JP3398962B2 - Ferroelectric porcelain composition - Google Patents
Ferroelectric porcelain compositionInfo
- Publication number
- JP3398962B2 JP3398962B2 JP13364891A JP13364891A JP3398962B2 JP 3398962 B2 JP3398962 B2 JP 3398962B2 JP 13364891 A JP13364891 A JP 13364891A JP 13364891 A JP13364891 A JP 13364891A JP 3398962 B2 JP3398962 B2 JP 3398962B2
- Authority
- JP
- Japan
- Prior art keywords
- ferroelectric
- ratio
- strain
- present
- constant
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 13
- 229910052573 porcelain Inorganic materials 0.000 title description 4
- 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 claims description 10
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002277 temperature effect Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000694 effects Effects 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
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は圧電セラミックスに代表
される強誘電体磁器組成物の改良技術に関する。
【０００２】
【従来の技術】強い電圧を印加した時に強誘電体が歪変
形する性質（逆圧電効果）を利用して微小位置決め装置
等の駆動部（アクチュエータ）に強誘電体磁器組成物
（以下、「強誘電体」と略す。）が採用されている。
【０００３】
【発明が解決しようとする課題】上記強誘電体は、一般
に１Ｖ（ボルト）程度の電圧が印加された際の、特性が
最も良いとされている相境界の値をとって応用化されて
いる。
【０００４】しかし、相境界付近の特性を基準に選定さ
れた強誘電体は、周囲温度の影響を受けやすく、適当な
温度補正を施す必要がある。
【０００５】又、アクチュエータとしては、歪変位が大
きい程良く、その為に印加電圧を例えば１ＫＶにアップ
したいが、従来のものはこのような高電圧を印加すると
へたってしまい実用に供さない。
【０００６】そこで本発明の目的は、高電圧に堪える電
界特性と、耐久性と、良い温度特性とを兼ね備えた強誘
電体を提供することにある。
【０００７】
【課題を解決するための手段及び作用】上記目的を達成
すべく本発明は、強誘電体磁気組成物をＰＺＴ系に添加
物としてＮｂ2Ｏ 5 、またはＳｎＯ 2 を添加してなり、そ
の結晶系が正方晶系とされ、Ｚｒ／（Ｚｒ+Ｔｉ）で表
されるＺｒ比が５０．０ｍｏｌ％〜５１．５ｍｏｌ％で
ある構成とした。
【０００８】
【実施例】本発明者は、従来のＰＺＴ系強誘電体の欠点
を改良すべく鋭意研究した結果、ＰＺＴ系強誘電体に微
量のＮｂ2Ｏ5，ＳｎＯ2を添加したもので且つ正方晶系
の強誘電体は良好な電界特性及び耐久性を有し、且つ環
境の温度変化に影響され難いという従来に見られない極
めて特徴のある強誘電体磁器組成物が得られることを見
い出し本発明に到達したものであり、その詳しい内容は
以下に述べる通りである。なお、ＰＺＴはＰｂ（Ｚｒ，
Ｔｉ）Ｏ3結晶体の略称である。
【０００９】図１は本発明に係る強誘電体を含む強誘電
体におけるＺｒ比と格子定数の関係図であり、ＰＺＴに
僅かなＮｂ2Ｏ5，ＳｎＯ2を加えた組成物を中心に、そ
のＺｒ比を変化させたところの複数種類の試料を通常の
圧電セラミックスの製法で製造し、これらを粉末Ｘ線回
析により、格子定数を求めたものである。
【００１０】なお、上記Ｚｒ比はＺｒ／（Ｚｒ+Ｔｉ）
で表わされ、組成物中に含まれるＺｒのモル分率を意味
する。表記上、これを１００倍してモルパーセントで表
わす。
【００１１】図１において、Ｚｒ比４９．０でｃ＝４．
１１３，ａ＝４．０４９オングストローム、軸比（ｃ／
ａ）＝１．０１５８であり、Ｚｒ比の増加と伴に、ｃ軸
は小さく、ａ軸は大きくなり、軸比（ｃ／ａ）が１．０
に近づき、Ｚｒ比が５２．０〜５２．２５付近で正方晶
から菱面体晶へ相転移が生じる相境界が存在しているこ
とが分かった。このことからＺｒ比が５２以下では正方
晶系であり、Ｚｒ比が５２．２５以上では菱面体晶系で
あることが分った。
【００１２】図２は本発明に係る強誘電体を含む強誘電
体のＺｒ比と歪の関係を示す図であり、前記試料を厚さ
１ｍｍに研削し、銀ペースト電極を焼き付けた後に７０
０Ｖの電圧を印加し、非接触式レーザ変位計及び歪ゲー
ジを用いて歪を測定したものを示す。
【００１３】図２によれば、Ｚｒ比が５２．０〜５２．
２５の付近で歪は最大となる。これは相境界付近の組成
物が軟かくて歪易い組成であると考えられる。そして、
従来、相境界付近の組成物が採用されていたのは、歪が
大きいことに起因している。
【００１４】図３（ａ）〜（ｃ）は本発明に係る強誘電
体を含む強誘電体に電圧を掛けた時のｄ定数の変化を示
す図であり、前記厚さ１ｍｍに研削された試料に１．２
ＫＶ／ｍｍまでの直流電圧を印加し、この際に発生した
３１方向の歪に基づいて算出した圧電ｄ定数（以下、
「ｄ定数」と略す。）をプロットしたものである。
【００１５】図３（ａ）はＺｒ比が４９．０〜５１．７
５、即ち正方晶系の試料におけるものであり、Ｚｒ比が
大きい程ｄ定数が大きくなり、Ｚｒ比が５１．０以下の
ものは電界の大きさにｄ定数はほぼ正比例している。し
かし、Ｚｒ比が５１．７５については１ＫＶ／ｍｍ付近
をピークに減少傾向にある。
【００１６】図３（ｂ）はＺｒ比が５２．０，５２．２
５、即ち相境界付近の試料に対するもので、ｄ定数は大
きいものの、０．７ＫＶ／ｍｍ付近から減少傾向にあ
る。
【００１７】図３（ｃ）はＺｒ比が５３．０，５５．
０、即ち菱面体晶系の試料に対するもので、ｄ定数が小
さいとともに電界の増加と比例関係にあるとは言えな
い。
【００１８】図３（ａ）〜（ｃ）から分かるように比較
的大きなｄ定数が得られ、且つ電界の強さに比例したｄ
定数を得るためには、正方晶系で且つ、Ｚｒ比が５１．
０付近の試料が好ましいと言える。
【００１９】図４は本発明に係る強誘電体を含む強誘電
体の温度影響性を示す図であり、縦軸は０℃を１．０と
したときの６０℃における歪率であり、正方晶系では歪
率が約１．１３であるのに対し、相境界及び菱面体晶系
では１．２倍以上に急増する。雰囲気温度の変化に対
し、正方晶系の試料が最も影響され難いことを示す。
【００２０】図５は本発明に係る強誘電体を含む強誘電
体の電圧繰返し耐久試験による歪の変化率を示す図であ
り、１．２ＶＫ／ｍｍ，１ＨＺの直流バイアスを１００
０回，１００００回及び７５０００回印加した後の歪の
変化率を示すもので、相境界では劣化が進み、菱面体晶
系も劣化が認められる。
【００２１】一方、正方晶系では７５０００回後でも劣
化の程度は微少であり、耐久性が大きい。
【００２２】
【００２３】なお、Zr比の設定が相境界に近すぎると各
特性が不安定になりやすく、又、Zr比の設定が大きすぎ
ると、図２、図３（ｃ）に示した通り発生歪が小さくな
り、実用に供さないので、図３（ａ）〜（ｃ）に示した
実施例においてはＺｒ比は５０．０〜５１．５０の範囲
に設定されることが好ましい。
【００２４】
【００２５】
【発明の効果】以上に述べた通り本発明の強誘電体磁器
組成物は、正方晶系なので強電界に対し良好な比例関係
を保って大きな歪を生じ、雰囲気の温度変化にもあまり
影響されず、且つ、耐久性良好である。よって、本発明
によれば高出力で信頼性の高い強誘電体磁器組成物が提
供できる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for improving a ferroelectric ceramic composition represented by piezoelectric ceramics. 2. Description of the Related Art A ferroelectric porcelain composition (hereinafter referred to as "actuator") is used in a driving unit (actuator) such as a micro-positioning device by utilizing the property of a ferroelectric material being deformed by strain (inverse piezoelectric effect) when a strong voltage is applied. , Abbreviated as “ferroelectric substance”). [0003] The above ferroelectric material is applied to a phase boundary which is generally considered to have the best characteristics when a voltage of about 1 V (volt) is applied. Have been. However, ferroelectrics selected based on the characteristics near the phase boundary are susceptible to the ambient temperature and need to be subjected to appropriate temperature correction. Further, as the actuator, the larger the strain displacement, the better, and it is desirable to increase the applied voltage to, for example, 1 KV. However, the conventional actuator is not practical when applied with such a high voltage, and is not practical. SUMMARY OF THE INVENTION It is an object of the present invention to provide a ferroelectric material having electric field characteristics capable of withstanding a high voltage, durability and good temperature characteristics. [0007] According and operation for solving the problems The present invention for achieving the above, Nb 2 O 5 as an additive to a ferroelectric magnetic composition PZT system, was or is added SnO 2 The crystal system was a tetragonal system, and the Zr ratio represented by Zr / (Zr + Ti) was 50.0 mol% to 51.5 mol %. The present inventors have conducted intensive studies to improve the drawbacks of the conventional PZT ferroelectrics. As a result, a small amount of Nb 2 O 5 or SnO 2 was added to the PZT ferroelectrics. In addition, a tetragonal ferroelectric material has excellent electric field characteristics and durability, and it is possible to obtain a ferroelectric porcelain composition having an unprecedented characteristic that is hardly affected by temperature changes in the environment. The present invention has been found, and the details thereof are as described below. In addition, PZT is Pb (Zr,
Ti) This is an abbreviation for O 3 crystal. [0009] Figure 1 is a graph showing the relationship Zr ratio and the lattice constant of the ferroelectric including a ferroelectric according to the present invention, mainly a composition with minor Nb 2 O 5, SnO 2 to PZT, A plurality of types of samples with different Zr ratios were produced by a usual method of producing piezoelectric ceramics, and the lattice constants were obtained by powder X-ray diffraction. [0010] tail, the Zr ratio of Zr / (Zr + Ti)
And means the molar fraction of Zr contained in the composition. For notation, this is multiplied by 100 and expressed in mole percent. In FIG. 1, when Zr ratio is 49.0 and c = 4.
113, a = 4.049 angstroms, axial ratio (c /
a) = 1.0158, and as the Zr ratio increases, the c-axis becomes smaller, the a-axis becomes larger, and the axial ratio (c / a) becomes 1.0.
, And it was found that there was a phase boundary where a phase transition from tetragonal to rhombohedral occurred when the Zr ratio was around 52.0 to 52.25. From this, it was found that when the Zr ratio was 52 or less, the particles were tetragonal, and when the Zr ratio was 52.25 or more, the particles were rhombohedral. FIG. 2 is a diagram showing the relationship between the Zr ratio and the strain of the ferroelectric including the ferroelectric according to the present invention. The sample is ground to a thickness of 1 mm, and after the silver paste electrode is baked, the sample is ground.
The figure shows the result of applying a voltage of 0 V and measuring the strain using a non-contact laser displacement meter and a strain gauge. According to FIG. 2, the Zr ratio is 52.0-52.
Near 25, the distortion is at a maximum. This is considered to be a composition in which the composition near the phase boundary is soft and easily deformed. And
Conventionally, the reason why the composition in the vicinity of the phase boundary has been adopted is that the strain is large. FIGS. 3 (a) to 3 (c) are diagrams showing a change in d constant when a voltage is applied to the ferroelectric including the ferroelectric according to the present invention. 1.2 for the sample
A DC voltage of up to KV / mm was applied, and a piezoelectric d constant (hereinafter, referred to as a piezoelectric d constant) calculated based on strain generated in this direction in 31 directions.
Abbreviated as "d constant". ) Is plotted. FIG. 3A shows that the Zr ratio is 49.0 to 51.7.
5, that is, in a tetragonal sample, the d constant increases as the Zr ratio increases, and when the Zr ratio is 51.0 or less, the d constant is almost directly proportional to the magnitude of the electric field. However, when the Zr ratio is 51.75, it tends to decrease with a peak around 1 KV / mm. FIG. 3B shows that the Zr ratio is 52.0, 52.2.
5, that is, for the sample near the phase boundary, the d constant is large, but tends to decrease from around 0.7 KV / mm. FIG. 3C shows that the Zr ratio is 53.0, 55.
0, that is, for a rhombohedral sample, it cannot be said that the d constant is small and that it is proportional to the increase in electric field. As can be seen from FIGS. 3A to 3C, a relatively large d constant is obtained, and d is proportional to the strength of the electric field.
In order to obtain a constant, a tetragonal system and a Zr ratio of 51.
It can be said that a sample near 0 is preferable. FIG. 4 is a graph showing the temperature effect of the ferroelectric material including the ferroelectric material according to the present invention. The vertical axis represents the strain rate at 60 ° C. when 0 ° C. is set to 1.0. In the crystal system, the strain rate is about 1.13, whereas in the phase boundary and the rhombohedral system, the strain rate increases sharply to 1.2 times or more. This shows that the tetragonal sample is least affected by changes in the ambient temperature. FIG. 5 is a graph showing the rate of change in strain of the ferroelectric including the ferroelectric according to the present invention in a voltage repetition durability test, in which a DC bias of 1.2 VK / mm and 1 HZ is applied to 100.
It indicates the rate of change of strain after application of 0 times, 10,000 times, and 75,000 times. Deterioration progresses at the phase boundary, and deterioration of the rhombohedral system is also recognized. On the other hand, in the tetragonal system, the degree of deterioration is small even after 75,000 times, and the durability is large. If the setting of the Zr ratio is too close to the phase boundary, each characteristic tends to be unstable, and if the setting of the Zr ratio is too large , FIGS. 2 and 3 ( As shown in FIG. 3C, the generated distortion is small and is not practically used. Therefore, in the embodiment shown in FIGS. 3A to 3C, the Zr ratio is set in the range of 50.0 to 51.50. Preferably. As described above, since the ferroelectric porcelain composition of the present invention is tetragonal, a large strain is generated while maintaining a good proportionality to a strong electric field, and the temperature of the atmosphere is reduced. It is hardly affected by changes and has good durability. Therefore, according to the present invention, a high-output and highly reliable ferroelectric ceramic composition can be provided.
【図面の簡単な説明】
【図１】本発明に係る強誘電体を含む強誘電体における
Ｚｒ比と格子定数の関係図
【図２】本発明に係る強誘電体を含む強誘電体のＺｒ比
と歪の関係を示す図
【図３】本発明に係る強誘電体を含む強誘電体に電圧を
掛けた時のｄ定数の変化を示す図
【図４】本発明に係る強誘電体を含む強誘電体の温度影
響性を示す図
【図５】本発明に係る強誘電体を含む強誘電体の電圧繰
返し耐久試験による歪の変化率を示す図BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a relationship between a Zr ratio and a lattice constant in a ferroelectric including a ferroelectric according to the present invention. FIG. 2 is a Zr of a ferroelectric including a ferroelectric according to the present invention. FIG. 3 is a diagram showing a relationship between a ratio and a strain. FIG. 3 is a diagram showing a change in d constant when a voltage is applied to a ferroelectric including a ferroelectric according to the present invention. FIG. 5 is a diagram showing a temperature effect of a ferroelectric material including the ferroelectric material according to the present invention.
フロントページの続き (56)参考文献 特開 昭63−299284（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01B 3/12 301 Continuation of the front page (56) References JP-A-63-299284 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01B 3/12 301
Claims (1)
ｂ 2 Ｏ 5 を添加してなり、その結晶系が正方晶系とされ、
Ｚｒ／（Ｚｒ+Ｔｉ）で表されるＺｒ比が５０．０ｍｏ
ｌ％〜５１．５ｍｏｌ％であることを特徴とする強誘電
体磁気組成物。(57) [Claims 1] SnO 2 and N as additives to PZT system
b 2 O 5 is added, and the crystal system is made tetragonal,
When the Zr ratio represented by Zr / (Zr + Ti) is 50.0 mo
1% to 51.5 mol% of the ferroelectric magnetic composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13364891A JP3398962B2 (en) | 1991-05-09 | 1991-05-09 | Ferroelectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13364891A JP3398962B2 (en) | 1991-05-09 | 1991-05-09 | Ferroelectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06150716A JPH06150716A (en) | 1994-05-31 |
| JP3398962B2 true JP3398962B2 (en) | 2003-04-21 |
Family
ID=15109714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13364891A Expired - Fee Related JP3398962B2 (en) | 1991-05-09 | 1991-05-09 | Ferroelectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3398962B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4629896B2 (en) * | 2001-03-30 | 2011-02-09 | セイコーエプソン株式会社 | Piezoelectric element and electric device using the same |
| JP2003133604A (en) * | 2001-10-26 | 2003-05-09 | Seiko Epson Corp | Piezoelectric thin film element, method of manufacturing the same, and ink jet recording head and ink jet printer using the same |
| JP3791614B2 (en) | 2002-10-24 | 2006-06-28 | セイコーエプソン株式会社 | Ferroelectric film, ferroelectric memory device, piezoelectric element, semiconductor element, piezoelectric actuator, liquid ejecting head, and printer |
| JP5164052B2 (en) * | 2005-01-19 | 2013-03-13 | キヤノン株式会社 | Piezoelectric element, liquid discharge head, and liquid discharge apparatus |
| JP4911907B2 (en) * | 2005-03-25 | 2012-04-04 | 京セラ株式会社 | Piezoelectric actuator and liquid ejection device |
| JP2007150037A (en) * | 2005-11-29 | 2007-06-14 | Kyocera Corp | Lead-containing piezoelectric body, piezoelectric actuator, and liquid ejection device |
-
1991
- 1991-05-09 JP JP13364891A patent/JP3398962B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06150716A (en) | 1994-05-31 |
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