JP2015202972A - 無鉛圧電磁器組成物、それを用いた圧電素子、及び、無鉛圧電磁器組成物の製造方法 - Google Patents
無鉛圧電磁器組成物、それを用いた圧電素子、及び、無鉛圧電磁器組成物の製造方法 Download PDFInfo
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- JP2015202972A JP2015202972A JP2014081770A JP2014081770A JP2015202972A JP 2015202972 A JP2015202972 A JP 2015202972A JP 2014081770 A JP2014081770 A JP 2014081770A JP 2014081770 A JP2014081770 A JP 2014081770A JP 2015202972 A JP2015202972 A JP 2015202972A
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- piezoelectric ceramic
- ceramic composition
- lead
- free piezoelectric
- crystal phase
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- 239000000203 mixture Substances 0.000 title claims abstract description 129
- 239000000919 ceramic Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title description 22
- 239000013078 crystal Substances 0.000 claims abstract description 104
- 239000010955 niobium Substances 0.000 claims abstract description 61
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 50
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052700 potassium Inorganic materials 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 229910052715 tantalum Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
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- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
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- 239000011734 sodium Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000011777 magnesium Substances 0.000 description 24
- 239000010936 titanium Substances 0.000 description 23
- 230000008878 coupling Effects 0.000 description 16
- 238000010168 coupling process Methods 0.000 description 16
- 238000005859 coupling reaction Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 230000007704 transition Effects 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
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- 238000011049 filling Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
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- 229910052701 rubidium Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction 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
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
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- H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
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- H10N30/093—Forming inorganic materials
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Abstract
Description
この無鉛圧電磁器組成物によれば、A2B6O13系化合物で構成される第2結晶相を含む副相が、主相の空孔を充填することによって主相の構造を安定化するので、圧電特性に優れた無鉛圧電磁器組成物を提供することができる。
この構成によれば、第2結晶相として、安定した構造の化合物を得ることができ、この結果、圧電特性に優れた無鉛圧電磁器組成物を提供することができる。
元素BとしてMgを含むことにより、圧電特性に優れる他、絶縁特性に優れる無鉛圧電磁器組成物を提供することができる。
層状構造を有する第2結晶相は、主相の空孔を充填して主相の構造を安定化する作用が高いので、圧電特性を向上させることができる。
この構成によれば、無鉛圧電磁器組成物の圧電特性を更に向上することができる。
この構成によれば、第2結晶相による第1結晶相の構造を安定化の効果が顕著となるので、無鉛圧電磁器組成物の特性を更に向上できる。
この構成によれば、圧電特性に優れた無鉛圧電磁器組成物を得ることができる。
この構成によれば、無鉛圧電磁器組成物の特性を向上させることができる。
この構成によれば、無鉛圧電磁器組成物の特性をさらに向上させることができる。
この方法によれば、圧電特性を有するニオブ/タンタル酸アルカリ系ペロブスカイト酸化物からなる第1結晶相と、A2B6O13系化合物からなる第2結晶相とを含む、圧電特性に優れた無鉛圧電磁器組成物を作成することができる。
主相を形成するペロブスカイト酸化物は、ニオブ酸アルカリ系ペロブスカイト酸化物とタンタル酸アルカリ系ペロブスカイト酸化物の少なくとも一方を含むことが好ましい。「ニオブ/タンタル酸アルカリ系ペロブスカイト酸化物」という用語は、これらの複数種類のペロブスカイト酸化物の総称である。ニオブ/タンタル酸アルカリ系ペロブスカイト酸化物のアルカリ系成分は、アルカリ金属(K(カリウム),Na(ナトリウム),Li(リチウム),Rb(ルビジウム)等)を少なくとも含み、また、アルカリ土類金属(Ca(カルシウム),Sr(ストロンチウム),Ba(バリウム)等)を含み得る。このようなニオブ/タンタル酸アルカリ系ペロブスカイト酸化物としては、以下の組成式で表されるものが好ましい。
ここで、元素CはCa(カルシウム),Sr(ストロンチウム),Ba(バリウム),Rb(ルビジウム)の一種以上、元素DはNb(ニオブ),Ta(タンタル),Ti(チタン),Zr(ジルコニウム)のうちの少なくともNb又はTaを含む一種以上、元素EはMg(マグネシウム),Al(アルミニウム),Sc(スカンジウム),Mn(マンガン),Fe(鉄),Co(コバルト),Ni(ニッケル),Zn(亜鉛),Ga(ガリウム),Y(イットリウム)の一種以上であり、a+b+c+d=1、eは任意、f+g=1、hはペロブスカイトを構成する任意の値である。
(KaNabLicC1d1C2d2)e(D1f1D2f2D3f3E1g1E2g2)Oh …(1a)
ここで、a+b+c+d1+d2=1、eは任意、f1+f2+f3+g1+g2=1、hはペロブスカイトを構成する任意の値である。この組成式(1a)は、上記組成式(1)と等価である。この例から理解できるように、元素Cが2種類の金属元素を含む場合には、元素Cの係数dの値は、2種類の元素C1,C2の係数d1,d2の和で表される。元素D,Eも同様である。
第2結晶相を形成するA2B6O13化合物において、元素Aは1価の元素、元素Bは2〜6価の一種以上の元素である。元素Aとしては、Li(リチウム),Na(ナトリウム),K(カリウム)のうちの少なくとも一種を含むことが好ましい。また、元素Bとしては、Co(コバルト),Fe(鉄),Mg(マグネシウム),Ni(ニッケル),Zr(ジルコニウム),Mn(マンガン),Al(アルミニウム),Nb(ニオブ),Ta(タンタル),W(タングステン),Ti(チタン)のうちの少なくとも一種を含むことが好ましい。また、元素Bは、少なくともMgを含むことが絶縁特性を高める観点から更に好ましい。
<第1のグループ(サンプルS02〜S12)>
(1)主相の元素Eは、Fe,Mgを含む。
(2)副相の元素Bは、Ti,Nb,Fe,Mgを含む。
<第2のグループ(サンプルS13〜S23)>
(1)主相の元素Eは、Feを含まずMgのみを含む。
(2)副相の元素Bは、Feを含まず、Ti,Nb,Mgを含む。
(i)圧電素子を恒温槽にいれ、室温での圧電特性を評価する(初期値)。
(ii)次に、2℃/分の温度変化率で−50℃から+150℃の間で温度を変化させる熱サイクルを、1000回繰り返す(−50℃と+150℃での保持時間は1時間)。
(iii)その後、室温にて圧電特性を再度、評価する(熱サイクル後の特性値)。
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。
200…圧電素子
301…電極
302…電極
Claims (11)
- 無鉛圧電磁器組成物であって、
圧電特性を有するニオブ/タンタル酸アルカリ系ペロブスカイト酸化物からなる第1結晶相で形成された主相と、
A2B6O13系化合物(元素Aは1価の元素、元素Bは2〜6価の一種以上の元素)からなる第2結晶相を含む副相と、
を含み、
前記副相は、前記主相の間に形成される空孔を充填することを特徴とする無鉛圧電磁器組成物。 - 請求項1に記載の無鉛圧電磁器組成物であって、
前記元素Aは、Li,Na,Kのうちの少なくとも一種の金属元素を含み、
前記元素Bは、Co,Fe,Mg,Ni,Zr,Zn,Mn,Al,Nb,Ta,W,Tiのうちの少なくとも一種の金属元素を含むことを特徴とする無鉛圧電磁器組成物。 - 請求項1又は2に記載の無鉛圧電磁器組成物であって、
前記元素Bは、少なくともMgを含むことを特徴とする無鉛圧電磁器組成物。 - 請求項1〜3のいずれか一項に記載の無鉛圧電磁器組成物であって、
前記A2B6O13系化合物は層状構造を有することを特徴とする無鉛圧電磁器組成物。 - 請求項1〜4のいずれか一項に記載の無鉛圧電磁器組成物であって、
前記無鉛圧電磁器組成物における前記第2結晶相の含有割合は、
(i)0.30体積%以上で3.10体積%以下、
(ii)0.50体積%以上で2.50体積%以下、
(iii)1.00体積%以上で2.00体積%以下、
のいずれかであることを特徴とする無鉛圧電磁器組成物。 - 請求項1〜5のいずれか一項に記載の無鉛圧電磁器組成物であって、
前記副相の全体を100%としたときの前記第2結晶相の体積割合が50%より大きい、ことを特徴とする無鉛圧電磁器組成物。 - 請求項1〜6のいずれか一項に記載の無鉛圧電磁器組成物であって、
前記第1結晶相を形成するニオブ/タンタル酸アルカリ系ペロブスカイト酸化物は、アルカリ土類金属を含むことを特徴とする無鉛圧電磁器組成物。 - 請求項1〜7のいずれか一項に記載の無鉛圧電磁器組成物であって、
前記第1結晶相を形成するニオブ/タンタル酸アルカリ系ペロブスカイト酸化物は、組成式(KaNabLicCd)e(DfEg)Oh (元素CはCa,Sr,Ba,Rbの一種以上、元素DはNb,Ta,Ti,Zrのうちの少なくともNb又はTaを含む一種以上、元素EはMg,Al,Sc,Mn,Fe,Co,Ni,Zn,Ga,Yの一種以上、a+b+c+d=1、eは任意、f+g=1、hはペロブスカイトを構成する任意の値)で表されることを特徴とする無鉛圧電磁器組成物。 - 請求項8に記載の無鉛圧電磁器組成物であって、
前記係数eが、0.80≦e≦1.30を満たすことを特徴とする無鉛圧電磁器組成物。 - 請求項1〜9のいずれか一項に記載の無鉛圧電磁器組成物で形成された圧電磁器と、
前記圧電磁器に取り付けられた電極と、
を備えることを特徴とする圧電素子。 - 請求項1〜9のいずれか一項に記載の無鉛圧電磁器組成物の製造方法であって、
前記第1結晶相の原料を混合し、仮焼して第1の粉末を作成する工程と、
前記第2結晶相の原料を混合し、仮焼して第2の粉末を作成する工程と、
前記第1と第2の粉末を混合し、成形し、焼成することによって、前記無鉛圧電磁器組成物を生成する工程と、
を備え、
前記焼成は、密閉容器内に成形体を封入して焼成を行う密閉焼成であることを特徴とする無鉛圧電磁器組成物の製造方法。
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WO2024070626A1 (ja) * | 2022-09-30 | 2024-04-04 | 日本特殊陶業株式会社 | 無鉛圧電組成物、及び圧電素子 |
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US20150295162A1 (en) | 2015-10-15 |
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JP6327914B2 (ja) | 2018-05-23 |
US9871187B2 (en) | 2018-01-16 |
EP2937322A3 (en) | 2015-11-18 |
CN104973863A (zh) | 2015-10-14 |
EP2937322B1 (en) | 2018-03-14 |
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