CN103765203B - The manufacturing method of sensor element - Google Patents
The manufacturing method of sensor element Download PDFInfo
- Publication number
- CN103765203B CN103765203B CN201280042715.2A CN201280042715A CN103765203B CN 103765203 B CN103765203 B CN 103765203B CN 201280042715 A CN201280042715 A CN 201280042715A CN 103765203 B CN103765203 B CN 103765203B
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- heating element
- insulating layer
- method described
- sensor element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 155
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000000523 sample Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims description 37
- 238000005245 sintering Methods 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 230000001680 brushing effect Effects 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000002241 glass-ceramic Substances 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims 1
- 238000005259 measurement Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 93
- 239000007789 gas Substances 0.000 description 30
- 239000000919 ceramic Substances 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 230000005611 electricity Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- 239000000454 talc Substances 0.000 description 7
- 235000012222 talc Nutrition 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 241000365446 Cordierites Species 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229910017083 AlN Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012671 ceramic insulating material Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001522319 Chloris chloris Species 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000126608 Ruta angustifolia Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
-
- 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
- G01N27/4067—Means for heating or controlling the temperature of the solid electrolyte
Abstract
The present invention relates to a kind of sensor elements（10）Manufacturing method, the sensor element for detect be located at measurement space in gas at least one performance, in particular for the gas componant or the temperature of gas in probe gas.It the described method comprises the following steps：The solid electrolyte being sintered is provided（12）, in the solid electrolyte（12）Thereon or middle arrangement heating element（18）It is heat-treated the solid electrolyte together（12）And heating element（18）.
Description
Background technology
It is first for obtaining the multiple sensors of at least one performance of gas in measurement gas space from known in the art
Part and method.Here, the performance of gas refers to any physical and/or chemical property of gas, one of which or more in principle
Kind performance can be acquired.Hereinafter, the quality and/or number of explanation of the invention more particularly to the gas componant of acquisition gas
Amount, and in particular to obtain oxygen content in gas.Oxygen content may, for example, be the form of partial pressure and/or the shape of percentage composition
Formula.However, alternatively, or additionally, other performances of gas can also be obtained.
For example, this sensor element may be designed as so-called lambda probe, such as from Konrad Reif（Hrsg.）：Sensoren
Im kraftfahrzeug, 2010 the 1st edition, known to the 160-165 pages.It is wide in particular with plane using broadband lambda probe
It for example can determine the oxygen concentration in big zone gas with lambda probe, thus derive the air-fuel ratio in combustion chamber, this
A air-fuel ratio is with representing air coefficient.
From especially ceramic sensor element known in the art, the basis of the ceramic sensor element is using electrolysis
The ion transmission performance of solid known to matter performance, i.e. this solid.Particularly, these solids refer to ceramiic solid electrolyte,
Such as zirconium oxide（ZrO2）, especially yttrium stablize zirconium oxide（yttriumstabilisiertes Zirkoniumdioxid
（YSZ））And/or zirconium oxide containing scandium（scandiumdotiertes Zirkoniumdioxid(ScSZ)）, they can contain oxidation
Aluminium（Al2O3）And/or silica（SiO2）Etc. a small amount of additive.
According to the measuring principle of lambda probe, lambda probe must generally be first heated to its running temperature, because of solid electrolytic
Matter ability conduction oxonium ion when higher than 350 DEG C of temperature.In the range of the running temperature is usually located at from 600 DEG C to 900 DEG C.
Thus lambda probe usually has heating element, for heating the solid electrolyte and electrode.This heating element leads to
Often installation（Such as it bonds or presses）In soft fluffy state（Or Garuda formula state, Gr ü nlingszustand）, i.e., do not burn
In the solid electrolyte of knot state or on solid electrolyte layer.Then, the solid electrolyte and the heating being disposed thereon
Element is sintered together, to ensure the lasting reliability of heating element on the solid electrolyte.
Motorcycle is all applied widely in Asian countries.These countries have formulated apparent more strict in recent years
Laws and regulations about motor-vehicle tail-gas.This causes to increase to the demand of sensor element, is based especially on the λ of Chemical Measurement
Probe, these sensor elements are used to adjust the mixture of the internal combustion engine of these motorcycles.But to cyclecar（Such as motor
Vehicle）The requirement of lambda probe differs markedly from the requirement to the lambda probe of automobile.Particularly, the automobile-used sensor of equipment of small motor
Element must also meet at low cost, the small requirement of structure.But different components（Such as solid electrolyte, sensor body or electricity
Cable exports）Temperature capacity and automobile sensor it is at least almost equally high, this is because cyclecar is normal
Often using the engine options of low cost, this engine combustion is insufficient, thus causes working efficiency not high.Therefore, in order to
Engine is made to reach full load operating status during very long operation, sensor element will be exposed to quite high exhaust gas temperature
In degree.
It is automobile in motor vehicle, even in the situation of commerial vehicle, the lambda probe of automobile-use has bigger heating
Element, the consumption power of this heating element are also very big.But applied in the case of this lambda probe is used low resistance,
High-power heater is not suitable for cyclecar due to structure is too big, also as the reason of extra cost and be not suitable for
Effective heat dissipation of efficient heater output stage and the controller of failure.
Invention content
Therefore, the present invention provides a kind of sensor element and its manufacturing method, and the sensor element is used to obtain gas
At least one performance of gas in space, the temperature of the ingredient of gas or acquisition gas especially in probe gas, the biography
Sensor component is all more compact-sized than hitherto known automobile sensor element, is particularly suitable for cyclecar, especially two
Take turns vehicle, such as motorcycle.
The method of this sensor element of manufacture of the present invention includes the following steps, is preferably held with the order being set forth below
Row：
The solid electrolyte being sintered is provided；
On the solid electrolyte or wherein arrange heating element；With
It is heat-treated the solid electrolyte and heating element together.
The heating element can be arranged on the solid electrolyte or wherein in un-sintered state, and the heat
Processing can be sintering.The solid electrolyte can have insulating layer, and the heating element is arranged on the insulating layer, described
Heating element can apply a layer insulating or protection glaze before sintering.The coefficient of thermal expansion of the insulating layer of the solid electrolyte
It can deviate the coefficient of thermal expansion maximum 10% of the insulating layer of the heating element, preferably at most 5% and particularly preferred maximum 2%, such as
1%.The thickness of the insulating layer of the solid electrolyte can be from 2 μm to 100 μm, preferably from 5 μm to 75 μm and particularly preferably from
10 μm to 50 μm.The methods of heating element can be by pressing, winding, brushing or smearing is arranged on the solid electrolyte
Or wherein.The heating element can also be arranged on the solid electrolyte or wherein in sintering state, and the heat
Processing can be annealing.The methods of heating element can be by bonding or being mechanically connected, especially squeeze is arranged in described solid
On body electrolyte or wherein.The heating element heat safe material can be used to connect with the solid electrolyte, especially make
With glass ceramics, vitrified bonding or glass frit connection.It is used herein binding agent and connects the heating element and solid electricity
Xie Zhi, the binding agent is by brushing, smearing, pressing, splash or is used as applique and is applied on the solid electrolyte.It is described viscous
The thickness of knot agent can be from 2 μm to 300 μm, preferably from 5 μm to 250 μm and particularly preferably from 10 μm to 200 μm.
The sensor element can have length maximum value 55mm, preferred maximum 45mm and particularly preferred maximum value
40mm, width maximum value 8mm, preferred maximum 7mm and particularly preferred maximum value 6mm, such as the sensor element have length
Spend 35mm and width 4mm.The heating element has from 6 to 22 ohm of cold conditions all-in resistance and cold preferably from 8 to 20 ohm
State all-in resistance.The heating element is electrical heating elements, and in working voltage 13V, the electrical heating elements have maximum consumption
Power maximum value 5W, preferred maximum 4W and particularly preferred maximum value 3.5W, such as 4W.
" solid electrolyte " is interpreted as the object with electrolyte performance or substance namely tool within the scope of the invention
There are the object or substance of ionic conduction performance.Particularly, " solid electrolyte " refers to ceramiic solid electrolyte.Particularly, it is described
Solid electrolyte is configured to solid electrolyte layer or is made of multiple solid electrolyte layers, and " layer " within the scope of the invention should
Same substance is interpreted as from planar expansion certain altitude, it is located on another element, under or it is intermediate.
" electrode " is generally understood that a kind of following element within the scope of this invention, it contacts the solid electrolyte,
Electric current can pass vertically through the solid electrolyte and electrode.Correspondingly, the electrode includes following element, in the element
On, ion is introduced in the solid electrolyte and/or is removed from the solid electrolyte.Typically, the electrode includes
Noble metal electrode, for example, may be mounted on the solid electrolyte as metal-ceramic electrode or in other manners with institute
Solid electrolyte is stated to be connected.Typical electrode material is platinum-gold category ceramic electrode.However other can also be used expensive in principle
Metal, such as gold and/or palladium.
" heating element " is generally understood that one kind is used to add the solid electrolyte and electrode in the scope of the present invention
Heat arrives the element of operating temperature.The heating element can have lead areas and heating region.A typically at least electrode arrangement
On the solid electrolyte or wherein.The heating element herein or by solid electrolyte, solid electrolyte layer or
The additional insulating materials of person's electrode separates." heating region of heating element " is being interpreted as the heating element with the electricity
Pole equitant region on the direction towards this layer of structure.Thus, for example in the case of lambda probe is planar structure, institute
It states and overlaps along can be seen on the direction of planar structure.The heating region is normally at the solid electricity herein
In the end regions for solving matter." lead areas " be interpreted as the heating element for solid electrolyte and electrode will to be heated
Energy transmission is to the region in the heating region.
" cold-state resistance " is interpreted as the resistance surveyed at 20 DEG C within the scope of this invention.It is defined according to this, always
The cold conditions all-in resistance of the resistance of heating element is interpreted as the summation of the resistance of heating region and the resistance of lead areas.
" insulating layer " is interpreted as a kind of electric insulation layer within the scope of the invention.This insulating layer generally includes aluminium oxide
（Aluminiumoxid）, silicon carbide (SiC), aluminium nitride (AlN), magnesia (MgO), barium talcum（Bariumsteatit）, it is sliding
Stone, cordierite（Cordierit）Or other commercial common ceramic insulating materials.
" protection glaze " is interpreted as a kind of glaze containing aluminium, silicon and/or barium within the scope of the invention, for making a structure
Part is not corroded by external action, such as thermal stress, mechanism or voltage.
" coefficient of thermal expansion " is interpreted as describing within the scope of the invention the measured value of the material in temperature change therewith
The characteristic value of the material property of variation.Particularly, the coefficient of thermal expansion should be particularly understood that the relative volume expansion dV/ of solid
V（That is the ratio between volume change and initial volume）The ratio between with temperature variation dT, thus the list of coefficient of thermal expansion this characteristic value
Position is 1/K.
" heat-resisting material " is interpreted as the state of such material, i.e. material, especially polymerization state in temperature, such as
Temperature in internal-combustion engine vent-pipe does not change at a temperature of that is, up to 1000 DEG C.Particularly, even if this material is in this way
At a high temperature of also keep form stable, do not start to flow and/or melt or chemically react.Particularly, this material example
Glass ceramics, vitrified bonding or glass frit in this way.Term " melt（Fritte）" be interpreted as glass or ceramics fusing when
Intermediate products.The glass frit is for example made up of the surface melting of glass powder, and wherein glass particle is bonded in one
It rises.The powder and made material are referred to as melt.In some manufacturing methods, made material is additionally quenched,
Form porous material.Finally, easily powder is made by grinding in the material of the quenching, these powder are also referred to as melt.
" platinum metal race " refers to the general definition according to chemistry subject within the scope of the invention, the 8 to 10 of the 5th period
Race's element, i.e., light platinum ruthenium (Ru), rhodium（Rh）, palladium（Pd）And the 6th period, i.e. heavy platinum osmium（Os）, iridium（Ir）、
Platinum（Pt）.
Within the scope of the invention, a kind of method that " sintering " is interpreted as manufacture material and/workpiece, in this method
In, fine grain ceramic material is heated to the temperature less than its fusion temperature under the pressure of raising mostly.In sintering, greatly
Partial particulate shape or dusty material mixing, are then connected with each other by heating.With it is pure fusing on the contrary, herein without or at least
Not all original material all melts.Therefore, sintering is a kind of method to hold its shape.Powder batch is initially formed as it is expected
Workpiece shapes, realization method here then dried by compressing powder blank or forming.The powder must be provided herein
At least one coupling of last particle.If not providing this coupling, bonding agent must be used.It is this so-called fluffy（Grü
nling）Heat treatment and hardening when saving less than fusion temperature.The present invention technical area in, be sintered from 900 DEG C to
It is performed at a temperature of 1400 DEG C.
Within the scope of the invention, " annealing " is interpreted as the temperature that solid is heated to below its fusion temperature.This
It may take a long time to complete, such as many hours.By improving the service ability of molecular solids, make fault of construction
Reach balanced, and then improved the far and near sequence of crystal structure.The molten of adjustment crystal structure can be avoided in this way
Change and cooling means.In the technical area of the present invention, annealing can in the temperature of 1000 DEG C of highest, preferably from 400 DEG C to
It is carried out at a temperature of 800 DEG C.
The present invention is suitable for various internal combustion engines in principle, and the internal combustion engine is used to obtain engine exhaust gas at least one
At least one performance ceramic sensor element, especially at least a lambda probe and/or at least one NOx sensor and/or
At least one HC sensors, wherein the ceramic sensor element has at least one heating element, for being passed to the ceramics
Sensor component is heated.Particularly, the internal combustion engine may include Otto engine and/or Di Saier engines.Alternatively or
Additionally, the internal combustion engine further includes hybrid drive, such as with an Otto engine and/or an at least Tai Disaier
Engine and an other at least motor.
The ceramic sensor element especially lambda probe or including lambda probe.The lambda probe can for example be embodied as finger-type spy
Needle or plane lambda probe, thus it is embodied as the lambda probe for example with layer shape structure.For example, the ceramic sensor element can be real
Apply into spring probe and/or broadband lambda probe.Alternatively or additionally, the ceramic sensor element may also comprise at least one
Other kinds of ceramic sensor element, such as NOx sensor.
The ceramic sensor element may include at least one electrochemical cell." electrochemical cell " is in the scope of the present invention
Inside it is understood to include the element of at least two electrodes and at least one solid electrolyte being connected with electrode.The ceramics pass
The temperature of sensor component can for example be determined by determining the interior resistance of electrochemical cell.For having the ceramics of this special battery of energy
Sensor element, the temperature of the ceramic sensor element are for example obtained by determining the interior resistance of this special battery of the energy.
The energy supply of the heating of the ceramic sensor element and/or the heating element can utilize power supply to realize, institute
It is, for example, the accumulator in automobile to state power supply.
Difference between manufacturing method according to the invention and method well known in the prior art is following characteristics：Such as profit
Using stencil, heater structure are pressed, wind, brush or are applied in the ceramic bases being sintered, such as the sensing of exhaust gas probe
Device element；Stablize the heating using the ink with platinum or platinum compounds or paste as electrical lead and high temperature liner part
Device structure and then one layer of thin oxide insulating layer of coating or protection glaze, such as aluminium, silicon and/or barium ingredient, Yi Jijie
The method and step for penetrating the heater structure and protection glaze.Alternatively, the sensor element also can be by will be prefabricated
Heating element bonding be mechanically connected on prefabricated sintering solid electrolyte ontology or wherein come made of.Example can be envisaged in this
It is such as heat-treated together with solid electrolyte by part or local bonding heat-resisting material, the heat-resisting material is, for example,
Glass ceramics, vitrified bonding or glass frit.It is installed together and leads to by the heating element and solid electrolyte ontology
Overshoot and convection current carry out heat and transmit to ensure that the connection is lasting.By using heating element, preferably aoxidized with base material
Aluminium, silicon carbide, aluminium nitride, barium talcum, talcum, cordierite or other common ceramic insulating materials are formed, these materials are resistance to
High temperature.It is possible using the heating element with heat safe heat lead material, the heat lead material is, for example,
Platinum, rhodium, palladium, gold, chromium, tungsten, molybdenum or corresponding alloy.
The heating element can especially realize the platinum metal race structure for sintering be sintered together or additional in principle.
Particularly, the heating element is weak heating element, for for example during spinning reconcile cold operation state, have maximum value 5W
Consumption performance number, but the often greater than 7W in the lambda probe for using automobile-use.The turn-on current of the heating element is no more than
2A, to keep the low requirement to the controller of sensor element.For the automobile-used exhaust gas probe of equipment of small motor, the spy
Needle bounce action at least need with 30 seconds, this is the situation not broken down because major part pollutant be not herein
What the incipient stage generated, but generated in corresponding driving cycle.Because of the high thermic load of hot waste gas, it is in full load
1000 DEG C are up to about during operation, so the structure of the heating element needs the metal using platinum metal race.The heating unit
Part is especially made of platinum-gold category ceramics, and can correspond to the material composition of the prior art, but the heating element of the present invention has
High temperature liner part and thin indentation structure and pin configuration, total cold-state resistance are from 8 ohm to 20 ohm.Heating power
Design meet in intrinsic heating in colder environment temperature, i.e., from -40 DEG C to -20 DEG C, sensor element temperature reaches
750 DEG C of maximum value.
Particularly, the present invention provides a kind of sensor element, with maximum length 35m and maximum width 4mm, and has
There is an integrated heating element, the heating element is at 20 DEG C with the minimum cold-state resistance from 8 to 20 ohm and in operation electricity
Consumption power with 5W when pressing as 13V.As a result, in the present invention, the heating element, which is installed to, has manufactured completion, i.e.,
On the solid electrolyte ontology being sintered, the heating element of different designs may be arranged on this solid electrolyte ontology.At this
Under kind situation particularly advantageously, the heating element has manufactured completion in itself, that is, has been sintered, so as to different heating units
Any combinations of part can be arranged on such solid electrolyte ontology.
Description of the drawings
The other details and feature of the present invention are obtained from the description below for the preferred embodiment being shown schematically in the figure,
In：
The cross-sectional view of the heating element of the sensor element of Fig. 1 first embodiments；
The cross-sectional view of the heating element of the sensor element of Fig. 2 second embodiments；
The cross-sectional view of the heating element of the sensor element of Fig. 3 3rd embodiments.
Specific embodiment
Fig. 1 shows the cross-sectional view of the first embodiment of inventive sensor element 10.Sensor element 10 shown in FIG. 1
Available for the physically and/or chemically performance of probe gas, wherein one or more performances can be obtained.The present invention is hereinafter especially
It is related to obtaining the oxygen content in the quality of the gas componant of gas and/or quantity more particularly to acquisition gas.The oxygen contains
Amount can be the form of such as partial pressure and/or the form of percentage composition.However, can obtain in principle different types of gas into
Point, such as nitrogen, hydrocarbon and/or hydrogen.However, alternatively, or additionally, the other performance of gas can also be obtained.This
Invention is particularly suitable for automotive field, specifically, cyclecar field, such as motorcycle, thus measure gas space
Between refer in particular to motorcycle internal combustion engine flue gas leading, gas refers in particular to exhaust gas.
Sensor element 10 is described as the typical members of plane lambda probe, but is not limited to such lambda probe, but
It may be embodied as finger-type probe.Because this lambda probe has compact structure form, suitable for cyclecar, sensor member
The size of part 10 is such as length, i.e., along the measured value of Fig. 1 observed directions, maximum 50mm, preferably at most 45mm and especially
In preferably at most 40mm and width, i.e. Fig. 1 from right to left or opposite measured value, maximum 10mm, preferably at most 8mm and spy
Not preferably at most 6mm.In example shown in Fig. 1, the size of sensor element 10 is, for example, length 35mm and width
4mm.Therefore, the cross-sectional view when view of Fig. 1 is perpendicular to the longitudinal 2 observation of sensor 10.
There is sensor element 10 solid electrolyte 12, first electrode 14, second electrode 16, heating element 18 and reference to lead to
The zirconium oxide that road 20, wherein solid electrolyte 12 are stablized containing yttrium, such as the yttrium oxide containing 6 to 10% weight.In lambda probe
During situation, the reference sample of suction is suitable for the cyclecar to break down, therefore in the example shown, preferably with air
Probe that is reference sample and accordingly being influenced on small heating power requirements generation is arranged.In cyclecar exhaust gas probe situation
In do not need to high heating power.The detail of the consumption power about heating element 18 is discussed in detail below.
Heating element 18 is provided for heating electrode 14,16 and solid electrolyte 12.Electrode 14,16 passes through solid electrolytic
Matter 12 is connected with each other and may make up can this special battery and/or electrochemical cell.It may also set up other functional layers, such as other electricity
Pole, ribbon lead, diffusion battery, diffusion interspace, other heating elements and/or oxygen-pump battery.These functional layers can be built
Or it is integrated into solid electrolyte 12.Optionally this special battery of energy is preferably provided in solid electrolyte layer, to measure burning
Thus remnant oxygen content in exhaust gas adjusts combustion air with fuel ratio fully to burn, neither makes fuel excess nor make
Air excess.
First insulating layer 22 be located at solid electrolyte 12 on the side of first electrode 14, its thickness be from 2 μm to
100 μm, preferably from 5 μm to 75 μm and particularly preferably from 10 μm to 50 μm.For example, the thickness of the first insulating layer 22 is 30 μm.The
One insulating layer 22 is with main member made of aluminium oxide.However, alternatively, or additionally, carbon can also be used in the first insulating layer 22
SiClx, aluminium nitride, barium talcum, talcum or cordierite.Heating element 18 is arranged on the first insulating layer 22.Heating element 18 is by
Two insulating layers 24 or the covering of protection glaze or coating second insulating layer 24 or protection glaze, so as to which heating element 18 is embedded into first absolutely
Between edge layer 22 and second insulating layer 24.For the symmetrical of the heating element 18 between the first insulating layer 22 and second insulating layer 24
Arrangement, second insulating layer 24 have the thickness identical with the first insulating layer 22.However, it is understood that the first insulating layer 22 and second is exhausted
Edge layer 24 can have different thickness.The modification of thickness for example may rely on installation site or specific application field.
When manufacturing sensor element 10, solid electrolyte 12 should be made to be in soft fluffy state, i.e. un-sintered state, with known
Mode for example, by thick-layer technology and/or film lamination and/or method for printing screen and/or spray method, function is set
Layer, especially electrode 14,16 and reference channel 20, but may also set up the first insulating layer 22.The application thickness of first insulating layer 22
It is to make the first insulating layer 22 that there is above-mentioned thickness after sintering, i.e., there is 30 μm of thickness after sintering.First insulating layer 22
The methods of by pressing, winding, brushing or smearing be applied to as described on solid electrolyte.Particularly, first insulating layer 22
Make is that its coefficient of thermal expansion is made to be retrodeviated in following heat treatments from the second insulating layer maximum 10% applied later, preferably
Maximum 5% and particularly preferably maximum 2%, such as 1%.The adjustment of each coefficient of thermal expansion herein can be by adding silica, oxidation
Calcium, magnesia, barium monoxide or other metal oxides are realized.Be also possible to and advantageously, by be suitably introduced into porosity with
The elasticity modulus of the first insulating layer 22 is made to adapt to the elasticity modulus of second insulating layer 24.The porosity is here by adding in
Infusion is adjusted, and the foaming agent is usually made of carbon-based material.These foaming agents sintering when volatilize or burn-up, preferably without
It residually volatilizees or burns up, leave cavity.Solid electrolyte 12 then with electrode 14,16,20 and first insulating layer of reference channel
22 are sintered together.The sintering for example can carry out many hours at a temperature of from 900 DEG C to 1400 DEG C.
Manufactured completion, that is, the solid electrolyte 12 being sintered together with the electrode 14 having been arranged at thereon, 16,
The reference channel 20 of introducing and the first insulating layer 22 applied are suitable for step arrangement heating element 18 according to the methods below.At this
In, heating element is pressed, wound, brushed or is applied on the first insulating layer 22 of the solid electrolyte 12 being sintered, such as
Prefabricated applique is embodied as by paste or ink or by transfer technique.Heating element 18 is preferably by platinum metal race
Metal is made, such as platinum, rhodium, palladium, gold or other transition metal, such as chromium, tungsten or molybdenum or their alloy.Particularly,
The geometry of the heating element 18 of solid electrolyte 12 adapts to installation requirement.Particularly, should make when designing heating element 18
Input electric power mainly in heating region, i.e., in the region of the measuring unit of sensor element 10, is converted.Measuring unit exists
Here it is the region of heating element 18, it overlaps with electrode 14,16, this can pass through the corresponding arrangement of the resistance of heating element 18
It realizes, wherein, in measured zone, i.e., such as 8 ohm to 20 ohm of resistance, such as 10 Europe are set in the region of measuring unit
The resistance of nurse, and resistance of the setting from 1 ohm to 3 ohm in lead areas.Its realization method is, for example, that calandria exists
Than having smaller cross section in lead areas in heating region.Heating element 18 then applies second insulating layer 24 or protection
Glaze, second insulating layer 24 or protection glaze can equally be applied for paste or ink or prefabricated applique.Then drying process is performed
Hereafter it can manage it heat treatment, such as perform sintering circuit again, such as stop at a temperature of from 900 DEG C to 1250 DEG C many small
When.Second insulating layer 24 or protection glaze are herein since the similar material of the first insulating layer 22 is made, but because second insulating layer
24 or the ingredient of glaze is protected to be combined in low temperature with heating element 18, second insulating layer 24 or glaze is protected to be baked and enduringly
It is pasted onto on the first insulating layer 22.First insulating layer 22 and second insulating layer 24 are preferably thinly implemented with so-called thickness, and
And with the material of such as aluminium oxide（The material is not only electrically insulated, but also with high thermal conductivity）It is made.
Fig. 2 shows the cross-sectional view of sensor element 10 according to second embodiment, below only description and first embodiment
Difference, wherein identical component is presented with like reference characters.
Sensor element 10 equally has solid electrolyte 12, wherein, heating element 18 is arranged in solid electrolyte 12
On the side opposed with first electrode 14.Particularly, heating element 18 is embedded into insulating layer 22, and secured using binding agent 26
Ground is arranged on solid electrolyte 12.Particularly, binding agent 26 is arranged as the form of layer, and the thickness of wherein binding agent 26 is 2 μm
To 300 μm, preferably 5 μm to 250 μm and particularly preferred 10 μm to 200 μm, such as 50 μm.Binding agent 26 is with heat-resisting material system
Into.Alternatively, it is possible to use other heat-resisting materials, these heat-resisting materials are suitable for holding heating element 18 or insulating layer 22
It is fixed on long on solid electrolyte 12, e.g. glass ceramics or glass frit.
The manufacturing method of sensor element 10 can be that solid electrolyte 12 is made to be in soft fluffy state herein, i.e., un-sintered
State, in a known way for example, by thick-layer technology and/or film lamination and/or method for printing screen and/or splash
Method sets functional layer, especially electrode 14,16 and reference channel 20.Solid electrolyte 12 then with electrode 14,16 and reference
Channel 20 is sintered together.The sintering can for example carry out at a temperature of from 900 DEG C to 1400 DEG C through many hours.
Manufactured completion, that is, the solid electrolyte 12 being sintered and have been arranged at electrode 14,16 thereon and
Then the reference channel 20 of introducing is suitable for arranging that the following methods of heating element 18 are walked on the side opposed with first electrode 14, apply
Coating method is, for example, by brush or squeegee brushing, using silk-screen printing or the pressing of plug extruding, splash or as applique
It pastes.The thickness of the binding agent 26 of selection should be heat-treated the thickness of binding agent 26, i.e., reached after the heat treatment then described
To 2 μm to 300 μm, preferably 5 μm to 250 μm and particularly preferred 10 μm to 200 μm, such as 50 μm.When necessary, in order to apply bonding
Agent 26 needs to make exploitation new material or adapts to existing material system.Therefore such as vitrified bonding, glass ceramics can be used
Or glass frit.Particularly, using binding agent 26, binding agent 26 carries out following heat treatments, its coefficient of thermal expansion and solid electricity
It solves the identical with the coefficient of thermal expansion of heating element 18 of matter 12 or although technically it is not possible that, its coefficient of thermal expansion is near
It is seemingly the arithmetic mean of instantaneous value of the coefficient of thermal expansion of solid electrolyte 12 and heating element 18.Such as the thermal expansion of solid electrolyte 12
Coefficient is 10x10-61/K, the coefficient of thermal expansion of heating element 18 is 6x10-61/K, thus the binding agent 26 used is being heat-treated
There is coefficient of thermal expansion 8x10 afterwards-61/K。
Prefabricated heating element 18 is applied on binding agent 26, and heating element 18 is embedded into insulating layer 22, i.e. heating unit
Part 18 and insulating layer 22 are in sintering state.It is, for example, heating unit by the realization method that heating element 18 is embedded into insulating layer 22
Part 18 for example by pressing or brushing paste, is applied in the first part of insulating layer 22, then the covering of heating element 18 insulation
The second part of layer 22.By subsequent sintering circuit, the first part of insulating layer 22 and second part form integrated connection, from
And two parts of insulating layer 22 also can be no longer distinguished, and heating element 18 is only equipped in insulating layer 22.It is heated calculating
It is noted that insulating layer 22 and the contact of heating element 18 being embedded during the above-mentioned coefficient of thermal expansion of element.Insulating layer 22 is thus
Load-bearing part as heating element 18 because it carries heating element 18, is especially carried in itself.As heating element 18
Loading material, workable material be, for example, preferably by aluminium oxide, silicon carbide, aluminium nitride, magnesia, barium talcum, talcum and/
Or cordierite or other commercial common ceramic insulating materials are formed.These materials are to be electrically insulated and led with high
It is hot.It is preferable to use the material of platinum, rhodium, palladium, gold, chromium, tungsten, molybdenum or its alloy as heating element 18.Particularly, solid electrolytic
The geometry of the heating element 18 of matter 12 meets matching requirements.The thickness of insulating layer 22 is, for example, 60 μm, therefore insulating layer 22
It is preferably implemented as thin.Particularly, the design method of heating element 18 is to make the electrical power of input mainly in heating region transfer
It changes, heating region is the occupied part in measuring unit region of sensor element 10 in heating element 18.The measuring unit
The region with electrode 14,16 with solid electrolyte 12 overlaps.
Then, solid electrolyte 12, binding agent 26 and insulating layer 22 together with the heating element 18 being embedded through overheat at
Reason.This heat treatment is, for example, the temperature in 1000 DEG C of highest, the temperature preferably from 400 DEG C to 800 DEG C, such as at 600 DEG C
At a temperature of pass through the annealing of 12 hours or more, be then sintered process at low temperature.It is carried out here by radiation and convection current
Heat is transmitted.It does not need to that solid electrolyte 12, binding agent 26 and insulating layer 22 is made together with what is be embedded to add in this embodiment
Thermal element 18 is sintered together, because solid electrolyte 12 and heating element 18 have gone through sintering separately manufactured in the case of
Process.The annealing is preferred for hardening binding agent 26, thus binding agent 26 makes insulating layer 22 and solid electrolyte 12 lasting
Ground connects.
Fig. 3 shows the cross-sectional view of sensor element 10 according to third embodiment, below only description and second embodiment
Difference, wherein identical component is presented with like reference characters.
Sensor element 10 equally has solid electrolyte 12 and first electrode 14, second electrode 16 and in solid electrolyte
The reference channel 20 arranged in 12.Heating element 18 is arranged on the side opposed with first electrode 14 of solid electrolyte 12, quilt
It is embedded into insulating layer 22.3rd embodiment the difference from the second embodiment is that solid electrolyte 12 and insulating layer 22 it
Between be not provided with binding agent for connection, i.e. insulating layer 22 is no longer fixed on together with the heating element 18 being embedded with binding agent
On solid electrolyte 12.
Compared with second embodiment, in the sensor element 10 for manufacturing 3rd embodiment without using binding agent 26, but
The solid electrolyte 12 of completion is manufactured, that is, the solid electrolyte 12 being sintered is with having been arranged at the electricity on solid electrolyte 12
Pole 14,16 and the reference channel 20 being introduced into solid electrolyte 12 are made.The system of solid electrolyte 12 and so-called functional layer
It makes and completes herein for example as described in second embodiment.Insulating layer 22 exists together with the heating element 18 being embedded
It has manufactured in completion status, i.e., has been arranged in sintering state on the side opposed with electrode 14 of solid electrolyte 12.Then, Gu
Body electrolyte 12 and the insulating layer 22 being applied to thereon are mechanically connected.This is for example by solid electrolyte 12 and will be arranged in solid
Insulating layer 22 on electrolyte 12 is arranged in moulding mould, is then squeezed.Power for squeezing is less than solid electrolyte
12 strength of materials can be such as 50kN again smaller than insulating layer 22 together with the strength of materials of heating element 18 being embedded.
By squeezing, compression is especially reached in the region of solid electrolyte 12 and the contact surface of insulating layer 22, so as to which this is depended on
Used power mutually squeezes on surface.Then, solid electrolyte 12 and the insulating layer 22 that is connected with solid electrolyte 12 from
Moulding mould demoulds, through Overheating Treatment.This heat treatment is, for example, the temperature in 1000 DEG C of highest, preferably from 400 DEG C to 800 DEG C
Temperature, such as 12 hours or more at a temperature of 600 DEG C, be embodied as annealing and be embodied as sintering circuit at low temperature.Lead at this time
It crosses heat radiation and convection current carries out hot transmission.Solid electrolyte 12 and insulating layer 22 are not needed in this embodiment together with embedded exhausted
Heating element 18 in edge layer 22 is sintered together because solid electrolyte 12 and heating element 18 when they are separately manufactured
It has passed through sintering circuit.The annealing is preferred for the mechanical connection between stabilization of solid electrolyte 12 and insulating layer 22.This is same
Sample causes solid electrolyte 12 to be enduringly adhesively joined with insulating layer 22.Perhaps the sky between insulating layer 22 and specific electrolyte 12
Air gap can be compensated by correspondingly increasing the heating power of heating element 18.It is further advantageous that insulating layer 22 and solid
The contact surface or at least one of insulating layer 22 and solid electrolyte contact surface of body electrolyte 12 are before mechanical connection
It is ground.Thus when squeezing, power is uniformly distributed in the contact surface of insulating layer 22 and solid electrolyte 12, and insulate
Connection between layer 22 and solid electrolyte 12 equably keeps stable by common contact surface.
For all previous embodiments, the heating element 18 used has cold conditions all-in resistance from 8 ohm to 20 ohm.This
Outside, the length maximum value of all the sensors element is 55mm, preferably 45mm, and more preferably up to value is 40mm, and width is maximum
It is worth for 8mm, preferred maximum is 7mm and more preferably up to value is 6mm, and sensor element is for example with length 35mm and width
5mm。
It should be understood that, it is emphasized that all features disclosed in the specification and in the claims should in the sense that original disclosure
Regard as separated and independent of each other, and equally should be viewed as independent of implementing in the sense that claimed invention is limited
Feature combination disclosed in example and/or claim.It should be clearly understood that it is limiting in the sense that original disclosure and equally
In the sense that claimed invention processed, the data of all range datas or unit group disclose each possible median or every
A possible subgroup especially also serves as the boundary value of range data.
Claims (31)
1. a kind of method for manufacturing sensor element (10), the sensor element (10) is for obtaining gas in the tested gas compartment
At least one characteristic of body, the described method comprises the following steps：
The solid electrolyte (12) being sintered is provided,
Heating element (18) is arranged on the solid electrolyte (12) or in the solid electrolyte (12) and
It is heat-treated the solid electrolyte (12) and heating element (18) together,
Wherein, the heating element (18) is arranged in the solid under un-sintered state by pressing, winding, brushing or smearing
On electrolyte (12) or in the solid electrolyte (12) and the heat treatment is sintering.
2. according to the method described in claim 1, it is characterized in that, the solid electrolyte (12) has insulating layer (22), institute
It states heating element (18) to be arranged on the insulating layer (22), and the heating element (18) applies one layer before the heat treatment
Insulating layer (24) and/or protection glaze.
3. according to the method described in claim 2, it is characterized in that, the heat of the insulating layer (22) of the solid electrolyte (12) is swollen
Swollen coefficient deviates the coefficient of thermal expansion maximum 10% of the insulating layer (24) of the heating element (18).
4. according to the method described in claim 2, it is characterized in that, the insulating layer (22) of the solid electrolyte (12) with institute
State the thickness having after heating element (18) is sintered together from 2 μm to 100 μm.
5. according to the method described in claim 1, it is characterized in that, the heating element (18) is arranged in institute under sintering state
It states on solid electrolyte (12) or in solid electrolyte (12), and the heat treatment is annealing.
6. according to the method described in claim 5, it is characterized in that, the heating element (18) is by bonding or being mechanically connected cloth
It puts on the solid electrolyte (12) or in solid electrolyte (12).
7. according to the method described in claim 6, it is characterized in that, the heating element (18) is utilized with solid electrolyte (12)
Heat-resisting material is attached.
8. the method described according to claim 6 or 7, which is characterized in that connect the heating element using binding agent (26)
(18) and solid electrolyte (12), the binding agent (26) is by brushing, smearing, pressing, splash or is used as applique and applies
Onto the solid electrolyte (12).
9. according to the method described in claim 8, it is characterized in that, the binding agent (26) has from 2 μm to 300 after sintering
μm thickness.
10. according to the method described in claim 1, it is characterized in that, the heating element (18) has from 6 ohm to 22 ohm
Cold conditions all-in resistance.
11. according to the method described in claim 1, it is characterized in that, the heating element (18) is electrical heating elements, running
During voltage 13V, the electrical heating elements have the consumption power that maximum value is 5W.
12. according to the method described in claim 1, it is characterized in that, it is 55mm that the sensor element (10), which has maximum value,
Length, maximum value be 8mm width.
13. according to the method described in claim 1, it is characterized in that, the sensor element (10) is in probe gas
The temperature of gas componant or gas.
14. according to the method described in preceding claims 3, which is characterized in that the insulating layer (22) of the solid electrolyte (12)
Coefficient of thermal expansion deviate the heating element (18) insulating layer (24) coefficient of thermal expansion maximum 5%.
15. according to the method described in preceding claims 3, which is characterized in that the insulating layer (22) of the solid electrolyte (12)
Coefficient of thermal expansion deviate the heating element (18) insulating layer (24) coefficient of thermal expansion maximum 2%.
16. according to the method described in preceding claims 3, which is characterized in that the insulating layer (22) of the solid electrolyte (12)
Coefficient of thermal expansion deviate the heating element (18) insulating layer (24) coefficient of thermal expansion 1%.
17. according to the method described in claim 4, it is characterized in that, the insulating layer (22) of the solid electrolyte (12) with
The heating element (18) has the thickness from 5 μm to 75 μm after being sintered together.
18. according to the method described in claim 4, it is characterized in that, the insulating layer (22) of the solid electrolyte (12) with
The heating element (18) has the thickness from 10 μm to 50 μm after being sintered together.
19. according to the method described in claim 6, it is characterized in that, the heating element (18) by squeeze be arranged in it is described
On solid electrolyte (12) or in solid electrolyte (12).
20. the method according to the description of claim 7 is characterized in that the heat-resisting material is glass ceramics, vitrified bonding
(26) or glass frit.
21. according to the method described in claim 9, it is characterized in that, the binding agent (26) after sintering have from 5 μm to
250 μm of thickness.
22. according to the method described in claim 9, it is characterized in that, the binding agent (26) after sintering have from 10 μm to
200 μm of thickness.
23. according to the method described in claim 10, it is characterized in that, the heating element (18) has the Europe from 8 ohm to 20
The cold conditions all-in resistance of nurse.
24. according to the method for claim 11, which is characterized in that in working voltage 13V, the electrical heating elements have
The consumption power of 4W.
25. according to the method for claim 11, which is characterized in that in working voltage 13V, the electrical heating elements have
The consumption power of 3.5W.
26. according to the method for claim 11, which is characterized in that in working voltage 13V, the electrical heating elements have
The consumption power of 5W.
27. according to the method for claim 12, which is characterized in that it is 45mm that the sensor element (10), which has maximum value,
Length.
28. according to the method for claim 12, which is characterized in that it is 40mm that the sensor element (10), which has maximum value,
Length.
29. according to the method for claim 12, which is characterized in that it is 7mm that the sensor element (10), which has maximum value,
Width.
30. according to the method for claim 12, which is characterized in that it is 6mm that the sensor element (10), which has maximum value,
Width.
31. according to the method for claim 12, which is characterized in that the sensor element (10) with 35mm length and
The width of 5mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011082175.9 | 2011-09-06 | ||
| DE201110082175 DE102011082175A1 (en) | 2011-09-06 | 2011-09-06 | Sensor element for detecting at least one property of a gas in a sample gas space |
| PCT/EP2012/064393 WO2013034352A1 (en) | 2011-09-06 | 2012-07-23 | Method for producing a sensor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103765203A CN103765203A (en) | 2014-04-30 |
| CN103765203B true CN103765203B (en) | 2018-06-08 |
Family
ID=46579020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280042715.2A Active CN103765203B (en) | 2011-09-06 | 2012-07-23 | The manufacturing method of sensor element |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN103765203B (en) |
| DE (1) | DE102011082175A1 (en) |
| WO (1) | WO2013034352A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015203050A1 (en) * | 2015-02-20 | 2016-08-25 | Robert Bosch Gmbh | Micro heater for a sensor and sensor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100466A (en) * | 1985-01-25 | 1986-07-23 | 株式会社日立制作所 | Oxygen sensor |
| US4697165A (en) * | 1984-11-01 | 1987-09-29 | Ngk Insulators, Ltd. | Ceramic heater and a method of manufacturing the same |
| CN1117761A (en) * | 1993-12-09 | 1996-02-28 | 罗伯特·博施有限公司 | Insulating layer system for gavanically separating circuits |
| CN1453581A (en) * | 2002-02-05 | 2003-11-05 | 京瓷株式会社 | Oxygen sensor |
| CN1493876A (en) * | 2002-11-01 | 2004-05-05 | 日本特殊陶业株式会社 | Gas sensor having laminate comprising solid electrolyte layer and alumina substrate |
| CN101413914A (en) * | 2008-09-26 | 2009-04-22 | 深圳市日理江澍实业有限公司 | Method for co-firing ceramic sensing head substrate and platinum gold electrode of oxygen sensor |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5660661A (en) * | 1993-04-13 | 1997-08-26 | Nippondenso Co., Ltd. | Oxygen sensor |
| FR2733453B1 (en) * | 1995-04-28 | 1997-07-25 | Heidelberg Harris Sa | FOLDER INCLUDING AN ADDITIONAL MODULE DELIVERING NOTEBOOKS |
| DE19946343B4 (en) * | 1999-09-28 | 2007-03-29 | Robert Bosch Gmbh | Method for producing a planar sensor element |
| DE10052948A1 (en) * | 2000-10-25 | 2002-05-08 | Dittrich Elektronic Gmbh & Co | Heating element used in electronic components such as sensors, comprises a one-piece base plate, a heating section supporting a heating spiral and a contact section supporting contacts |
| 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, |
| DE10249466B4 (en) * | 2002-10-24 | 2006-03-09 | Robert Bosch Gmbh | sensor element |
| US8168053B2 (en) * | 2006-01-23 | 2012-05-01 | Denso Corporation | Gas sensing member used for gas sensor and method of manufacturing the member |
| CN101008630A (en) * | 2006-01-23 | 2007-08-01 | 株式会社电装 | Gas sensing member used for gas sensor and method of manufacturing the member |
-
2011
- 2011-09-06 DE DE201110082175 patent/DE102011082175A1/en not_active Withdrawn
-
2012
- 2012-07-23 CN CN201280042715.2A patent/CN103765203B/en active Active
- 2012-07-23 WO PCT/EP2012/064393 patent/WO2013034352A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4697165A (en) * | 1984-11-01 | 1987-09-29 | Ngk Insulators, Ltd. | Ceramic heater and a method of manufacturing the same |
| CN86100466A (en) * | 1985-01-25 | 1986-07-23 | 株式会社日立制作所 | Oxygen sensor |
| CN1117761A (en) * | 1993-12-09 | 1996-02-28 | 罗伯特·博施有限公司 | Insulating layer system for gavanically separating circuits |
| CN1453581A (en) * | 2002-02-05 | 2003-11-05 | 京瓷株式会社 | Oxygen sensor |
| CN1493876A (en) * | 2002-11-01 | 2004-05-05 | 日本特殊陶业株式会社 | Gas sensor having laminate comprising solid electrolyte layer and alumina substrate |
| CN101413914A (en) * | 2008-09-26 | 2009-04-22 | 深圳市日理江澍实业有限公司 | Method for co-firing ceramic sensing head substrate and platinum gold electrode of oxygen sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103765203A (en) | 2014-04-30 |
| WO2013034352A1 (en) | 2013-03-14 |
| DE102011082175A1 (en) | 2013-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR970003282B1 (en) | Ptc temperature sensors, processor for producing ptc temperature sensing elements for ptc temperature sensors | |
| JP4050593B2 (en) | Gas sensor element and gas sensor using the same | |
| EP0134709A1 (en) | An oxygen sensor element | |
| JP2002174618A (en) | Solid electrolyte gas sensor | |
| CN103748460A (en) | Sensor element for capturing at least one property of gas in measurement gas space | |
| JP2001165440A (en) | Glow plug and its manufacturing method | |
| CN110612277B (en) | Sensor for determining gas parameters | |
| CN103765203B (en) | The manufacturing method of sensor element | |
| JP4093784B2 (en) | Multilayer gas sensor element, manufacturing method thereof, and gas sensor | |
| JP4980996B2 (en) | Gas sensor element and gas sensor | |
| JP3572241B2 (en) | Air-fuel ratio sensor element | |
| JPH06317550A (en) | Ceramic heater | |
| JPS60227158A (en) | Gas sensor | |
| JP2004327255A (en) | Manufacturing method for ceramic heater structure and ceramic heater structure | |
| JP2004325196A (en) | Oxygen sensor element | |
| JP3677920B2 (en) | Oxygen concentration detector | |
| JP2000338078A (en) | Heater one-piece type oxygen sensor and manufacture thereof | |
| JP2002228622A (en) | Oxygen sensor and its manufacturing method | |
| JP3840107B2 (en) | Oxygen sensor element | |
| JP2005005057A (en) | Ceramic heater and ceramic heater structural body | |
| JP4262764B2 (en) | Multilayer gas sensor element | |
| JP3987708B2 (en) | Theoretical air-fuel ratio sensor element | |
| JP2004296142A (en) | Ceramic heater and detecting element using the same | |
| JP2003014690A (en) | Gas sensor element and gas sensor | |
| JPH10335050A (en) | Ceramic heater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |