JP2007326768A - Kf-containing barium titanate-based piezoelectric substance, and its production method - Google Patents
Kf-containing barium titanate-based piezoelectric substance, and its production method Download PDFInfo
- Publication number
- JP2007326768A JP2007326768A JP2007122088A JP2007122088A JP2007326768A JP 2007326768 A JP2007326768 A JP 2007326768A JP 2007122088 A JP2007122088 A JP 2007122088A JP 2007122088 A JP2007122088 A JP 2007122088A JP 2007326768 A JP2007326768 A JP 2007326768A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- tio
- piezoelectric
- batio
- flux
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910002113 barium titanate Inorganic materials 0.000 title claims description 12
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims description 12
- 239000000126 substance Substances 0.000 title abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 59
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000004907 flux Effects 0.000 claims abstract description 9
- 238000007716 flux method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000004453 electron probe microanalysis Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 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 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 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 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
本発明は、ＫＦを含有するチタン酸バリウム系圧電体またはその製造方法に関し、特に、圧電定数ｄ３３が大きく、また室温における比誘電率が大きなチタン酸バリウム系素材またはその製造方法に関する。 The present invention relates to a barium titanate-based piezoelectric body containing KF or a method for manufacturing the same, and more particularly to a barium titanate-based material having a large piezoelectric constant d 33 and a large relative dielectric constant at room temperature or a method for manufacturing the same.
チタン酸バリウム（ＢａＴｉＯ３）は強誘電体として知られている。強誘電体は圧電材料として用いることができるので、電子部品材料として広く利用されている。中でも、セラミック系圧電材料としては、チタン酸ジルコニウム酸鉛（ＰＺＴ）がその圧電定数も大きく、最もよく用いられてきている経緯がある。 Barium titanate (BaTiO 3 ) is known as a ferroelectric. Ferroelectrics can be used as piezoelectric materials and are therefore widely used as electronic component materials. Among them, as a piezoelectric ceramic material, lead zirconate titanate (PZT) has a large piezoelectric constant and has been most often used.
しかしながら、ＰＺＴは鉛を含むため、環境面への配慮から近年では鉛フリーな圧電材料が求められている。 However, since PZT contains lead, in recent years, a lead-free piezoelectric material has been demanded in consideration of environmental considerations.
本発明は上記に鑑みてなされたものであって、鉛を含まない新規な強誘電体または圧電定数の大きい新規な圧電体を提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide a novel ferroelectric material containing no lead or a novel piezoelectric material having a large piezoelectric constant.
請求項１に記載の発明は、ＢａＴｉＯ３結晶のうち、Ｂａの一部がＫに置換され、Ｏの一部がＫと実質的に同量のＦに置換された組成を有するチタン酸バリウム系圧電体である。ここで、実質的に同量とは数量が同じ、すなわち、電気的に中性であることを意味し、ＥＰＭＡにより分析した場合に誤差により若干の数量の違いがあっても原子数が同数であると結論づけられることを含む意味である。
The invention according to
また、請求項２に記載の発明は、一般式がＢａ１−ｘＫｘＴｉＯ３−ｘＦｘ（ただし、０＜ｘ＜０．１３）として表される組成を有する圧電体である。
The invention according to
また、請求項３に記載の発明は、Ｂａに対するＴｉのモル比が大きくなるように原料を調製し、仮焼きにより実質的にＢａＯとＴｉＯ２のみからなる混合物を生成し、これに、ＫＦを融剤としたフラックス法により請求項１または２に記載の結晶を得ることを特徴とする圧電体製造方法である。ここで原料はたとえば、ＢａＣＯ３のような化合物であってもよく、仮焼きにより余分な化合物が含まれなくなるのであれば特に限定されない。実質的にとは、仮焼きにより余分な化合物が含まれなくなることをいう。
In the invention of
また、請求項４に記載の発明は、Ｂａに対するＴｉのモル比が大きくなるように原料を配合する原料配合工程と、ＫＦを融剤としたフラックス法によりＢａＴｉＯ３結晶を成長させようとする結晶成長工程と、を含み、Ｂａの一部がＫに置換され、また、Ｏの一部がＦに置換された結晶を得ることを特徴とする圧電体製造方法である。換言すれば、請求項２に記載の発明は、ＢａよりもＴｉのモル比が大きくなるように原料を配合し、ＫＦを融剤としたフラックス法によりＢａＴｉＯ３結晶を成長させようとして、Ｂａの一部がＫに置換され、また、Ｏの一部がＦに置換されたチタン酸バリウム系結晶を得ることを特徴とする圧電体製造方法である。
Further, the invention according to claim 4 is a crystal which is intended to grow a BaTiO 3 crystal by a raw material blending step of blending the raw material so as to increase the molar ratio of Ti to Ba and a flux method using KF as a flux. A method of manufacturing a piezoelectric body, comprising: a growth step, wherein a crystal in which a part of Ba is substituted with K and a part of O is substituted with F is obtained. In other words, in the invention according to
なお、Ｂａに対するＴｉのモル比とは、原料として元素単体を用いるという意味ではなく、それぞれ化合物中に存在するＢａとＴｉのモル比をいう。また、Ｂａの一部がＫに置換され、また、Ｏの一部がＦに置換され、とは、Ｋの置換量とＦの置換量が実測結果として同量であることを厳密に求めることを意図するものではなく、たとえばＥＰＭＡにより分析した場合、必ずしもＫの置換量とＦの置換量が同一でなくともよいものも含むことを意味する。 In addition, the molar ratio of Ti to Ba does not mean that an elemental element is used as a raw material, but refers to the molar ratio of Ba and Ti present in each compound. In addition, a part of Ba is replaced with K, and a part of O is replaced with F. This means that the replacement amount of K and the replacement amount of F are the same as the actual measurement result. For example, when analyzed by EPMA, it means that the substitution amount of K and the substitution amount of F do not necessarily have to be the same.
また、請求項５に記載の発明は、請求項３または４に記載の圧電体製造方法において、原料にＢａＴｉ２Ｏ５を用いたこと、または、ＢａＴｉＯ３とＴｉＯ２とを用いたことを特徴とする圧電体製造方法である。すなわち、請求項５に記載の発明は、ＢａＴｉＯ３結晶を得るには、チタンの含有量が相対的に多いことを意味している。
The invention according to
また、請求項６に記載の発明は、請求項３または４に記載の圧電体製造方法において、ＴｉＯ２とＢａＯとを、そのモル比がＴｉＯ２／ＢａＯ＞１となるようにして原料を調整したことを特徴とする圧電体製造方法である。すなわち、請求項６に記載の発明は、ＢａＴｉＯ３結晶を得るには、チタンの含有量が相対的に多いことを意味している。
The invention of claim 6, adjusted in the piezoelectric method according to
また、請求項７に記載の圧電体は、一般式がＢａ１−ｘＫｘＴｉＯ３−ｘＦｘとして表され、一次から二次へ相転移が移行するｘ＝０．１近傍の組成である圧電体である。ここで、相転移があると種々の物性が変化するが、たとえば、キュリーワイス則による誘電率の二次転移を挙げることができる。
In the piezoelectric body according to
本発明によれば、鉛を含まない新規な強誘電体または圧電定数の大きい新規な圧電体を得ることができる。 According to the present invention, a novel ferroelectric material containing no lead or a novel piezoelectric material having a large piezoelectric constant can be obtained.
以下、本発明を詳細に説明する。
＜製造＞
原料の調整をするにあたり、まず、ＢａＣＯ３：ＴｉＯ２＝１：２（モル比）を混合し、アルミナるつぼに入れ、８００℃で８時間仮焼きしてＣＯ２を飛ばした。なお、ＢａＣＯ３は関東化学株式会社製の純度９９．９％の試薬を９．８７６９ｇ（０．０５ｍｏｌ）用い、ＴｉＯ２はＡＬＤＲＩＣＨ社製の純度９９．８％の試薬を８．００６０ｇ（０．１ｍｏｌ）用いた。
Hereinafter, the present invention will be described in detail.
<Manufacturing>
In adjusting the raw materials, first, BaCO 3 : TiO 2 = 1: 2 (molar ratio) was mixed, put into an alumina crucible, and calcined at 800 ° C. for 8 hours to fly CO 2 . For BaCO 3 , 9.8769 g (0.05 mol) of a 99.9% purity reagent manufactured by Kanto Chemical Co., Ltd. was used, and for TiO 2, a 99.8% purity reagent manufactured by ALDRICH was used. 1 mol) was used.
続いて、仮焼きにより得られたＢａＴｉＯ３＋ＴｉＯ２の混合物にＫＦをフラックスとしてチタン酸バリウム系結晶を成長させた。すなわち、フラックス法による結晶成長を試みた。なお、ＢａＴｉＯ３＋ＴｉＯ２：ＫＦ＝１：１０（モル比）とした。ＢａＴｉＯ３＋ＴｉＯ２は９．３９１８ｇ（Ｂａ換算で０．０３ｍｏｌ）用い、ＫＦは、メルク株式会社製の純度９９％の試薬を１７．４３ｇ（０．３ｍｏｌ）用いた。 Subsequently, a barium titanate-based crystal was grown on the BaTiO 3 + TiO 2 mixture obtained by calcining using KF as a flux. That is, crystal growth by the flux method was tried. Note that BaTiO 3 + TiO 2 : KF = 1: 10 (molar ratio). BaTiO 3 + TiO 2 used was 9.3918 g (0.03 mol in terms of Ba), and KF used 17.43 g (0.3 mol) of a 99% pure reagent manufactured by Merck Co., Ltd.
結晶成長に際しては、ふた付き白金るつぼを用い、室温から２時間かけて６１６℃まで、その後４時間かけて１０７３℃まで温度を上昇させ、１０７３℃を４時間維持し、その後２時間かけて９７６℃まで冷却し、その後８時間かけて７９６℃まで冷却した。その後制御を解除し、るつぼを室温まで自然冷却した。 For crystal growth, using a platinum crucible with a lid, the temperature was increased from room temperature to 616 ° C. over 2 hours, then to 1073 ° C. over 4 hours, maintained at 1073 ° C. for 4 hours, and then 976 ° C. over 2 hours. And then cooled to 796 ° C. over 8 hours. Thereafter, the control was released, and the crucible was naturally cooled to room temperature.
るつぼの中から、固まったフッ化カリウムと、結晶化しなかったチタン酸バリウムを洗い流し、単結晶を取り出した。単結晶の大きさは数ミリ程度であった。 From the crucible, the solidified potassium fluoride and the barium titanate that was not crystallized were washed away, and the single crystal was taken out. The size of the single crystal was about several millimeters.
以上は、ＢａＣＯ３：ＴｉＯ２＝１：２、すなわち、ＢａＣＯ３＋（１＋α）ＴｉＯ２と表現するとα＝１．０の場合であるが、この表記に従って、α＝０．３，０．５，０．７，１．２として原料を配合し、同様な方法で結晶を得た。 The above is the case where BaCO 3 : TiO 2 = 1: 2, ie, BaCO 3 + (1 + α) TiO 2 is α = 1.0. According to this notation, α = 0.3, 0.5 , 0.7 and 1.2, the raw materials were blended, and crystals were obtained in the same manner.
＜評価：組成＞
得られた単結晶を、ＥＰＭＡ定量分析したところ、α＝１．０のときＢａ０．８９Ｋ０．１０ＴｉＯ２．８８Ｆ０．１３であり、融剤のＫＦがＢａＴｉＯ３に約０．１ｍｏｌ取り込まれた結晶であることが確認できた。また、粉末ＸＲＤ解析をおこなったところ、ＢａＴｉＯ３結晶であれば２θが４５°付近で二つに分かれるピークが一つであるなど若干の相違が見られるものの、得られた結晶は基本的にＢａＴｉＯ３結晶に極めて近似した構造であることも確認できた（図１参照）。これらの結果から、得られた結晶は、ＢａＴｉＯ３のＢの一部がＫに置換され、電荷の関係からＫと等量のＯがＦに置換された結晶であるといえる。すなわち、この結晶は、一般式をＢａ１−ｘＫｘＴｉＯ３−ｘＦｘとして表すことのできるチタン酸バリウム系結晶である。上記の製造工程を経れば、ｘ＝０．１のチタン酸バリウムＢａ０．９Ｋ０．１ＴｉＯ２．９Ｆ０．１を得ることができる。なお、以降ではこの一般式で表される結晶を適宜新結晶と称することとする。
<Evaluation: Composition>
When the obtained single crystal was quantitatively analyzed by EPMA, it was Ba 0.89 K 0.10 TiO 2.88 F 0.13 when α = 1.0, and the KF of the flux was about 0.000 in BaTiO 3 . It was confirmed that the crystals were incorporated by 1 mol. Further, when powder XRD analysis was performed, a slight difference such as one peak split into two when 2θ was around 45 ° was observed in the case of BaTiO 3 crystal, but the obtained crystal was basically BaTiO 3. It was also confirmed that the structure was very close to 3 crystals (see FIG. 1). From these results, it can be said that the obtained crystal is a crystal in which a part of B of BaTiO 3 is substituted with K and an equivalent amount of O to K is substituted with F due to the charge relationship. That is, the crystal is a general formula Ba 1-x K x TiO 3 -x F barium titanate-based crystal, which can be expressed as x. Through the above manufacturing steps, barium titanate Ba 0.9 K 0.1 TiO 2.9 F 0.1 with x = 0.1 can be obtained. Hereinafter, the crystal represented by this general formula will be referred to as a new crystal as appropriate.
α＝０．５と０．７についてのＥＰＭＡ定量分析結果もあわせて表１に示す。
次に、新結晶の物性を評価した。
＜評価：誘電率＞
新結晶の自然面である（１００）面に銀ペーストを塗り、比誘電率ε’の温度依存を測定した。数ｋＨｚ以上では圧電共振が現れるため、３００Ｈｚの低周波における比誘電率を測定した。なお、あわせて誘電損失ｔａｎδも測定した。図２は、新結晶の比誘電率ε’および誘電損失ｔａｎδの測定結果を示したグラフである。なお、図示は省略するが、周波数が３０Ｈｚ、または、１００Ｈｚにおいても、ほぼ同一の曲線が得られた。
Next, the physical properties of the new crystals were evaluated.
<Evaluation: Dielectric constant>
Silver paste was applied to the (100) plane, which is the natural plane of the new crystal, and the temperature dependence of the relative dielectric constant ε ′ was measured. Since piezoelectric resonance appears above a few kHz, the relative dielectric constant at a low frequency of 300 Hz was measured. In addition, dielectric loss tan δ was also measured. FIG. 2 is a graph showing the measurement results of the relative permittivity ε ′ and dielectric loss tan δ of the new crystal. Although illustration is omitted, substantially the same curve was obtained even when the frequency was 30 Hz or 100 Hz.
新結晶の比誘電率ε’は、室温近くの約３５℃で１２０００近くのピーク値を有することがわかった。また、−５３℃、−１０℃でも同様のピーク値（相転移点）が観測された。ＢａＴｉＯ３の相転移点が１３０℃、−５℃、−９０℃であるため、ＫおよびＦの混入により新結晶の高温の相転移点Ｔｃは約１００℃低下し、低温の相転移点は約４０℃上昇したことが確認できた。なお、新結晶の誘電損失ｔａｎδは１％程度であり、良好な強誘電体であることも確認できた。 It was found that the relative permittivity ε ′ of the new crystal had a peak value near 12000 at about 35 ° C. near room temperature. Further, similar peak values (phase transition points) were observed at −53 ° C. and −10 ° C. Since the phase transition point of BaTiO 3 is 130 ° C., −5 ° C., and −90 ° C., mixing of K and F causes the high temperature phase transition point Tc of the new crystal to decrease by about 100 ° C., and the low temperature phase transition point is about It was confirmed that the temperature rose by 40 ° C. The dielectric loss tan δ of the new crystal was about 1%, and it was confirmed that the new crystal was a good ferroelectric.
同様に、α＝０．３，０．５，１．２についても比誘電率ε’を測定した。結果を図３に示す。図示したように、誘電曲線のＴｃはαが大きくなるにつれ徐々に低温側にシフトしていくが、Ｔｃにおける比誘電率ε’はいったん小さくなりα＝１．０（ｘ＝０．１０）あたりで急激に上昇し、その後再び小さくなっていくことがわかった。 Similarly, the relative dielectric constant ε ′ was also measured for α = 0.3, 0.5, and 1.2. The results are shown in FIG. As shown in the figure, the Tc of the dielectric curve gradually shifts to a lower temperature side as α increases, but the relative dielectric constant ε ′ at Tc once decreases and becomes around α = 1.0 (x = 0.10). It suddenly rose and became smaller after that.
図４は、比誘電率の逆数プロットである。常誘電相ではCurie-Weiss則ε’＝Ｃ／（Ｔ−Ｔ０）が成り立つ（ここでＣはCurie-Weiss定数、Ｔ０は常誘電Curie温度である）。一般に、一次転移の場合にはＴ０＜Ｔｃであり、二次転移ではＴ０＝Ｔｃとなる。図4の結果が明確に示すように、α＝０．３，０．５の場合、Ｔ０はＴｃより２０℃〜３０℃低く、一次転移の特徴を表している。一方、α＝１．０では、Ｔ０＝Ｔｃとなり、二次転移の性質を示すようになる。さらにα＝１．２では、転移のブロード化が起きており、ε’＝Ｃ／（Ｔ−Ｔ０）２に近似していくことから二次転移からさらに散漫相転移に移行していくことがわかった。以上から、α＝１．０近傍（ｘ＝０．１近傍）での急激な誘電率の上昇は、転移の次数が一次から二次に変化する臨界点近傍での誘電率の振る舞いを反映したものとして理解できることが確認できた。 FIG. 4 is a reciprocal plot of relative permittivity. In the paraelectric phase, the Curie-Weiss rule ε ′ = C / (T−T 0 ) holds (where C is the Curie-Weiss constant and T 0 is the paraelectric Curie temperature). In general, T 0 <Tc for the first order transition and T 0 = Tc for the second order transition. As clearly shown in the results of FIG. 4, when α = 0.3, 0.5, T 0 is 20 ° C. to 30 ° C. lower than Tc, and represents the characteristic of the first order transition. On the other hand, when α = 1.0, T 0 = Tc, indicating the nature of the second order transition. Furthermore, when α = 1.2, the transition is broadened, and since it approximates to ε ′ = C / (T−T 0 ) 2 , the transition from the second-order transition to the more diffuse phase transition is required. I understood. From the above, the sudden increase in the dielectric constant in the vicinity of α = 1.0 (in the vicinity of x = 0.1) reflects the behavior of the dielectric constant in the vicinity of the critical point where the order of transition changes from the first order to the second order. It was confirmed that it can be understood as a thing.
次に、各周波数における比誘電率の温度依存性を測定した結果を図５に示す。周波数は、１０２Ｈｚ，１０４Ｈｚ，１０６Ｈｚである。なお、図５は図３と異なり温度を℃で表記している。また、測定点を各周波数で７点としているので、図３のように精細な曲線とはなっていないが、大きな周波数依存性は特に認められなかった。 Next, the results of measuring the temperature dependence of the relative dielectric constant at each frequency are shown in FIG. The frequencies are 10 2 Hz, 10 4 Hz, and 10 6 Hz. In FIG. 5, the temperature is expressed in ° C. unlike FIG. In addition, since the measurement points are 7 points at each frequency, it is not a fine curve as shown in FIG. 3, but a large frequency dependency was not particularly recognized.
また、常誘電相（Ｔ＞Ｔｃ）と強誘電相（Ｔ＜Ｔｃ）における比誘電率の周波数依存性を測定した。結果を図６および図７に示す。各温度域で、ほぼフラットであることが確認できた。なお、ｆ＝１０５Ｈｚでプロットの様子が異なっているが、測定装置であるＬＣＲメータをＨＰ４２８４ＡからＨＰ４２８５Ａに切り替えているためである。 Further, the frequency dependence of the relative permittivity in the paraelectric phase (T> Tc) and the ferroelectric phase (T <Tc) was measured. The results are shown in FIG. 6 and FIG. It was confirmed that the temperature was almost flat in each temperature range. Note that although the appearance of the plot is different at f = 10 5 Hz, the LCR meter, which is a measuring device, is switched from HP4284A to HP4285A.
＜評価：圧電定数ｄ３３＞
新結晶の圧電定数ｄ３３をｄ３３メータにより測定した。測定装置は、ＩＡＣＡＳ製 ＸＪ−６Ｂ ｄ３３／ｄ３１ Ｍａｔｅｒを用いた。なお、測定用試料に４００Ｖ〜５００Ｖの電圧を印加した状態で、試料を１００℃から冷却して分極処理をおこなった。測定結果を図８に示した。グラフからわかるように、新結晶の室温における圧電定数は、ｄ３３＝３００ｐＣ／Ｎであった。この値は、ＢａＴｉＯ３の室温における値の約６倍であり、ＰＺＴの室温における値の２００ｐＣ／Ｎよりも大きい。すなわち、新結晶は極めて有望な圧電特性を有することが確認できた。なお、３５℃までの測定結果を図９に示す。温度が高くなると若干圧電定数が小さくややばらつきも見られるものの、ｄ３３＞２００ｐＣ／Ｎであり依然として大きな値であることが確認できた。
<Evaluation: the piezoelectric constant d 33>
The piezoelectric constant d 33 of the new crystals was measured by d 33 meter. The measuring device used was XJ-6B d 33 / d 31 Mater manufactured by IACAS. In addition, in the state which applied the voltage of 400V-500V to the sample for a measurement, the sample was cooled from 100 degreeC and the polarization process was performed. The measurement results are shown in FIG. As can be seen from the graph, the piezoelectric constant of the new crystal at room temperature was d 33 = 300 pC / N. This value is about 6 times the value of BaTiO 3 at room temperature and is larger than the value of PZT at room temperature of 200 pC / N. That is, it was confirmed that the new crystal has extremely promising piezoelectric characteristics. In addition, the measurement result to 35 degreeC is shown in FIG. As the temperature increased, the piezoelectric constant was slightly small and slightly varied, but it was confirmed that d 33 > 200 pC / N and still a large value.
＜評価：ＤＥヒステリシスループ測定＞
新結晶には、Ｔｃ＝３５℃以下において、強誘電体特有のＤＥ履歴曲線が観測されたので、新結晶の残留分極Ｐｒと抗電界Ｅｃとを測定した。図１０は、新結晶の残留分極Ｐｒと抗電界Ｅｃのそれぞれの温度依存を測定した結果を示したグラフである。
<Evaluation: DE hysteresis loop measurement>
In the new crystal, a DE history curve peculiar to the ferroelectric was observed at Tc = 35 ° C. or lower, and therefore, the residual polarization Pr and coercive electric field Ec of the new crystal were measured. FIG. 10 is a graph showing the results of measuring the temperature dependence of the remanent polarization Pr and coercive electric field Ec of the new crystal.
＜評価：ＴｃのＫ濃度依存＞
図１１は、新結晶Ｂａ１−ｘＫｘＴｉＯ３−ｘＦｘのＫの濃度ｘを０〜０．１２付近までふったときの転移温度とＫ濃度の関係を表した相図である。得られたチタン酸バリウム系結晶は、立方晶、正方晶、斜方晶、菱面体晶と逐次転移をするが、その相転移温度はほぼＫＦ濃度に比例して連続的に変化する。高温から二つの転移温度は減少傾向であり、最後の転移温度は増加傾向であることがわかった。したがって、ｘ＝０．１６〜０．１７付近でピンチングが起こることが示唆された。なお、ＫＦの置換量を変化させるために、原料中のＴｉ量や融剤ＫＦの量を相対的に変化させて先に示したのと同様な方法により結晶を作成した。なお、それぞれの結晶についてはＥＰＭＡ定量分析してｘを決定している。
<Evaluation: T concentration dependence of K>
Figure 11 is a phase diagram showing a relationship between transition temperature and K concentration when shook the concentration x of the new crystal Ba 1-x K x TiO 3 -x F x of K to around 0 to 0.12. The obtained barium titanate-based crystal undergoes sequential transition to cubic, tetragonal, orthorhombic, and rhombohedral, but its phase transition temperature changes continuously in proportion to the KF concentration. From the high temperature, it was found that the two transition temperatures were decreasing and the final transition temperature was increasing. Therefore, it was suggested that pinching occurs near x = 0.16 to 0.17. In order to change the amount of KF substitution, crystals were prepared in the same manner as described above by relatively changing the amount of Ti in the raw material and the amount of the flux KF. Note that x is determined by EPMA quantitative analysis for each crystal.
本発明によれば、圧電定数ｄ３３の値が常温でＰＺＴより高く、鉛フリーであるので、コンデンサー材料としてはもとより、広く圧電材料として、インクジェットプリンタのプリンタヘッド、液晶画面のバックライト用の圧電トランスなどにも適用可能である。すなわち、本発明である物質または本発明である製造方法により得られる物質は、強誘電体としても圧電体（または圧電材料）としても使用できる According to the present invention, higher than the PZT at room temperature is the value of the piezoelectric constant d 33, since it is lead-free, as well as a condenser material, widely as a piezoelectric material, the ink jet printer printhead, a piezoelectric for back light of a liquid crystal display It can also be applied to transformers. That is, the substance according to the present invention or the substance obtained by the production method according to the present invention can be used as a ferroelectric substance or a piezoelectric substance (or piezoelectric material).
Claims (7)
Ｂａ１−ｘＫｘＴｉＯ３−ｘＦｘ（ただし、０＜ｘ＜０．１３）
として表される組成を有する圧電体。 The general formula is Ba 1−x K x TiO 3−x F x (where 0 <x <0.13)
A piezoelectric body having a composition expressed as:
仮焼きにより実質的にＢａＯとＴｉＯ２のみからなる混合物を生成し、
これに、ＫＦを融剤としたフラックス法により請求項１または２に記載の結晶を得ることを特徴とする圧電体製造方法。 Prepare the raw material so that the molar ratio of Ti to Ba is large,
Producing a mixture consisting essentially of BaO and TiO 2 by calcination,
3. A method for manufacturing a piezoelectric body, wherein the crystal according to claim 1 is obtained by a flux method using KF as a flux.
ＫＦを融剤としたフラックス法によりＢａＴｉＯ３結晶を成長させようとする結晶成長工程と、
を含み、
Ｂａの一部がＫに置換され、また、Ｏの一部がＦに置換された結晶を得ることを特徴とする圧電体製造方法。 A raw material blending step of blending raw materials so that the molar ratio of Ti to Ba is increased;
A crystal growth step for growing BaTiO 3 crystals by a flux method using KF as a flux;
Including
A method for producing a piezoelectric body, characterized in that a crystal in which a part of Ba is substituted with K and a part of O is substituted with F is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007122088A JP5526422B2 (en) | 2006-05-09 | 2007-05-07 | Barium titanate crystal piezoelectric material containing KF |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006130539 | 2006-05-09 | ||
| JP2006130539 | 2006-05-09 | ||
| JP2007122088A JP5526422B2 (en) | 2006-05-09 | 2007-05-07 | Barium titanate crystal piezoelectric material containing KF |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007326768A true JP2007326768A (en) | 2007-12-20 |
| JP5526422B2 JP5526422B2 (en) | 2014-06-18 |
Family
ID=38927505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007122088A Expired - Fee Related JP5526422B2 (en) | 2006-05-09 | 2007-05-07 | Barium titanate crystal piezoelectric material containing KF |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5526422B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215450A (en) * | 2009-03-17 | 2010-09-30 | Shimane Univ | Method for producing barium titanate crystal |
| JP2011006266A (en) * | 2009-06-23 | 2011-01-13 | Shimane Univ | METHOD OF MANUFACTURING BaTi2O5 TYPE FERROELECTRIC CERAMIC |
| JP2015067462A (en) * | 2013-09-27 | 2015-04-13 | 国立大学法人島根大学 | Method for producing hexagonal barium titanate-based dielectric material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4843715B1 (en) * | 1970-06-13 | 1973-12-20 | ||
| JPS63503456A (en) * | 1986-06-02 | 1988-12-15 | ヒユーズ・エアクラフト・カンパニー | Method for producing single-crystal binary metal oxides with improved purity |
-
2007
- 2007-05-07 JP JP2007122088A patent/JP5526422B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4843715B1 (en) * | 1970-06-13 | 1973-12-20 | ||
| JPS63503456A (en) * | 1986-06-02 | 1988-12-15 | ヒユーズ・エアクラフト・カンパニー | Method for producing single-crystal binary metal oxides with improved purity |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215450A (en) * | 2009-03-17 | 2010-09-30 | Shimane Univ | Method for producing barium titanate crystal |
| JP2011006266A (en) * | 2009-06-23 | 2011-01-13 | Shimane Univ | METHOD OF MANUFACTURING BaTi2O5 TYPE FERROELECTRIC CERAMIC |
| JP2015067462A (en) * | 2013-09-27 | 2015-04-13 | 国立大学法人島根大学 | Method for producing hexagonal barium titanate-based dielectric material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5526422B2 (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qiao et al. | Enhanced energy density and thermal stability in relaxor ferroelectric Bi0. 5Na0. 5TiO3-Sr0. 7Bi0. 2TiO3 ceramics | |
| Badapanda et al. | Dielectric, ferroelectric and piezoelectric study of BNT-BT solid solutions around the MPB region | |
| Park et al. | Highly enhanced mechanical quality factor in lead-free (K0. 5Na0. 5) NbO3 piezoelectric ceramics by co-doping with K5. 4Cu1. 3Ta10O29 and CuO | |
| Zhao et al. | Improved temperature stability and high piezoelectricity in lead-free barium titanate-based ceramics | |
| JP5219921B2 (en) | Metal oxide, piezoelectric material and piezoelectric element | |
| GB2349272A (en) | Piezoelectric paste and piezoelectric film and piezoelectric part using the same | |
| Wang et al. | Phase transition characteristics and associated piezoelectricity of potassium-sodium niobate lead-free ceramics | |
| Lin et al. | Ferroelectric and piezoelectric properties of Bi0. 5Na0. 5TiO3–SrTiO3–Bi0. 5Li0. 5TiO3 lead-free ceramics | |
| Yan et al. | Effect of Mn doping on the piezoelectric properties of 0.82 Pb (Zr1/2Ti1/2) O3–0.03 Pb (Mn1/3Sb2/3) O3–0.15 Pb (Zn1/3Nb2/3) O3 ferroelectric ceramics | |
| Xing et al. | Structure and electrical properties of (0.965− x)(K 0.48 Na 0.52) NbO 3–x BiGaO 3–0.035 (Bi 0.5 Na 0.5) ZrO 3 piezoelectric ceramics | |
| Fuentes et al. | Structural and dielectric properties of La-and Ti-modified K 0.5 Na 0.5 NbO 3 ceramics | |
| Zeng et al. | Growth and characterization of lead-free Ba (1− x) CaxTi (1− y) ZryO3 single crystal | |
| Xu et al. | Exploration on the origin of enhanced piezoelectric properties in transition-metal ion doped KNN based lead-free ceramics | |
| Chen et al. | Piezoelectric and dielectric properties of 0.995 K0. 48Na0. 48Li0. 04Nb (1− x) SbxO3–0.005 BiAlO3 lead-free piezoelectric ceramics | |
| Wang et al. | Origin of superior hardening properties in KCuTa3O9-doped K0. 5Na0. 5NbO3 lead-free piezoelectric ceramics | |
| Chen et al. | Enhancement of piezoelectric properties in low-temperature sintering PZN–PZT ceramics by Sr2+ substitution | |
| Jaiban et al. | The effects of donor (Nb5+) and acceptor (Cu2+, Zn2+, Mn2+, Mg2+) doping at B-site on crystal structure, microstructure, and electrical properties of (Ba0. 85Ca0. 15) Zr0. 1Ti0. 9O3 ceramics | |
| JP5526422B2 (en) | Barium titanate crystal piezoelectric material containing KF | |
| Li et al. | Relaxor behavior and Raman spectra of CuO-doped Pb (Mg 1/3 Nb 2/3) O 3-PbTiO 3 ferroelectric ceramics | |
| Xue et al. | The dielectric and ferroelectric properties of (Ba 0. 5 Sr 0. 5) TiO3-doped (Bi 0. 5 Na 0. 5) TiO3 lead-free ceramics | |
| Wang et al. | Phase transition and piezoelectric properties of alkali niobate ceramics through composition tuning | |
| Mazumder et al. | ‘Ultra’-low-temperature sintering of PZT: A synergy of nano-powder synthesis and addition of a sintering aid | |
| Adamczyk-Habrajska et al. | Impedance Studies of K0. 5Na0. 5NbO3 ceramics prepared from mechanochemically activated powders | |
| Liu et al. | Growth and characterization of Mn-doped Na1/2Bi1/2TiO3 lead-free ferroelectric single crystal | |
| Lin et al. | Structure and electrical properties of Bi 0.5 Na 0.5 TiO 3-Y 0.5 Na 0.5 TiO 3-BaTiO 3 lead-free piezoelectric ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100430 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121213 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121218 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130214 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131105 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140121 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140304 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140325 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140327 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5526422 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |