201105961 六、發明說明： 【發明所屬之技術領域】 本發明係根據習知之用於檢出一種氣體的至少一種性 質的檢出器元件以及用於製造這種感測器元件的習知製造 方法。舉例而言，該感測器元件設計成將「測量氣體室」 中的氣體一種物理及/或化學性質檢出。以下所述的發明 的一特別重點在於將測量氣體室中的氣體組成檢出，特別 疋將測量氣體室的氣體成分的比例檢出，例如該氣體成分 的分壓及/或濃度，氣體成分特別可指氧。尤其是使用該 感測器檢出一内燃機的廢氣的空氣值又。這類感測器元‘ 往往也稱為Λ探棒。λ探棒（它們在本發明的範疇中也可 用二發明的方法製造）舉例而言’在R〇bert B〇sch公司的 車中的感測器」，2007版，154〜159頁提到。特別是 X感則器元件可為所謂的時間點λ探棒。特別是該方法可 :於製造及調理（Konditionierung，英：c〇ndiu〇ni =而=單的感測元件（它們不具有整合的加熱元件），例 :吻的不加熱的λ探棒。舉例而言’這類几探棒當作低 =探棒用於二輪車的用途’例如當作感測器元件、告作 口疋在一殼體中的感測器元件（ 田 或當作完整探棒（這點在以下也稱「感測器」）構 【先前技術】 上其m不加熱Μ探棒在許多情形在建構後，在Μ 上其反應時間（細㈣㈣. 仕愿用 此t2時間表_产卜 央.response time) t2太長。 1表不在燃燒器測架中該λ探棒所需的—種時間— 201105961 用於在從含油乳體（肥氣）（Fettgas，英：fat㈣或訂⑸代 州）的操作更換到無油氣體（痩氣）（Magergas，英：thin gas)的操作後將探棒電壓從議mV降到遍…所需的時 間。此外，當該感測器元件多次建入到該測試架中然後作 測量的場合，在許多情形中，該反應時間&不能重現或很 難重現。因此人們希望右銥彳忐 _ 叩至有新式感測|§疋件，其反應時間t2 比傳統感測器元件更短，日Θ處全 尺 且反應時間t2可穩定化（有可重 【發明内容】 因此本發明提供一種將上述種類的感測器元件作調 理（K〇nditionierung)的方法，它至少可大大地避免習知之 製造及調理方法或利用這些方法製造及調理的感測器元 件、構造組及感測器的缺點。此方法用於將至少-感測器 兀件、或-個包含感測器元件的構造組、或—個包含此感 測器元件：感測器作調理。如上述，「構造組」一詞此 处表丁固定在至；一殼體中的至少一個感測器元件，而「感 、】器」闲係㊣完成之可操作的構造元件，它包含該構 w .·及可月b的其他元件，例如插接件。「調理」一詞在 此在本發明的範疇指一種過程，在此過程時，該感測元件 作預備處理以供使用，這種調理特別可用於一種目的：將 感、J器7L件作_ 互定且可重現（repmduzierbar )的測量 業例如將由特定製造步驟引起的雜質（污染物）（它 們會〜響測1值）除去，因此該調理係包含-過程，此過 在製k該感測器凡件之時或之後達成。依此，該調理作 4 201105961 業可在一個部分地製成（但已至少部分地可操作）的感測 器7C件上’例如一個沒有殼體的感測器元件、一個在殼體 中的感測器疋件（構造組）或在完全製成的感測器上達成。 因此該調理作業可為該製造方法的一部分。對應於此可提 4一種製造方法，它包含以下所述的調理方法，但此調理 方法也可分別實施’在該感測器之步驟式構造時，或在完 全製成時’例如在一分別的測試架中及/或已在完全之終 使用地點（例如在—汽車中）實施。 該感測器元件用於將在一「測量氣體室」中 的至少一性質檢出。關於此點，舉例而言，可參考上述之 習知感測II 7L件的說明，特別是該感測器元件可為一不加 …、的感測器元件，亦即不具整合的加熱元件的感測器元 件。如上述，這類感測器元件可特別應用在二輪車的用途， 特別是該感測器元件可為—種單晶胞< (einzellig，英： one-cell)感測器元件’亦即剛好具有，「測量晶胞」的感 測器το件，例如具有—個「跳躍晶胞」（外⑶叫“…，英： jump cell)或一個稱為跳躍晶胞的「測量晶胞」。但基本上 也可為感測器元件的其他設計，λ中的細節，舉例而言， 可參考以上說明。肖別是該感測器元件可為-種二點式λ 探棒依上述方法基本上也可製造多晶胞式感測器元件或 依其他測量原理工作的感測器元件；例如寬頻帶感測器元 件0 在所述之方法中至少提供 的製造作業本身可為該方法的 的程序實施，因此只有提供該 一個測量晶胞，此測量晶胞 一部分，但也可在一道分別 測量晶胞的作業是上述方g 201105961 的-部分。如上述，該調理方法也可在—個只部分地製成 的感測器上實施。但此感測器的完成度須達到可提供上述 的測量晶胞，該測量晶胞已能至少部分地操作。 該測量晶胞有至少一個第一電極及至少一個第二電 極。在此該第一電極可施以來自測量氣體室的氣體，此施 ^作業可直接或間接達纟，例如可將第-電極直接施以測 量氣體室的氣體，及//或經由一多孔隙透氣的護層間接施 以氣體，但如果不採此方式（或除了此方式外同時另外） 也可考慮經由一個或數個「趨近通道」（Zutrittskana卜英： access canal)施以來自測量氣體室的氣體，舉例而言，葬 體可流過及/或擴散通過該通道到第一電極或沿相反方2 由電極到該通道。舉例而言，第二電極可與一「參考氣葡 空間」連接，舉例而言，此參考氣體空間可與測量氣體宣 的構件完全相同或部分相肖，但也可完全地或部分地與泪 量氣體室隔開。如果第二電極與至少一參考氣體空間連為 〔。亥參考氣體空間設計成與該測量氣體室隔開，該參氣谱 空間特別是一條參考通道〕則特佳。舉例而言，它係為— 種參考空氣通道，與一内燃機的引擎室連接且與一廢氣货 $隔開〔在該廢氣通道中要測量氣體混合物的組成（例女 二氣值）〕。此外，該測量晶胞有至少一種固體電解質， 該固體電解質連接第一電極與第二電極H 「固體零 解質」（它宜為-種陶瓷電解質）一詞係指一種材料1 材料至少在高溫（例如在60(rc以上的溫度且宜至少8 = °c )對一種或數種離子（例如氧離子）有離子傳導能力。1 舉例而言，在此可使用習知的固體電解質材料’例如用 6 201105961 (Yttrium )穩定化的二氧化錯（ySZ )。然而，如果不用 这種材料（或除了這種材料外同時另外）也可使用其他固 體電解質材料’例如銳（Scan(jiuln )穩定化的二氧化锆或 其他種類的固體電解質。 該感測器元件除了該「測量晶胞」外，還可包含其他 上文未提到的成分。如上述，舉例而言，該感測器元件除 了測量晶胞外可包含其他晶胞，且對應地設計成單晶胞物 (Einzeller ’ 英：one_celler)或多晶胞物（Mehrzeller，英： multi-celler )。測量晶胞宜可呈能斯脫晶胞（NernstzeUe， 央.Nernst cell )形式（亦即呈跳躍晶胞形式）操作，但基 本上也可當作泵晶胞（Pumpzelle)使用。對於這種當作能 斯脫晶胞方式的操作，該感測器元件可具有一相關的控制_ 及/或分析電路，但該電路也可完全地或部分地為一個外 界裝置（匕與感測器元件分開）的構件。對應地，一般細 節可參考先前技術◊此外，可將感測器元件建構到一探棒 殼體中。舉例而言，測量晶胞可做在一種層構造中，且宜 在一陶瓷層構造中。舉例而言，該層構造可被一護管圍住， 例如一金屬濩管，特別是具有槽孔者，氣體可經該槽孔從 測量氣體室出來，例如從一内燃機的廢氣通道出來，進到 該層構造。舉例而言，此層構造可做成使得第一電極與第 二電極設成上下重疊或相鄰。特佳的做法係將第一電極設 計成-種層構造的外電極…二電極設計成在裡面的内 電極。此外，該感測器元件可包含一個或數個密封元件（這 點下文還要詳述），例如一個或數個密封盤及/或密封包 裝。關於這方面’舉例而言’也可參考上述先前技術 201105961 如Robert Bosch公司的「汽車中的感測器」，2〇〇7版，156 157 百 v 貝’這個文獻中所述的感測器元件基本上也可用本 發明的方法製造及/或調理（Konditionieren)。 依本發明’該測量晶胞在感測器元件進入操作之前受 到道調理程序。在作此調理程序時，該測量晶胞受到一 提间的調理溫度，也可視需要（〇pti〇nal )在調理程序時將 §亥測量晶胞另外施以一調理電流。 在此’ 「提高的調理溫度」基本上指在室溫以上的溫 度，且且在200。(：以上的溫度，尤宜高於3〇〇<>c。此調理溫 度可特別為至少800°C，且宜至少90〇π ,尤宜至少1〇〇〇 C。要作此調理程序，宜使用一外界加熱器，此加熱器不 是感測器元件本身的構體，特別是可使用以下的一種或數 種加熱器：電加熱器’特別是熱電阻繞組的電加熱器，例 如一個將該感測器元件及//或它的一些部分完全或部分圍 住的電加熱器；一可加熱的感測器保持器，特別是一個用 於谷納一個或數個感測器元件的可加熱的插槽（SchHtz ); 一股火焰，特別是一氣體火焰；一種被加熱過的氣體。 在此調理程序時，還可使感測器元件的至少一密封元 件（例如一盤形密封元件及/或一密封包裝）玻璃化 (Verglasen ) ^在此，它可特別為一種或數種以下的密封 70件：一個包含至少一種玻璃成分的密封元件及/或一種 由玻璃成分構成的元件，特別是一種氮化硼密封元件；一 種含有至少一破璃成分的滑石瓷（Steati〇 (含有大量滑石 成分的陶瓷）元件。此情形表示.一例：該所提議的調理程 序可為該感測器元件製造方法的一部分。在此情形中，施 8 201105961 加該提高的調理溫度的作業同時也當作該感測器元件的製 造作業的一部分使用，因為玻璃化就是此製造程序的一部 分。 。 ’亦即該 。舉例而 此調理溫度可特別在一定的氣體大氣中進行 氣體大氣的組成至少有一種或數種成分為已知者 了’該調理程序可在—含油（fett，英：fatty或⑽…的 氣體大氣中進行’ i宜在—油燃料燒掉的空氣，氣體混合 物中，及/或在一種變換（含油和不含油的氣體交替變換〜 的氣體大氣中進行。該一定的氣體大氣特別可為—種已知 之空氣值（Luftzahl )的氣體組成，例如空氣及/或特別是 含油氣體（Fettgas ) ^如果不採此方式（或者除了用此方 式外同時另外）也可將此調理程序在一變換式的 (WeChSelnd)的氣體大氣中進行，例如該氣體大氣中^少 從-種不含油（mager’英：thin)的空氣值變到含油的二 氣值或反過來，從一種含油的空氣值變到不含油的空氣 值。也可有-序列的數個空氣變換…加他⑴（= 空氣#不含油空氣）。此調理程序可特別地（如下文還:詳 述者）包含數個部分步驟’纟中在至少一個部分步驟中使 用-第-氣體大氣（例如一種含油氣體大氣）而在至少一 第二部分步驟中使用另-種氣體大氣（例如—種不含^ 體大氣），或反過來。 氣 (Brennerprtifstand ’ 英：burner test sUnd)中實施。 「燃燒器測試架」一詞泛指—種裝置，其中該至少一」 器或該感測器的一部分（例如該至少一測試晶胞^或4 201105961 一個包含該測試晶胞的感測器元件、或至少一個包含該感 測器儿件的構造組）受到由燃燒器產生的熱及/或受到一 股由一燃燒器產生或影響的氣流。如不採此方式（或者除 了採此方式外同時另外）也可施以—種—定的氣體大氣。 aa 除了將該測量晶胞施以提高的調理溫度外，還可如上 述，在調理程序時，也將測量晶胞施以一股調理電流。即 使該測量晶胞在感測器元件正常操作時呈能斯脫（心贈） 胞方式操作（亦即沒有電流，且只測試該至少二個電極 之間的電位），在調理程序時也可施以該調理電流。特別 是在該調理程序的至少一個部分步驟令（例如在調理程序 2-第-部分步驟中）將調理電流選設成使得第二電極的 赍权, 軋軋且由於一種泵動程序由第 一電極（例如外電極）流到第— 電極（例如内電極）。如 上述，該調理程序也可包含數個 , ，驟，其中該測量晶 胞在至少二個部分步驟中各施以 雷芦。與為丨A a . j €机方向的一股調理 電肌舉例而吕，該調理電流的量 里 1mA，士- — 士 ， 0-5mA，且宜至少 1mA尤且在lmA〜3〇mA之間，如果在 v 將測量晶胞施以lmA〜3()mA 第一。^刀步驟中 第二部分步驟中將測量晶胞施以相反-中在一 為bA〜-30mA之間的調理電流），則圭—理電流（宜 此調理程序（特別是調理程序的…知、 宜為至少1秒，且宜在5秒〜90秒間，步驟）的期間 此程序可特別結合到-測試序列至少3〇秒。 調理程序宜吉桩力咕… 在此’該至少一 程序且直接在該測試序列 之後及/或之間進行。 』忒步驟之前及/或 10 201105961 利用上述的-個或數個實施例t所提議的方法 二大大縮短且穩定化。利用上述的措施（不論是 早獨或組合）彳將留在感測器元件上（特別是在 個電極上）的含油氣體成分除去或至少大大減少，此外τ 在一個或二個電極的電極表面上及/或内的毒性物質，例 如矽、硼、鉻或其他過渡金屬的化合物的毒性物質，都能 可靠地蒸發掉或至少能減少。 該至少一第一電極及/或該至少一第二電極可包含至 少一種金屬陶-是（Cermet)電極，亦即一種金屬_陶竟電極。 在此，舉例而言，它可為一種二氧化锆-鉑-電極。但基本上 也可使用其他種類的金屬陶瓷電極。在此，利用上二措施 (不論單獨或組合方式）可將金屬m氣體（例如銘、 二氧化鍅及氣體）的三相界限的比例提高，舉例而言，用 此方式可使毒性物質的關係（Relevanz)減弱，且電極可設 計成（特別在低溫範圍）更敏感。這點特別是對於上述不 加熱的感測器元件很有利《此外也可將氧化物質層從電極 表面除去且可用此方式同樣地使電極在低溫範圍更敏感。 利用這些措施（不論單獨或組合方式）利用上述作用，可 使感測器元件呈不加熱的感測器元件的形式良好地使用。201105961 VI. Description of the Invention: [Technical Field] The present invention is a conventionally known method for detecting at least one property of a gas and a conventional manufacturing method for manufacturing such a sensor element. For example, the sensor element is designed to detect a physical and/or chemical property of the gas in the "measuring gas chamber." A particular focus of the invention described below is to detect the composition of the gas in the measuring gas chamber, in particular to detect the proportion of the gas component of the measuring gas chamber, for example the partial pressure and/or concentration of the gas component, the gas component is particularly May refer to oxygen. In particular, the sensor is used to detect the air value of the exhaust gas of an internal combustion engine. Such sensor elements are often referred to as sputum probes. λ probes (which can also be manufactured by the method of the invention in the scope of the invention) are exemplified by the "sensors in the car of R〇bert B〇sch", 2007 edition, pages 154 to 159. In particular, the X sensor element can be a so-called time point λ probe. In particular, the method can be: manufacturing and conditioning (Konditionierung, English: c〇ndiu〇ni = and = single sensing elements (they do not have integrated heating elements), for example: kiss unheated λ probe. In the case of 'such probes are used as low = probes for the purpose of two-wheeled vehicles', for example as sensor elements, sensor elements that are used as a mouthpiece in a housing (field or as a complete probe) (This point is also referred to below as "sensor") [previous technique] The m is not heated. In many cases, after the probe is constructed, the reaction time is on Μ (thin (4) (4). The official is willing to use this t2 timetable. _产卜.response time) t2 is too long. 1 The table is not required for the λ probe in the burner frame - 201105961 For use in oily milk (fertilizer) (Fettgas, English: fat (four) or Order (5) Daizhou) operation to replace the oil-free gas (痩 gas) (Magergas, English: thin gas) after the operation of the probe voltage from the mV to the time ... ... In addition, when the sensor Where the component is built into the test frame multiple times and then measured, in many cases, the reaction time &a Mp; can not be reproduced or difficult to reproduce. Therefore, people hope that the right 铱彳忐 叩 有 has a new sensing | § ,, the reaction time t2 is shorter than the traditional sensor components, the full length of the sundial and reaction The time t2 can be stabilized (there is a repetitive aspect). Therefore, the present invention provides a method of conditioning a sensor element of the above kind, which at least greatly avoids the conventional manufacturing and conditioning methods or utilization. The disadvantages of these methods of manufacturing and conditioning sensor elements, construction sets, and sensors. This method is used to include at least a sensor element, or a construction group containing sensor elements, or - Sensor component: sensor for conditioning. As mentioned above, the term "structure group" is fixed here; at least one sensor component in a housing, and the "sensing," device is free A completed operative structural element comprising the other components of the structure w and the month b, such as a connector. The term "conditioning" is used herein to refer to a process within the scope of the invention, in the course of which The measuring component is prepared for use, this In particular, it can be used for one purpose: to measure the sense, the JL 7L as a mutual and reproducible measurement industry, for example, to remove impurities (contaminants) caused by specific manufacturing steps (they will be ~1) Thus, the conditioning system comprises a process which is achieved at or after the manufacture of the sensor component. Accordingly, the conditioning process 4 201105961 can be partially made (but at least partially operational) On the sensor 7C, for example, a sensor element without a housing, a sensor element (construction group) in the housing or on a fully fabricated sensor. The work can be part of the manufacturing process. Corresponding to this, a manufacturing method can be provided, which comprises the conditioning method described below, but the conditioning method can also be implemented separately in the stepwise construction of the sensor, or in the case of complete fabrication, for example in a separate The test rack is implemented and/or has been implemented at the end of the complete use location (eg in a car). The sensor element is for detecting at least one property in a "measurement gas chamber". In this regard, for example, reference may be made to the above description of the conventional sensing II 7L device, in particular, the sensor element may be a sensor element without an addition, that is, a heating element without integration. Sensor component. As described above, such a sensor element can be particularly applied to the use of a two-wheeled vehicle, in particular, the sensor element can be a single crystal cell (einzellig, one-cell sensor element) The sensor τ, which has a "measuring unit cell", has, for example, a "jumping cell" (outer (3) is called "..., English: jump cell" or a "measuring unit cell" called a jumping cell. However, it can basically be other designs of the sensor elements, details of λ, for example, reference to the above description. Xiaobei is a sensor element that can be a two-point λ probe. Basically, it can also manufacture a multi-cell sensor element or a sensor element that works according to other measurement principles; for example, a broadband sense Detector element 0 The manufacturing operation provided at least in the method described may itself be performed by the method of the method, so that only one of the measuring unit cells is provided, which measures a part of the unit cell, but may also measure the unit cell separately in one The assignment is part of the above paragraph g 201105961. As mentioned above, the conditioning method can also be carried out on a sensor that is only partially fabricated. However, the completion of the sensor must be such that the measurement unit cell described above can be provided, and the measurement unit cell can be operated at least partially. The measuring cell has at least one first electrode and at least one second electrode. Here, the first electrode can be applied with gas from the measuring gas chamber, and the operation can be performed directly or indirectly, for example, the first electrode can be directly applied to the gas of the measuring gas chamber, and/or via a porous layer. The gas permeable sheath is indirectly applied with gas, but if this method is not used (or in addition to this method), it may also be considered to apply the gas from the measurement gas via one or several "access canals" (Zutritskana). The gas of the chamber, for example, can pass through and/or diffuse through the channel to the first electrode or along the opposite side 2 from the electrode to the channel. For example, the second electrode may be connected to a "reference gas space". For example, the reference gas space may be identical or partially opposite to the gas-measuring member, but may also be completely or partially with the tear. The gas chambers are separated. If the second electrode is connected to at least one reference gas space. The reference gas space is designed to be spaced apart from the measurement gas chamber, and the gas spectrum space, particularly a reference channel, is particularly preferred. For example, it is a reference air passage that is connected to the engine compartment of an internal combustion engine and is separated from an exhaust gas quantity [in which the composition of the gas mixture (e.g., female gas value) is to be measured]. In addition, the measuring unit cell has at least one solid electrolyte, and the solid electrolyte is connected to the first electrode and the second electrode H. "Solid zero-solution" (which is preferably a ceramic electrolyte) means a material 1 material at least at a high temperature (For example, at 60 (temperature above rc and preferably at least 8 = °c), there is ionic conductivity to one or several ions (e.g., oxygen ions). 1 For example, a conventional solid electrolyte material can be used herein, for example. Use 6 201105961 (Yttrium) to stabilize the dioxins (ySZ). However, if this material is not used (or in addition to this material), other solid electrolyte materials such as sharp (Scan (jiuln) stabilization) can be used. Zirconium dioxide or other kind of solid electrolyte. The sensor element may contain other components not mentioned above in addition to the "measuring unit cell". As mentioned above, for example, the sensor element is The measurement unit cell may contain other unit cells, and is correspondingly designed as a single crystal cell (Einzeller 'English: one_celler) or polycrystalline cell material (Mehrzeller, English: multi-celler). It is operated in the form of NernstzeUe (NernstzeUe), that is, in the form of a jumping cell, but can basically be used as a pump cell (Pumpzelle). In the operation of the cell mode, the sensor element may have an associated control and/or analysis circuit, but the circuit may also be wholly or partially a component of an external device (the sensor is separated from the sensor element). In general, reference may be made to the prior art. In addition, the sensor elements can be constructed into a probe housing. For example, the measurement unit cell can be made in a layer configuration, and preferably in a ceramic layer configuration. For example, the layer structure can be enclosed by a protective tube, such as a metal manifold, in particular having a slot through which gas can exit the measuring gas chamber, for example from an exhaust passage of an internal combustion engine. For example, the layer structure can be configured such that the first electrode and the second electrode are arranged to overlap each other or adjacent to each other. It is particularly preferable to design the first electrode as an outer electrode of a seed layer structure... The two electrodes are designed to be inside In addition, the sensor element may comprise one or several sealing elements (described in more detail below), such as one or several sealing discs and/or sealed packages. For example, 'for example' Reference may also be made to the prior art 201105961, such as Robert Bosch's "Sensor in the Car", version 2〇〇7, 156 157 百v'. The sensor elements described in this document can also basically be used with the present invention. Method of manufacture and/or conditioning. According to the invention, the measuring unit cell is subjected to a conditioning process prior to the sensor element entering the operation. In the conditioning process, the measuring unit cell is subjected to a conditioning temperature. It is also possible (〇pti〇nal) to apply a conditioning current to the measurement cell during the conditioning process. Here, "increased conditioning temperature" basically means a temperature above room temperature, and is at 200. (: The above temperature is particularly preferably higher than 3 〇〇 <> c. The conditioning temperature may be at least 800 ° C, and preferably at least 90 〇 π, particularly preferably at least 1 〇〇〇 C. To do this conditioning The procedure should preferably use an external heater which is not a component of the sensor element itself, in particular one or more of the following heaters can be used: an electric heater, in particular an electric heater of a thermal resistance winding, for example An electric heater that completely or partially encloses the sensor element and/or some of its parts; a heatable sensor holder, in particular one or several sensor elements for the valley Heatable socket (SchHtz); a flame, in particular a gas flame; a heated gas. In this conditioning procedure, at least one sealing element of the sensor element (for example a disk shape) Sealing element and/or a sealed package) Verglasen ^ In this case, it can be used in particular for one or several types of sealing 70 parts: a sealing element comprising at least one glass component and/or a glass component Component, especially a boron nitride Sealing element; a talc porcelain (Steati® (ceramic containing a large amount of talc) component) containing at least one glass component. This case is shown. An example: the proposed conditioning procedure can be part of the method of manufacturing the sensor element. In this case, application 8 201105961 plus the increased conditioning temperature is also used as part of the manufacturing operation of the sensor element, as vitrification is part of the manufacturing process. 'That is the case. This conditioning temperature can be carried out especially in a certain gas atmosphere. At least one or several components are known. The conditioning procedure can be carried out in a gas atmosphere containing oil (fett, English: fatty or (10)... 'i should be carried out in the air burned by the oil fuel, in the gas mixture, and/or in a gas atmosphere in which the oil-containing and oil-free gases are alternately changed. The certain gas atmosphere is particularly known. The gas composition of the air value (Luftzahl), such as air and / or especially oily gas (Fettgas) ^ if this method is not adopted (or In this way, it is also possible to carry out the conditioning process in a gas atmosphere of a modified type (WeChSelnd), for example, the gas value in the gas atmosphere is changed from the air value of the oil-free (mager'ying: thin). To the oil-containing two gas values or vice versa, from an oil-containing air value to an oil-free air value. There may also be a sequence of several air changes... plus him (1) (= air # oil-free air). This conditioning procedure In particular, the following may also comprise a plurality of partial steps 'in the at least one partial step using a -first gas atmosphere (for example an oil-containing gas atmosphere) and in at least one second partial step using another - a gaseous atmosphere (eg, a species that does not contain a body atmosphere), or vice versa. Gas (Brennerprtifstand ‘英:burner test sUnd) is implemented. The term "burner test stand" generally refers to a device in which the at least one device or a portion of the sensor (eg, the at least one test cell or 4 201105961 a sensor element including the test cell) And at least one of the structural groups comprising the sensor member is subjected to heat generated by the burner and/or subjected to a flow of air generated or affected by a burner. If this method is not adopted (or in addition to this method), a gas atmosphere can be applied. Aa In addition to applying the measured unit cell to an elevated conditioning temperature, as described above, the conditioning cell is also subjected to a conditioning current during the conditioning process. Even if the measuring cell is operated in a cell mode when the sensor element is operating normally (ie, there is no current, and only the potential between the at least two electrodes is tested), it can also be used in the conditioning process. This conditioning current is applied. In particular, at least one partial step of the conditioning procedure (eg, in the conditioning procedure 2-part-part step) selects the conditioning current such that the second electrode is rolled, rolled and due to a pumping procedure by the first The electrode (e.g., the outer electrode) flows to the first electrode (e.g., the inner electrode). As described above, the conditioning program may also include a plurality of steps, wherein the measuring cells are each applied with a staghorn in at least two partial steps. For example, a conditioning electric muscle for the direction of the 丨A a. j € machine, the amount of the conditioning current is 1 mA, 士-士士, 0-5 mA, and preferably at least 1 mA, especially at lmA~3〇mA Between, if v will measure the unit cell, apply lmA~3() mA first. In the second part of the step of the knife step, the unit cell will be measured in the opposite direction - the middle of the conditioning current between bA and -30 mA), then the current - the conditioning program (especially the conditioning program Preferably, the program may be at least 1 second, and preferably between 5 seconds and 90 seconds, during the step of the procedure, the program may be specifically combined with the test sequence for at least 3 seconds. The conditioning program is Yiji Pile Force 咕... Here at least one program and Directly after and/or between the test sequences. 忒 忒 before the step and/or 10 201105961 The method 2 proposed by the above-mentioned one or several embodiments t is greatly shortened and stabilized. It is early or combined) that the oil-containing gas component remaining on the sensor element (especially on one electrode) is removed or at least greatly reduced, in addition to τ on and/or within the electrode surface of one or both electrodes Toxic substances, such as toxic substances of compounds of cerium, boron, chromium or other transition metals, can be reliably evaporated or at least reduced. The at least one first electrode and / or the at least one second electrode may comprise at least one metal A ceramic-ceramic electrode, that is, a metal-ceramic electrode. Here, for example, it may be a zirconium dioxide-platinum-electrode. However, other kinds of cermet electrodes can basically be used. Therefore, the ratio of the three-phase limits of the metal m gas (for example, indium, cerium oxide, and gas) can be increased by the above two measures (either alone or in combination), for example, the relationship of toxic substances can be obtained by this method ( Relevant) is weakened and the electrodes can be designed to be more sensitive (especially in the low temperature range), which is particularly advantageous for the above-mentioned unheated sensor elements. Furthermore, the oxidized material layer can also be removed from the electrode surface and can be used in this way. The electrodes are made more sensitive in the low temperature range. With these measures, either alone or in combination, the sensor elements can be used well in the form of unheated sensor elements.
在所提議的調理程序，如上述，該測量晶胞及/或一 個包含e亥晶胞的構造組可用不同方式處理，這些方式可包 含達到上述作用的負荷。因此可將該測量晶胞及/或構造 組在至少800°c的溫度（且宜在更高的溫度）在含油的氣體 大氣中在作低溫測量之前（亦即在感測器元件進入操作之 前）加熱。如不採此方式（或者除了用此方式外同時另外A 201105961 也可將該測量晶胞及/或包含此晶胞的構造組在至少800 °C的溫度（且宜在更高的溫度）在交替變換的氣體大氣中 加熱’特別是在作低溫測量之前’亦即在感測器元件進入 操作之則。又，如果不用此方式（或除了用此方式外同時 另外）也可將該測量晶胞或該包含此測量晶胞的構造組施 以電流，特別是在800〇c以下的溫度在該至少一第一電極及 /或至少一第二電極上施電流’或在至少800〇C的溫度範圍 (且宜更向）在該至少一第一電極及/或該至少—第二電 極上施電流。 當由外界將測量晶胞加熱（特別是將一個包含該測量 晶胞的構造組的一前區域加熱）時，也可在該至少一密封 元件的區域（例如該至少一密封包裝的區域）預期有高溫。 用此方式，也可當程序適當進行時，將該加熱程序（一般 此加熱程序係必要者，用以將CSD強度〔CSD:characteristic shift-down (特性下移）：含油氣體成分侵入參考區域中引 起之信號移動〕藉著玻璃化（例如在密封包裝中的氮化硼 片）而確保}取代。此加熱程序一般稱為加熱程序AH〇。 本發明的實施例示於圖式中並在以下說明中詳述。 【實施方式】 圖1以示意方式顯示一燃燒器測試架（11〇)，利用它以 示意方式說明本發明的方法。此燃燒器測試架（11〇)包含一 殼體（112)，殼體（112)具有一調理室（n 4)。調理室（H 4)中容 納一感測器元件（116)，它呈完成產品或中間產品的形式。 在此實施例，感測器元件（116)包含一測量晶胞（1 18)，〔該 12 201105961 測量晶胞⑴8)可呈對本發明的方法已有功能的狀態提供， 例如呈燒、、Ό凡成的層構造形式〕及/或一包含此測量晶胞 (118)的構造組。圖中未顯示該感測器元手（116)的其他元 件，例如殼體元件、密封包裝、插接件或類似物。測量晶 胞（118)包含一第一電極（12〇)，它在此實施例中設計成外電 極形式且可經一多孔隙的護層（i 22)由_測量氣體室供以氣 體此外，測量晶胞（118)包含一第二電極（丨24)，它設計成 内電極形式且在測量晶胞（118)的一層構造内部形成，它與 測量氣體室隔開。在此，第二電極（124)在一參考通道（126) 中形成且舉例而言，可經由此參考通道施以空氣。第一電 極（120)與第二電極（124)利用一固體電解質（127)互相連 接。舉例而言，此固體電解質（127)可為釔穩定化的二氧化 錯（YSZ)。電極（120)(124)可經由電極供電路連接及/或施 以一電流（此處用IB表示）及/或一電壓。 在調理室（114)中，「測量晶胞」（118)可視需要施以一 調理電流，例如利用一相關之電流源。此調理電流（它在 圖1中用IB表示）宜受控制及/或調節且宜可交替地帶正 負號（± )。控制手段（1 34)宜設計成使它能影響該調理電流 Ib，特別是影響其方向及/或其大小及/或其期間長短。舉 例而言，整個燃燒器測試架（1 1〇)設計成用電腦控制。 此外，在圖1令所示的實施例，燃燒器測試架（11〇)宜 包含一加熱器（130)。如不採此方式（或除了用此方式外同 時另外）也可使燃燒器測試架（110)宜包含一氣體供應手段 (132)。經此氣體供應用段可將調理室〇 14)施以準確限定的 「總大氣」（GesamtatmosphSre，英·· total atmosphere)。 【S 2 13 201105961 其他的設計，（例如下文詳述者）也可行，例如可用一些 ^汁，其中殼體（112)及/或氣體供應手段（132)省卻。此外， -亥燃燒器測s式架（11〇)可包含一控制手段（13句，例如，經由 該控制手段（134)可將燃燒器測試架⑴〇)完全地或部分地控 制，舉例而言，控制供到電極（12〇)(124)的電流及/或控制 加熱器（130)的功能及/或控制氣體供應手段（132)。 在所提議的方法中進行一調理程序，在此程序中宜能 單獨地或組合地實施以下方法步驟： •在作本來的低溫測量之前，亦即在感測器元件（1工6) 進入操作前，在高於800t的溫度在帶油的氣體大氣中將測 量晶胞（11 8)及/或感測器元件（丨丨6)的其他構件加熱； •在交替變換的氣體大氣中在高於8〇(rc的溫度〔特別 是在作低溫測量之前，亦即在感測器元件（1 16)進入操作之 前〕將晶胞（118)及/或感測器元件〇16)的其他構件加熱； •在第一電極（120)上在低於8〇〇〇c的溫度範圍將測量 晶胞（Π 8)及/或感測器元件（116)其他構件施加電流； •在第一電極（120)上在高於8〇〇«c的溫度範圍將測量 晶胞（118)及/或感測器元件（116)其他構件施加電流。 帶油氣體成分的反應可在85〇t的燃燒器測試架中在 實驗至中進行。這種反應在帶油氣體大氣下已發生，但藉 著交替地供應不含油氣體（Magergas )與帶油氣體以及將溫 度提高可使反應加強。 因此一種可能的措施係在不含油氣體及/或在空氣中 將測量晶胞（118)加熱，特別是將前感測器區域加熱。在此， 只有護管區域〔還可包含感測器元件（116)的一繞組〕的加 201105961 熱有意義。舉例而言，對於個別的感測器元件而言，這點 可利用繞組式加熱器（13〇)達成，或對數個感測器元件（116) 或數個晶胞（11 8)則可用一電加熱的插槽達成，測量晶胞 (118)或感測器元件（116)可插入該插槽中。 交替更換的含油及不含油氣體操作，在最簡單的例子 係利用一氣體火焰改變。理論上，也可利用電加熱作改變， 特別是使用桶裝瓦斯（瓶裝氣體）（Flaschengas，英^〇ttie gas )加熱。基本上同樣地可將感測器的整個構件組加熱， 包括殼體與密封元件^但如果只有測量晶胞（118)的區域加 熱則特別有利。這點受下述條件限件，例如，由於感測器 元件（116)的密封包裝對熱不穩定，例如密封包裝的滑石瓷 (Steatit)，在超過72(rc在許多目前的感測器元件在超過 7 2 0 °C時會造成損壞。 如果不利用加熱器（130)加熱〔或者除了利用該加熱器 加熱外同時〕也可施以一調理電流加熱而加強加熱作用， 該調理電流因此也可稱為「測試電流供應」。在高溫的場 合，這點可導致在第一電極（120)及/或第二電極（124)的電 極構造發生所要的變化。為此所需的前提可為在調理室（ιΐ4) 中的帶油的大氣，俾使得氧的送走作用在鄰界到電極（12〇) 或（124)的界限層加強，而不僅是使氧氣從氣體運離◊在此 在許多情形中，重要的一點為外電極（12〇)的負荷。這點表 示：電流方向宜選設成使得最先外電極（4〇)在低電位而内電 極（124)在高電位，而氧要從廢氣或由調理室（ιΐ4)被泵入參 考通道（126)中。因此最初外電極（12〇)須在此内電極（12句 更低的電住。如此，會由於氧氣變少，在電極與電解質咍$ 15 201105961 界限區域會造成材料破壞。在第二步驟中，此區域由於電 流方向反轉而再生’對典型的几探棒而言，所測定之有用 的數值為電流10mA為時30秒，對於回反應（Rtickreaktion: 英：back-reaction)為-1mA為時30秒。整體上在「去（正In the proposed conditioning procedure, as described above, the measuring unit cell and/or a group of structures comprising the e-cell can be treated in different ways, which may include the load to achieve the above effects. The measuring unit cell and/or the structural group can thus be subjected to a low temperature measurement in the atmosphere of the oil-containing gas at a temperature of at least 800 ° C (and preferably at a higher temperature) (ie before the sensor element enters the operation). )heating. If this method is not used (or in addition to this method, the other A 201105961 can also measure the unit cell and / or the structural group containing the unit cell at a temperature of at least 800 ° C (and preferably at a higher temperature) The alternating atmosphere of the gas is heated 'especially before the low temperature measurement', that is, when the sensor element enters the operation. Also, if this method is not used (or in addition to this method), the measurement crystal can also be used. Applying a current to the structural group comprising the measuring unit cell, in particular applying a current on the at least one first electrode and/or the at least one second electrode at a temperature below 800 〇c or at least 800 〇C a temperature range (and preferably more) is applied to the at least one first electrode and/or the at least-second electrode. When the measuring unit cell is heated by the outside (especially a structural group containing the measuring unit cell) When a front zone is heated, a high temperature is also expected in the area of the at least one sealing element (for example, the area of the at least one sealed package). In this manner, the heating process can also be performed when the program is properly performed (generally heating The program is necessary for the CSD intensity [CSD: characteristic shift-down: the signal movement caused by the intrusion of the oil-containing gas component into the reference area] by vitrification (for example, boron nitride sheets in a sealed package) And the heating process is generally referred to as the heating program AH. The embodiments of the present invention are shown in the drawings and are described in detail in the following description. [Embodiment] FIG. 1 shows a burner test stand in a schematic manner ( 11 〇), using it to illustrate the method of the present invention. The burner test stand (11〇) comprises a casing (112), the casing (112) has a conditioning chamber (n 4). Conditioning room (H 4) accommodating a sensor element (116) in the form of a finished product or intermediate product. In this embodiment, the sensor element (116) comprises a measuring cell (1 18), [12 201105961 measurement The unit cell (1) 8) may be provided in a state in which the method of the present invention has been functioning, for example, in the form of a layer of a fire, a layer, and/or a structure comprising the unit cell (118). Other components of the sensor element hand (116) For example, a housing element, a sealed package, a connector or the like. The measuring unit cell (118) comprises a first electrode (12A), which in this embodiment is designed as an external electrode and can be protected by a porous The layer (i 22) is supplied with gas by the measuring gas chamber. Further, the measuring unit cell (118) comprises a second electrode (丨24) which is designed in the form of an internal electrode and which is formed inside a layer of the measuring unit cell (118). Is separated from the measurement gas chamber. Here, the second electrode (124) is formed in a reference channel (126) and, for example, air can be applied via the reference channel. The first electrode (120) and the second electrode The electrodes (124) are connected to each other by a solid electrolyte (127). For example, the solid electrolyte (127) can be yttrium stabilized dioxin (YSZ). The electrodes (120) (124) may be connected to the circuit via an electrode and/or apply a current (herein indicated by IB) and/or a voltage. In the conditioning chamber (114), the "measuring unit cell" (118) may be subjected to a conditioning current, such as with an associated current source. This conditioning current (which is indicated by IB in Figure 1) is preferably controlled and/or regulated and may alternately have a positive sign (±). The control means (34) should preferably be designed such that it affects the conditioning current Ib, in particular its direction and/or its size and/or its length. For example, the entire burner test rack (1 1〇) is designed to be computer controlled. Further, in the embodiment shown in Fig. 1, the burner test stand (11) preferably includes a heater (130). If not (or in addition to this), the burner test stand (110) may also include a gas supply means (132). Through this gas supply section, the conditioning chamber 〇 14) can be applied with an accurately defined "total atmosphere" (GesamtatmosphSre, total atmosphere). [S 2 13 201105961 Other designs, such as those detailed below, are also possible, for example, some juices may be used, with the housing (112) and/or gas supply means (132) being omitted. In addition, the shovel s-frame (11 〇) may include a control means (13 sentences, for example, the burner test rig (1) 经由 can be completely or partially controlled via the control means (134), for example In other words, the current supplied to the electrode (12) (124) is controlled and/or the function of the heater (130) and/or the control gas supply means (132) are controlled. In the proposed method, a conditioning procedure is carried out, in which the following method steps can be carried out individually or in combination: • Before the original cryogenic measurement, ie in the sensor element (1) Before, the unit cell (11 8) and/or other components of the sensor element (丨丨6) are heated in an atmosphere of oily gas at a temperature higher than 800 t; • high in an alternating atmosphere of gas The other elements of the unit cell (118) and/or the sensor element 〇16) at 8 〇 (the temperature of rc (especially before the low temperature measurement, ie before the sensor element (16) enters the operation) Heating; • applying a current to the measuring unit cell (Π 8) and/or other components of the sensor element (116) over a temperature range of less than 8〇〇〇c on the first electrode (120); • at the first electrode A current is applied to the measuring unit cell (118) and/or other components of the sensor element (116) at a temperature range above 8 〇〇 «c. The reaction with the oil gas component can be carried out in the experiment to the 85 〇t burner test stand. This reaction has occurred in an oil-laden atmosphere, but the reaction is enhanced by alternately supplying an oil-free gas (Magergas) with an oil-bearing gas and increasing the temperature. One possible measure is therefore to heat the measuring unit cell (118) in the absence of oil gas and/or in air, in particular to heat the front sensor region. Here, only the protection of the tube area (which may also include a winding of the sensor element (116)] is meaningful. For example, for individual sensor elements, this can be achieved with a winding heater (13〇), or for a number of sensor elements (116) or a number of cells (11 8). The electrically heated slot is reached and the measurement cell (118) or sensor element (116) can be inserted into the slot. Alternate replacement of oil- and oil-free gas operations, in the simplest case, uses a gas flame change. In theory, it is also possible to make changes using electric heating, in particular using barreled gas (bottled gas) (Flaschengas, English). Substantially the entire set of components of the sensor can be heated, including the housing and the sealing element, but it is particularly advantageous if only the area of the measuring cell (118) is heated. This is limited by the following conditions, for example, because the sealed package of the sensor element (116) is thermally unstable, such as a sealed package of talc porcelain (Steatit) at over 72 (rc in many current sensor elements) Damage will occur if it exceeds 720 ° C. If it is not heated by the heater (130) (or in addition to heating with the heater), a conditioning current heating can be applied to enhance the heating, and the conditioning current is therefore also This may be referred to as "test current supply." In the case of high temperatures, this may result in a desired change in the electrode configuration of the first electrode (120) and/or the second electrode (124). In the oily atmosphere in the conditioning chamber (ιΐ4), helium causes the oxygen to move away from the boundary layer of the neighboring electrode to the electrode (12〇) or (124), not only to transport oxygen from the gas. In many cases, the important point is the load of the outer electrode (12 〇). This means that the direction of the current should be chosen such that the first outer electrode (4 〇) is at a low potential and the inner electrode (124) is at a high potential. And oxygen is to be taken from the exhaust gas or by the conditioning chamber (ιΐ4) Into the reference channel (126). Therefore, the initial external electrode (12〇) must be inside the electrode (12 sentences lower electricity. So, due to less oxygen, the electrode and electrolyte 咍 $ 15 201105961 boundary area will cause Material destruction. In the second step, this region is regenerated due to the reversal of the current direction. For a typical probe, the useful value measured is 30 mA for 30 s. For the reaction (Rtickreaktion: English: Back-reaction) is -1mA for 30 seconds. Overall on "go (正
向）反應」（Hinreaktion，英：to-reaction )時，1 mA〜3〇mA 的電流使反應時間改善。在此，回反應的參數一般不改變， 回反應不得對正向反應作補償作過頭。對應於此，對於回 反應’有用的電流區間（Strominterval，英：current interval ) 為0 A A〜-30mA。舉例而言，施加電流的期間，對各個部 分步驟係可為3 0秒’換言之，對各反應路徑為3 〇秒，對 於各個部分步驟’換言之，對各反應路徑，有意義的時間 區間’舉例而言’係在5秒〜90秒之間。依目前的理解， 在施電流時’由於固體電解質（127)的晶格發熱，故需要有 充分的離子傳導性。因此之故，廢氣溫度或者在調理室（114) 内的溫度宜大於800°C。對於感測器元件溫度在施電流時， 重要的參數一般為測量晶胞（118)的内電阻。在施電壓時， 17歐姆的内電阻一般可造成高度改善。這一點典型地相當 於廢氣溫度〔或調理室（114)内氣體溫度〕約1097 °C以及電 極溫度約908°C。對應於此，宜使用至少8〇〇。(：的電極溫度， 且且更咼。然而，基本上也可在低溫範圍用少於°c的極 溫度施加電流。 在圖1中所示的實施例，要實施此方法係使用為此本 身ex a十的燃燒器測试架（110)。但如果不採用此方式（或者 除了用此方式外同時另外）也可在已用過的感測器元件（116) 上實施此方法’例如在第一次進入操作前，在一個使用在 16 201105961 一内燃機廢氣通道上的感測器元件（116)上實施。所提議的 措施可在已建構的感測器元件（116)上及/或在未建構的感 測器元件上實施。然而如果這些措施在未建構的感測器元 ，件（16)上實施，則這些措施_般不再能將㈣物質的蒸氣捕 獲（這些毒性物質係在建入程序時才帶入者）。而且要變 換這些措施，亦即實施本發明的方法，基本上可以在已安 褒完成的感測器⑴6)上，在制於—裝置（例如内辦機女 特別是内燃機的廢氣通道）中之前或之後實施。舉例而言， 該方法可在已安裝完成的感測器元件（116)〔例如具有 的電纜束（Kabelbaum ’英：cable harness)者〕上實施。 旦此處特別是由於高溫所致’當程序進行不良時 纜束扣傷。對應於此，宜在一分別的測試架中實施此方法， 例如在圖1的燃燒器測試架（1 10)中。 【圖式簡單說明】 圖1係用於將一感測器元件作調理的本發 圖。 π々凌的 【主要元件符號說明】 (110) 燃燒器測試架 (112) 殼體 (114) 調理室 (116) 感測器元件 (118) 測量晶胞 (120) 第一電極 17 201105961 (122) 多孔隙的護層 (124) 第二電極 (126) 參考通道 (130) 加熱器 (132) 氣體供應手段 (134) 控制手段 Ib 調理電流 18In the case of "reaction" (Hinreaktion, English: to-reaction), a current of 1 mA to 3 mA improves the reaction time. Here, the parameters of the reaction are generally not changed, and the reaction cannot be over-compensated for the positive reaction. Corresponding to this, the useful current interval (Strominterval, English: current interval) for the reaction is 0 A A to 30 mA. For example, during the application of the current, each partial step can be 30 seconds 'in other words, for each reaction path is 3 〇 seconds, for each partial step 'in other words, for each reaction path, a meaningful time interval' is exemplified Words are between 5 seconds and 90 seconds. According to the current understanding, since the lattice heating of the solid electrolyte (127) occurs when the current is applied, sufficient ion conductivity is required. Therefore, the temperature of the exhaust gas or the temperature in the conditioning chamber (114) should be greater than 800 °C. For the sensor element temperature when applying current, an important parameter is generally to measure the internal resistance of the unit cell (118). A 17 ohm internal resistance generally results in a high degree of improvement when voltage is applied. This is typically equivalent to the exhaust gas temperature (or gas temperature in the conditioning chamber (114)) of about 1097 °C and the electrode temperature of about 908 °C. Corresponding to this, it is preferable to use at least 8 inches. (: the electrode temperature, and more ambiguous. However, it is basically also possible to apply a current in the low temperature range with a pole temperature of less than °c. In the embodiment shown in Figure 1, the method is implemented using this for itself Ex a ten burner test rack (110). However, if this method is not used (or in addition to this method), the method can also be implemented on the used sensor element (116) 'for example Prior to the first entry operation, it is implemented on a sensor element (116) that is used on an exhaust passage of an internal combustion engine on 16 201105961. The proposed measure can be on the constructed sensor element (116) and/or Implemented on unconstructed sensor elements. However, if these measures are implemented on unconstructed sensor elements, (16), these measures will no longer be able to capture (iv) the vapor of the substance (these toxic substances are It is only brought into the process when the program is built in.) And to change these measures, that is, to implement the method of the present invention, basically on the sensor (1) 6) that has been installed, in the device (for example, the internal machine) Female, especially the exhaust passage of internal combustion engines) Before or after. For example, the method can be implemented on a sensor component (116) that has been installed (e.g., with a cable harness (Kabelbaum's cable harness). This is especially due to the high temperature. When the program is bad, the cable is buckled. Corresponding to this, the method should be implemented in a separate test stand, such as in the burner test stand (1 10) of FIG. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram of the present invention for conditioning a sensor element. Π々凌 [Main component symbol description] (110) Burner test stand (112) Housing (114) Conditioning chamber (116) Sensor element (118) Measuring unit cell (120) First electrode 17 201105961 (122 ) Porous sheath (124) Second electrode (126) Reference channel (130) Heater (132) Gas supply means (134) Control means Ib Conditioning current 18