JPS637677A - Piezoelectric ceramic composition - Google Patents
Piezoelectric ceramic compositionInfo
- Publication number
- JPS637677A JPS637677A JP61151199A JP15119986A JPS637677A JP S637677 A JPS637677 A JP S637677A JP 61151199 A JP61151199 A JP 61151199A JP 15119986 A JP15119986 A JP 15119986A JP S637677 A JPS637677 A JP S637677A
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric
- piezoelectric ceramic
- nb2o5
- composition
- electromechanical coupling
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 239000000919 ceramic Substances 0.000 title claims description 15
- 230000008878 coupling Effects 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 16
- 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 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 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
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電気エネルギーと機械エネルギーとの変換に使
用する圧電磁器に関し、特に電気機械結合係数を改良し
た圧電磁器組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a piezoelectric ceramic used for converting electrical energy to mechanical energy, and particularly relates to a piezoelectric ceramic composition with an improved electromechanical coupling coefficient.
圧電磁器は鉛、チタン、ジルコニウムの酸化物で構成さ
れたチタン酸ジルコン酸鉛を主成分としているが、これ
に様々な微量酸化物を添加すると圧電特性が著しく向上
することは広く知られている。たとえば、酸化ニオブ、
酸化タンタル、酸化ランタン、酸化タングステン、酸化
アンチモンなどを添加すると圧電性が向上し、電気的品
質係数ＱＥ（＝１／ｌａｎ δ）並びに機械的品質係数
Ｑ？ｌの値は小さくなる。−方、酸化鉄、酸化クロム、
酸化マンガンなどを添加すると、ＱＥ並びにＱ、の値は
大きくなる。Piezoelectric ceramics are mainly composed of lead zirconate titanate, which is composed of oxides of lead, titanium, and zirconium, and it is widely known that adding various trace oxides to this can significantly improve piezoelectric properties. . For example, niobium oxide,
When tantalum oxide, lanthanum oxide, tungsten oxide, antimony oxide, etc. are added, piezoelectricity is improved, and the electrical quality coefficient QE (=1/lan δ) and mechanical quality coefficient Q? The value of l becomes smaller. −, iron oxide, chromium oxide,
When manganese oxide or the like is added, the values of QE and Q increase.
近年、圧電センサーの需要が高まり、上記圧電磁器は例
えば粉体検知センサー等に利用されている。これらの素
子若しくは部材を構成する材料として１例えばｐ ｂ
（Ｚｒ ＋ Ｔ ｉ ） Ｏ：ｌにＮｂ２Ｏ５を添加し
た材料がある。In recent years, the demand for piezoelectric sensors has increased, and the piezoelectric ceramics described above are used, for example, in powder detection sensors. Materials constituting these elements or members include 1, for example, p b
There is a material in which Nb2O5 is added to (Zr + T i ) O:l.
上記、圧電磁器において２例えば粉体検知センサーのよ
うに、電気的エネルギーを機械的エネルギーに変換し、
さらにこの機械的エネルギーを再度電気的エネルギーに
変換する素子においては。In the piezoelectric ceramics mentioned above, 2. For example, as in powder detection sensors, electrical energy is converted into mechanical energy,
Furthermore, in the element that converts this mechanical energy back into electrical energy.
圧電歪定数ｄおよび電圧出力係数ｇの両者が大きい程効
率が良い。The larger both the piezoelectric strain constant d and the voltage output coefficient g, the better the efficiency.
ここで横振動モードに対応するｄ３２．およびｇ３、は
次式により求められる。Here, d32.corresponds to the transverse vibration mode. and g3 are determined by the following equation.
（σ；ポアソン比＋ Ｓ １４ ；弾性コンプライア
ンス。(σ; Poisson's ratio + S 14 ; elastic compliance.
Ｋｐ；電気機械結合係数、ε晶／εＧ ；比誘電率。Kp: electromechanical coupling coefficient, ε crystal/εG: relative dielectric constant.
ε。：真空の誘電率） 上式において、σおよびＳ八は圧電磁器では。ε. : Dielectric constant of vacuum) In the above formula, σ and S8 are for piezoelectric ceramics.
ホホＷＴ：アルカラ、 ｄ ３＋ハＫ ｐ トｒ璽に
／ ｇ 、−の積に比例し、−方＋ｇ３＋はＫｐに比例
し。Hoho WT: Alcala, d 3 + ha K p is proportional to the product of / g , -, and - side + g 3 + is proportional to Kp.
７ｇ１に／ ｅ （１−に反比例する。したがって＋ｄ
３１。7g1 to / e (inversely proportional to 1-. Therefore +d
31.
ｇｉ＋両者が大きい材料を得るには、Ｋｐが大きいこと
が必要である。しかしながら、前記の従来材料において
は、Ｋｐは０．６程度であり＋ｄ３１＋ｇｉｎ両方共大
きい、両方長大な材料は存在しない。In order to obtain a material in which both gi+ are large, it is necessary that Kp be large. However, in the conventional materials mentioned above, Kp is about 0.6, and there is no material in which both +d31+gin are large and both are large.
本発明は上記従来の材料に存在する問題点を解消し、高
効率のエネルギー交換が可能である圧電磁器組成物を提
供することを目的とする。An object of the present invention is to provide a piezoelectric ceramic composition that solves the problems existing in the conventional materials and allows highly efficient energy exchange.
上記従来の問題点の解決のために９本発明ではＰｂ （
Ｚｒｘ Ｔｉｙ ）Ｏ３ （但し、ｘ＋ｙ＝１）にお
いて、 ０．４６≦ｙ≦０．４７の組成範囲で０．５〜
１．５重量％のＮｂｚｏｓを含有する。という技術的手
段を採用した。In order to solve the above-mentioned conventional problems, the present invention has nine Pb (
Zrx Tiy ) O3 (however, x+y=1), 0.5 to 0.5 in the composition range of 0.46≦y≦0.47
Contains 1.5% by weight of Nbzos. A technical method was adopted.
詳細な検討を行った結果、上記組成範囲において、
Ｐ ｂ （Ｚｒｘ Ｔｉｙ ）Ｏ３ （０，４６≦ｙ
≦０．４７）は。As a result of detailed study, in the above composition range,
P b (Zrx Tiy ) O3 (0,46≦y
≦0.47).
正方晶系および菱面体晶系強誘電体が混在する状態であ
り、電気機械結合係数Ｋｐが非常に大きくなる。ざらに
Ｎｂ２Ｏ５を添加することにより、圧電特性は極めて向
上する。This is a state in which tetragonal and rhombohedral ferroelectrics coexist, and the electromechanical coupling coefficient Kp becomes extremely large. By adding Nb2O5, the piezoelectric properties are significantly improved.
一酸化鉛（ＰｂＯ） 、酸化チタン（ＴｉＯｚ） 、酸
化ジルコニウム（Ｚｒ Ｏ□）、炭酸ストロンチウム（
ＳｒＣＯ３）、五酸ニオブ（Ｎｂ２Ｏ５ ）を、所定量
となるように秤量し、これらをボールミルに入れ２時間
混合した６得られたスラリーを、１５０°Ｃで２時間乾
燥し原料粉末とした。この原料粉末を８５０°Ｃで仮焼
し、粉砕後造粒し、２０・〆×２′にプレス成形した。Lead monoxide (PbO), titanium oxide (TiOz), zirconium oxide (ZrO□), strontium carbonate (
SrCO3) and niobium pentate (Nb2O5) were weighed to a predetermined amount, and placed in a ball mill and mixed for 2 hours. 6. The resulting slurry was dried at 150°C for 2 hours to obtain a raw material powder. This raw material powder was calcined at 850°C, pulverized, granulated, and press-molded to a size of 20×2'.
これを酸素中、 １２６０’ Ｃで２時間焼結し、焼結
体を得た。得られた焼結体の両面に、銀ペース１−を印
刷し、乾燥後５５０’ Ｃで２０分間焼き付けをした。This was sintered in oxygen at 1260'C for 2 hours to obtain a sintered body. Silver paste 1- was printed on both sides of the obtained sintered body, and after drying, it was baked at 550'C for 20 minutes.
次に分極装置にセットし、シリコンオイル中で３ＫＶ／
ｍｍの直流電圧を５分間印加して分極処理した。Next, set it in a polarizer and put it in silicone oil at 3KV/
Polarization treatment was performed by applying a DC voltage of mm for 5 minutes.
第１図にｇｆｆ＋およびｄ３１のＮｂ２Ｏ５含有量依存
性を示すが、第１図より明らかなように、 Ｎｂ２Ｏ５
含有量が０．５〜１．５重量％の範囲においてｇｊ＋。Figure 1 shows the dependence of gff+ and d31 on Nb2O5 content, and as is clear from Figure 1, Nb2O5
gj+ in a content range of 0.5 to 1.5% by weight.
ｄ３１が共に大なる値を示し、 ＮｂｔＯＳが１．０重
量％においてｇｓ＋が最大値を示している。而してＮｂ
２Ｏ５が０．５重量％未満ではｇ ３１＋ ｄ ｆｆ
Ｉ共に低い値を示し、圧電磁器組成物としての特性が低
いため不都合である。−方Ｎｂ、Ｏ，が１．５重量％を
越えると。d31 both showed large values, and gs+ showed the maximum value when NbtOS was 1.0% by weight. Then Nb
If 2O5 is less than 0.5% by weight, g 31+ d ff
This is disadvantageous because both I values are low and the properties as a piezoelectric ceramic composition are poor. - When Nb, O, exceeds 1.5% by weight.
ｄ３１は更に増加するが＋ｇ３＋が低い値を示すので不
都合である。Although d31 increases further, +g3+ shows a low value, which is disadvantageous.
第２図および第３図は、 Ｎｂ２Ｏ２を１，０重量％含
有したＰ ｂ （Ｚｒ、Ｔｉ）Ｏ３における各々電気機
械結合係数Ｋｐおよび比誘電率ε晶／ε。のＴｉ／Ｚｒ
比依存性を示す図である。FIGS. 2 and 3 show the electromechanical coupling coefficient Kp and relative dielectric constant ε crystal/ε, respectively, in P b (Zr, Ti) O3 containing 1.0% by weight of Nb2O2. of Ti/Zr
It is a figure showing ratio dependence.
両図から明らかなように、Ｔｉが４６〜４７モル％にお
いて、上記両圧電特性が他の領域よりも顕著に高い値を
示している。特に電気機械結合係数ＫｐＯ値は、Ｔｉが
４６．５モル％の時０．７２の値を示しており、従来材
料が０．６程度であったのに対して２０％向上している
。この値は圧電磁器としては穫めて大きな値である。同
様に比誘電率ε晶／ε。も、Ｔｉが４６．５モル％付近
で最大値２１００を示す。As is clear from both figures, when Ti is 46 to 47 mol %, both of the above piezoelectric properties exhibit significantly higher values than in other regions. In particular, the electromechanical coupling coefficient KpO value shows a value of 0.72 when Ti is 46.5 mol %, which is an improvement of 20% compared to about 0.6 for the conventional material. This value is an extremely large value for a piezoelectric ceramic. Similarly, the relative permittivity is ε crystal/ε. Also, the maximum value is 2100 when Ti is around 46.5 mol%.
上記結果より算出した圧電歪定数ａＳ＋の値は２００
×１Ｑ−１２ｍ／Ｖであり、−方、電圧出力係数ｇｘ＋
の値はｌｌＸｌ０−’ Ｖｍ／Ｎと２両者共充分に大き
い値となっている。これらの圧電定数の値は前述した粉
体探知センサーの如き、！気的エネルギーおよび機械的
エネルギー両者の相互エネルギー変換を利用する圧電素
子には、極めて有用なものである。The value of the piezoelectric strain constant aS+ calculated from the above results is 200
×1Q-12m/V, - side, voltage output coefficient gx+
The values of llXl0-'Vm/N and 2 are both sufficiently large values. The values of these piezoelectric constants are similar to the powder detection sensor mentioned above! It is extremely useful for piezoelectric elements that utilize mutual energy conversion of both gaseous energy and mechanical energy.
本発明の圧電セラミックスは９以上記述のように電気機
械結合係数Ｋｐを飛躍的に向上させたものであるから、
圧電定数を大幅に向上させることができ、圧電セラミッ
クスを構成部材とする電気機械エネルギー変換装置の効
率を飛躍的に向上させ得るという効果がある。Since the piezoelectric ceramic of the present invention has dramatically improved electromechanical coupling coefficient Kp as described in 9 above,
This has the effect that the piezoelectric constant can be significantly improved, and the efficiency of an electromechanical energy conversion device using piezoelectric ceramics as a component can be dramatically improved.
第１図は本発明の実施例における圧電歪定数ｄ３、およ
び電圧出力係数ｇｘ＋のＮｂＺＯ５含有量依存性を示す
図、第２図および第３図は各々本発明の実施例における
電気機械結合係数および比誘電率のＴｉ／Ｚｒ比依存性
を示す図である。FIG. 1 is a diagram showing the NbZO5 content dependence of the piezoelectric strain constant d3 and the voltage output coefficient gx+ in the example of the present invention, and FIGS. 2 and 3 are the electromechanical coupling coefficient and FIG. 3 is a diagram showing the dependence of relative dielectric constant on Ti/Zr ratio.
Claims (3)
１）で表される組成をもって基本組成とし、０．４６≦
ｙ≦０．４７の範囲内の組成から成り、Ｎｂ＿２Ｏ＿５
を０．５〜１．５重量％含有することを特徴とする圧電
磁器組成物。(1) Pb(Zr_xTi_y)O_3 (where x+y=
The composition expressed by 1) is the basic composition, and 0.46≦
Consisting of a composition within the range of y≦0.47, Nb_2O_5
A piezoelectric ceramic composition characterized by containing 0.5 to 1.5% by weight of.
請求の範囲第１項記載の圧電磁器組成物。(2) The piezoelectric ceramic composition according to claim 1, which has an electromechanical coupling coefficient Kp of 0.66 or more.
２ｍ／Ｖ以上である特許請求の範囲第１項もしくは第２
項記載の圧電磁器組成物。(3) Piezoelectric strain constant d_3_1 is 130×10^-^1^
Claim 1 or 2 which is 2m/V or more
The piezoelectric ceramic composition described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61151199A JPS637677A (en) | 1986-06-27 | 1986-06-27 | Piezoelectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61151199A JPS637677A (en) | 1986-06-27 | 1986-06-27 | Piezoelectric ceramic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS637677A true JPS637677A (en) | 1988-01-13 |
Family
ID=15513412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61151199A Pending JPS637677A (en) | 1986-06-27 | 1986-06-27 | Piezoelectric ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS637677A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994024203A1 (en) * | 1993-04-19 | 1994-10-27 | Kabushiki Kaisha Meiji Gomu Kasei | Method of manufacturing fine piezoelectric ceramic balls for piezoelectric elastomer |
-
1986
- 1986-06-27 JP JP61151199A patent/JPS637677A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994024203A1 (en) * | 1993-04-19 | 1994-10-27 | Kabushiki Kaisha Meiji Gomu Kasei | Method of manufacturing fine piezoelectric ceramic balls for piezoelectric elastomer |
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