JP6475074B2 - ガスセンサ素子 - Google Patents
ガスセンサ素子 Download PDFInfo
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- JP6475074B2 JP6475074B2 JP2015091445A JP2015091445A JP6475074B2 JP 6475074 B2 JP6475074 B2 JP 6475074B2 JP 2015091445 A JP2015091445 A JP 2015091445A JP 2015091445 A JP2015091445 A JP 2015091445A JP 6475074 B2 JP6475074 B2 JP 6475074B2
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- 239000011241 protective layer Substances 0.000 claims description 103
- 239000010410 layer Substances 0.000 claims description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 77
- 230000004044 response Effects 0.000 description 37
- 238000002474 experimental method Methods 0.000 description 15
- 230000035515 penetration Effects 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000005871 repellent Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000002940 repellent Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 231100000614 poison Toxicity 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000005856 abnormality Effects 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Images
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
- G01N27/4067—Means for heating or controlling the temperature of the solid electrolyte
-
- 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
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4077—Means for protecting the electrolyte or the electrodes
-
- 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
- G01N27/409—Oxygen concentration cells
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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)
Description
図1は本発明のガスセンサ素子の実施の形態1を説明した模式図である。図1で示すガスセンサ素子100は、排気ガス中の酸素濃度を検知する検知部10と、この検知部10の周囲を排気ガス中の水分から防護して、この水分が検知部10に到達して検知部10の温度低下に起因する出力異常が発生するのを抑制するとともに、通過する水素ガスや一酸化炭素ガス等をトラップする多孔質保護層20から大略構成されている。
図2は本発明のガスセンサ素子の実施の形態2を説明した模式図である。同図で示すガスセンサ素子100Aは、検知部10に接する下層20Abと、外側に面する上層20Aaの二層積層構造の多孔質保護層20Aを具備するものである。
本発明者等は、ガスセンサが制御される温度範囲である400〜850℃の温度範囲において、多孔質保護層に対して要求される滴下量3μLの水滴に対し、良好な撥水性の指標となる二つの物性値である、多孔質保護層の熱伝導率およびλCpρ値と環境温度との関係を特定する実験をおこなった。
本発明者等は、気孔率を変化させ、各気孔率と熱伝導率および応答特性の関係や、各気孔率とλCpρ値および応答特性の関係を特定する実験をおこなった。なお、多孔質保護層の製作方法や使用は既述する実験と同様である。
本発明者等は、水滴断面積比と撥水性の関係を特定する実験をおこなった。この実験では、多孔質保護層に対して要求される滴下量3μLの水滴を滴下させた際に、膜沸騰現象を発現して撥水性を示す多孔質保護層上の固液の接触面積と水滴断面積の比率を検証したものである。検証結果を以下の表1に示す。
本発明者等は、多孔質保護層表面の温度変化と撥水性の関係を特定する実験をおこなった。この実験では、多孔質保護層に対して要求される滴下量3μLの水滴を滴下させた際に、膜沸騰現象を発現して撥水性を示す多孔質保護層表面の温度変化の程度を検証したものである。検証結果を以下の表2に示す。
本発明者等はさらに、毛管半径とガス応答時間および染み込み距離の関係を特定する実験をおこなった。ここで、毛管半径は、多孔質保護層の一部を掻き取り、細孔分布を水銀ポロシメータで測定した測定結果に基づいて規定している。
Claims (3)
- 少なくとも一対の電極を両側に備えた固体電解質体と、発熱源を含む発熱体とが積層されて検知部を成し、この検知部の周囲に多孔質保護層が形成されてなるガスセンサ素子であって、
前記多孔質保護層は、アルミナからなる骨材と、シリカからなるコート材とから形成されており、
前記多孔質保護層の気孔率が10〜50%の範囲にあり、
前記多孔質保護層の毛管半径が0.01〜10μmの範囲にあり、
熱伝導率λが0.2〜5W/mKの範囲にあり、熱伝導率λ(W/mK)と密度ρ(g/m3)と比熱Cp(J/gK)の積であるλCpρが5.3×105〜2.1×107WJ/m4K2の範囲にあるガスセンサ素子。 - 前記多孔質保護層は、一層構造体である請求項1に記載のガスセンサ素子。
- 前記多孔質保護層は、ガスセンサ素子の内側に位置する検知部に接する下層と、外側に面する上層の積層構造をなしており、
前記下層に比して前記上層の気孔率が相対的に低い二層構造体である請求項1に記載のガスセンサ素子。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015091445A JP6475074B2 (ja) | 2014-07-18 | 2015-04-28 | ガスセンサ素子 |
US14/793,211 US9958412B2 (en) | 2014-07-18 | 2015-07-07 | Gas sensor element |
DE102015111681.2A DE102015111681B4 (de) | 2014-07-18 | 2015-07-17 | Gassensorelement |
CN201510424695.0A CN105277605B (zh) | 2014-07-18 | 2015-07-17 | 气体传感器元件 |
Applications Claiming Priority (3)
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---|---|---|---|
JP2014147482 | 2014-07-18 | ||
JP2014147482 | 2014-07-18 | ||
JP2015091445A JP6475074B2 (ja) | 2014-07-18 | 2015-04-28 | ガスセンサ素子 |
Publications (2)
Publication Number | Publication Date |
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JP2016029360A JP2016029360A (ja) | 2016-03-03 |
JP6475074B2 true JP6475074B2 (ja) | 2019-02-27 |
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JP2015091445A Active JP6475074B2 (ja) | 2014-07-18 | 2015-04-28 | ガスセンサ素子 |
Country Status (4)
Country | Link |
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US (1) | US9958412B2 (ja) |
JP (1) | JP6475074B2 (ja) |
CN (1) | CN105277605B (ja) |
DE (1) | DE102015111681B4 (ja) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6493281B2 (ja) * | 2016-04-11 | 2019-04-03 | トヨタ自動車株式会社 | 排気センサの制御装置 |
JP6857051B2 (ja) * | 2016-04-20 | 2021-04-14 | 日本特殊陶業株式会社 | ガスセンサ素子およびガスセンサ |
JP6406311B2 (ja) * | 2016-05-09 | 2018-10-17 | トヨタ自動車株式会社 | 排気センサの制御装置 |
JP6451697B2 (ja) | 2016-06-14 | 2019-01-16 | トヨタ自動車株式会社 | 排気センサの制御装置 |
JP6485411B2 (ja) * | 2016-06-14 | 2019-03-20 | トヨタ自動車株式会社 | 排気センサの制御装置 |
JP6761371B2 (ja) | 2017-03-30 | 2020-09-23 | 日本碍子株式会社 | ガスセンサ素子 |
JP6761369B2 (ja) | 2017-03-30 | 2020-09-23 | 日本碍子株式会社 | ガスセンサ素子 |
DE102017218469A1 (de) * | 2017-06-28 | 2019-01-03 | Robert Bosch Gmbh | Sensorelement zur Erfassung mindestens einer Eigenschaft eines Messgases in einem Messgasraum und Verfahren zur Herstellung desselben |
JP6708184B2 (ja) * | 2017-08-22 | 2020-06-10 | 株式会社デンソー | ガスセンサ素子及びガスセンサ |
JP6909706B2 (ja) * | 2017-10-31 | 2021-07-28 | 株式会社デンソー | ガスセンサ |
JP6919996B2 (ja) | 2018-02-06 | 2021-08-18 | トヨタ自動車株式会社 | ガスセンサ素子 |
JP7183910B2 (ja) * | 2019-03-28 | 2022-12-06 | 株式会社デンソー | ガスセンサ |
JP7070514B2 (ja) | 2019-06-27 | 2022-05-18 | 株式会社デンソー | ガスセンサ及びその製造方法 |
JP2022143611A (ja) * | 2021-03-18 | 2022-10-03 | 日本碍子株式会社 | センサ素子 |
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JP3402106B2 (ja) * | 1996-01-31 | 2003-04-28 | 株式会社デンソー | 酸素濃度検出素子およびその製造方法 |
JP3736020B2 (ja) * | 1997-04-16 | 2006-01-18 | 松下電器産業株式会社 | ガスセンサ |
JP2003050223A (ja) * | 2001-08-07 | 2003-02-21 | Matsushita Electric Ind Co Ltd | ガスセンサ |
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, |
JP4624946B2 (ja) * | 2006-03-17 | 2011-02-02 | 日本特殊陶業株式会社 | ガスセンサ素子の製造方法およびガスセンサの製造方法ならびにガスセンサ素子およびガスセンサ |
JP5024243B2 (ja) | 2007-09-07 | 2012-09-12 | 株式会社デンソー | ガス濃度検出素子及びその製造方法 |
JP2009080110A (ja) | 2007-09-07 | 2009-04-16 | Denso Corp | ガスセンサ素子及びその製造方法 |
JP4762338B2 (ja) | 2008-12-22 | 2011-08-31 | 株式会社日本自動車部品総合研究所 | ガスセンサ素子及びこれを備えたガスセンサ |
JP5005745B2 (ja) * | 2009-09-04 | 2012-08-22 | 日本特殊陶業株式会社 | 積層型ガスセンサ素子、積層型ガスセンサ素子を備えたガスセンサ、及び、積層型ガスセンサ素子の製造方法 |
JP5287807B2 (ja) * | 2009-10-28 | 2013-09-11 | 株式会社デンソー | ガスセンサ素子 |
JP2011237222A (ja) | 2010-05-07 | 2011-11-24 | Toyota Motor Corp | ガスセンサ素子とガスセンサ |
JP5182321B2 (ja) * | 2010-05-13 | 2013-04-17 | 株式会社デンソー | ガスセンサ素子、及び、これを内蔵したガスセンサ |
JP5218477B2 (ja) | 2010-06-04 | 2013-06-26 | 株式会社デンソー | ガスセンサ素子及びその製造方法 |
JP5387555B2 (ja) * | 2010-09-27 | 2014-01-15 | 株式会社デンソー | ガスセンサ素子及びガスセンサ |
JP5500148B2 (ja) * | 2011-09-27 | 2014-05-21 | 株式会社デンソー | ガスセンサ素子とその製造方法並びにガスセンサ |
JP2013104706A (ja) * | 2011-11-11 | 2013-05-30 | Ngk Spark Plug Co Ltd | ガスセンサ素子及びガスセンサ |
JP6121178B2 (ja) | 2013-01-31 | 2017-04-26 | 株式会社ギコウ | 人工歯 |
JP5920500B2 (ja) | 2015-02-10 | 2016-05-18 | 株式会社三洋物産 | 遊技機 |
-
2015
- 2015-04-28 JP JP2015091445A patent/JP6475074B2/ja active Active
- 2015-07-07 US US14/793,211 patent/US9958412B2/en active Active
- 2015-07-17 DE DE102015111681.2A patent/DE102015111681B4/de active Active
- 2015-07-17 CN CN201510424695.0A patent/CN105277605B/zh active Active
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Publication number | Publication date |
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US20160018357A1 (en) | 2016-01-21 |
CN105277605B (zh) | 2018-10-09 |
JP2016029360A (ja) | 2016-03-03 |
DE102015111681A1 (de) | 2016-01-21 |
US9958412B2 (en) | 2018-05-01 |
CN105277605A (zh) | 2016-01-27 |
DE102015111681B4 (de) | 2018-12-27 |
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