CN1142428C - Oxygen sensor and its making method - Google Patents
Oxygen sensor and its making method Download PDFInfo
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- CN1142428C CN1142428C CNB001206370A CN00120637A CN1142428C CN 1142428 C CN1142428 C CN 1142428C CN B001206370 A CNB001206370 A CN B001206370A CN 00120637 A CN00120637 A CN 00120637A CN 1142428 C CN1142428 C CN 1142428C
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- electrode
- porous protective
- zro
- lambda sensor
- zirconia
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Abstract
The present invention relates to an oxygen sensor and the making method thereof. The internal surface and the external surface of a tubular ceramic oxygen sensing element 4 with one open end and one closed end are provided with a porous reference electrode 5 and a measuring electrode 2 which are provided with conductive connecting wires, and the electrode surface of the measuring electrode 2 is orderly provided with a zirconia porous protecting layer 3 and an alumina porous protecting layer 1. The making method comprises the following steps: mixing and grinding metal powder, a pore-creating agent and an organic dispersing agent, regulating viscidity, and applying the mixture to the internal wall and the external wall of the oxygen sensing element 4 by using a coating or printing or spraying method so as to make the electrodes and the protecting layers. The oxygen sensor has the advantages of obvious increase of a response time and service life prolonging.
Description
The present invention is relevant with the lambda sensor that is used for the controlling combustion engine burning and exhausting.The present invention relates to the manufacture method of this lambda sensor again.
In recent years, being used for car combustion engine combustion tail gas mensuration oxygen concentration comes the lambda sensor (detector or detecting device) of controlling combustion engine burning extensively to be utilized.Be used for the air input of controlling combustion engine and the quantitative proportioning of fuel oil input, make burning reach abundant as much as possible, give off harmful gas as much as possible less.The lambda sensor that uses on the internal combustion engine requires very fast response and long mission life.Both are indispensable, and this also is the problem that researcher all over the world pays close attention to and endeavours to solve.Opening at one end, on the ceramic pipe of an end closure, the application of the lambda sensor of inside and outside making electrode is comparatively extensive.Being used for internal combustion engine is to be to make progress to some extent and obtained achievement (as CN1121177A) preferably in recent years for the work that improves its sensitivity.Be aspect the long-term work life-span in that good durability is provided in addition.Also obtained bigger progress (CN1217790A).
Along with the improvement of internal combustion engine, countries in the world progressively are familiar with and are deepened atmospheric environment is destructive automotive emissions, have put into effect the standard of the pollutant emission of many policys and regulation file restricting vehicle in succession.A new height has been mentioned in the burning control that also just requires internally to fire machine, and corresponding demand is also just given birth to thereupon.Make automotive emissions few as much as possible, the lambda sensor that is used to control plays critical measuring ability, requires to have higher sensitivity, also should have more lasting mission life.
The purpose of this invention is to provide a kind of highly sensitive, the lambda sensor of long working life and manufacture method thereof.
The present invention is achieved in that
Lambda sensor of the present invention comprises an end opening; the tubular ceramic oxygen sensitive element 4 of one end sealing; this sensitive element surfaces externally and internally has contrast electrode 5 and potential electrode 2; at contrast electrode 5 and potential electrode 2 is the porous metals electrode; potential electrode 2 pole-faces are outside equipped with zirconia porous protective layer 3, and protective seam 3 is outside equipped with aluminum oxide porous protective seam 1.
The thickness of potential electrode 2 of the present invention is 5-15 μ m, and porosity is 40-60%.
The thickness of contrast electrode 5 of the present invention is 2-50 μ m, and porosity is 30-60%.
The average pore size of contrast electrode 5 of the present invention is 0.1-20 μ m.
The average pore size of potential electrode 2 of the present invention is 0.1-10 μ m.
The porosity of protective seam 3 of the present invention is 10-15%, and the porosity of protective seam 1 is 15-60%.
Protective seam 1 of the present invention is α-Al
2O
3, γ-Al
2O
3, MgO mixed-powder layer, the powder particle diameter is 5-100 μ m, the thickness of protective seam 1 is 200-450 μ m.
The irregularity degree of protective seam 1 outside surface of the present invention is 5-200 μ m.
The manufacture method of lambda sensor of the present invention, contrast electrode 5 manufacturing steps comprise:
(1) with metal powder, pore creating material and the organic dispersing agent mixed grinding of 0.01～5 μ m, regulates viscosity; With coating or printing or spraying method potpourri is arranged on the inwall of tubular ceramic sensitive element 4, forms contrast electrode after 1～24 hour 800-1350 ℃ of thermal treatment;
(2) with the platinum powder of 0.01～1 μ m, pore creating material and organic dispersing agent mixed grinding are regulated viscosity; With coating or printing or spraying method potpourri is arranged on the outside surface of tubular ceramic sensitive element 4, forms potential electrode after 0.5～12 hour 800-1200 ℃ of thermal treatment.
To account for weight percent be 1-20% to pore creating material in the contrast electrode of the present invention, in the potential electrode in the pore creating material weight percent be 4-30%.
The step that the surface of potential electrode of the present invention is provided with protective seam 3 and 1 comprises:
(1) uses ZrO
2Y
2O
3, ZrO
2Al
2O
3Y
2O
3, ZrO
2The CaO mixed-powder is in potential electrode
(2) surface makes porous ceramics protective seam 3, dry 12-24 hour with the method for spraying and molten dipping.
(2) with α-Al
2O
3, γ-Al
2O
3, the MgO mixed-powder makes porous ceramics protective seams 1, dry 2-24 hour on protective seam 3 surface with the methods of spraying and molten dipping.
(3) with protective seam 3 and 1 thermal treatment.
The emphasis that the present invention mainly pays close attention to is the difference between internal reference electrode and the external pelivimetry electrode, the different satisfied optimum performance requirements of using separately of the means of making.The external pelivimetry electrode is to be in the mensuration environment of utmost point low oxygen concentration, should have sensitive active and stronger catalytic capability, guarantees to obtain optimum performance, setting be that 5～15 μ m are thick, porosity is 40～60%, the aperture is the metal active layer of 0.1～100 μ m.Contrast electrode is to be on the environment of comparatively stable higher concentration, does not need highly sensitive than measuring the utmost point.The porosity of its design is 30～60%, and the aperture is the metal level of 0.1～20 μ m.For guaranteeing the thermotolerance under its long term high temperature, long-term work validity has also proposed difference to the requirement in aperture, and the difference of potential electrode and contrast electrode is guaranteed to be combined under the varying environment condition and had more as effectively measure and the lambda sensor of high sensitivity.As the above, in addition the present invention also is concerned about is the effect of the protective seam that is provided with above of sensor sensing element external pelivimetry electrode.Internal layer adopts ZrO
2Y
2O
3, ZrO
2MgO, ZrO
2Y
2O
3Al
2O
3, ZrO
2The CaO powder bed, based on thermotolerance is considered that more approaching expansion coefficient can be arranged, the internal layer by the various powders layer is formed also has the function as the cladding material trapezoidal transition simultaneously.Fine and close structure has more good adhesion, the outer γ-Al that is provided with
2O
3, α-Al
2O
3, MgO loose powdered layer comparatively; protective seam is set to the two-layer foreign matter that stops effectively and enters on the electrode layer (external pelivimetry utmost point electrode layer); protect foreign matter effectively, particularly the oxide that is formed by K, Na, Pb can obtain lasting effectively protection to the blocking action of electrode hole.The immersion or both combinations of barrier gas via hole that can stop foreign matter have effectively guaranteed the stronger heat resistanceheat resistant performance and the stability of permanance and work.
The present invention has following marked improvement: the response time of lambda sensor has obtained significantly improving, by bibliographical information can investigate＜100ms, bring up to＜30ms.Improved the burning control of the various car combustion engines that lambda sensor is suitable for, its life-span 100,000 kilometers of can be investigated by document are brought up to 300,000 kilometers travelling serviceable life.
Following is accompanying drawing of the present invention:
Fig. 1 is the structural drawing of lambda sensor.
Fig. 2 is the enlarged diagram of lambda sensor contrast electrode.
Fig. 3 is the enlarged diagram of lambda sensor potential electrode.
Fig. 4 is the enlarged diagram of lambda sensor internal layer protective seam.
Fig. 5 protects outer field enlarged diagram for lambda sensor.
Following is embodiments of the invention:
The present invention proposes a kind of lambda sensor comprises: an end opening, the oxygen photosensitive elements 4 of an end closure.The inside and outside wall of oxygen photosensitive elements requires to be provided with contrast electrode porous metallic layers, potential electrode porous metallic layers according to usability.To be provided with internal layer be ZrO on the potential electrode surface outside
2Y
2O
3, ZrO
2MgO, ZrO
2Y
2O
3AL
2O
3, ZrO
2Many kinds of ceramics layers of CaO and skin are γ-Al
2O
3, α-Al
2O
3, MgO multiple ceramic powders.Wherein oxygen sensitive element contrast electrode metal level is that a bed thickness is 2～50 μ m, and porosity is 30～60%, and the aperture is the porous electrode layer of 0.1～20 μ m.The external pelivimetry electrode metal layer is one deck 0.5～15 μ m, and porosity is 40～60%, and the aperture is the porous electrode layer of 0.1～10 μ m.The difference of inside and outside electrode is guaranteed to be combined under different environmental baselines to have more and is effectively measured high with it sensitivity.The internal layer that is provided with in external pelivimetry extremely is ZrO
2Y
2O
3, ZrO
2MgO, ZrO
2Y
2O
3Al
2O
3, ZrO
2The powder bed thickness of CaO is 30～1O0 μ m, and porosity is 10～50%, and the diameter of particle is internal layer 3 restraining barriers of 1～80 μ m, and outer 1 is γ-Al
2O
3, α-Al
2O
3, MgO powder bed thickness be 200～450 μ m, porosity is 15～60%, particle diameter is the outer layer barrier of 50～100 μ m.
The present invention has introduced the manufacture method of this lambda sensor, can realize by following technical measures.
Soak sensitive element 4～24h, dried behind the water cleaning element with 10～38%HF solution.Metal powder and pore creating material, organic dispersing agent with 0.01～5 μ m make up, and mixing ratio is 1～20%, and ball milling 12～72h takes out the metal paste powder.With coating, spraying or method of printing it is provided with in the sensitive element and surveys.80～250 ℃ of dry 10min～4h, the heat back is at 800～1350 ℃ of sintering 1～24h.Survey contrast electrode in obtaining, metal powder and pore creating material with 0.01～1 μ m, spreading agent connects 4～30% percentage by weight batch mixes, ball milling 12～96h, take out the metal paste powder, with coating, spraying or method of printing it is arranged on sensitive element and surveys outward, 80～250 ℃ of dry 10min～4h, at 800～1200 ℃ of sintering 0.5～12h, obtain the external pelivimetry electrode then.ZrO with 1～80 μ m
2Y
2O
3, ZrO
2MgO, ZrO
2Y
2O
3Al
2O
3, ZrO
2After the CaO powder carries out ball milling 24～120h, with dipping and spraying, the formation porosity is that 10～50% thickness is the porous ceramic layer of 30～100 μ m on sensitive element, before dipping and spraying sensitive element is carried out mechanical alligatoring, makes that surfaceness is 0.1～10 μ m.After the ceramic porous layer 3 of making internal layer is heat-treated, with γ-Al of 5～10 μ m
2O
3, α-Al
2O
3Carry out mechanical mixture 12h with the MgO powder, be produced on internal layer ceramic layer 3 surfaces with the method for flooding or spray and form thick 200～450 μ m, porosity is 15～60% porous ceramic layer 1, and possesses the surface irregularity degree that 5～200 μ m are arranged.
Claims (7)
1, a kind of lambda sensor, comprise an end opening, the tubular ceramic oxygen sensitive element (4) of one end sealing, this sensitive element surfaces externally and internally has contrast electrode (5) and potential electrode (2) respectively, it is characterized in that contrast electrode (5) and potential electrode (2) are the porous metals electrode, potential electrode (2) is outside equipped with the zirconia porous protective layer, and the zirconia porous protective layer is outside equipped with aluminum oxide porous protective seam, the thickness of potential electrode (2) is 5-15 μ m, and porosity is 40-60%; The thickness of contrast electrode (5) is 2-50 μ m, and porosity is 30-60%.
2, lambda sensor according to claim 1, the average pore size that it is characterized in that contrast electrode (5) are 0.1-20 μ m.
3, lambda sensor according to claim 1, the average pore size that it is characterized in that potential electrode (2) are 0.1-10 μ m.
4, lambda sensor according to claim 1, the porosity that it is characterized in that the zirconia porous protective layer is 10-15%, and the porosity of aluminum oxide porous protective seam is 15-60%, and the zirconia porous protective layer is ZrO
2MgO
2, ZrO
2Y
2O
3, ZrO
2Al
2O
3Y
2O
3, ZrO
2CaO mixed-powder layer, powder particle diameter are 1-80 μ m, and the thickness of zirconia porous protective layer is 30-100 μ m, and aluminum oxide porous protective seam is α-Al
2O
3, γ-Al
2O
3, MgO mixed-powder layer, the powder particle diameter is 5-100 μ m, the thickness of aluminum oxide porous protective seam is 200-450 μ m.
5, lambda sensor according to claim 1 and 2, the irregularity degree that it is characterized in that aluminum oxide porous protective seam outside surface are 5-200 μ m.
6, the manufacture method of lambda sensor according to claim 1 is characterized in that the manufacturing step of contrast electrode (5) comprising:
(1) with metal powder, pore creating material and the organic dispersing agent mixed grinding of 0.01～5 μ m, regulates viscosity; With coating or printing or spraying method potpourri is arranged on the inwall of tubular ceramic sensitive element (4), forms contrast electrode after 1～24 hour 800-1350 ℃ of thermal treatment,
(2) with metal powder, pore creating material and the organic dispersing agent mixed grinding of 0.01～1 μ m, regulate viscosity; With coating or printing or spraying method potpourri is arranged on the outside surface of tubular ceramic sensitive element (4), forms potential electrode after 0.5～24 hour 800-1200 ℃ of thermal treatment,
The step that aluminium oxide and zirconia porous protective layer are set on the surface of potential electrode comprises:
(1) uses ZrO
2Y
2O
3, ZrO
2Al
2O
3Y
2O
3ZrO
2The CaO mixed-powder is made porous ceramics zirconia porous protective layer on potential electrode (2) surface with the method for spraying and molten dipping, and dry 12-24 hour,
(2) with α-Al
2O
3, γ-Al
2O
3, MgO mixed-powder layer on zirconia porous protective layer surface the method with spraying and molten dipping make the aluminum oxide porous protective seam of porous ceramics, dry 2-24 hour,
(3) with zirconia and aluminum oxide porous protective seam thermal treatment.
7, the manufacture method of lambda sensor according to claim 1 is characterized in that in the contrast electrode that it is 1-20% that pore creating material accounts for weight percent, and to account for weight percent be 4-30% to pore creating material in the potential electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001206370A CN1142428C (en) | 2000-12-28 | 2000-12-28 | Oxygen sensor and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001206370A CN1142428C (en) | 2000-12-28 | 2000-12-28 | Oxygen sensor and its making method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1329247A CN1329247A (en) | 2002-01-02 |
| CN1142428C true CN1142428C (en) | 2004-03-17 |
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ID=4588314
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001206370A Expired - Fee Related CN1142428C (en) | 2000-12-28 | 2000-12-28 | Oxygen sensor and its making method |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030146093A1 (en) * | 2002-02-05 | 2003-08-07 | Kyocera Corporation | Oxygen sensor |
| GB2387230B (en) | 2002-02-28 | 2005-12-21 | Ngk Spark Plug Co | Prismatic ceramic heater for heating gas sensor element, prismatic gas sensor element in multi-layered structure including the prismatic ceramic heater, |
| CN100340855C (en) * | 2003-08-26 | 2007-10-03 | 北京市科海龙华工业自动化仪器有限公司 | Making process of oxygen-measuring copper solution sensor |
| DE102006014892B4 (en) * | 2005-03-31 | 2020-09-24 | Ngk Spark Plug Co., Ltd. | Gas sensor element, method for its manufacture, and gas sensor |
| CN101251509B (en) * | 2008-04-16 | 2010-12-29 | 湖南大学 | Zirconium oxide oxygen sensor for automobile |
| CN101424656B (en) * | 2008-09-09 | 2012-02-01 | 深圳市日理江澍实业有限公司 | Method for producing oxygen sensor ceramic sensing head outer electrode double-layer porous protection film |
| DE102009047530A1 (en) * | 2009-12-04 | 2011-06-09 | Robert Bosch Gmbh | Protective pipe for gas sensor of exhaust systems of internal-combustion engine, has through openings provided in region of longitudinal section that is enclosed by toroidal-shaped section with respect to longitudinal axis |
| JP5416757B2 (en) | 2011-02-22 | 2014-02-12 | 日本特殊陶業株式会社 | Gas sensor element and gas sensor |
| JP2013104706A (en) * | 2011-11-11 | 2013-05-30 | Ngk Spark Plug Co Ltd | Gas sensor element and gas sensor |
| CN103901074A (en) * | 2012-12-29 | 2014-07-02 | 赣州虔东稀土集团股份有限公司 | Preparation method of porous ceramic material protective layer coated on oxygen sensor chip |
| CN103529105B (en) * | 2013-11-06 | 2015-09-02 | 惠州市富济电子材料有限公司 | A kind of tubular oxygen sensor test electrode and protective seam |
| CN105301076B (en) * | 2015-11-24 | 2018-04-13 | 哈尔滨中科盈江科技有限公司 | A kind of method for electrochemical gas sensor electrode pore-creating |
| WO2017146121A1 (en) * | 2016-02-24 | 2017-08-31 | 田中貴金属工業株式会社 | Gas sensor electrode and method for producing same |
| CN105652905A (en) * | 2016-03-18 | 2016-06-08 | 柳州易旺科技有限公司 | Automatic oxygen adjusting system and method thereof |
| CN106242625A (en) * | 2016-08-02 | 2016-12-21 | 西安电子科技大学 | The low temperature preparation method of gas sensor sensitive layer ultrathin alumina protecting film |
| CN110044990A (en) * | 2019-03-31 | 2019-07-23 | 苏州工业园区传世汽车电子有限公司 | A kind of lambda sensor post-processing approach |
| CN115385686A (en) * | 2022-09-22 | 2022-11-25 | 北京中电伊川测控技术有限公司 | Preparation method of zirconium oxide sensor electrode protective coating |
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2000
- 2000-12-28 CN CNB001206370A patent/CN1142428C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1329247A (en) | 2002-01-02 |
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Owner name: CHENGDU XUGUANG SCIENCE AND TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: KANGDA (CHENGDU) ELECTRONIC CO. LTD. Effective date: 20051202 |
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Effective date of registration: 20051202 Address after: Two, 610100 section, Park Road, Longquanyi District, Chengdu, Sichuan, China Patentee after: Chengdu Xuguang Tech. Co., Ltd. Address before: 610041, Sichuan Province, Chengdu Province High-tech Zone standard factory district 22 Patentee before: Kangda (Chengdu) Electronic Co., Ltd. |
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