CN102759555B - The sensor element of gas characteristic in air chamber is surveyed in detection - Google Patents
The sensor element of gas characteristic in air chamber is surveyed in detection Download PDFInfo
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- CN102759555B CN102759555B CN201210127449.5A CN201210127449A CN102759555B CN 102759555 B CN102759555 B CN 102759555B CN 201210127449 A CN201210127449 A CN 201210127449A CN 102759555 B CN102759555 B CN 102759555B
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
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Abstract
The present invention relates to the gas componant in a kind of at least one characteristic prepared for detecting gas in air chamber, particularly calibrating gas or the sensor element of gas temperature（10）Method, this method comprises the following steps：At least one layer of contain by the interior solid electrolyte layer (12 of the zirconium dioxide of stabilized with yttrium oxide is provided, 14,16), in the interior solid electrolyte layer (12,14,16) at least one layer outer layer (18 made of containing Yttrium oxide material are applied on, 20), the wherein outer layer (18,20) is than interior solid electrolyte layer (12,14,16) solid electrolyte layer (12,14 in the yittrium oxide containing higher amount, and common sintering, and outer layer (18,20) 16).
Description
Technical field
The present invention relates to a kind of method prepared for detecting the sensor element of at least one characteristic of gas in air chamber
And the sensor element that can be prepared in this way.
Background technology
By known in the art a variety of for detecting the sensor element of at least one characteristic of gas and side in survey air chamber
Method.It substantially can relate to any physical characteristic of the gas and/or chemical characteristic, wherein detectable one or more special
Property.It is with the gas componants of qualitative and/or quantitative detection gas particularly below, is particularly retouched with the oxygen content in detection gas
State the present invention.The oxygen content can for example be detected in the form of partial pressure and/or percentage.But it also or can additionally detect the gas
Other characteristics.
Such as this kind of sensor element may be designed as so-called λ probes, such as in Konrad Reif (publisher)：
Sensoren im Kraftfahrzeug, 1. Auflage 2010, it is known in the 160-165 pages.Visited with broadband λ
It head, particularly can for example determine the oxygen concentration in waste gas on a large scale with the broadband λ probes of plane, and conclude therefrom that combustion chamber
In air-fuel ratio.The air coefficient λ-description air-fuel ratio.
By the special known ceramics sensor element of prior art, its electrolyte properties based on some solids of application, that is, it is based on
The ionic conduction characteristic of these solids.These solids particularly ceramiic solid electrolyte, such as zirconium dioxide (ZrO2), especially
Yttria stabilized zirconia (YSZ) and/or the zirconium dioxide (ScSZ) of scandium doping, it can contain small amounts aluminium (Al2O3) and/or
Silica (SiO2) additive.Yittrium oxide (Y2O3) content be usually 4-5 moles of %.This problem of be, this kind of solid electricity
In the case of solving matter paper tinsel or solid electrolyte layer, can due to mechanical load or the stress as caused by temperature difference cause it is cracked.Especially
It is that i.e. mechanical strength property deterioration can cause sensor element and thus cause λ to visit so-called Thermal degradation effect at low temperature
The defects of head.This effect occurs under the running temperature less than 400 DEG C, and based on less than Tetragonal dioxy at a temperature of this
Change zirconium and be transformed into monoclinic phase zirconium dioxide, wherein volume increase occurs in phase transformation.This expansion can cause sensor ceramics broken
Split.
To avoid this phenomenon, it is known that by there is the zirconium dioxide of high content as far as possible on the surface of solid electrolyte paper tinsel
Emission in Cubic or stable Tetragonal can reduce Thermal degradation.The possibility for realizing this point is to grind sintered contain by aoxidizing
The surface of yttria stabilized zirconia, so that tetragonal zirconium dioxide is transformed into monoclinic zirconium dioxide on a surface.It is 1200-
In heat treatment at 1400 DEG C then, the monocline crystal grain of the formation is converted into the cubic crystal grain of very fine grain shape, and the latter is due to it
Small granularity and be resistant to very much Thermal degradation.Its shortcoming is to control and monitor grinding steps compared with consuming.Particularly it is difficult to reach
Result, i.e., flat workpiece surface are ground to Jun Yun Subcommittee-to.The same cubic crystal grain pole for being also known that fine grain shape of the diameter less than 300 nm
It is stable, it is difficult to is transformed into monoclinic phase.The preparation of this structure is the process relatively expended, and is difficult to form uniform particle size.By
This reason, attempt to improve the yttria levels in base ceramic, as described in the A1 of DE 10337573, thus generally speaking
Reach the higher zirconium dioxide content of Tetragonal or Emission in Cubic.
Although the method that preparation known in the art is used for the sensor element of λ probes has many merits, these sides
Method also has improved potentiality.Such as the technical difficulty that the method finally referred to includes is, the yittrium oxide increased in base ceramic contains
Amount can cause the sintering behavior of difference and thus cause the mechanical strength reduced.
The content of the invention
Therefore the present invention proposes a kind of prepare for detecting the sensor element of at least one characteristic of gas in air chamber
Method and the sensor element that can be prepared in this way, its at least big degree avoid lacking for known method and sensor element
Point, and at least reduce above-mentioned Thermal degradation.
This method includes the following steps preferably according to the sequence：
- interior solid electrolyte layer of at least one layer containing the zirconium dioxide by stabilized with yttrium oxide is provided,
- apply at least one layer outer layer, the wherein outer layer made of containing Yttrium oxide material on the interior solid electrolyte layer
Than yittrium oxide of the interior solid electrolyte layer containing higher amount, and
- the interior solid electrolyte layer and outer layer is sintered jointly.
The sensor element for example can be made into finger-type probe or plane probe, is especially formed into plane λ probes, i.e., for example may be used
The λ probes with layer structure are made.Such as transition probe and/or broadband λ probes can be realized.
The present invention thinking be, on the interior solid electrolyte layer containing zirconium dioxide as substrate, at least behind
Or provided in method and step then and apply or coat at least one layer of as thin as possible contain in the region of electrode or contact conductor
The layer of high content yittrium oxide, so that it is preferred that only main on the surface is in very high yttria levels.Then this two layers is carried out
Common sintering.The dioxy in stable cube or four directions is preferably produced by high oxidation yttrium content on the surface of the substrate in sintering
Change zirconium, the zirconium dioxide in terms of monoclinic phase is transformed into is stable in sensor element operation when less than 400 DEG C.
It particularly can be prepared as follows the sensor element of the layer structure of plane：There is provided or configuration has with stabilized with yttrium oxide
Zirconium dioxide at least one layer in solid electrolyte layer, and thereon apply or coat at least one layer by the material containing yittrium oxide
The yttria levels of the outer layer of composition, the wherein outer layer are higher than the content in interior solid electrolyte layer, and sintering should jointly
Interior solid electrolyte layer and outer layer, so as to produce or form cubic zirconium dioxide or tetragonal zirconium dioxide in outer layer.
Here, term " interior solid electrolyte layer " and " outer layer " are related to position of these layers relative to the surface of sensor element
Put, for example, relative to sensor element Rotating fields surface and be particularly preferably configured with sensor element thereon extremely relatively
The position on the surface of the sensor element of a few electrode.Such as the surface can be surface of the sensor element towards air chamber
And/or sensor element is towards the side of surrounding space.At least one layer of outer layer configuration solid electrolyte layer at least one layer
It between surface and can for example form surface or one part.But also may be present interior solid electrolyte layer it is one or more not by
The region of outer layer covering.Such as the interior solid electrolyte layer can play carrier function, solid outside it applies towards at least side on surface
Body dielectric substrate, preferable applying mode, which is so that between the two layers, has the directly contact with preferred large area.Art used
Language " outer " and " interior " especially can relate to the Rotating fields of sensor element in itself, wherein can not for example consider other components.This definition
It is especially important in finger-type probe, such as in Konrad Reif (publisher)：Sensoren im Kraftfahrzeug, 1.
Auflage 2010, described in the 160-162 pages.In this kind of finger-type probe, configured in the outside of " finger " towards air chamber
There is one or more layers outer layer and/or one or more layers outer layer is configured with the inside of the finger in surrounding air.
In the method for the invention, it especially can apply outer layer by means of at least one printing method, be preferably selected from silk screen
Printing, mechanical printing, at least one printing method of impressing.This kind of printing method is particularly well-suited for automating, so that can
This method step is implemented in low cost and automation.
The outer layer also especially can so apply, i.e., make its thickness be 1-100 μm, especially 3-30 μm after sintered.By
This for example provides the thin surface layer for having excellent stability to Thermal degradation.
The outer layer especially may include zirconium dioxide, and the content of zirconium dioxide is preferably at least 80 weight % after sintering.The outer layer
It especially may include the either thickener containing zirconium dioxide before sintering.
8.0-20.0 weight % yittrium oxide can especially be contained after the outer layer is sintered.Such as the outer layer can contain titanium dioxide
The thickener of zirconium and/or prepared by this thickener, and the % of weight containing 8.0-20.0 yittrium oxide before sintering.
By required application or the composition of sensor element, the outer layer can contain at least 40 weight %, preferably at least after sintering
60 weight %, even particularly preferably at least 80 weight % or 100 weight % yittrium oxide.
One or more layers described interior solid electrolyte layer especially can be prepared so, that is, make it that each thickness is 50 after sintering for it
μm -1000 μm, especially 100 μm -700 μm, particularly preferably 200 μm -500 μm.Thus have the sensor element excellent
Choosing corresponds to the thickness or intensity of conventional sensor element, so that the sensor element is replaceable, without to other
Component carries out structural change.
The interior solid electrolyte layer rubs can especially contain 1-20 moles of % yittrium oxide, especially 2-16 after common sintering
Your % and particularly preferred 4-8 moles of % yittrium oxide.Thus the sensor ceramics with excellent mechanical strength can be made.
In addition, preferably so providing at least two outer layers, that is, make it that solid electrolyte layer is at least partially embedded at least one layer
Between outer layer.
At least one layer of outer layer can completely or at least partially cover the interior solid electrolyte layer.Such as the outer layer can cover to
Few 10%, preferably at least 20%, the surface of the particularly preferably at least 40% or even at least 50% interior solid electrolyte layer.
At least one electrode and/or at least one contact conductor can be applied in the outside of the outer layer.The electrode or electrode draw
Line can remain not covered, but also can and then be covered completely or partially by least another element, such as by least one layer of exhausted
Edge layer and/or covered by least one layer of porous sheath.The outside of the outer layer can refer to particularly that outer layer is not by above-mentioned definition
On interior solid electrolyte layer, but backwards to that side of the interior solid electrolyte layer.
After applying outer layer, the component that can implement so to prepare is separated at least one step of two or more elements
Suddenly, described two or more elements respectively include solid electrolyte layer and at least one layer of outer layer at least one layer.The separate pieces example
The part of the smaller piece in single separation, such as the smaller piece of same structure can be such as included, itself can be used as sensor element
Or the part of sensor element.The division step can especially be carried out before or after at least one sintering step is implemented.
It can apply at least another outer layer on each element after separating.Herein or be also it is common can be by least another outer layer
It is applied at least one side of the element.This can especially be carried out by means of impressing, but other methods can also be used.
As described above, another aspect of the present invention is to provide at least one at least one spy for being used to detect gas in air chamber
The sensor element of property, its content for example at least one of detection gas gas componant.It is, for example, internal combustion engine to survey air chamber
Waste line.The sensor element can be prepared by the method for the present invention, therefore see in possible configuration aspects above-mentioned
Method explanation.In addition, in addition to the above-mentioned Rotating fields for pressing the present invention, can also especially join in terms of the preferred structure of the sensor element
Read Konrad Reif (publisher)：Sensoren im Kraftfahrzeug, 1. Auflage 2010,160-165
Page.The sensor element that can be prepared by the method for the present invention especially may include it is at least one selected from can this special battery, pump battery plus
The add ons of thermal element.To realize air coefficient λ broadband measurement, the sensor element especially can be used as band pump battery and
The broadband λ probes of this special battery of energy are popped one's head in as the miniature probe according to carrying current principle or as the transition with pumping benchmark
Run together.The heating element heater is particularly useful for adjusting the temperature of the sensor element, the especially sensor element components
Temperature.The heating element heater may be preferably used for improving the catalytic activity of one or more of electrodes and/or for adjusting the sensing
The internal resistance of device element and/or its part.
Brief description of the drawings
Accompanying drawing 1 shows the diagrammatic side view of sensor of the invention element.
Embodiment
A kind of embodiment of sensor of the invention element 10 is illustrated with schematic side in unique accompanying drawing.The biography
Sensor component 10 can be used for the physically and/or chemically characteristic of calibrating gas, wherein can detect one or more characteristics.Particularly below
The present invention is described with reference to the qualitative and/or quantitative detection of the gas componant of gas, referring particularly to the inspection of oxygen content in gas
Survey to describe the present invention.The oxygen content for example can use partial pressure and/or the form of percentage to detect.But also it can detect in principle other
The gas componant of species, such as nitrogen oxide, hydrocarbon and/or hydrogen.Also can alternately or additionally detection gas other characteristics.It is of the invention special
Not Ke Yongyu automobile technical field, therefore it is described survey the waste line that air chamber especially can be internal combustion engine, and the gas is special
Can not be waste gas.
In Fig. 1, sensor element 10 is exemplarily plane λ probes.The sensor element 10 has solid in three layers
Dielectric substrate 12,14,16, two outer layers 18,20 and two electrodes 22,24.The interior solid electrolyte layer 12,14,16
Configuration is layered on top of each other with stratiform with outer layer 18 and 20, therefore it forms a kind of overlapping piece, the wherein interior solid electrolyte layer 12,14,
16 are embedded between outer layer 18,20.The interior solid electrolyte layer 12,14,16 forms the substrate of sensor element 10, and has
By the zirconium dioxide of stabilized with yttrium oxide.This in first solid electrolyte layer 12 for example containing it is not shown further can this special battery.
This in second solid electrolyte layer 14 for example containing unshowned baseline air passage.In 3rd solid electrolyte layer 16 for example containing
Unshowned heating element heater.The energy this special battery, baseline air passage and heating element heater are preferably embedded or are integrated into interior solid
In dielectric substrate.This assembling or integration are corresponding to the sensor element for example popped one's head in by above-mentioned plane λ known in the art
Usual structure.
There is the He of outer layer 18 respectively on each outside of the solid electrolyte layer 16 of solid electrolyte layer 12 and the 3rd in first
One of 20.Solid electrolyte layer 12 in the outer layer 18 and 20 encapsulating, 14,16, so that the interior solid electrolyte layer 12,14,
16 are completely embedded between outer layer 18,20.Pass through interior solid electrolyte layer 12,14,16 and stacked, outer layer of outer layer 18,20
18 and 20 preferably completely cover the upside of the overlapping piece formed by interior solid electrolyte layer 12,14,16 and downside in parallel.
The outer layer 18 and 20 is preferably made up of the material containing tetragonal zirconium dioxide, and wherein the yttria levels of the outer layer 18 and 20 are higher than interior
The yttria levels of solid electrolyte layer 12,14,16.It is detailed together with preferable preparation method below the preferred content of the component
State.The basic structure of sensor of the invention element 10 is only described here.It should be noted that the diagram in Fig. 1 is schematical
And it is simplified, therefore the optional interior electrode that may be present in optional baseline air passage is for example not shown and can encapsulate optionally
Heating element heater one or more layers optional insulating barrier.But these components are in this sensor element that plane λ pops one's head in
Generally comprise, therefore its function is also known, therefore functional mode is not described in itself.
It is the solid electrolyte layer 16 in solid electrolyte layer 12 and the 3rd in first in the outside of the outer layer 18 and 20
That side on be respectively present electrode 22,24.Thus exist in electrode 22 and first between solid electrolyte layer 12 outside first
Layer 18, and in electrode 24 and the 3rd solid electrolyte layer 16 to exist the second outer layer 20.In addition, in electrode 22,24 and outside
Regionality is configured with insulator 26 between layer 18,20.The outer layer 18,20 shows that it is completely or gross area covers first He
Solid electrolyte layer 12,16 in 3rd.But if the outer layer 18,20 is only regional application, such as it is applied to and is mounted with electrode
In those regions of 22,24 interior solid electrolyte layer, and enough.
Optional energy this special battery being preferably provided in first in solid electrolyte layer 12, to measure in burning waste gas
Each residual oxygen, thus, it is possible to adjust ratio of the required combustion air to fuel that burn away, both to occur without fuel mistake
Amount also occurs without air excess.Because temperature is also far below 300 DEG C, when λ pops one's head in thus cold start-up in cold engine
Regulation do not work or only act on very slow.Therefore the sensor element 10 is preferred in solid electrolyte layer 16 in the 3rd
Electrical heating battery is configured with, so that probe can shortly be raised to required temperature after a cold start.Thus in the heat operation of engine
The interim operation for ensuring that optimum discharge.Because the operation of λ probes is for example by the known, not
Its functional mode is described in detail.
The sensor element 10 especially can be prepared as follows.Solid electrolyte layer 12,14,16 is used as base in being provided during beginning
Paper tinsel or blank simultaneously make its superposed, so that it forms above-mentioned overlapping piece form.The in the upper side and lower side for forming the overlapping piece
Solid electrolyte layer 12 in one and the 3rd, 16 those outsides are on Free Surface, such as are used by means of silk screen printing and contain two
The thickener printing outer layer 18,20 of zirconium oxide, so that the unfertile land as far as possible of outer layer 18,20 is applied or applied, and contains 8.0-
20.0 weight % yittrium oxide.Covered completely by outer layer 18,20 in the outside of the solid electrolyte layer 12,16 in first and the 3rd
Lid.The yttria levels of the outer layer 18,20 are higher than the yttria levels of the interior solid electrolyte layer 12,14,16.Then with
Known method applies electrode 22,24.Finally at about 1200-1400 DEG C with solid electrolyte layer 12,14 in common sinter,
16 and the form of outer layer 18,20 be heat-treated.At this due to the very high yttria levels in outer layer 18,20 shape
Into tetragonal zirconium dioxide.Thus the sensor element 10 has the thin surface layer being made up of tetragonal zirconium dioxide, and the layer exists in itself
It is difficult to be transformed into monoclinic phase at a temperature of less than 400 DEG C.To form the tetragonal zirconium dioxide of enough high contents in each outer layer, weight
What is wanted is that the outer layer mainly contains yittrium oxide as inorganic component.It should be noted that solid electrolyte layer 12,14,16 here
Referred to as solid electrolyte paper tinsel.But two term is paper tinsel and layer represents identical component in the technical field of the present invention, with whether
Foil shape formula exists unrelated.
The zirconium dioxide content included after the outer layer 18,20 is sintered is preferably at least 80 weight %.By to sensor member
The application that part 10 is drafted, the yttria levels in outer layer can be at least 40 weight %, more preferably at least 60 weight %, especially excellent
Choosing is at least 80 weight % or even 100 weight %.The outer layer 18,20 it is sintered after thickness be respectively 1-100 μm, especially 3-
30 μm。
For the interior solid electrolyte layer 12,14,16 after being sintered jointly with outer layer 18,20, its yttria levels is preferably 1-
20 moles of %, especially 2-16 moles of %, particularly preferably 4-8 moles of %.After the interior solid electrolyte layer 12,14,16 is sintered
Thickness respectively be preferably 50-1000 μm, especially 100-700 μm, particularly preferably 200-500 μm.
Also to optimize the side of sensor ceramics corresponding to the above method, i.e., the non-shape in stacked interior solid electrolyte layer
Into above and below, but the front selected from the stack, the back side, those faces of at least one side in the face of left and right are formed, can
Above the stack of the interior solid electrolyte layer and after the first and/or second outer layer of following application, before or during and
Separated before the sensor element blank is sintered by shearing, punching press or the like or be separated into by internal layer and outer layer and appoint
The discrete component that the electrode of choosing is formed.Then the internal layer side not yet covered during the first printing by outer layer also may be used
Handled by suitable method with the thickener containing yittrium oxide, and apply another outer layer in the free side.Such as this can pass through
So-called stamped method is carried out.Then it is sintered again.
Corresponding oxidation yttrium content in the sensor element surface or outer layer for example can be by means of SEM
Method (REM) and Formula X-spectroscopic methodology can be dissipated（EDX）Measure.Thus a kind of quality control can be realized, with determine in outer layer whether
It is enough to be formed cube or tetragonal zirconium dioxide.
It should be understood that, it is emphasized that all features disclosed in specification and/or claim for original disclosure and
It should regard single and separate as to limit invention claimed, and in embodiment and/or claim
In combinations of features it is unrelated.To be well established that, for original disclosure and in order to limit invention claimed, each list
All range datas or grouped data of position show each possible median or subgroup value of constituent parts, especially also serve as model
Enclose the limit value of data.
Claims (11)
1. prepare at least one characteristic of the gas of the temperature for detecting gas componant and gas in air chamber in gas
Sensor element（10）Method, wherein the sensor element is the plane λ probes with layer structure, this method includes
The following steps：
- interior solid electrolyte layer (12,14,16) of at least one layer containing the zirconium dioxide by stabilized with yttrium oxide is provided,
- apply at least one layer outer layer made of containing Yttrium oxide material on the interior solid electrolyte layer (12,14,16)
(18,20), the wherein outer layer (18,20) than the yittrium oxide of interior solid electrolyte layer (12,14,16) containing higher amount, and
- the interior solid electrolyte layer (12,14,16) and outer layer (18,20) are sintered jointly,
This method also comprises the following steps：
- prepared component is separated into two or more elements after outer layer is applied, and
- another outer layer is applied at least one side of the element after described separate.
2. the method for claim 1 wherein apply outer layer (18,20) by means of at least one printing method.
The thickness after 3. the method for claim 1 or 2, wherein outer layer (18,20) are sintered is 1 μm -100 μm.
4. the method for claim 1 or 2, wherein outer layer (18,20) include zirconium dioxide.
5. the method for claim 1 or 2, wherein outer layer (18,20) include the thickener containing zirconium dioxide before sintering.
6. the method for claim 1 or 2, the wherein yttria levels of outer layer (18,20) after sintering are 8.0-20.0 weights
Measure %.
7. the method for claim 1 or 2, the wherein yttria levels of outer layer (18,20) after sintering are at least 40 weight %.
8. the method for claim 1 or 2, wherein at least two outer layers (18,20) are provided, so that solid electrolytic at least one layer
Matter layer (12,14,16) is at least partially embedded between outer layer (18,20).
9. the method for claim 1 or 2, its China and foreign countries' solid electrolyte layer (18,20) completely or at least partially cover in solid electricity
Solve matter layer (12,14,16).
10. the method for claim 1 or 2, wherein applying at least one electrode (22,24) on the outside of outer layer (18,20)
And/or at least one contact conductor.
11. the sensing for being used to detect at least one characteristic of gas in air chamber that can be prepared by one of claim 1-10 method
Device element (10).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011017711A DE102011017711A1 (en) | 2011-04-28 | 2011-04-28 | Method for manufacturing sensor element for detecting temperature and oxygen concentration in exhaust gas of combustion engine, involves performing common sintering of electrolyte layers and exterior layers on electrolyte layers |
| DE102011017711.6 | 2011-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102759555A CN102759555A (en) | 2012-10-31 |
| CN102759555B true CN102759555B (en) | 2017-11-14 |
Family
ID=47007563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210127449.5A Expired - Fee Related CN102759555B (en) | 2011-04-28 | 2012-04-27 | The sensor element of gas characteristic in air chamber is surveyed in detection |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102759555B (en) |
| DE (1) | DE102011017711A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014195111A1 (en) | 2013-06-04 | 2014-12-11 | Siemens Aktiengesellschaft | Storage structure |
| JP6418120B2 (en) * | 2015-02-12 | 2018-11-07 | 株式会社デンソー | Gas sensor |
| ES2899404T3 (en) * | 2016-08-31 | 2022-03-11 | Shell Int Research | Process for preparing a methane oxidation catalyst |
| WO2018041632A1 (en) | 2016-08-31 | 2018-03-08 | Shell Internationale Research Maatschappij B.V. | Methane oxidation catalyst, process to prepare the same and method of using the same |
| JP6897503B2 (en) * | 2017-11-03 | 2021-06-30 | 株式会社デンソー | Solid electrolyte, its manufacturing method, gas sensor |
| DE102019200405A1 (en) * | 2019-01-15 | 2020-07-16 | Robert Bosch Gmbh | Exhaust gas sensor |
| WO2020181464A1 (en) * | 2019-03-11 | 2020-09-17 | 京东方科技集团股份有限公司 | Micro-channel and preparation method and operating method therefor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6514397B2 (en) * | 2000-12-21 | 2003-02-04 | Delphi Technologies, Inc. | Gas sensor |
| DE10337573B4 (en) | 2003-08-14 | 2006-02-09 | Robert Bosch Gmbh | sensor element |
| DE102007025234A1 (en) * | 2007-05-31 | 2008-12-04 | Robert Bosch Gmbh | Sensor element for determining a physical property of a measurement gas |
-
2011
- 2011-04-28 DE DE102011017711A patent/DE102011017711A1/en not_active Withdrawn
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2012
- 2012-04-27 CN CN201210127449.5A patent/CN102759555B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE102011017711A1 (en) | 2012-10-31 |
| CN102759555A (en) | 2012-10-31 |
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