JP2008056549A - Unleaded piezoelectric porcelain composition - Google Patents
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- 239000000203 mixture Substances 0.000 title claims abstract description 101
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 34
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011591 potassium Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 100
- 239000002994 raw material Substances 0.000 claims description 19
- 229910013641 LiNbO 3 Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 229910002367 SrTiO Inorganic materials 0.000 claims description 13
- -1 composed of NaNbO 3 Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000010955 niobium Substances 0.000 description 9
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005467 ceramic manufacturing process Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UTBYQPSPFXHANA-UHFFFAOYSA-N [K].[Na].[Li] Chemical compound [K].[Na].[Li] UTBYQPSPFXHANA-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical group [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、ニオブ酸系の圧電磁器、その製造方法、及び圧電素子に関するものであり、更に詳しくは、NaNbO3−LiNbO3−SrTiO3を主成分とするペロブスカイト化合物を主体とした新規な圧電磁器及び圧電素子、特に、圧電フィルタ、及び圧電共振子に好適な圧電磁器に関するものである。 The present invention, piezoelectric ceramic niobate-based, a manufacturing method thereof, and relates to a piezoelectric element, and more particularly to a novel piezoelectric ceramic consisting mainly of perovskite compound whose main component is NaNbO 3 -LiNbO 3 -SrTiO 3 Further, the present invention relates to a piezoelectric ceramic suitable for a piezoelectric element, in particular, a piezoelectric filter and a piezoelectric resonator.
本発明は、カリウムを含まない組成において、高いキュリー温度及び良好な圧電特性を実現したニオブ酸系圧電磁器を提供するものである。本発明の圧電磁器は、製造に際して、吸湿性を有するカリウム原料を使用する必要がないことから、本発明は、従来材のKNbO3−NaNbO3を主成分とするニオブ酸アルカリ系の圧電磁器に見られるような、カリウムの原料として一般に使用される炭酸カリウムに起因する吸湿性の問題を確実に回避することができる。更に、本発明は、低温で揮発性の極めて高い酸化鉛(PbO)を含有していない組成物からなる、生態学的な見地、及び公害防止の面からも好ましい無鉛圧電磁器を提供するものである。 The present invention provides a niobic acid-based piezoelectric ceramic that realizes a high Curie temperature and good piezoelectric characteristics in a potassium-free composition. Since the piezoelectric ceramic of the present invention does not require the use of a hygroscopic potassium raw material in the production, the present invention is applied to an alkali niobate-based piezoelectric ceramic mainly composed of KNbO 3 —NaNbO 3. The problem of hygroscopicity due to potassium carbonate generally used as a raw material for potassium as seen can be reliably avoided. Furthermore, the present invention provides a lead-free piezoelectric ceramic that is composed of a composition that does not contain lead oxide (PbO) that is extremely volatile at low temperatures, which is preferable from the viewpoint of ecology and pollution prevention. is there.
圧電セラミックスは、各種センサや超音波振動子といった従来の応用に加えて、最近ではパーソナルコンピュータの液晶バックライト用トランスやインクジェットプリンタ用ヘッド部品材料として使用されるなど、電子機器の小型化や高性能化に多大な貢献をしている。現在、圧電セラミック材料としては、ジルコン酸鉛(PbZrO3)とチタン酸鉛(PbTiO3)の固溶体に添加物を少量加えた、いわゆるPZT系や、PZTにPb(Mg1/3Nb2/3)O3といった複合ペロブスカイト化合物を固溶させた、いわゆる三成分系の固溶体が主に使用されている。 In addition to conventional applications such as various sensors and ultrasonic vibrators, piezoelectric ceramics have recently been used as liquid crystal backlight transformers for personal computers and head part materials for inkjet printers. Has made a great contribution to the development. At present, as a piezoelectric ceramic material, a so-called PZT system in which a small amount of an additive is added to a solid solution of lead zirconate (PbZrO 3 ) and lead titanate (PbTiO 3 ), or Pb (Mg 1/3 Nb 2/3 ) is added to PZT. ) A so-called ternary solid solution in which a complex perovskite compound such as O 3 is dissolved is mainly used.
しかし、これらの圧電セラミック材料は、環境に対して有害な酸化鉛を重量にして70%程度含むことから、圧電素子を用いた電子機器が不法廃棄された場合、酸性雨による自然環境への鉛化合物の拡散が懸念されている。そこで、従来の鉛系材料に代替できる実用化可能な無鉛圧電セラミック材料の開発が強く求められている。 However, since these piezoelectric ceramic materials contain about 70% by weight of lead oxide harmful to the environment, when electronic devices using piezoelectric elements are illegally discarded, lead to the natural environment due to acid rain There is concern about the diffusion of compounds. Therefore, there is a strong demand for the development of a practical lead-free piezoelectric ceramic material that can be substituted for a conventional lead-based material.
現在、主な無鉛圧電セラミック用化合物としては、ペロブスカイト型、タングステン・ブロンズ型、及びビスマス層状構造型強誘電体が知られており、例えば、複合ペロブスカイト化合物の(Bi0.5Na0.5)TiO3と単純ペロブスカイト化合物であるBaTiO3系との固溶体である(Bi0.5Na0.5)TiO3−BaTiO3固溶体(BNT−BT系固溶体)が、キュリー温度が高く、1200℃程度で焼結可能であることから有力な無鉛圧電セラミック候補材料として考えられている。 At present, perovskite type, tungsten bronze type, and bismuth layered structure type ferroelectrics are known as main lead-free piezoelectric ceramic compounds. For example, a composite perovskite compound (Bi 0.5 Na 0.5 ) is known. (Bi 0.5 Na 0.5 ) TiO 3 —BaTiO 3 solid solution (BNT-BT solid solution), which is a solid solution of TiO 3 and a simple perovskite compound BaTiO 3 system, has a high Curie temperature at about 1200 ° C. Since it can be sintered, it is considered as a leading lead-free piezoelectric ceramic candidate material.
更に、近年、自然環境に対して有害な酸化鉛を含有せず、比較的良好な圧電性を示すセラミック材料として、ニオブ酸アルカリ系の圧電磁器が注目されている。ニオブ酸アルカリ系の圧電磁器に関する先行技術としては、例えば、ニオブ酸リチウムナトリウムを基本組成とする固溶体に、副成分として、酸化アルミニウム、酸化鉄を添加した、高密度で機械的強度が大きい圧電磁器が提案されている(特許文献1参照)。また、例えば、ニオブ酸アルカリを主成分とした圧電磁器として、一般式:{Lix(K1−yNay)1−x}{Nb1−z−wTazSbw}O3からなる等方性ペロブスカイト型ニオブ酸カリウムナトリウムを基本組成とし、優れた圧電特性を示す結晶配向セラミックスが提案されている(特許文献2参照)。 Further, in recent years, alkaline niobate-based piezoelectric ceramics have attracted attention as ceramic materials that do not contain lead oxide harmful to the natural environment and exhibit relatively good piezoelectricity. As prior art related to alkali niobate-based piezoelectric ceramics, for example, piezoelectric ceramics having high density and high mechanical strength, in which aluminum oxide and iron oxide are added as secondary components to a solid solution having a basic composition of lithium sodium niobate Has been proposed (see Patent Document 1). Further, for example, as a piezoelectric ceramic mainly composed of an alkali niobate, the general formula: {Li x (K 1−y Na y ) 1−x } {Nb 1−z−w Ta z Sb w } O 3 There has been proposed a crystallographically oriented ceramic having an isotropic perovskite-type potassium sodium niobate as a basic composition and exhibiting excellent piezoelectric characteristics (see Patent Document 2).
また、ニオブ酸カリウム(KNbO3)とニオブ酸ナトリウム(NaNbO3)を主成分としたニオブ酸アルカリ系の圧電磁器として、これに銅を添加して焼結性を改善した組成物や、リチウム及びタンタルを添加することによって温度特性を高くした組成物が提案されている(特許文献3参照)。 Further, as an alkaline niobate-based piezoelectric ceramic mainly composed of potassium niobate (KNbO 3 ) and sodium niobate (NaNbO 3 ), a composition in which copper is added thereto to improve sinterability, lithium and A composition having improved temperature characteristics by adding tantalum has been proposed (see Patent Document 3).
また、(Li、K、Na)(Nb、Ta、Sb)O3系のセラミックスは、キュリー温度が高く、比較的高い電気機械結合係数を有することから、圧電素子としての利用が考えられている(特許文献4参照)。他の事例として、ニオブ酸カリウムナトリウムリチウムを主成分とし、Bi等の2価の金属、Ti、Zr、Sn、Hf等の4価の金属を含む組成からなる、高周波領域での使用に適した圧電磁器組成物が提案されている(特許文献5参照) In addition, (Li, K, Na) (Nb, Ta, Sb) O 3 -based ceramics are considered to be used as piezoelectric elements because they have a high Curie temperature and a relatively high electromechanical coupling coefficient. (See Patent Document 4). As another example, composed of lithium sodium potassium niobate as a main component and composed of a divalent metal such as Bi and a tetravalent metal such as Ti, Zr, Sn, and Hf, it is suitable for use in a high frequency region. A piezoelectric ceramic composition has been proposed (see Patent Document 5).
従来のKNbO3−NaNbO3を主成分とするニオブ酸アルカリ系の圧電磁器は、比較的高い電気機械結合係数、及び高い圧電歪定数を示すものの、組成に応じて、室温〜100℃付近に斜方晶から正方晶に相転位する温度、いわゆる相転移点が存在し、その温度範囲内において圧電特性の著しい変化を生じさせることから、このことが、KNbO3−NaNbO3を主成分とするニオブ酸アルカリ系の圧電磁器の製品化における問題点となっていた。 The piezoelectric ceramic of the alkali niobate-based mainly composed of conventional KNbO 3 -NaNbO 3 is relatively high electromechanical coupling coefficient, and while indicating high piezoelectric strain constant, depending on the composition, oblique to about room temperature to 100 ° C. There is a temperature at which a phase transition from tetragonal to tetragonal, a so-called phase transition point, which causes a significant change in piezoelectric characteristics within the temperature range. This is why niobium containing KNbO 3 —NaNbO 3 as a main component. This was a problem in the commercialization of acid-alkali piezoelectric ceramics.
また、このKNbO3−NaNbO3を主成分とするニオブ酸アルカリ系の圧電磁器は、その製造過程においてカリウムの原料として一般に使用される炭酸カリウムは、吸湿性が高く、工業規模でのセラミックスの生産において取り扱いが困難であるという製造技術上の問題があり、セラミックスの構成元素としてカリウムを含むことが、KNbO3−NaNbO3を主成分とするニオブ酸アルカリ系の圧電磁器を実用化する上での問題の一つとなっていた。 In addition, the alkaline niobate-based piezoelectric ceramic mainly composed of KNbO 3 —NaNbO 3 , potassium carbonate generally used as a raw material of potassium in the production process thereof has high hygroscopicity, and produces ceramics on an industrial scale. Is difficult to handle in the manufacturing technology, and the fact that potassium is included as a constituent element of ceramics, in practical use of an alkali niobate piezoelectric ceramic mainly composed of KNbO 3 —NaNbO 3 It was one of the problems.
このような状況の中で、本発明者は、上記従来技術に鑑みて、簡便に製造することが可能であり、カリウムを含まない組成において、高いキュリー温度及び良好な圧電特性を実現することが可能なニオブ酸系圧電磁器を開発することを目標として鋭意研究を積み重ねた結果、Na、Li、Sr、Nb、Tiを主成分とするペロブスカイト化合物を主体とした新しいニオブ酸系圧電磁器を開発することに成功し、本発明を完成するに至った。 Under such circumstances, the present inventor can easily manufacture in view of the above prior art, and can achieve a high Curie temperature and good piezoelectric characteristics in a composition not containing potassium. As a result of intensive research aimed at developing possible niobic acid-based piezoelectric ceramics, new niobic acid-based piezoelectric ceramics mainly composed of perovskite compounds mainly composed of Na, Li, Sr, Nb, and Ti are developed. In particular, the present invention has been completed.
本発明は、カリウムを含まない組成において、高いキュリー温度及び良好な圧電特性を実現したニオブ酸系の新規圧電磁器を提供することを目的とするものである。また、本発明は、吸湿性が高いために工業的に取り扱いが困難なカリウム原料を使用しないで、すなわち、カリウムを含まない組成を用いて、高いキュリー温度及び良好な圧電特性を有するニオブ酸系圧電磁器を製造する方法を提供することを目的とするものである。 An object of the present invention is to provide a novel niobate-based piezoelectric ceramic that realizes a high Curie temperature and good piezoelectric characteristics in a potassium-free composition. Further, the present invention does not use a potassium raw material that is difficult to handle industrially due to its high hygroscopicity, that is, a niobic acid system having a high Curie temperature and good piezoelectric properties using a composition not containing potassium. It aims at providing the method of manufacturing a piezoelectric ceramic.
また、本発明は、高いキュリー温度、高い電気機械結合係数、及び高い圧電歪定数を有する圧電磁器を提供することを目的とするものである。更に、本発明は、上記圧電磁器を使用した、自然環境に優しい、鉛を含まない実用的なニオブ酸系圧電素子、及びその応用製品を提供することを目的とするものである。 Another object of the present invention is to provide a piezoelectric ceramic having a high Curie temperature, a high electromechanical coupling coefficient, and a high piezoelectric strain constant. Furthermore, an object of the present invention is to provide a practical niobic acid-based piezoelectric element that does not contain lead and that uses the above-described piezoelectric ceramic, and its applied product.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
(1)NaNbO3を主成分とするペロブスカイト化合物を主体としたニオブ酸系圧電磁器であって、1)該圧電磁器の組成の一部がLiNbO3及びSrTiO3で置換されていること、2)該圧電磁器がカリウム成分を実質的に含まないこと、を特徴とする圧電磁器。
(2)Na、Li、Sr、Nb、及びTiを主成分とするペロブスカイト化合物を主体としたニオブ酸系圧電磁器であって、モル比による組成式をxNaNbO3+yLiNbO3+zSrTiO3(ただし、x+y+z=1)とした時、該圧電磁器の組成が、(x=0.93、y=0.05、z=0.01)組成、(x=0.89、y=0.10、z=0.01)組成、(x=0.83、y=0.10、z=0.07)組成、及び(x=0.88、y=0.05、z=0.07)組成で囲まれる範囲にある、上記(1)に記載の圧電磁器。
(3)上記(1)又は(2)に記載の圧電磁器を主要材料として含むことを特徴とする圧電素子。
(4)上記(3)に記載の圧電素子を構成要素として含むことを特徴とする圧電フィルタ又は圧電共振子。
(5)NaNbO3、LiNbO3、及びSrTiO3を主要構成成分とするペロブスカイト化合物を主体としたニオブ酸系圧電磁器の製造方法であって、モル比による組成式をxNaNbO3+yLiNbO3+zSrTiO3(ただし、x+y+z=1)とした時、該圧電磁器の組成が、(x=0.93、y=0.05、z=0.01)組成、(x=0.89、y=0.10、z=0.01)組成、(x=0.83、y=0.10、z=0.07)組成、及び(x=0.88、y=0.05、z=0.07)組成で囲まれる範囲となるように原料粉末を配合し、これを仮焼し、成形し、焼成することを特徴とする上記ニオブ酸系圧電磁器の製造方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) A niobic acid-based piezoelectric ceramic mainly composed of a perovskite compound mainly composed of NaNbO 3 , 1) a part of the composition of the piezoelectric ceramic is replaced with LiNbO 3 and SrTiO 3 , 2) A piezoelectric ceramic characterized in that the piezoelectric ceramic does not substantially contain a potassium component.
(2) A niobic acid-based piezoelectric ceramic mainly composed of a perovskite compound mainly composed of Na, Li, Sr, Nb, and Ti, and the composition formula based on the molar ratio is xNaNbO 3 + yLiNbO 3 + zSrTiO 3 (where x + y + z = 1), the composition of the piezoelectric ceramic is (x = 0.93, y = 0.05, z = 0.01) composition, (x = 0.89, y = 0.10, z = 0) .01) composition, (x = 0.83, y = 0.10, z = 0.07) composition, and (x = 0.88, y = 0.05, z = 0.07) composition. The piezoelectric ceramic according to (1), which is in a range.
(3) A piezoelectric element comprising the piezoelectric ceramic according to (1) or (2) as a main material.
(4) A piezoelectric filter or a piezoelectric resonator comprising the piezoelectric element according to (3) as a constituent element.
(5) A method for producing a niobic acid piezoelectric ceramic mainly composed of a perovskite compound mainly composed of NaNbO 3 , LiNbO 3 , and SrTiO 3 , wherein the composition formula based on the molar ratio is expressed as xNaNbO 3 + yLiNbO 3 + zSrTiO 3 , X + y + z = 1), the composition of the piezoelectric ceramic is (x = 0.93, y = 0.05, z = 0.01) composition, (x = 0.89, y = 0.10, z = 0.01) composition, (x = 0.83, y = 0.10, z = 0.07) composition, and (x = 0.88, y = 0.05, z = 0.07) composition. A method for producing a niobic acid-based piezoelectric ceramic as described above, wherein the raw material powder is blended so as to be in a range surrounded by, calcined, molded, and fired.
次に、本発明について更に詳細に説明する。
本発明の圧電磁器は、NaNbO3を主成分とするペロブスカイト化合物を主体としたニオブ酸系圧電磁器であって、(1)該圧電磁器の組成の一部がLiNbO3及びSrTiO3で置換されていること、(2)該圧電磁器がカリウム成分を実質的に含まないこと、を特徴とするものである。
Next, the present invention will be described in more detail.
The piezoelectric ceramic according to the present invention is a niobic acid-based piezoelectric ceramic mainly composed of a perovskite compound mainly composed of NaNbO 3 , wherein (1) a part of the composition of the piezoelectric ceramic is replaced with LiNbO 3 and SrTiO 3. (2) The piezoelectric ceramic is substantially free of potassium components.
本発明では、Na、Li、Sr、Nb、及びTiを主成分とするペロブスカイト化合物を主体とした圧電磁器であって、モル比による組成式をxNaNbO3+yLiNbO3+zSrTiO3(ただし、x+y+z=1)とした時、該圧電磁器の組成が、(x=0.93、y=0.05、z=0.01)組成、(x=0.89、y=0.10、z=0.01)組成、(x=0.83、y=0.10、z=0.07)組成、及び(x=0.88、y=0.05、z=0.07)組成で囲まれる範囲にあること、を好ましい実施の態様としている。 In the present invention, a piezoelectric ceramic mainly composed of a perovskite compound mainly composed of Na, Li, Sr, Nb, and Ti, the composition formula based on the molar ratio being xNaNbO 3 + yLiNbO 3 + zSrTiO 3 (where x + y + z = 1) The composition of the piezoelectric ceramic is (x = 0.93, y = 0.05, z = 0.01) composition, (x = 0.89, y = 0.10, z = 0.01). ) Composition, (x = 0.83, y = 0.10, z = 0.07) composition, and (x = 0.88, y = 0.05, z = 0.07) in the range surrounded by the composition This is a preferred embodiment.
本発明の圧電磁器の上記組成範囲には、上記組成により囲まれた範囲内の組成、及びそれらの組成に相当する組成が含まれる。具体的には、本発明の圧電磁器は、Na、Li、Sr、Nb、及びTiを主成分とするペロブスカイト化合物を主体とした圧電磁器であって、モル比による組成式をxNaNbO3+yLiNbO3+zSrTiO3(ただし、x+y+z=1)とした時、c:(x=0.93、y=0.05、z=0.01)組成、a:(x=0.89、y=0.10、z=0.01)組成、b:(x=0.83、y=0.10、z=0.07)組成、及びd:(x=0.88、y=0.05、z=0.07)組成の、a、b、c、dで囲まれる範囲を満足する組成(ただし、a、b、c、dの各点、及びそれらを結ぶ線上の組成に該当する組成を含む)を有することが重要である。 The composition range of the piezoelectric ceramic of the present invention includes compositions within the range surrounded by the composition and compositions corresponding to those compositions. Specifically, the piezoelectric ceramic of the present invention is a piezoelectric ceramic mainly composed of a perovskite compound mainly composed of Na, Li, Sr, Nb, and Ti, and a composition formula based on a molar ratio is expressed as xNaNbO 3 + yLiNbO 3 + zSrTiO. 3 (where x + y + z = 1), c: (x = 0.93, y = 0.05, z = 0.01) composition, a: (x = 0.89, y = 0.10, z = 0.01) composition, b: (x = 0.83, y = 0.10, z = 0.07) composition, and d: (x = 0.88, y = 0.05, z = 0 .07) Composition satisfying the range surrounded by a, b, c, and d (including the composition corresponding to each point of a, b, c and d and the composition on the line connecting them) It is important to have.
更に、本発明の圧電磁器は必要に応じて各種の副成分を含むことができるが、例えば、酸化鉄(FeO)や酸化マンガン(MnO)を副成分として含む組成とすることにより、機械的品質係数(Qm)を改善することができる。図1に、本発明の圧電磁器の3成分組成図を示す。同図において、a、b、c、dは上記の4点の組成に相当する位置を示しており、これらの各点a〜dを結ぶ線分で囲まれた領域(線分上を含む)内の組成物により本発明の圧電磁器が構成される。本発明の上記組成範囲にあるNaNbO3、LiNbO3、及びSrTiO3を主成分とする圧電磁器は、高いキュリー温度、高い電気機械結合係数、及び高い圧電歪定数を示す等の優れた圧電特性を有する。 Furthermore, the piezoelectric ceramic according to the present invention can contain various subcomponents as required. For example, by making the composition contain iron oxide (FeO) or manganese oxide (MnO) as subcomponents, the mechanical quality can be improved. The coefficient (Qm) can be improved. FIG. 1 shows a three-component composition diagram of the piezoelectric ceramic according to the present invention. In the figure, a, b, c, and d indicate positions corresponding to the composition of the above four points, and a region surrounded by a line segment connecting these points a to d (including on the line segment). The piezoelectric ceramic of the present invention is constituted by the composition inside. Piezoelectric ceramics mainly composed of NaNbO 3 , LiNbO 3 , and SrTiO 3 in the above composition range of the present invention have excellent piezoelectric properties such as high Curie temperature, high electromechanical coupling coefficient, and high piezoelectric strain constant. Have.
本発明の圧電磁器の前記構成において、NaNbO3の含有割合を0.83〜0.93の範囲としたのは、実験の結果、この範囲が、キュリー温度が高く、良好な圧電特性を示した組成であることによる。また、前記構成において、LiNbO3による置換割合を0.1〜0.05の範囲としたのは、LiNbO3は、NaNbO3と異なる結晶構造であり、0.1以上含む組成ではペロブスカイトの単一相にはならないことによる。また、前記構成において、SrTiO3による置換割合を0.01〜0.07の範囲としたのは、SrTiO3はキュリー温度が低いために、0.07以上含む組成では、磁器のキュリー温度が250℃以下となり、工業的な実用性が下がることによる。 In the configuration of the piezoelectric ceramic according to the present invention, the content ratio of NaNbO 3 was set to a range of 0.83 to 0.93. As a result of experiments, this range showed a high Curie temperature and good piezoelectric characteristics. Depending on the composition. Also, in the structure, was in the range of 0.1 to 0.05 substitution ratio by LiNbO 3, the LiNbO 3 is a different crystal structure and NaNbO 3, a single perovskite with the composition containing 0.1 or higher By not being in phase. Also, in the structure, was in the range of 0.01 to 0.07 substitution ratio by SrTiO 3, to SrTiO 3 has Curie temperature is low, the composition containing less than 0.07, the Curie temperature of the porcelain 250 This is due to the fact that the temperature becomes below ℃ and industrial practicality decreases.
次に、本発明の圧電磁器の製造方法について説明すると、本発明の圧電磁器は、例えば、次のようにして製造することができる。まず、Na2CO3、Li2CO3、SrCO3、Nb2O5、TiO2原料を用いて、予め所定の組成になるよう秤量し、これを、例えば、ZrO2ボールを用いた湿式方式で混合する。次に、この混合粉体を、例えば、600〜900℃で、3時間程度仮焼成し、所定の組成の合成粉体を得る。得られた合成粉体については、例えば、ZrO2ボールを用いて湿式粉砕し、乾燥させ、この混合粉末に有機バインダーを加え、金型プレス、静水圧プレス等により所望の形状に成形した後、大気中、例えば、1100〜1200℃で3時間程度焼成して磁器を得る。上記仮焼及び焼成の条件は、組成、製品の形態、種類等に応じて任意に設定することができる。 Next, the manufacturing method of the piezoelectric ceramic according to the present invention will be described. The piezoelectric ceramic according to the present invention can be manufactured as follows, for example. First, Na 2 CO 3 , Li 2 CO 3 , SrCO 3 , Nb 2 O 5 , and TiO 2 raw materials are weighed in advance to have a predetermined composition, and this is, for example, a wet system using ZrO 2 balls Mix with. Next, this mixed powder is calcined at 600 to 900 ° C. for about 3 hours to obtain a synthetic powder having a predetermined composition. About the obtained synthetic powder, for example, after wet-grinding using ZrO 2 balls and drying, an organic binder is added to this mixed powder, and after molding into a desired shape by a die press, an isostatic press, etc. The porcelain is obtained by firing at 1100 to 1200 ° C. for about 3 hours in the atmosphere. The calcination and firing conditions can be arbitrarily set according to the composition, product form, type, and the like.
使用する各原料粉末は、酸化物だけでなく、炭酸塩、酢酸塩、又は有機金属等の化合物のいずれであっても、焼成等の熱処理プロセスによって酸化物になるものであれば何ら差し支えない。上記圧電磁器の製造工程においては、原料粉末を上記組成範囲内になるように任意の方法及び手段で秤量し、これらを混合して混合粉末とし、これを仮焼し、粉砕し、成形し、焼成することによって圧電磁器を製造する。 Each raw material powder to be used is not limited to an oxide, and any compound such as carbonate, acetate, or organic metal may be used as long as it becomes an oxide by a heat treatment process such as firing. In the piezoelectric ceramic manufacturing process, the raw material powder is weighed by an arbitrary method and means so as to be within the above composition range, and these are mixed to obtain a mixed powder, which is calcined, pulverized, molded, A piezoelectric ceramic is manufactured by firing.
原材料の混合方式としては、例えば、乾式混合、湿式混合が例示される。また、粉砕方法としては、例えば、乾式粉砕方法、湿式粉砕方法が例示される。また、成形方法としては、例えば、乾式プレス法、冷間等方プレス法(CIP)が例示され、また、加熱処理としては、大気中や、アルゴン、窒素、酸素フロー中の雰囲気中での加熱処理が例示される。しかし、上記圧電磁器の製造工程における混合方式、成形方式や、加熱処理が、上記のものに限定されるものではない。 Examples of the raw material mixing method include dry mixing and wet mixing. Examples of the pulverization method include a dry pulverization method and a wet pulverization method. Further, examples of the molding method include a dry press method and a cold isotropic press method (CIP), and examples of the heat treatment include heating in air or in an atmosphere of argon, nitrogen, or oxygen flow. The process is illustrated. However, the mixing method, molding method, and heat treatment in the piezoelectric ceramic manufacturing process are not limited to those described above.
本発明のニオブ酸系の圧電磁器は、原料の吸湿性が高いことから、工業的に取り扱いが困難なカリウムをその構成成分として含まない組成を用いているため、工業的な取り扱いが困難となるカリウム原料を用いることなく実用的なニオブ酸系圧電磁器の生産を可能とすることができる。この圧電磁器は、高いキュリー温度及び良好な圧電特性を有し、しかも低温で揮発性の高い酸化鉛を含有していない組成を用いていることから、本発明により、自然環境に優しい、鉛を含まない、良好な圧電特性を有する、実用的なニオブ酸系の圧電磁器を製造し、提供することが可能となる。 The niobic acid-based piezoelectric ceramic of the present invention has a high hygroscopic property of the raw material, and therefore uses a composition that does not contain potassium, which is difficult to handle industrially, as its constituent component, and therefore, industrial handling becomes difficult. It is possible to produce a practical niobic acid piezoelectric ceramic without using a potassium raw material. This piezoelectric ceramic has a high Curie temperature and good piezoelectric characteristics, and uses a composition that does not contain lead oxide that is low in temperature and high in volatility. It is possible to manufacture and provide a practical niobic acid-based piezoelectric ceramic that does not contain and has good piezoelectric characteristics.
本発明は、炭酸カリウム等の吸湿性の高いカリウム原料を使用することなく、カリウムを含まない組成において、高いキュリー温度及び良好な圧電特性を有しているニオブ酸系の圧電磁器を製造することを可能としたことを特徴とするものである。従来、KNbO3−NaNbO3を主成分とするニオブ酸アルカリ系の圧電磁器の製造において、カリウムの原料として、一般に使用される炭酸カリウムは、吸湿性が高く、工業規模での圧電セラミックスの生産において取り扱いが困難という問題があり、そのことが、ニオブ酸系の圧電磁器の実用化を阻む問題の一つとなっていた。これに対し、本発明は、カリウムを含まない組成において、高いキュリー温度及び良好な圧電特性を実現した新しいニオブ酸系圧電磁器を製造し、提供することを可能とするものである。 The present invention produces a niobic acid-based piezoelectric ceramic having a high Curie temperature and good piezoelectric characteristics in a composition not containing potassium without using a potassium material having high hygroscopicity such as potassium carbonate. It is characterized by making it possible. Conventionally, in the production of an alkaline niobate-based piezoelectric ceramic mainly composed of KNbO 3 —NaNbO 3 , potassium carbonate generally used as a raw material of potassium has high hygroscopicity, and in the production of piezoelectric ceramics on an industrial scale. There was a problem that it was difficult to handle, and this was one of the problems that prevented the practical use of niobic acid-based piezoelectric ceramics. On the other hand, the present invention makes it possible to manufacture and provide a new niobic acid-based piezoelectric ceramic that realizes a high Curie temperature and good piezoelectric characteristics in a composition that does not contain potassium.
本発明のニオブ酸系圧電磁器は、高いキュリー温度、高い電気機械結合係数、及び高い圧電歪定数を有しており、本発明は、上述の、特定のxNaNbO3+yLiNbO3+LiNbO3の組成からなる新規ニオブ酸系圧電磁器を主要な材料として含む圧電素子、当該圧電素子を構成要素として含む圧電フィルタ又は圧電共振子等の圧電部材を構築し、提供することを実現できる。 The niobic acid-based piezoelectric ceramic of the present invention has a high Curie temperature, a high electromechanical coupling coefficient, and a high piezoelectric strain constant, and the present invention is composed of the above-described specific xNaNbO 3 + yLiNbO 3 + LiNbO 3 composition. Construction and provision of a piezoelectric element including a novel niobic acid-based piezoelectric ceramic as a main material, a piezoelectric filter or a piezoelectric resonator including the piezoelectric element as a constituent element can be realized.
本発明により、次のような効果が奏される。
(1)NaNbO3、LiNbO3、及びSrTiO3を主成分とするペロブスカイト化合物を主体とした新しいニオブ酸系の圧電磁器を提供することができる。
(2)カリウムの原料として一般に使用される炭酸カリウムは、吸湿性が高く、工業規模でのセラミックスの生産において取り扱いが困難という問題があるが、本発明では、カリウム原料を使用することなく、簡便にニオブ酸系の圧電磁器を生産することが可能である。
(3)カリウムを含まない組成において、高いキュリー温度、及び良好な圧電特性を有するニオブ酸系の圧電磁器を実現することができる。
(4)自然環境に優しい、鉛を含まない実用的なニオブ酸系の圧電磁器の生産が可能である。
(5)実用化が可能な、新規ニオブ酸系の圧電磁器組成物からなる圧電材料を製造し、提供することができる。
The present invention has the following effects.
(1) It is possible to provide a new niobic acid type piezoelectric ceramic mainly composed of a perovskite compound mainly composed of NaNbO 3 , LiNbO 3 , and SrTiO 3 .
(2) Potassium carbonate, which is generally used as a raw material for potassium, has high hygroscopicity and has a problem that it is difficult to handle in the production of ceramics on an industrial scale, but in the present invention, it is easy to use without using a potassium raw material. It is possible to produce a niobic acid-based piezoelectric ceramic.
(3) A niobic acid-based piezoelectric ceramic having a high Curie temperature and good piezoelectric characteristics can be realized in a composition not containing potassium.
(4) It is possible to produce a practical niobic acid-based piezoelectric ceramic that does not contain lead and is friendly to the natural environment.
(5) A piezoelectric material made of a novel niobic acid piezoelectric ceramic composition that can be put into practical use can be manufactured and provided.
次に、本発明を実施例に基づいて具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
本実施例では、本発明の圧電磁器を構成するNaNbO3、LiNbO3、及びSrTiO3の組成割合が所定の値になるように配合した原料粉末を使用してニオブ酸系の圧電磁器を作製し、得られた圧電磁器のキュリー温度、圧電定数(d33定数)、電気機械結合係数、機械的品質係数等の圧電特性を評価した。 In this example, a niobic acid-based piezoelectric ceramic was produced using raw material powder blended so that the composition ratio of NaNbO 3 , LiNbO 3 and SrTiO 3 constituting the piezoelectric ceramic of the present invention would be a predetermined value. The piezoelectric characteristics of the obtained piezoelectric ceramic, such as the Curie temperature, the piezoelectric constant (d33 constant), the electromechanical coupling coefficient, and the mechanical quality coefficient, were evaluated.
出発原料として、Na2CO3、Li2CO3、SrCO3、Nb2O5、及びTiO2の原料粉末を使用した。これらの原料粉末を表1に記載した各々の所定の組成となるように秤量、配合し、次いで、これらの原料粉末に、各々、エタノールを加え、直径10mmのZrO2ボールを用いて24時間湿式混合した後、乾燥機で十分に乾燥させた。この混合粉体を900℃で3時間仮焼して仮焼粉体を作製した。 Raw material powders of Na 2 CO 3 , Li 2 CO 3 , SrCO 3 , Nb 2 O 5 , and TiO 2 were used as starting materials. These raw material powders are weighed and blended so as to have respective predetermined compositions described in Table 1, and then ethanol is added to each of these raw material powders, and wet for 24 hours using ZrO 2 balls having a diameter of 10 mm. After mixing, it was sufficiently dried with a dryer. This mixed powder was calcined at 900 ° C. for 3 hours to prepare a calcined powder.
これらの仮焼粉体に、エタノールを加え、直径10mmのZrO2ボールを用いて2時間ボールミル粉砕を行った。ボールミル粉砕した仮焼粉体については、乾燥機で十分に乾燥させた後、有機バインダーを混合して造粒し、得られた粉末を、200MPaの圧力で直径17mm、厚さ1.5mmの円板に成形した後、この成形体を大気中において1200℃で3時間焼成して磁器を得た。その後、この磁器を、ラップ盤を用いて厚さ1mmに研磨した。 Ethanol was added to these calcined powders, and ball milling was performed for 2 hours using ZrO 2 balls having a diameter of 10 mm. The calcined powder that has been pulverized by ball milling is sufficiently dried by a drier, mixed with an organic binder and granulated, and the resulting powder is a circle having a diameter of 17 mm and a thickness of 1.5 mm at a pressure of 200 MPa. After forming into a plate, this molded body was fired at 1200 ° C. for 3 hours in the air to obtain a porcelain. Thereafter, this porcelain was polished to a thickness of 1 mm using a lapping machine.
研磨した試料については、上下面に銀ペーストを塗布し、700℃で30分間熱処理して銀電極を形成した。その後、試料を室温のシリコンオイル中で、4kV/mmの直流電界を10分間印加して分極処理を行った。分極処理した試料については、室温で一晩放置することによって、圧電特性を安定化させた後、静電容量、及び共振・反共振周波数を、インピーダンスアナライザを用いて測定し、比誘電率、電気機械結合係数(kp)、機械的品質係数(Qm)を求めた。また、分極後の位相を測定した。 For the polished sample, a silver paste was applied to the upper and lower surfaces, and heat treated at 700 ° C. for 30 minutes to form a silver electrode. Thereafter, the sample was subjected to polarization treatment by applying a DC electric field of 4 kV / mm for 10 minutes in silicon oil at room temperature. For a sample subjected to polarization treatment, the capacitance and resonance / antiresonance frequency were measured by using an impedance analyzer after stabilizing the piezoelectric characteristics by leaving it at room temperature overnight, and the relative permittivity, A mechanical coupling coefficient (kp) and a mechanical quality coefficient (Qm) were obtained. Moreover, the phase after polarization was measured.
また、d33メータを用いて、試料の圧電歪d33定数(pm/V)を測定した。更に、静電容量の温度変化を測定することによって、キュリー温度を求めた。これらの測定値を表1に示す。表1中では、NaNbO3をNN、LiNbO3をLN、SrTiO3をSTと略記した。表1において、第1段目(最上段)の組成(0.94NN−0.05LN−0.01ST)に対応する記載は、比較例の組成及び測定値であり、第2〜26段目(最下段まで)に対応する記載は、本発明の実施例(実施例1〜25)の組成及び測定値である。 Further, the piezoelectric strain d33 constant (pm / V) of the sample was measured using a d33 meter. Furthermore, the Curie temperature was determined by measuring the temperature change of the capacitance. These measured values are shown in Table 1. In Table 1, NaNbO 3 is abbreviated as NN, LiNbO 3 as LN, and SrTiO 3 as ST. In Table 1, the description corresponding to the composition of the first stage (uppermost stage) (0.94NN-0.05LN-0.01ST) is the composition and measured value of the comparative example, and the second to 26th stages ( The description corresponding to (up to the lowest level) is the composition and measured values of the examples (Examples 1 to 25) of the present invention.
その結果、NaNbO3を主成分とするペロブスカイト化合物を主体とした圧電磁器において、該圧電磁器の組成の一部をLiNbO3、及びSrTiO3で置換し、カリウム成分を実質的に含まない組成とした本発明の圧電磁器は、高いキュリー温度及び良好な圧電特性を達成できることが分かった。 As a result, the piezoelectric ceramic mainly composed of perovskite compound whose main component is NaNbO 3, part of the composition of the piezoelectric ceramic vessel was replaced with LiNbO 3, and SrTiO 3, and the composition containing no potassium component substantially It has been found that the piezoelectric ceramic of the present invention can achieve a high Curie temperature and good piezoelectric properties.
そして、これらの実験結果から、Na、Li、Sr、Nb、及びTiを主成分とするペロブスカイト化合物を主体とした圧電磁器において、モル比による組成式をxNaNbO3+yLiNbO3+zSrTiO3(ただし、x+y+z=1)とした時、該圧電磁器の組成が、(x=0.93、y=0.05、z=0.01)組成、(x=0.89、y=0.10、z=0.01)組成、(x=0.83、y=0.10、z=0.07)組成、及び(x=0.88、y=0.05、z=0.07)組成で囲まれる組成範囲内にある圧電磁器が、優れた圧電性能を有することが実証された。 From these experimental results, in a piezoelectric ceramic mainly composed of a perovskite compound mainly composed of Na, Li, Sr, Nb, and Ti, the composition formula based on the molar ratio is expressed as xNaNbO 3 + yLiNbO 3 + zSrTiO 3 (where x + y + z = 1), the composition of the piezoelectric ceramic is (x = 0.93, y = 0.05, z = 0.01) composition, (x = 0.89, y = 0.10, z = 0) .01) composition, (x = 0.83, y = 0.10, z = 0.07) composition, and (x = 0.88, y = 0.05, z = 0.07) composition. Piezoelectric ceramics within the composition range have been demonstrated to have excellent piezoelectric performance.
以上詳述したように、本発明は、Na、Li、Sr、Nb、及びTiを主成分とするペロブスカイト化合物を主体とした新しいニオブ酸系の圧電磁器、その製造方法、及び圧電素子に係るものであり、本発明により、カリウムを含まない組成において、高いキュリー温度及び良好な圧電特性を有している圧電磁器を提供することができる。本発明は、自然環境に優しい、鉛を含まない圧電磁器を提供するものであり、それにより、鉛を含まない環境低負荷の実用可能なニオブ酸系の圧電素子、及びそれを利用した圧電部材を製造し、提供することを可能とするものである。本発明は、ニオブ酸系の圧電磁器の実用可能な新規組成物及びその製品に関する新技術・新製品を提供するものとして有用である。 As described above in detail, the present invention relates to a novel niobic acid-based piezoelectric ceramic mainly composed of a perovskite compound mainly composed of Na, Li, Sr, Nb, and Ti, a manufacturing method thereof, and a piezoelectric element. Thus, according to the present invention, it is possible to provide a piezoelectric ceramic having a high Curie temperature and good piezoelectric characteristics in a composition not containing potassium. The present invention provides a piezoelectric ceramic that is friendly to the natural environment and does not contain lead. Thus, the niobic acid-based piezoelectric element that does not contain lead and has a low environmental load and that can be used practically, and a piezoelectric member using the same. Can be manufactured and provided. INDUSTRIAL APPLICABILITY The present invention is useful as a new composition and a new product related to a niobic acid-based piezoelectric ceramic that can be practically used and its products.
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