CN105092674A - A method of manufacturing a sensor element for detecting at least one property of a sample gas in a gas measurement space - Google Patents
A method of manufacturing a sensor element for detecting at least one property of a sample gas in a gas measurement space Download PDFInfo
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- 238000005259 measurement Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title abstract 2
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- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910020068 MgAl Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 3
- 229910002367 SrTiO Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims 1
- 238000010422 painting Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 59
- 239000010410 layer Substances 0.000 description 59
- 230000035939 shock Effects 0.000 description 33
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000011796 hollow space material Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 238000002294 plasma sputter deposition Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- -1 porosity Substances 0.000 description 2
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- 238000005086 pumping Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
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- 235000019698 starch Nutrition 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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Classifications
-
- G—PHYSICS
- 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
- G01N27/4073—Composition or fabrication of the solid electrolyte
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
The invention relates to a method for producing a sensor element (10) for detecting at least one property of gas in a measurement gas space. The sensor element (10) can be used to measure the content and temperature of a gas component. The method comprises the following steps: preparing solid electrolyte (12) comprising at least one functional element (14,16,18), preparing suspension comprising at least ceramic filler and at least one raw material parent body, and painting at least one first layer of suspension on the solid electrolyte (12) in sections.
Description
Technical field
By the known many sensor elements of prior art and the method at least one characteristic of detecting the measurement gas inside measurement gas space.The arbitrary physics of measurement gas and/or the measurement gas characteristic of chemistry can be related in principle at this, wherein can detect one or more characteristic.Especially based on gas composition content that is qualitative and/or that detect measurement gas quantitatively, the present invention is described below, especially to detect based on the oxygen content inside measurement gas.Oxygen content such as can detect with the form of partial pressure and/or with the form of number percent.But alternative or additional other characteristic that also can detect measurement gas, such as temperature.
Background technology
Such as this sensor element such as can be made up of so-called oxygen level sensor (exhaust gas oxygensensor), such as, by KonradReif (Hrsg.): the sensor in motor vehicle, and the known this sensor of 2010 first published 160-165 page.By broadband-oxygen level sensor, such as can determine oxygen concentration in waste gas on a large scale particularly by the broadband-oxygen level sensor of plane and infer air-fuel ratio in a combustion chamber thus.This air-fuel ratio of air number λ-description.
By the sensor element of prior art especially known ceramics, it is to use based on the solid determined by electrolyte properties, namely based on the ion conductor characteristic of this solid.These solids especially can be the solid electrolytes of pottery, such as zirconium dioxide (ZrO
2), the zirconium dioxide (ScSZ) of especially yttria stabilized zirconia (YSZ) and scandium doping, they can containing a small amount of alundum (Al2O3) (Al
2o
3) and/or silicon dioxide (SiO
2) add.
This sensor element is proposed to the functional requirement increased.The quick operation characteristic of oxygen level sensor after engine start is especially significant.This characteristic is subject to the impact of two aspects substantially.First aspect relates to oxygen level sensor and is heated to rapidly its running temperature, and it is usually located at more than 600 DEG C, and this can be realized by the scope of correspondingly laying heating element or reduce to heat.Relate to the soundness resisted due to the thermal shock of run duration water hammer on the other hand.Described thermal shock based on, the determining time temperature in gas outlet later for engine start is positioned at below the dew point of water, makes the water vapor condensation in gas outlet produced when fuel combustion thus.Cause thus forming water droplet in gas outlet.The oxygen level sensor pottery of heating by occurring that water droplet sustains damage due to the fracture in thermal stress or sensor pottery, or even can damage.
Therefore develop oxygen level sensor, they have the ceramic protective layer of porous in its surface, and it is also referred to as Thermo-Shock-Protection-Schicht(TSP) or thermal shock protection layer.This protective seam is responsible for, and makes the droplet size distribution that occurs on oxygen level sensor on large area and reduces the localized temperature gradients that occurs inside solid electrolyte or sensor pottery.These oxygen level sensors also tolerate certain condensing drip size in heated condition, and are not damaged.Protective seam generally with the coating of additional processing step on the sensor element.Different materials, such as alundum (Al2O3) or spinel (MgAl can be used to this
2o
4) and paint-on technique, such as sputtering or impregnation technology.Such as known, utilize atmospheric plasma to sputter thermal shock protection layer that (APS) applies uniform thickness, that be made up of porous alumina.Melted the particle added by this thermal technology cladding process, and accelerate on the surface at solid electrolyte, apply thermal shock protection layer on the surface at whole solid electrolyte thus.TSP enters into inside the solid electrolyte of the sensor element be made up of zirconium dioxide at least in part due to the anti-sealing of its limited perviousness, and the cooling of restricted passage heat transfer.
Although by prior art known, for the method for the sensor element processing oxygen level sensor, there is many advantages, they still have improvement potentiality.In order to not affect the function of sensor element, simultaneously reliably from water droplet, such as from the waste gas streams of explosive motor, the thickness of thermal shock protection layer, porosity, pore size, material and possible sequence and thickness must be selected best.Goal conflicts different in above-mentioned two affecting parameters is obtained when optimizing sensor element at this.Such as, thick thermal shock protection layer reliably prevents water hammer, but adversely affects the heat characteristic of sensor element as additional material.In addition because heat ageing changes the porosity of opening wide of plasma sputtering layer, the function of oxygen level sensor is affected thus.
Summary of the invention
Therefore, advise a kind of method for processed sensor element, it is for detecting at least one characteristic of measurement gas in measurement space, and a sensor element made according to the method, they avoid the defect of known method and sensor element at least to a great extent, and the firmness that wherein can improve relative to thermal shock, and not too improve thermal mass.
Step is below comprised, preferably with described order according to method of the present invention:
-prepare at least one solid electrolyte with at least one function element,
-preparation has the suspension of parent (precursor) of the filling material of at least one pottery and at least one raw material, such as ceramic raw material, and
-at least piecewise on solid electrolyte, apply at least one ground floor, if desired multilayer suspension thing.
Described suspension can utilize dipping and/or sputtering to be coated on solid electrolyte.Described suspension can have the pore former be made up of at least one Organic Ingredients.This method can also be included at least one heat treatment step of the later solid electrolyte of coating suspension.Described heat treatment step can perform with the temperature of 100 DEG C to 200 DEG C, such as 150 DEG C.This method can also be included at least one annealing steps of the later solid electrolyte of coating suspension.Described annealing steps can perform with the temperature of 500 DEG C to 1500 DEG C, preferably with 1000 DEG C to 1200 DEG C.Described sensor element can also comprise the heating element for heating solid electrolyte, and wherein said heating element performs annealing steps.The parent of described ceramic raw material is preferably by SiO
2, especially silicon dioxide (colloid silica gel) composition, alternatively by Al
2o
3, especially boehmite composition.
As ceramic raw material, especially Al that filling material uses
2o
3, ZrO
2, MgO, TiO
2, MgAl
2o
4, Al
2tiO
5, Mg (SiO
4), SrTiO
3, and/or CeO
2can with mean diameter 1 μm to 50 μm and preferably the particle of about 5 μm to 20 μm present in suspension, such as, with the mean diameter of 10 μm.Preferred described filling material is made up of particle, and the distribution of its diameter is rather narrow, and the standard deviation of such as particle size distribution is less than half mean diameter.Particularly relate to unimodal diameter distribution.
Described suspension can have at least one pore former.At least piecewise applies second layer suspension on the first layer, and wherein the second layer can have the porosity different from ground floor, pore size and different raw materials after annealing steps.Described suspension can coating after sensor element sintering.Solid electrolyte can have side surface and lateral edges, and wherein said suspension applies like this, makes ground floor thicker than on the side surface in lateral edges.Repeatedly can perform this method, for successively applying multiple layer and/or producing porosity gradient.Such as described suspension can repeatedly as layer coating and drying.Then jointly annealed layer.Described suspension alternatively can be made repeatedly to apply as layer and anneal.
Within the scope of the invention, be interpreted as an object or object about solid electrolyte, there is the electrolyte characteristics of at least segmentation, namely there is ion conductor characteristic.Especially can completely or piecewise relate to pottery solid electrolyte.This also comprises the raw material of solid electrolyte, and is therefore made up of so-called setation base or grey blank, and they only have and just become solid electrolyte after sintering.
Be interpreted as an element within the scope of the invention about function element, it is selected by element group below: electrode, conductor belt, diffusion barrier, diffusion gap, reference gas passage, heating element, Nai Site battery and pump battery.Especially be interpreted as those elements to this, they meet the basic chemistry of the sensor element of oxygen content probe and/or physics and/or electricity and/or electrochemical function.
Be interpreted as coating suspension within the scope of the invention about piecewise coating suspension, wherein the outside surface of solid electrolyte or surface or the layer that applies suspension are thereon hidden at least in part by colloidal sol, and need not hide it completely.Therefore, it is possible to only apply suspension in the determination segmentation of solid electrolyte or sensor element, such as only on the side surface determined or lateral edges, or only inside the determination portion position of solid electrolyte, this position is such as observed and is positioned at more inside measurement gas space than other position of solid electrolyte on the longitudinal extent direction of sensor element.
The hollow space volume of raw material or raw mixture and the ratio of cumulative volume is interpreted as within the scope of the invention, as nondimensional measurement parameter about porosity.This measurement parameter especially can provide with percentage.Be interpreted as that those each other and be in the ratio of hollow space volume on total hollow space volume of the hollow space be connected with surrounding air at this about the porosity of opening wide.Be interpreted as at least 20% about the porosity determined at this, preferably at least 30% and more preferably at least 40% porosity, such as 45%.At this because technical reason does not comprise the porosity of more than 80%, because the stability of this porosity possibility lower layer.
Be interpreted as various material within the scope of the invention about pore former, it is applicable to, by applying the ceramic layer porous of suspension and lighter.These materials are such as sawdust and cork end, starch, coal dust, polymer drops or polymer fiber, especially staple fibre.Especially be interpreted as carbon-based material to this, they burn when so-called annealing, leave hollow space simultaneously.
Basic thought of the present invention is, utilize sol-gel technology pottery, the sensor element that sinters if desired applies especially uniform, homogeneous, micropore, thin ceramic layer.The SiO of very particulate is devoted to have as colloidal sol
2or selectively Al
2o
3the liquation of prime, parent (precursor).In order to apply thicker thickness, and in order to ensure for the required porosity of gas exchanges (sensor function) and thermomechanical firmness, colloidal sol is added to the filling material of pottery, such as the oxide of pottery, especially Al
2o
3, ZrO
2, MgO, TiO
2, MgAl
2o
4, Al
2tiO
5, Mg (SiO
4), SrTiO
3, and/or CeO
2, and add organic pore former if desired.The average particle size particle size of filling material be such as 1 μm to 50 μm and preferably about 10 μm.
After coating processes, such as dipping or sputtering, heat-treat with about 100 DEG C to 200 DEG C, it is for drying solution, such as evaporating solvent, such as water.In thermal technology technique then, make layer with 500 DEG C of annealing temperatures to 1500 DEG C, preferably 1000 DEG C to 1200 DEG C.Aggregate into long-chain at this parent and form the complex compound around ceramic fillers.
After thermal technology technique, be devoted to have the ceramic layer of especially 30% to 50% porosity.In this ceramic layer, the particle of filling material presents with the film/base body of the parent of polymerization.Can be the SiO of amorphous/crystal at this according to raw material
2or the Al of fine crystals
2o
3.By compatibly selecting the kind of suspension, filler particle and additional pore former, such as sawdust and cork end, starch, coal dust, polymer drops or polymer fiber, especially staple fibre can adjust porosity.Confining gas access aperture can be saved, such as, by wax, ethylene glycol or water by adjustment viscosity and technological parameter.
Ceramic thermal shock protection layer segment or fully protection sensor element are from water hammer (water slug).In addition can change thickness in large scope thus: thinner thermal shock protection layer has less thermal capacity, and detecting function faster can be realized with identical porosity, the dynamic specification namely improved.In addition can by selecting two or more different suspension with the thermal shock characteristic of the best coating gradient layer according to method of the present invention.The ground floor such as applied on the sensor element can have higher porosity, that is, the capacity of heat transmission of reduction, and then the second thicker layer has higher thermal capacity, and it does not allow water to enter.By sensor element from heating because small thickness can realize the heating of thermal shock protection layer.Certainly, alternatively, or additionally furnaceman's skill can be used in order to heat.When using as bottom before thermal technology cladding process, the temperature load of sensor element reduces during coating.This causes the serviceable life of the increase of the sensor element of oxygen content probe.
According to the alternative approach that method of the present invention is for applying thermal shock protection layer on the sensor element.By using dipping or collective lens technique not to produce mechanical damage, as issuable when thermal technology cladding process.Uniformly, homogeneous, micropore, thin ceramic layer provides thermal shock protection wholly or in part, has Billy by the less thermal capacity of atmospheric plasma sputtering coating simultaneously, that is, extinguish less.This is also applicable to, and time a sol-gel layer providing unit divides protection, and need the protection tube of oxygen content probe additionally to retrofit, it causes protecting completely in compound.
Can be improved further in thermal shock protection and sensor function by measure below according to the thermal shock protection layer of the present invention's coating.Measure is such as heating process by optimizing coating and particularly by the large crackle reducing heat rate and avoid macroscopically.Another measure is, improves porosity by the kind and content changing colloidal sol, micropore formation and ceramic particle.Another measure is the undried suspension by removing on heating and induction side, and be on purpose coated in lateral edges and realize the higher thickness in lateral edges, it can by purpose adjusting the rheological properties of suspension or passing through repeatedly to apply realization.Another measure is that lateral edges passes through to change the grinding of sensor element seamed edge, such as chamfering justifies grinding or repeatedly multiaspect grinding realizes the higher thickness in lateral edges by infiltrating better.
Accompanying drawing explanation
By below, the description of preferred embodiment that shows in the accompanying drawings provides other details of the present invention and feature.Accompanying drawing illustrates:
Fig. 1 according to the longitudinal diagram of sensor element of the present invention,
Fig. 2 A-2B sensor element is at the different partial enlarged drawing at gas access holes position.
Embodiment
Sensor element 10 in FIG may be used for the physics of confirmatory measurement gas and/or the characteristic of chemistry, wherein can detect one or more characteristics.Especially based on gas composition that is qualitative and/or that detect gas quantitatively, describe the present invention below, especially detect based on the oxygen content in measurement gas.Such as oxygen content can be detected with the form of partial pressure and/or percentile form.But also can detect the gas composition of other form in principle, such as oxides of nitrogen, hydrocarbon and/or hydrogen.But also can detect other characteristic of measurement gas alternatively or additionally, such as temperature or pressure.The present invention especially can use in automotive field, thus the gas outlet of measurement gas space especially explosive motor, and measurement gas especially waste gas.
Sensor element 10 has solid electrolyte 12 as the ingredient of the example of the oxygen content probe (lambda seeker) of plane.Solid electrolyte 12 can be made up of multiple solid electrolyte layer, or comprises multiple solid state electrode layer.Electrolyte 12 especially can be ceramic solid electrolyte 12, such as zirconium dioxide (ZrO
2), the zirconium dioxide (ScSZ) of especially yttria stabilized zirconia (YSZ) and scandium doping, it can containing a small amount of alundum (Al2O3) (Al
2o
3) and/or silicon dioxide (SiO
2) add.Solid electrolyte 12 has at least one function element.Solid electrolyte 12 such as has the first electrode 14, second electrode 16 and heating element 18 in the embodiment shown.First electrode 14 is arranged on the surface 20 of solid electrolyte 12.It is inner that second electrode 16 is arranged on solid electrolyte 12.
In addition, sensor element 10 has gas access path 22.Gas access path 22 comprises gas access holes 24.Not only the first electrode 14, and the second electrode 16 such as surrounds gas access holes 24 circlewise.Such as the second electrode 16 is arranged on inside the electrode hollow space that is not shown specifically, and it is connected with gas access holes 24 by passage.Such as arrange diffusion barrier in the channel, its reduces or even prevents gas to flow to inside electrode hollow space from measurement gas space again and only can realize diffusion.Therefore by the gas-loaded of the measurement gas space since diffusion barrier second electrode 16.First electrode 14 and the second electrode 16 are interconnected by solid electrolyte 12 and form pump battery 26.The limit stream of pump battery 26 can be adjusted by diffusion barrier.
On the extended line of the bearing of trend of gas access holes 24, heating element 18 is arranged on inside solid electrolyte 12.Heating element 18 for heat pump battery 26, especially to a temperature, such as 750 DEG C to 900 DEG C, can directing ion, especially oxygen ion with this temperature pump battery 26.Heating element 18 comprises heating zone 28 and is connected wire 30.Such as, heating element 18 is made up of stratie and utilizes connection wire 30 to be connected with voltage source.
In addition solid electrolyte 12 can comprise the reference gas passage be not shown specifically.Reference gas passage can be made up of the baseline air passage of macroscopic view, and air occurs with known characteristic, such as oxygen partial pressure wherein.Reference gas passage can be selected to be made up of the passage of non-macroscopic view, but by pumping benchmark, namely, be made up of artificial benchmark.3rd electrode is such as set inside electrode hollow space.Second electrode 16 is such as positioned at the 3rd electrode opposite.4th electrode can be arranged on inside reference gas passage, or on isolation layer, be arranged on solid electrolyte 12 when the benchmark of pumping inner.3rd electrode, the 4th electrode and part solid electrolyte 12 between the two electrodes form electrochemical battery, such as Nai Site battery (Nernstzelle).Utilize pump battery 26 such as by pump battery 26 adjustment pump stream like this, existence condition λ=1 or other known composition inside electrode hollow space can be made.This composition still by Nai Site battery detecting, by measuring the how nernst voltage between the 3rd electrode and the 4th electrode.Composition inside electrode hollow space can be inferred according to the how nernst voltage recorded and change pump stream if desired, for regularization condition λ=1.The composition of waste gas can be inferred according to pump stream.
Preferably inside solid electrolyte 12, be provided with selectable Nai Site battery, for measuring the corresponding remaining oxygen content in burnt gas, for the ratio of combustion air and fuel can be regulated thus, thus for burning away, make neither to produce fuel unnecessary, also do not produce air unnecessary.Because temperature is also far below 300 DEG C in cold engine, therefore oxygen content probe and thus governor motion do not work when cold start-up or only work very slow.Therefore the solid electrolyte 12 of sensor element 10 is preferably equipped with electrical heating elements 18, makes probe take required temperature fast to thus after cold start-up.Thus can, ensured the operation of optimum discharge in the engine heat engine operation phase.Because fully understand the operation of oxygen content probe, such as, by above-mentioned prior art, therefore save and describe principle of work in detail.
Sensor element 10 also comprises thermal shock protection layer 32.Thermal shock protection layer 32 can be made up of stupalith at least in part.The such as aluminium oxide of thermal shock protection layer 32 containing porous.Such as thermal shock protection layer 32 has the porosity of 50%.Solid electrolyte 12 along the longitudinal length direction extends to inside measurement gas space, and the view with reference to Fig. 1 extends from left to right.Therefore sensor element 10 comprises the end 34 of connection side, and it is positioned at left side and the end 36 of measurement gas space side with reference to the view of Fig. 1, and it is positioned at right side with reference to the view of Fig. 1.Shown in FIG, pump battery 26 is positioned near the end 36 of measurement gas space side.Solid electrolyte 12 also comprises side surface 38, and one of them is surface 20, and also comprises end face and lateral edges 40, and they make side surface 38 be interconnected, and forms the transition between side surface 38 in other words.Lateral edges 40 can be formed on rounding, right angle or chamfering ground.Thermal shock protection layer 32 at least piecewise is coated on solid electrolyte 12.Such as thermal shock protection layer 32 is only coated near the end 36 of measurement gas space side with 1/3rd of longitudinal length dimension, and hides all side surfaces there.Therefore with reference to the view of Fig. 1, thermal shock protection layer 32 has the xsect of U-shaped.Especially thermal shock protection layer 32 hides the first electrode 14, wherein can be provided with the ceramic electrode protective seam of porous between the first electrode 14 and thermal shock protection layer 32.In a modification preferably, gas access holes 24 is not closed by thermal shock protection layer 32, but freely leads to measurement gas space.Opposite side confining gas access aperture or even can be desirably in when enough porositys.Thermal shock protection layer 32 also can be selected to hide all side surfaces 38 completely, or only hides the first electrode 14 and gas access holes 24.The accurate location that thermal shock protection layer 32 is set can be selected according to each self-application of sensor element 10 or installation site.
Sensor element 10 is made as follows according to the present invention.First preparation has the solid electrolyte 12 of above-mentioned function element 14,16 and 18.Such as, solid electrolyte 12 is made up of multiple solid electrolyte layer, and they and above-mentioned function element are printed in known manner, that is, have the first electrode 14, second electrode 16 and heating element 18.Known technique is such as so-called thin-film technique or multilayer technology.Then jointly solid electrolyte 12 and the first electrode 14, second electrode 16 and heating element 18 is sintered.Such as can with 1350 DEG C to 1550 DEG C, especially sinter with the temperature of 1385 DEG C, wherein temperature such as 5.5 hours keep constant.This structure of planar sensor element 10 is fully understood by above-mentioned prior art, therefore explains no longer in detail.
In addition preparation has the suspension of at least one ceramic fillers and at least one raw material parent.Parent is preferably by SiO
2, alternatively by Al
2o
3, especially boehmite composition.Parent preferably presents in granular form, and its diameter is positioned at 5nm to 50nm.The content of parent in suspension is such as 10-20 mass percent.The content of ceramic fillers in suspension is such as 20-40 percentage by weight.
Fig. 2 A and 2B is the different partial enlarged drawing of sensor element 10 at gas access holes 24 position.Especially Fig. 2 A and 2B is the vertical view applying the later sensor element 10 of suspension.As known in Figures 2 A and 2 B and seeing, can be saved by such as wax, ethylene glycol or water confining gas access aperture during solid electrolyte 2 is impregnated into inside suspension by adjustment viscosity and technological parameter.If also will prevent suspension from clamp-oning when larger-diameter gas access holes 24, and ensure the thermal shock firmness of gas access holes 24, then there is possibility, before coating suspension is in gas access holes 24, utilizes the ceramic layer of serigraphy or mould printing coating porous and then sinters solid electrolyte 12.Then coating colloidal sol, wherein can perform dipping/sputtering technology like this, avoids the gas access holes 24 that closed porous hides.The such as external pump electrode of the first electrode 14, its formation pump battery 28, by electrode protecting layer or by utilizing porous ceramic layer that silk screen or mould printing apply, sintering to hide.By the technical process control that is applicable to and the viscosity adjusting suspension can avoid infiltrating electrode protecting layer by suspension and infiltrating the first electrode 14 thus.Utilize pump flow measurement can get rid of closing of diffusion barrier after completing sensor element 10.
The heat treatment step of solid electrolyte 12 is connected after coating suspension.With 100 DEG C to 200 DEG C and preferably 140 DEG C of temperature to 160 DEG C, such as 150 DEG C perform heat treatment step.
Then, after coating suspension, perform at least one annealing steps of solid electrolyte 12.Annealing steps can carry out at the temperature of at least 500 DEG C.Annealing steps can be performed by outside device, or is performed by heating element 18.Such as on heating element 18, apply voltage, heat this element thus.Such as silicon dioxide (silica gel) polymerization is realized by water-splitting by annealing steps.It is favourable for utilizing heating element 18 to perform annealing steps, because ensure the better degassed of the oxygenated products of organic component thus.Burnt by annealing steps pore former, thus in the ceramic layer formed by colloidal sol, it is thermal shock protection layer 32, forms the porosity determined, the porosity of such as 50%.Ensure thus, only slightly change gas phase process compared with common sensor element, such as, spread.Porosity can by compatibly selecting the kind of suspension, ceramic filler composition granule and pore former to adjust.To emphasize especially, also can realize the porosity of higher such as 50%, 60% or 70% thus.Apply suspension like this at this, consequent thermal shock protection layer 32 has above-mentioned thickness after annealing steps, such as the thickness of 400 μm.If perform annealing steps with the rate of heat addition reduced, that is, improve temperature more lentamente, can avoid or reduce the crackle in the thermal shock protection layer of pottery.
Certainly, above-mentioned steps can repeat.Such as the coating of second layer suspension on the first layer, and wherein ground floor has the porosity higher than the second layer after annealing steps.Such as can form thermal shock protection layer by multilayer thus, they have porosity gradient.Such as repetitive coatings layer, then thermal treatment.If apply the layer of all expectations, they are annealed jointly.Selectively can perform annealing steps after each thermal treatment layer.
Claims (15)
1. for a method for processed sensor element (10), it is for detecting at least one characteristic of the gas in measurement gas space, is particularly useful for verifying the content of gas composition in measurement gas or the temperature of measurement gas, comprises step:
-prepare at least one solid electrolyte (12) with at least one function element (14,16,18),
-preparation has the filling material of at least one pottery and the suspension of at least one raw material parent, and
-at least piecewise at least one ground floor suspension of coating on solid electrolyte (12).
2. the method as described in the claims, wherein, described suspension utilizes dipping and/or sprays and is coated on solid electrolyte (12).
3. the method according to any one of the preceding claims, wherein, described suspension has SiO
2as parent and have ceramic oxide, especially Al
2o
3, ZrO
2, MgO, TiO
2, MgAl
2o
4, Al
2tiO
5, Mg (SiO
4), SrTiO
3, and/or CeO
2as ceramic fillers.
4. the method according to any one of the preceding claims, wherein, described method is also included at least one heat treatment step of the later solid electrolyte (12) of coating suspension.
5. the method as described in the claims, wherein, performs described heat treatment step at 100 DEG C to during 200 DEG C of temperature.
6. the method according to any one of the preceding claims, wherein, described method is also included at least one annealing steps of the later solid electrolyte (12) of coating suspension.
7. the method as described in the claims, wherein, 500 DEG C to 1500 DEG C of temperature time, preferably at 1000 DEG C to 1200 DEG C time perform described annealing steps.
8. the method according to any one of the preceding claims, wherein, described solid electrolyte (12) also comprises the heating element (18) for heating solid electrolyte (12), and wherein said heating element (18) performs annealing steps.
9. the method according to any one of the preceding claims, wherein, described parent presents in granular form, and its diameter is positioned at the scope of 5nm to 50nm.
10. the method according to any one of the preceding claims, wherein, described ceramic fillers presents with particle in suspension, has 1 μm of to 50 μm and preferably diameter of about 10 μm.
11. the method according to any one of the preceding claims, wherein, described suspension has at least one pore former.
12. the method according to any one of the preceding claims, wherein, at least piecewise applies second layer suspension on the first layer, and wherein ground floor has the porosity higher than the second layer after annealing steps.
13. the method according to any one of the preceding claims, wherein, apply suspension at sintering solid electrolyte (12) later.
14. the method according to any one of the preceding claims, wherein, described solid electrolyte (12) has side surface (38) and lateral edges (40), and wherein said suspension applies like this, makes ground floor upper than thicker on side surface (38) in lateral edges (40).
15. the method according to any one of the preceding claims, wherein, in order to successively apply multiple layer and/or repeat described method in order to the gradient producing porosity.
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| DE102014208832.1A DE102014208832A1 (en) | 2014-05-12 | 2014-05-12 | Method for producing a sensor element for detecting at least one property of a measuring gas in a measuring gas space |
| DE102014208832.1 | 2014-05-12 |
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|---|---|---|---|---|
| CN107159507A (en) * | 2017-05-27 | 2017-09-15 | 广州华凌制冷设备有限公司 | Senser element protective layer coats frock and technique, senser element and air conditioner |
| CN113552201A (en) * | 2021-09-01 | 2021-10-26 | 浙江百岸科技有限公司 | Nitrogen-oxygen sensor chip with protective cap coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102016212349A1 (en) * | 2016-07-06 | 2017-08-24 | Continental Automotive Gmbh | Method for operating an oxygen sensor and oxygen sensor for determining an oxygen concentration in an intake tract |
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| DE3017947A1 (en) * | 1980-05-10 | 1981-11-12 | Bosch Gmbh Robert | ELECTROCHEMICAL SENSOR FOR DETERMINING THE OXYGEN CONTENT IN GAS AND METHOD FOR PRODUCING SENSOR ELEMENTS FOR SUCH SENSOR |
| CN1441245A (en) * | 2002-02-28 | 2003-09-10 | 日本特殊陶业株式会社 | Prismatic ceramic heater, prismatic gas sensitive element and its producing method |
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| US4199425A (en) * | 1978-11-30 | 1980-04-22 | General Motors Corporation | Solid electrolyte exhaust gas sensor with increased NOx sensitivity |
| DE3017947A1 (en) * | 1980-05-10 | 1981-11-12 | Bosch Gmbh Robert | ELECTROCHEMICAL SENSOR FOR DETERMINING THE OXYGEN CONTENT IN GAS AND METHOD FOR PRODUCING SENSOR ELEMENTS FOR SUCH SENSOR |
| CN1441245A (en) * | 2002-02-28 | 2003-09-10 | 日本特殊陶业株式会社 | Prismatic ceramic heater, prismatic gas sensitive element and its producing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107159507A (en) * | 2017-05-27 | 2017-09-15 | 广州华凌制冷设备有限公司 | Senser element protective layer coats frock and technique, senser element and air conditioner |
| CN107159507B (en) * | 2017-05-27 | 2020-08-14 | 广州华凌制冷设备有限公司 | Sensor device protective layer coating tool and process, sensor device and air conditioner |
| CN113552201A (en) * | 2021-09-01 | 2021-10-26 | 浙江百岸科技有限公司 | Nitrogen-oxygen sensor chip with protective cap coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105092674B (en) | 2020-09-08 |
| DE102014208832A1 (en) | 2015-11-12 |
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