JPH04170364A - Piezoelectric porcelain composition - Google Patents
Piezoelectric porcelain compositionInfo
- Publication number
- JPH04170364A JPH04170364A JP2298641A JP29864190A JPH04170364A JP H04170364 A JPH04170364 A JP H04170364A JP 2298641 A JP2298641 A JP 2298641A JP 29864190 A JP29864190 A JP 29864190A JP H04170364 A JPH04170364 A JP H04170364A
- Authority
- JP
- Japan
- Prior art keywords
- curie point
- piezoelectric
- present
- electromechanical coupling
- dielectric 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 229910052573 porcelain Inorganic materials 0.000 title claims description 6
- 230000008878 coupling Effects 0.000 abstract description 10
- 238000010168 coupling process Methods 0.000 abstract description 10
- 238000005859 coupling reaction Methods 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 2
- 229910020698 PbZrO3 Inorganic materials 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、磁器組成物、特に、圧電性磁器組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to porcelain compositions, particularly piezoelectric porcelain compositions.
ブザーやスピーカー等の圧電発音体素子の材料として、
たとえば特公昭５４−３６７５６号公報に記載の圧電性
磁器材料がある。この圧電性磁器材料は、Ｐｂ （Ｓｎ
Ｉ−α ５ｂｚ７ｓ ）＊ Ｔｉ 、Ｚｒ、Ｏｌと、
これに対して０．０５〜１．５重置％のＳｉｎ、とを含
んでいる。ここで、Ｐｂ（ＳｎＩ−α Ｓ ｂｔｙｚ
） Ｘ Ｔ ｉ ｙＺ ｒ、 Ｏｓは、次の条件を満
たしている。As a material for piezoelectric sounding elements such as buzzers and speakers,
For example, there is a piezoelectric ceramic material described in Japanese Patent Publication No. 54-36756. This piezoelectric porcelain material is Pb (Sn
I-α5bz7s)* Ti, Zr, Ol,
On the other hand, it contains 0.05 to 1.5% of Sin. Here, Pb(SnI-α S btyz
) X T i yZ r, Os satisfies the following conditions.
ｘ＋ｙ＋ｚ＝１
０、Ｏ１≦ｘ≦０．５
０．０１≦ｙ≦０．７５
０．００５≦ｚ≦０．９
また、この化合物には、Ｐｂの２０モル％以下がＳｒ、
ＢａまたはＣａで置換されたものが含まれている。x+y+z=1 0, O1≦x≦0.5 0.01≦y≦0.75 0.005≦z≦0.9 In addition, in this compound, 20 mol% or less of Pb is Sr,
Contains those substituted with Ba or Ca.
前記従来の圧電性磁器材料は、電気機械結合係数と比誘
電率とが高く、出力電圧の反復加圧力に対する耐劣化性
が良好であるが、キュリー点が低い、キュリー点が低い
圧電性磁器材料を用いた圧電発音体素子は、高温環境に
おいて消極が起こるため、高温環境で高い信頼性（特性
安定性）が求められている自動車電話等の機器には不適
当である。一般に、このような機器に用いられる圧電発
音体素子のキュリー点は、その機器が使用される温度環
境の最高温度の約２倍以上が好ましいとされている。た
とえば、８５〜１２５℃の温度環境下で用いられる圧電
発音体素子のキュリー点は、３００°Ｃ以上が好ましい
とされている。The conventional piezoelectric porcelain material has a high electromechanical coupling coefficient and dielectric constant, and has good resistance to deterioration against repeated pressure of output voltage, but has a low Curie point. A piezoelectric sounding element using a piezoelectric sound element undergoes depolarization in a high-temperature environment, so it is unsuitable for devices such as car phones that require high reliability (characteristic stability) in a high-temperature environment. Generally, it is said that the Curie point of a piezoelectric sounding element used in such equipment is preferably about twice or more the maximum temperature of the temperature environment in which the equipment is used. For example, it is said that the Curie point of a piezoelectric sounding element used in a temperature environment of 85 to 125°C is preferably 300°C or higher.
本発明の目的は、キュリー点が高く、機械的品質係数が
小さく、かつ電気機械結合係数及び比誘電率が大きな圧
電性磁器組成物を提供することにある。An object of the present invention is to provide a piezoelectric ceramic composition that has a high Curie point, a small mechanical quality factor, and a large electromechanical coupling coefficient and dielectric constant.
本発明の圧電性磁器組成物は、ＸモルのＰｂＺｒ０１と
、ｙモルのＰ ｂ Ｔ ｉ Ｏｓと、２モルのＰｂ （
Ｓ ｎ ＋ｙｘ Ｎ ｂ ｔａｉｘｓ ｂ ｚ（＋−ａ
＞ｚｓ） Ｏｘとを含み、次の式を満たしていることを
特徴としている。The piezoelectric ceramic composition of the present invention contains X moles of PbZr01, y moles of P b T i Os, and 2 moles of Pb (
S n +yx N b taixs b z(+-a
>zs) Ox, and is characterized by satisfying the following formula.
ｘ ＋ ｙ ＋ ｚ ＝ １
０．４７≦ｘ≦０．５２
０．４３≦ｙ≦０．４８
０．０２≦ｚ≦０．０８
０．２ ≦α≦０．６
ホ ＊＊＊＊＊＊
本発明の圧電性磁器組成物は、次の３種類の圧電磁器材
料を含んでいる。x + y + z = 1 0.47≦x≦0.52 0.43≦y≦0.48 0.02≦z≦0.08 0.2 ≦α≦0.6 E ＊＊＊＊＊＊ The piezoelectric ceramic composition of the present invention contains the following three types of piezoelectric ceramic materials.
ＰｂＺｒコｂ−
この成分は、本発明に係る組成物中に０．４７モル以上
０．５２モル以下含まれる。この含有量（ｘ）が前記範
囲外の場合は、組成物の電気機械結合係数及び比誘電率
が小さくなる。したがって、出力電圧の反復加圧力に対
する耐劣化性が悪い圧電素子しか得られない。PbZrcob- This component is contained in the composition according to the present invention in an amount of 0.47 mol or more and 0.52 mol or less. If this content (x) is outside the above range, the electromechanical coupling coefficient and dielectric constant of the composition will be small. Therefore, only a piezoelectric element with poor resistance to deterioration against repeated pressure of output voltage can be obtained.
ＰｂＴｉ０゜
この成分は、本発明の組成物中に０．４３モル以上０．
４８モル以下含まれる。この物質の割合（ｙ）が前記範
囲外の場合は、上述のＰｂＺｒ０１が上述の範囲を超え
た場合と同様の結果になる。PbTi0゜This component is contained in the composition of the present invention in an amount of 0.43 mol or more.
Contains 48 moles or less. If the proportion (y) of this substance is outside the above range, the same result as in the case where the above-mentioned PbZr01 exceeds the above range will be obtained.
Ｐ ｂ Ｓ ｎ ｚｓ Ｎ ｂｚｅ／ｚｓ ｂｚ Ｉ
−ａ Ｏこの成分のαΦ値は、０．２以上０．６以
下に設定されている。αの値が０．２未満の場合は、組
成物のキュリー点が低くなる。したがって、高温環境下
での特性が安定した圧電素子が得られなり、逆に、αが
０．６を鰯える場合は、キュリー点はより大きくなるが
、電気機械結合係数及び比誘電率が低下してしまう。P b S n zs N bze/zs bz I
-a O The αΦ value of this component is set to 0.2 or more and 0.6 or less. If the value of α is less than 0.2, the Curie point of the composition will be low. Therefore, a piezoelectric element with stable characteristics in a high-temperature environment cannot be obtained. Conversely, when α is 0.6, the Curie point becomes larger, but the electromechanical coupling coefficient and dielectric constant decrease. Resulting in.
本発明の組成物において、この物質は０．０２モル以上
０．０８モル以下含まれている。この物質の割合（ｚ）
が０．０２モル未満の場合は、電気機械結合係数及び比
誘電率が低下してしまう。In the composition of the present invention, this substance is contained in an amount of 0.02 mol or more and 0.08 mol or less. Proportion of this substance (z)
If it is less than 0.02 mol, the electromechanical coupling coefficient and dielectric constant will decrease.
逆に、０．０８モルを超える場合は、電気機械結合係数
及び比誘電率はより大きくなるが、キュリー点が低下し
てしまう。On the other hand, if it exceeds 0.08 mol, the electromechanical coupling coefficient and dielectric constant will increase, but the Curie point will decrease.
本発明の組成物では、上述のｘ、ｙ及び２の和が１とな
るように混合割合が調整されている。この関係を満たさ
ない場合は、発音体材料として好ましくない。In the composition of the present invention, the mixing ratio is adjusted so that the sum of x, y, and 2 described above is 1. If this relationship is not satisfied, it is not preferable as a material for a sounding body.
なお、本発明の組成物には、本組成物１００重量部に対
してＭ ｇ Ｏ、Ｃｒｈｏ ｓ、 Ｍ ｍ Ｏｔのいず
れかまたはこれらの組合せが０．０５〜０．２重量部含
まれていてもよい。The composition of the present invention contains 0.05 to 0.2 parts by weight of MgO, Crhos, MmOt or a combination thereof based on 100 parts by weight of the composition. Good too.
純度９９．０％以上の市販のＰｂ、Ｏａ 、ＺｒＯｘ
、Ｔ ｉＯｘ 、５ｎＯｚ 、Ｎｂｔ Ｏｓ及び５ｂ２
０、の各粉末を用意し、ｘ、ｙ、ｚ及びαが表の値とな
るように各粉末を秤量した。そして、各粉末をボールミ
ルを用いて湿式混合し、乾燥した後、８００〜１０００
°Ｃで３時間仮焼成した。Commercially available Pb, Oa, ZrOx with purity of 99.0% or more
, T iOx , 5nOz , NbtOs and 5b2
Each powder was prepared and weighed so that x, y, z, and α became the values shown in the table. Then, each powder was wet mixed using a ball mill, and after drying, 800 to 1000
It was pre-baked at °C for 3 hours.
次に、得られた仮焼成物を比表面積が２ボ／ｇ以上にな
るようボールミルを用いて湿式粉砕した。Next, the obtained calcined product was wet-pulverized using a ball mill so that the specific surface area became 2 bo/g or more.
乾燥後、有機系粘結剤を添加し、加圧成形して直径１２
ＩＩＩＩ１１、厚さ１．５ｍｍのディスクを製造した。After drying, an organic binder is added and pressure molded to a diameter of 12 mm.
III11, a 1.5 mm thick disk was manufactured.
そして、酸化性雰囲気において、そのディスクを１１５
０〜１２５０°Ｃで３時間焼成した。Then, in an oxidizing atmosphere, the disk was
It was baked at 0 to 1250°C for 3 hours.
次に、ディスク状の焼成体を厚さ１■に研磨加工し、両
面に銀ペーストを焼き付けた。そして、銀ペーストが焼
き付けられたディスクを８０℃の絶縁油中に浸漬し、そ
の両面に３ｋＶ／−の直流電圧を印加して分極処理した
。Next, the disk-shaped fired body was polished to a thickness of 1 inch, and silver paste was baked on both sides. Then, the disk on which the silver paste was baked was immersed in insulating oil at 80° C., and a DC voltage of 3 kV/− was applied to both sides of the disk to perform polarization treatment.
分極処理されたディスクを２４時間以上放置した後、そ
のディスクの機械的品質係数、電気機械結合係数、比誘
電率及びキュリー点を調べた。測定は、電子材料工業会
の標準規格に準じて行った。After the polarized disk was left for 24 hours or more, the mechanical quality factor, electromechanical coupling coefficient, dielectric constant, and Curie point of the disk were examined. The measurements were conducted in accordance with the standards of the Electronic Materials Industries Association.
すなわち、インピーダンスアナライザーを用いて拡がり
振動モードの共振周波数及び反共振周波数、抵抗値、及
びＩＫＨｚでの静電容量を測定した後、計算式にて算出
した。ただし、キュリー点については、試料をシリコン
オイル中に浸漬し、加熱しなお、機械的品質係数（Ｑｍ
）は、２００以下が良好な値である。電気機械結合係数
（Ｋｂ）は、６５％以上が良好な値である。比誘電率（
ε、３１／ε。）は、２０００以上が良好な値である。That is, after measuring the resonant frequency and anti-resonant frequency of the spreading vibration mode, resistance value, and capacitance at IKHz using an impedance analyzer, calculation was performed using a calculation formula. However, regarding the Curie point, the mechanical quality factor (Qm
) is a good value of 200 or less. A good electromechanical coupling coefficient (Kb) is 65% or more. Relative permittivity (
ε, 31/ε. ) is a good value of 2000 or more.
さらに、キュリー点（Ｔｃ）は、３００°Ｃ以上が良好
な値である。Furthermore, a good value for the Curie point (Tc) is 300°C or higher.
結果を表に示す。なお、括弧付の番号は比較例である。The results are shown in the table. Note that the numbers in parentheses are comparative examples.
結果に基づいて、図に示す三角ダイヤグラムを作成した
。この三角ダイヤグラムは、ｘ、ｙ及び２と、測定結果
との関係を示すものである０図中、白丸は測定結果が全
て良好であったものを示し、また黒丸は１つでも測定結
果に不良のあったものを示している。また、黒丸及び白
丸を指す矢印に付された番号は、試料番号である。Based on the results, the triangular diagram shown in the figure was created. This triangular diagram shows the relationship between x, y, and 2 and the measurement results.In the diagram, white circles indicate that all measurement results were good, and black circles indicate that even one measurement result was defective. It shows what was there. Further, the numbers attached to the arrows pointing to the black circles and white circles are the sample numbers.
表及び図から明らかなように、ｘ、ｙ及び２が本発明の
範囲内（図の斜線内）の場合は、αが本発明の範囲内で
あれば良好な測定結果が得られた。As is clear from the table and figure, when x, y, and 2 were within the range of the present invention (within the diagonal lines in the figure), good measurement results were obtained as long as α was within the range of the present invention.
これに対し、ｘ、ｙ及びＺが本発明の範囲内であっても
αが本発明の範囲外の場合、及びｘ、ｙ及びＺが本発明
の範囲外の場合は、良好な結果は得られなかった。On the other hand, even if x, y, and Z are within the scope of the present invention, if α is outside the scope of the present invention, and if x, y, and Z are outside the scope of the present invention, good results may not be obtained. I couldn't.
本発明に係る圧電性磁器組成物は、上述の３種の成分を
含み、かつ上述の各関係を満たしている。The piezoelectric ceramic composition according to the present invention contains the above-mentioned three types of components and satisfies each of the above-mentioned relationships.
このため、本発明によれば、キュリー点が高く、機械的
品質係数が小さく、かつ電気機械結合係数及び比誘電率
が大きな圧電性磁器組成物が実現できる。Therefore, according to the present invention, a piezoelectric ceramic composition having a high Curie point, a small mechanical quality factor, and a large electromechanical coupling coefficient and dielectric constant can be realized.
図は実施例の結果を示す３角ダイヤグラムである。 The figure is a triangular diagram showing the results of the example.
Claims (1)
＿３と、ｚモルのＰｂ（Ｓｎ＿１＿／＿３Ｎｂ＿２＿α
＿／＿３Ｓｂ＿２＿（＿１＿−＿α＿）＿／＿３）Ｏ＿
３とを含み、下式を満たしていることを特徴とする圧電
性磁器組成物。 ｘ＋ｙ＋ｚ＝１ ０．４７≦ｘ≦０．５２ ０．４３≦ｙ≦０．４８ ０．０２≦ｚ≦０．０８ ０．２≦α≦０．６(1) x moles of PbZrO_3 and y moles of PbTiO
_3 and z moles of Pb (Sn_1_/_3Nb_2_α
＿／＿3Sb＿２＿(＿１＿−＿α＿)＿／＿３）O＿
3. A piezoelectric porcelain composition characterized in that it contains the following formula: x+y+z=1 0.47≦x≦0.52 0.43≦y≦0.48 0.02≦z≦0.08 0.2≦α≦0.6
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2298641A JP2957002B2 (en) | 1990-10-31 | 1990-10-31 | Piezoelectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2298641A JP2957002B2 (en) | 1990-10-31 | 1990-10-31 | Piezoelectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04170364A true JPH04170364A (en) | 1992-06-18 |
| JP2957002B2 JP2957002B2 (en) | 1999-10-04 |
Family
ID=17862366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2298641A Expired - Fee Related JP2957002B2 (en) | 1990-10-31 | 1990-10-31 | Piezoelectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2957002B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009234904A (en) * | 2008-03-05 | 2009-10-15 | Ngk Spark Plug Co Ltd | Piezoceramic composition, piezoelectric element using the same and non-resonance knock sensor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8040024B2 (en) | 2008-03-05 | 2011-10-18 | Ngk Spark Plug Co., Ltd. | Piezoceramic material, piezoelectric element and non-resonance knock sensor |
| JP5170905B2 (en) * | 2009-10-13 | 2013-03-27 | 日本特殊陶業株式会社 | Non-resonant knock sensor |
-
1990
- 1990-10-31 JP JP2298641A patent/JP2957002B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009234904A (en) * | 2008-03-05 | 2009-10-15 | Ngk Spark Plug Co Ltd | Piezoceramic composition, piezoelectric element using the same and non-resonance knock sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2957002B2 (en) | 1999-10-04 |
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