または２に記載のガスセンサ素子であることを特徴とするガスセンサ。 A cylindrical metal shell,
A gas sensor element held by the metal shell,
A gas sensor comprising:
The gas sensor element according to claim 1, wherein the gas sensor element is the gas sensor element according to claim 1.
該第１セルに積層される第１多孔質部と、
該第１多孔質部を介して前記第１セルと積層される遮蔽体と、
前記第１多孔質部、前記第１セル及び前記遮蔽体で区画され、前記電極の一方が配置された測定室と、
を有する板状のガスセンサ素子の製造方法であって、
前記ガスセンサ素子は、前記第１多孔質部を介して前記測定室とは反対側に配置され、前記第１多孔質部よりも拡散抵抗が小さい多孔質状をなす第２多孔質部を有し、
焼成後に前記第１セルとなる未焼成第１セルと、焼成後に前記第１多孔質部となる未焼成第１多孔質部と、焼成後に遮蔽体となる未焼成遮蔽体とを積層し、焼成後に積層体となる未焼成積層体を作成する積層工程と、
前記未焼成積層体を焼成する焼成工程と、
前記焼成工程後に、熱処理後に第２多孔質部となる未処理第２多孔質部を前記積層体上に配置し、前記焼成工程よりも低温度で熱処理を行って、第２多孔質部を形成する熱処理工程と、
を有することを特徴とするガスセンサ素子の製造方法。 A first cell having a solid electrolyte layer extending in the longitudinal direction and electrodes facing the front and back surfaces of the solid electrolyte layer;
A first porous portion laminated in the first cell;
A shield laminated with the first cell via the first porous portion;
A measurement chamber defined by the first porous portion, the first cell, and the shield, in which one of the electrodes is disposed;
A plate-shaped gas sensor element manufacturing method comprising:
The gas sensor element has a second porous portion that is disposed on the opposite side of the measurement chamber via the first porous portion and has a porous shape having a diffusion resistance smaller than that of the first porous portion. ,
An unfired first cell that becomes the first cell after firing, an unfired first porous portion that becomes the first porous portion after firing, and an unfired shield that becomes a shield after firing are laminated and fired A laminating step for creating an unfired laminated body to be a laminated body later;
A firing step of firing the unfired laminate;
After the firing step, an untreated second porous portion that becomes a second porous portion after heat treatment is disposed on the laminate, and heat treatment is performed at a temperature lower than that in the firing step to form a second porous portion. A heat treatment process,
A method for producing a gas sensor element, comprising:
該主体金具に保持されるガスセンサ素子と、
を有するガスセンサの製造方法であって、
前記ガスセンサ素子は、請求項４に記載のガスセンサ素子を用いて形成されることを特徴とするガスセンサの製造方法。 A cylindrical metal shell,
A gas sensor element held by the metal shell,
A method for manufacturing a gas sensor comprising:
The said gas sensor element is formed using the gas sensor element of Claim 4, The manufacturing method of the gas sensor characterized by the above-mentioned.
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| JP2012064696A (en) * | 2010-09-15 | 2012-03-29 | Tdk Corp | Thermistor element |
| JP2012064694A (en) * | 2010-09-15 | 2012-03-29 | Tdk Corp | Laminated thermistor element |
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| JPH10221304A (en) * | 1997-02-04 | 1998-08-21 | Ngk Spark Plug Co Ltd | Gas sensor |
| JP2000121597A (en) * | 1998-10-16 | 2000-04-28 | Ngk Spark Plug Co Ltd | Oxygen sensor and its manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10221304A (en) * | 1997-02-04 | 1998-08-21 | Ngk Spark Plug Co Ltd | Gas sensor |
| JP2000121597A (en) * | 1998-10-16 | 2000-04-28 | Ngk Spark Plug Co Ltd | Oxygen sensor and its manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012064696A (en) * | 2010-09-15 | 2012-03-29 | Tdk Corp | Thermistor element |
| JP2012064694A (en) * | 2010-09-15 | 2012-03-29 | Tdk Corp | Laminated thermistor element |
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