JP2016210661A - 酸素センサ電極用導電性酸化物焼結体、及び、それを用いた酸素センサ - Google Patents
酸素センサ電極用導電性酸化物焼結体、及び、それを用いた酸素センサ Download PDFInfo
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- JP2016210661A JP2016210661A JP2015097946A JP2015097946A JP2016210661A JP 2016210661 A JP2016210661 A JP 2016210661A JP 2015097946 A JP2015097946 A JP 2015097946A JP 2015097946 A JP2015097946 A JP 2015097946A JP 2016210661 A JP2016210661 A JP 2016210661A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000001301 oxygen Substances 0.000 title claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 60
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000010304 firing Methods 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004121 SrRuO Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 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
- 238000000465 moulding Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Abstract
【解決手段】酸素センサ電極用導電性酸化物焼結体は、少なくともLa、Fe、及びNiを含むペロブスカイト型導電性酸化物で形成された結晶相を含み、770℃における熱起電力の絶対値が21.0μV/K以下である。
【選択図】図4
Description
この導電性酸化物焼結体によれば、熱起電力の絶対値が小さく酸素センサ電極用に適した電極材料を提供できる。
0.474≦a≦0.512、
0≦b≦0.225、
0<c≦0.300、
0.200≦d≦0.350
を満たすものとしても良い。
この構成によれば、導電率が高く、B定数の絶対値が小さい酸素センサ電極用導電性酸化物焼結体を提供できる。
0.474≦a<0.512、
0≦b<0.100、
を満たすものとしても良い。
この構成によれば、熱起電力の絶対値を更に小さくできる。
この構成によれば、酸素センサ電極用導電性酸化物焼結体で形成された電極から、酸素センサの他の部材にアルカリ土類金属元素が拡散することが無いので、アルカリ土類金属元素の拡散による電極自体の特性の劣化や、又は、酸素センサの性能(インピーダンス等)の低下を生じることが無い。
0.474≦a≦0.512、
0≦b≦0.225、
0<c≦0.300、
0.200≦d≦0.350
を満たすことを特徴とする。
この酸素センサ電極用導電性酸化物焼結体によれば、導電率が高く、B定数の絶対値が小さく、かつ、熱起電力の絶対値が小さな電極材料を提供できる。
本発明の一実施形態としての導電性酸化物焼結体は、少なくともLa、Fe、及びNiを含むペロブスカイト型導電性酸化物で形成された結晶相を含み、770℃における熱起電力の絶対値が21.0μV/K以下である導電性酸化物焼結体である。各種のペロブスカイト型酸化物のうち、La、Fe、及びNiを含む導電性酸化物は、導電率が高く、B定数(温度係数)の絶対値が小さいという好ましい特性が得られるので、電極材料として好適である。このようなペロブスカイト型酸化物のうち、770℃における熱起電力の絶対値が21.0μV/K以下である導電性酸化物焼結体は、酸素センサ電極用の導電性酸化物焼結体として特に適したものである。すなわち、酸素センサでは、電極の両端に約500℃にも達する温度差が生じる可能性があるが、770℃における熱起電力の絶対値が21.0μV/K以下である導電性酸化物焼結体を電極材料として用いることにより、電極の両端の温度差に応じて発生するノイズが十分に小さくなるので、測定誤差の増大を抑制することができる。
LaaCobFecNidOx …(1)
ここで、a+b+c+d=1、1.25≦x≦1.75である。また、係数a,b,c,dは以下の関係を満たすことが好ましい。
0.474≦a≦0.512 …(2a)
0≦b≦0.225 …(2b)
0<c≦0.300 …(2c)
0.200≦d≦0.350 …(2d)
0.474≦a<0.512 …(3a)
0≦b<0.100 …(3b)
0<c≦0.300 …(3c)
0.200≦d≦0.350 …(3d)
係数a,b,c,dがこれらの関係を満足すれば、熱起電力の絶対値を10.0μV/K以下の小さな値とすることができる。
図1は、本発明の一実施形態における導電性酸化物焼結体の製造方法を示すフローチャートである。工程T110では、導電性酸化物焼結体の原料粉末を秤量した後、湿式混合して乾燥することにより、原料粉末混合物を調整する。原料粉末としては、例えば、La(OH)3、Co3O4、Fe2O3及びNiOを用いることができる。これらの原料粉末としては、すべて純度99%以上のものを用いることが好ましい。なお、La原料としては、La(OH)3の代わりにLa2O3を利用することも可能であるが、La(OH)3を用いることが好ましく、La2O3を用いないことが好ましい。この理由は、La2O3には吸水性があるので正確に調合することが困難であり、導電率の低下や再現性の低下を招く可能性があるためである。工程T120では、この原料粉末混合物を大気雰囲気下、700〜1200℃で1〜5時間仮焼して仮焼粉末を作成する。工程T130では、この仮焼粉末に適量の有機バインダを加え、これを分散溶媒(例えばエタノール)と共に樹脂ポットに投入し、ジルコニア玉石を用いて湿式混合粉砕してスラリーを得る。工程T130では、得られたスラリーを80℃で2時間ほど乾燥し、さらに、250μmメッシュの篩を通して造粒し、造粒粉末を得る。工程T140では、得られた造粒粉末をプレス機(成形圧力;98MPa)によって成形する。工程T150では、大気雰囲気下、工程T120における仮焼温度よりも高い焼成温度(1300〜1600℃)で1〜5時間焼成することによって導電性酸化物焼結を得る。焼成の後には、必要に応じて導電性酸化物焼結体の平面を研磨してもよい。
図4は、実施例及び比較例としての複数のサンプルの組成及び特性を示している。図面において、サンプル番号に「*」が付されたサンプルは比較例であり、「*」が付されていないサンプルは実施例である。各サンプルの酸化物焼結体は、図1で説明した製造方法に従ってそれぞれ作製し、最後に平面研磨を行って、3.0mm×3.0mm×15.0mmの直方体状のサンプルを得た。なお、工程T110では、図4に示す組成に従って原料を秤量・混合した。
導電率は、直流4端子法により測定した。測定に用いる電極及び電極線にはPtを用いた。また、導電率の測定には、電圧・電流発生器(エーディーシー社製のモニタ6242型)を用いた。
B定数(K-1)は、25℃と870℃の導電率から次式に従って算出した。
B定数=ln(ρ1/ρ2)/(1/T1−1/T2) …(4)
ρ1=1/σ1
ρ2=1/σ2
ρ1:絶対温度T1(K)における抵抗率(Ωcm)
ρ2:絶対温度T2(K)における抵抗率(Ωcm)
σ1:絶対温度T1(K)における導電率(S/cm)
σ2:絶対温度T2(K)における導電率(S/cm)
T1=298.15(K)
T2=1143.15(K)
熱起電力は、定常直流法により測定した。各サンプル(3.0mm×3.0mm×15mm)の長手方向両端よりもやや中央寄りで互いに所定距離だけ離れた2箇所にPt線を巻きつけ、導電率の電位差測定用電極として利用した。また、サンプルの両端にスパッタでAuを蒸着し、その両端にPt板またはPt網で形成された外側白金電極をそれぞれ設けた状態でサンプルの両端を石英管で挟み込んでサンプルを固定した。測定時には、2つの外側白金電極の間に定電流を印加するとともに、片側の石英管に高温の空気を送り込むことによって外側白金電極間に温度差を発生させた。さらに、外側白金電極にR熱電対(Pt−Pt13Rh)を取り付けて、温度差を読み取った。空気流量を変化させることによって温度差を段階的に生じさせ、電位差−温度差の相関関係を求め、最小二乗法により770℃における熱起電力を算出した。なお、測定にはオザワ科学社製RZ2001kを用いた。また、測定は大気雰囲気下で行った。
なお、この発明は上記の実施例や実施形態に限られるものではなく、その要旨を逸脱しない範囲において種々の態様において実施することが可能である。
110…基材
120…外部電極
130…基準電極
Claims (7)
- 少なくともLa、Fe、及びNiを含むペロブスカイト型導電性酸化物で形成された結晶相を含む酸素センサ電極用の導電性酸化物焼結体であって、
770℃における熱起電力の絶対値が21.0μV/K以下であることを特徴とする酸素センサ電極用導電性酸化物焼結体。 - 請求項1に記載の酸素センサ電極用導電性酸化物焼結体であって、
前記結晶相は、組成式:LaaCobFecNidOx(但し、a+b+c+d=1、1.25≦x≦1.75)で表されるペロブスカイト型酸化物結晶構造を有し、前記a,b,c,dが、
0.474≦a≦0.512、
0≦b≦0.225、
0<c≦0.300、
0.200≦d≦0.350
を満たすことを特徴とする酸素センサ電極用導電性酸化物焼結体。 - 請求項2に記載の酸素センサ電極用導電性酸化物焼結体であって、
前記a,bが、
0.474≦a<0.512、
0≦b<0.100、
を満たすことを特徴とする酸素センサ電極用導電性酸化物焼結体。 - 請求項1〜3のいずれか一項に記載の酸素センサ電極用導電性酸化物焼結体であって、
アルカリ土類金属元素を実質的に無含有とすることを特徴とする酸素センサ電極用導電性酸化物焼結体。 - 酸素センサ電極用の導電性酸化物焼結体であって、
組成式:LaaCobFecNidOx(但し、a+b+c+d=1、1.25≦x≦1.75)で表されるペロブスカイト型酸化物結晶構造を有する結晶相を含み、前記a,b,c,dが、
0.474≦a≦0.512、
0≦b≦0.225、
0<c≦0.300、
0.200≦d≦0.350
を満たすことを特徴とする酸素センサ電極用導電性酸化物焼結体。 - 請求項1〜5のいずれかに記載の酸素センサ電極用導電性酸化物焼結体で形成された電極を備えることを特徴とする酸素センサ。
- 請求項6に記載の酸素センサであって、
前記電極は、基準電極であることを特徴とする酸素センサ。
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