JPH0244273B2 - - Google Patents
Info
- Publication number
- JPH0244273B2 JPH0244273B2 JP61276729A JP27672986A JPH0244273B2 JP H0244273 B2 JPH0244273 B2 JP H0244273B2 JP 61276729 A JP61276729 A JP 61276729A JP 27672986 A JP27672986 A JP 27672986A JP H0244273 B2 JPH0244273 B2 JP H0244273B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- composition
- coupling coefficient
- dielectric constant
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 230000008878 coupling Effects 0.000 description 13
- 238000010168 coupling process Methods 0.000 description 13
- 238000005859 coupling reaction Methods 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 3
- 229910020698 PbZrO3 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Description
産業上の利用分野
本発明は、圧電性磁器組成物において、比誘電
率ξおよび電気機械結合係数Krの高い材料であ
つて、常温かつ短時間で分極可能な材料を提供す
るにある。
従来技術
圧電性磁器組成物は、窯業的方法で磁器体に焼
結した後、直流電圧を印加することによつて電気
的に活性化し得て、その残留圧電特性を利用でき
る窯業的組成物に関するものであり、約200℃以
下の高温領域まで、この圧電性の使用温度範囲を
拡大することによつて工業的利用価値を附加する
と共に、さらに特定の組成を選択することによつ
て、セラミツクピツクアツプあるいはマイクロフ
オン用の素子としての応用に好適な径方向結合係
数の大きい圧電磁器組成を新規な成分構成で得る
ところにある。
特公昭42−9716号公報には、ペロブスカイト型
構造を有するPb（Mg1/3・Nb2/3）O3と同じくペ
ロブスカイト型構造を有するPbTiO3および
PbZrO3の三成分系から構成され、その組成比は
モル百分率で、Pb（Mg1/3・Nb2/3）O3：69〜４
モル％、PbTiO3：52−30モル％、PbZrO3：62−
１モル％の範囲からなる複合酸化物型の圧電性の
固溶体磁器組成物である。
発明の解決しようとする問題点
しかしながら、従来公知の圧電性磁器組成物
は、比誘電率ξと電気機械結合係数Krとが共に
高い材料は少なかつた。また焼結温度（普通1250
〜1350℃）も高く、また分極が容易ではなかつた
（普通100℃、１時間）。
問題点を解決するための手段
本発明は、組成物の重量基準で、PbO60ないし
70重量％、TiO27ないし12重量％、ZrO21ないし
17重量％、WO30.1重量％より大ないし５重量％
より小、MgO0.4ないし2.5重量％およびNb2O53
ないし15重量％からなる磁器組成物に関するもの
である。
さらに、本発明では、Pb元素の一部をSr、
Ca、Baの群から選ばれた少なくとも一つの元素
で組成物の重量基準でＯないし19重量％の範囲で
置換することができる。Pb元素の１部をSr、
Ca、Baの少なくとも一つの元素で置換すること
もできる。
本発明は、組成物の重量基準でPbO60ないし70
重量％、TiO27ないし12重量％、ZrO21ないし17
重量％の公知の磁器組成物に特定割合のWO3、
MgOおよびNb2O5を添加し、比誘電率（ξ）約
3000以上、電気機械結合係数（Kr）約60％以上
の圧電性磁器組成物を得ることを目的としたもの
である。
Nb2O5の添加量は、３ないし15重量％である。
Nb2O53重量％未満では電気機械結合係数Kr、比
誘電率ξともに低く添加効果が全くみられない。
３重量％以上では添加効果が認められるが、15重
量％以上ではコストが高くなり、実用的でない。
MgOの添加量は、0.4ないし2.5重量％である。
MgO0.4重量％未満では、電気機械結合係数Kr、
比誘電率ξともに低く、添加効果は見られない。
0.4重量％以上で添加効果が認められ、比誘電率
ξ、および電気機械結合係数Krともに上昇する
が、2.5重量％以上になると比誘電率ξおよび電
気機械結合係数Krともに低下する。
WO3の添加量は0.1重量％より大ないし５重量
％より小である。0.1重量％より大きくなると電
気機械結合係数Kr、比誘電率ξともに上昇し、
添加量が増すにつれて、特に比誘電率ξの上昇が
著しく、５重量％以上では逆にξ、Krともに低
下する。
実施例
PbO、TiO2、ZrO2、WO3、MgOおよびNb2O5
を第１表に示す配合割合で秤量し、ボールミルに
て24時間粉砕後、800〜900℃で４時間〓焼する。
得られた反応生成物を再びボールミルで24時間
粉砕後、ポリビニルアルコールを加えて均質にな
るように混合し、乾燥させる。
これを円板上に形成し、PbO雰囲気中で1100〜
1700℃で焼成し、直径20mm、厚さ１mmの円板を得
た。得られた円板を3Kvの直流電圧で常温、１分
間分極した。これを大気中で１周間保持した後電
気特性を測定した。
第１表に各試料の組成比と、比誘電率ξ、電気
機械結合係数Krとの関係を示した。
INDUSTRIAL APPLICATION FIELD The present invention provides a piezoelectric ceramic composition having a high dielectric constant ξ and an electromechanical coupling coefficient Kr, which can be polarized at room temperature in a short time. PRIOR ART A piezoelectric porcelain composition relates to a ceramic composition that can be electrically activated by applying a direct current voltage after being sintered into a porcelain body by a ceramic method to utilize its residual piezoelectric properties. By expanding the operating temperature range of this piezoelectricity to a high temperature range of about 200℃ or less, we will add industrial value, and by selecting a specific composition, we will be able to improve ceramic pick-up. Alternatively, it is possible to obtain a piezoelectric ceramic composition with a large radial coupling coefficient suitable for application as a microphone element with a new composition. Japanese Patent Publication No. 42-9716 describes Pb(Mg1/3・Nb2/3)O 3 having a perovskite structure as well as PbTiO 3 and PbTiO 3 having a perovskite structure.
It is composed of a three-component system of PbZrO3 , and its composition ratio is expressed as a molar percentage: Pb(Mg1/3・Nb2/3) O3 : 69 to 4
Mol%, PbTiO3 : 52-30 mol%, PbZrO3 : 62-
This is a composite oxide type piezoelectric solid solution ceramic composition consisting of 1 mol %. Problems to be Solved by the Invention However, there are few piezoelectric ceramic compositions known in the art that have both a high dielectric constant ξ and a high electromechanical coupling coefficient Kr. Also, the sintering temperature (normally 1250
~1350°C), and polarization was not easy (usually at 100°C for 1 hour). Means for Solving the Problems The present invention provides that, based on the weight of the composition, PbO60 or
70% by weight, TiO 2 7 to 12% by weight, ZrO 2 1 to 12% by weight
17% by weight, WO 3 greater than 0.1% to 5% by weight
Less than 0.4 to 2.5% by weight of MgO and Nb 2 O 5 3
and 15% by weight. Furthermore, in the present invention, a part of the Pb element is Sr,
At least one element selected from the group of Ca and Ba can be substituted in an amount of O to 19% by weight based on the weight of the composition. Part of the Pb element is Sr,
It can also be replaced with at least one element of Ca or Ba. The present invention provides PbO60 to PbO70 based on the weight of the composition.
% by weight, TiO 2 7 to 12 % by weight, ZrO 2 1 to 17
WO 3 in a specific proportion to a known porcelain composition in weight %,
Added MgO and Nb 2 O 5 , relative dielectric constant (ξ) approx.
The purpose is to obtain a piezoelectric ceramic composition having an electromechanical coupling coefficient (Kr) of 3000 or more and an electromechanical coupling coefficient (Kr) of about 60% or more. The amount of Nb 2 O 5 added is 3 to 15% by weight.
When Nb 2 O 5 is less than 3% by weight, both the electromechanical coupling coefficient Kr and the dielectric constant ξ are low, and no effect of addition is observed.
At 3% by weight or more, the addition effect is recognized, but at 15% by weight or more, the cost increases and is not practical. The amount of MgO added is 0.4 to 2.5% by weight.
For less than 0.4% by weight of MgO, the electromechanical coupling coefficient Kr,
Both the dielectric constant ξ are low, and no effect of addition is observed.
At 0.4% by weight or more, the addition effect is recognized, and both the dielectric constant ξ and the electromechanical coupling coefficient Kr increase, but when it exceeds 2.5% by weight, both the dielectric constant ξ and the electromechanical coupling coefficient Kr decrease. The amount of WO 3 added is greater than 0.1% by weight and less than 5% by weight. When it becomes larger than 0.1% by weight, both the electromechanical coupling coefficient Kr and relative permittivity ξ increase;
As the amount added increases, the relative permittivity ξ in particular increases markedly, and at 5% by weight or more, both ξ and Kr decrease. Examples PbO, TiO2 , ZrO2 , WO3 , MgO and Nb2O5
were weighed in the proportions shown in Table 1, ground in a ball mill for 24 hours, and then baked at 800 to 900°C for 4 hours. The obtained reaction product is ground again in a ball mill for 24 hours, then polyvinyl alcohol is added thereto, mixed until homogeneous, and dried. This was formed on a disk and heated to 1100 ~
It was fired at 1700°C to obtain a disc with a diameter of 20 mm and a thickness of 1 mm. The obtained disk was polarized at room temperature for 1 minute with a DC voltage of 3Kv. After holding this in the atmosphere for one round, the electrical characteristics were measured. Table 1 shows the relationship between the composition ratio of each sample, relative dielectric constant ξ, and electromechanical coupling coefficient Kr.
【表】【table】
【表】
第１表から明らかなように、各成分をPbO60な
いし70重量％、TiO27ないし12重量％、ZrO21な
いし17重量％、WO30.1〜10.0重量％、MgO0.35
ないし3.0重量％、Nb2O52.0ないし17重量％の範
囲にて、28種類の組成物を作成し、これらの試料
の電気特性（誘電率、電気機械結合係数）を測定
した。
上記試料のうち、試料番号６、10、14、18およ
び22は比誘電率3000以上、電気機械係数60以上で
あり、圧電ブザー、圧電スピーカーなどの音響変
換素子用として有用な磁器を得ることができる。
上記試料番号No.６、10、14、18、22の組成より
下記の組成物が特に音響変換素子としてよいこと
がわかつた。すなわち、
組成（重量％）
PbO60ないし70％、TiO27ないし12％、ZrO21
ないし17％、WO30.1％より大ないし５％より小、
MgO0.4ないし2.5％、Nb2O53ないし15％からな
る磁器組成物である。
発明の効果
(1) 本発明の圧電性磁器組成物は比誘電率（ξ）
（約3000以上）および電気機械結合係数（Kr）
（約60％以上）が共に高い。
(2) 組成物の焼結温度は通常1250〜1350℃である
が、本発明の組成物では、1150〜1250℃で通常
の組成物より焼結温度が低く焼結しやすい。[Table] As is clear from Table 1, each component is PbO 60 to 70% by weight, TiO 2 7 to 12% by weight, ZrO 2 1 to 17% by weight, WO 3 0.1 to 10.0% by weight, MgO 0.35
28 types of compositions were prepared in the range of Nb 2 O 5 to 3.0% by weight and 2.0 to 17% by weight of Nb 2 O 5 , and the electrical properties (dielectric constant, electromechanical coupling coefficient) of these samples were measured. Among the above samples, sample numbers 6, 10, 14, 18 and 22 have a dielectric constant of 3000 or more and an electromechanical coefficient of 60 or more, making it possible to obtain porcelain useful for acoustic transducer elements such as piezoelectric buzzers and piezoelectric speakers. can. From the compositions of sample numbers 6, 10, 14, 18, and 22, it was found that the following compositions are particularly suitable for use as acoustic transducer elements. That is, composition (wt%) PbO 60 to 70%, TiO 2 7 to 12%, ZrO 2 1
more than 17%, WO 3 more than 0.1% and less than 5%,
It is a porcelain composition consisting of 0.4 to 2.5% MgO and 3 to 15% Nb 2 O 5 . Effects of the invention (1) The piezoelectric ceramic composition of the invention has a relative dielectric constant (ξ)
(about 3000 or more) and electromechanical coupling coefficient (Kr)
(approximately 60% or more) are both high. (2) The sintering temperature of the composition is usually 1250 to 1350°C, but the composition of the present invention has a lower sintering temperature of 1150 to 1250°C than ordinary compositions and is easier to sinter.
Claims (1)
％、TiO27ないし12重量％、ZrO21ないし17重量
％、WO30.1重量％より大ないし５重量％より小、
MgO0.4ないし2.5重量％およびNb2O53ないし15
重量％からなる磁器組成物。 ２ Pb元素をSr、Ca、Baの群から選ばれた少な
くとも一つの元素で０ないし19重量％の範囲で置
換して得られる特許請求の範囲第１項記載の組成
物。[Claims] 1 Based on the weight of the composition, PbO 60 to 70% by weight, TiO 2 7 to 12% by weight, ZrO 2 1 to 17% by weight, WO 3 greater than 0.1% and less than 5% by weight,
MgO0.4 to 2.5% by weight and Nb 2 O 5 3 to 15
A porcelain composition consisting of % by weight. 2. The composition according to claim 1, which is obtained by replacing the Pb element with at least one element selected from the group of Sr, Ca, and Ba in a range of 0 to 19% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61276729A JPS63134563A (en) | 1986-11-21 | 1986-11-21 | Piezoelectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61276729A JPS63134563A (en) | 1986-11-21 | 1986-11-21 | Piezoelectric ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63134563A JPS63134563A (en) | 1988-06-07 |
| JPH0244273B2 true JPH0244273B2 (en) | 1990-10-03 |
Family
ID=17573526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61276729A Granted JPS63134563A (en) | 1986-11-21 | 1986-11-21 | Piezoelectric ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63134563A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6830527B2 (en) * | 2017-05-09 | 2021-02-17 | 富士フイルム株式会社 | Piezoelectric Microphone Chips and Piezoelectric Microphones |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5227359A (en) * | 1975-08-27 | 1977-03-01 | Hitachi Ltd | Face down bonding method |
-
1986
- 1986-11-21 JP JP61276729A patent/JPS63134563A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5227359A (en) * | 1975-08-27 | 1977-03-01 | Hitachi Ltd | Face down bonding method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63134563A (en) | 1988-06-07 |
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