JPH0788252B2 - Oxide piezoelectric material - Google Patents
Oxide piezoelectric materialInfo
- Publication number
- JPH0788252B2 JPH0788252B2 JP59250486A JP25048684A JPH0788252B2 JP H0788252 B2 JPH0788252 B2 JP H0788252B2 JP 59250486 A JP59250486 A JP 59250486A JP 25048684 A JP25048684 A JP 25048684A JP H0788252 B2 JPH0788252 B2 JP H0788252B2
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric
- piezoelectric material
- present
- piezoelectric strain
- pbtio
- 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
- 239000000463 material Substances 0.000 title claims description 10
- 229910020684 PbZr Inorganic materials 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 108010013381 Porins Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 102000007739 porin activity proteins Human genes 0.000 description 1
- 239000000843 powder Substances 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
- C04B35/493—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】 〔発明の技術分野〕 本発明は、Pb（Zn1/3Nb2/3）O3PbTiO3−PbZrO3系の酸化
物圧電材料に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to a Pb (Zn 1/3 Nb 2/3 ) O 3 PbTiO 3 —PbZrO 3 -based oxide piezoelectric material.
圧電磁器には超音波発生源、音響機器等のトランスジュ
ーサ、セラミックフィルター、超音波遅延線等の用途が
ある。近年特に注目をあびているものとして、微小変位
をミクロンオーダでコントロールする圧電アクチュエー
タ素子がある。この素子にはバイモルフ型、積層型等の
タイプがあり、このような素子に要求される特性とし
て、圧電ひずみ定数ｄの大きいことがあげられる。Piezoelectric ceramics have applications such as ultrasonic generators, transducers for audio equipment, ceramic filters, and ultrasonic delay lines. A piezoelectric actuator element that controls minute displacements on the order of micron is particularly attracting attention in recent years. There are types of this element such as a bimorph type and a laminated type, and a characteristic required for such an element is that the piezoelectric strain constant d is large.
Pb（Zn1/3Nb2/3）O3−PbTiO3−PbZrO3系の圧電磁器材料
が特公昭44−17344号公報に記載されている。直接圧電
歪定数ｄについての記載もなく、アクチュエータ素子へ
の応用についても記載されていない。しかしながら圧電
歪定数は、ほぼ （ε；誘電率,Kp;広がりモードの結合係数）なる関係を
満たし、またd33は通常のPZT系では2.2〜2.4×d31であ
るから、 の値を比較することによりｄの大きさを比較できる。特
公昭44−17344号公報に記載されたものは、Kp＝6.1〜4
8.6（％）、ε＝272〜1348であり である。 Pb (Zn 1/3 Nb 2/3) O 3 -PbTiO 3 -PbZrO 3 based piezoelectric ceramic material is described in JP-B-44-17344. There is no mention of direct piezoelectric strain constant d, nor is there any mention of application to actuator elements. However, the piezoelectric strain constant is almost (Ε; permittivity, Kp; coupling coefficient of spread mode) is satisfied, and d 33 is 2.2 to 2.4 × d 31 in a normal PZT system. The magnitudes of d can be compared by comparing the values of. What is described in JP-B-44-17344 has Kp = 6.1-4.
8.6 (%), ε = 272-1348 Is.
ヤング率、ポアリン比が３成分圧電磁器の相境界近傍で
はあまり変化しないことを考慮すると、d33≦250（×10
-12C/N）程度と小さい。Considering that Young's modulus and Porin's ratio do not change much in the vicinity of the phase boundary of the three-component piezoelectric ceramic, d 33 ≦ 250 (× 10
It is as small as -12 C / N).
又、特公昭45−39977号公報には、Pb（Zn1/3Nb2/3）O3
−PbTiO3−PbZrO3系材料の鉛原子の10％までをCa,Sr,Ba
で置換した圧電材料が記載されている。圧電歪定数ｄに
ついては記載がないものの、 であり、d33≦500（×10-12C/N）程度である。In addition, Japanese Patent Publication No. 45-39977 discloses Pb (Zn 1/3 Nb 2/3 ) O 3
−PbTiO 3 −PbZrO 3 up to 10% of lead atoms in Ca, Sr, Ba
Piezoelectric material substituted with. Although there is no description about the piezoelectric strain constant d, And d 33 ≦ 500 (× 10 −12 C / N).
本発明は以上の点を考慮してなされたもので、Pb（Zn
1/3Nb2/3）O3−PbTiO3−PbZrO3系の酸化物圧電材料の圧
電歪定数を向上させることを目的とする。The present invention has been made in consideration of the above points, and Pb (Zn
The purpose is to improve the piezoelectric strain constant of 1/3 Nb 2/3 ) O 3 -PbTiO 3 -PbZrO 3 -based oxide piezoelectric material.
本発明は、一般式xPb（Zn1/3Nb2/3）O3−yPbTiO3−zPbZ
rO3で表わしたとき、Pb（Zn1/3Nb2/3）O3,PbTiO3及びPb
ZrO3を頂点とする三角図表（第１図で、 Ａ（x,y,z）＝（0.05,0.35,0.60） Ｂ（z,y,z）＝（0.05,0.45,0.50） Ｃ（z,y,z）＝（0.40,0.35,0.25） Ｄ（z,y,z）＝（0.40,0.25,0.35） の各点を結ぶ線内の領域で、かつ、Pbの11〜20mol％をb
a1-aSra（ａ＝0.6〜0.8）で置換したことを特徴とする
酸化物圧電材料である。The present invention has the general formula xPb (Zn 1/3 Nb 2/3 ) O 3 −yPbTiO 3 −zPbZ
When expressed as rO 3 , Pb (Zn 1/3 Nb 2/3 ) O 3 , PbTiO 3 and Pb
Triangular diagram with ZrO 3 as a vertex (In Fig. 1, A (x, y, z) ＝ (0.05,0.35,0.60) B (z, y, z) ＝ (0.05,0.45,0.50) C (z, y, z) = (0.40, 0.35, 0.25) D (z, y, z) = (0.40, 0.25, 0.35) is the area within the line connecting the points and 11 to 20 mol% of Pb is b
It is an oxide piezoelectric material characterized by being substituted with a 1-a Sr a (a = 0.6 to 0.8).
本発明者等の研究によれば、Pb（Zn1/3Nb2/3）O3−PbTi
O3−PbZrO3系の材料で、そのPbを特定の比率のBa及びSr
で置換した時、大きい圧電歪定数が得られることがわか
った。すなわち、（Ba1-aSra）で表記したとき、ａ＝0.
6〜0.8の時、誘電率及び結合係数ともに向上し、圧電歪
定数が増加するのである。この効果はPbの（Ba＋Sr）に
よる置換量が5mol％以上で顕著となり、11mol％以上で
特に良好である。また、20mol％を越えると圧電磁器の
使用限界を示すキュリー温度Tcが150℃以下程度と低く
なるため実用的ではなくなる。従って、［Pb1-b（Ba1-a
Sra）ｂ］［（Zn1/3Nb2/3,Ti,Zr］O3と表記したとき、
0.6≦ａ≦0.8かつ0.05≦ｂ≦0.20、好ましくは0.6≦ａ
≦0.8かつ0.11≦ｂ≦0.20のときに優れた圧電歪特性を
有するようになる。According to the study by the present inventors, Pb (Zn 1/3 Nb 2/3 ) O 3 -PbTi
O 3 -PbZrO 3 system material whose Pb is mixed with Ba and Sr in a specific ratio.
It was found that a large piezoelectric strain constant can be obtained by replacing with. That is, when expressed by (Ba 1-a Sr a ), a = 0.
When it is 6 to 0.8, both the dielectric constant and the coupling coefficient are improved, and the piezoelectric strain constant is increased. This effect becomes remarkable when the amount of Pb replaced by (Ba + Sr) is 5 mol% or more, and is particularly good when it is 11 mol% or more. On the other hand, if it exceeds 20 mol%, the Curie temperature Tc, which is the limit of use of the piezoelectric ceramic, becomes as low as about 150 ° C. or less, which is not practical. Therefore, [Pb 1-b (Ba 1-a
Sr a ) b ] [(Zn 1/3 Nb 2/3 , Ti, Zr] O 3
0.6 ≦ a ≦ 0.8 and 0.05 ≦ b ≦ 0.20, preferably 0.6 ≦ a
When ≦ 0.8 and 0.11 ≦ b ≦ 0.20, excellent piezoelectric strain characteristics are obtained.
このような本発明の効果は、PbとBa,Srとのイオン半径
の大きさが主たる原因であると考えられる。It is considered that the effect of the present invention is mainly due to the size of the ionic radii of Pb and Ba or Sr.
圧電歪定数の大きいPb（Zn1/3Nb2/3）O3−PbTiO3−PbZr
O3の相境界近傍の組成には理想的な格子定数があり、こ
れをあまり変化させるようなPbサイトの置換は圧電歪定
数を低下させるのである。Pb (Zn 1/3 Nb 2/3 ) O 3 −PbTiO 3 −PbZr with large piezoelectric strain constant
The composition near the phase boundary of O 3 has an ideal lattice constant, and substitution of the Pb site that changes this too much lowers the piezoelectric strain constant.
Ba1-aSra（ａ＝0.6〜0.8）とすることにより、Pbのイオ
ン半径1.26Åに対しBa1-aSraの平均イオン半径が1.24〜
1.27ÅとほぼPbと同等となり、このような比率での置換
は、誘電率、結合係数を向上させ、その結果として圧電
歪定数を増加させるのである。By setting Ba 1-a Sr a (a = 0.6 to 0.8), the average ion radius of Ba 1-a Sr a is 1.24 to Pb ionic radius 1.26Å.
Substitution with 1.27Å is almost equivalent to Pb, and substitution at such a ratio improves the dielectric constant and coupling coefficient, and consequently increases the piezoelectric strain constant.
第２図に［Pb0.875（Ba1-aSra）0.125］［（Zn1/3N
b2/3）0.125Ti0.405Zr0.47］O3の組成系でａを変化させ
たときのd33の変化を曲線ａとして示す。又、［Pb0.92
（Ba1-aSra）0.08］［（Zn1/3Nb2/3）0.25Ti0.36Z
r0.39］O3の場合を曲線ｂとして示す。何れも、ａ＝0.6
〜0.8で最大を示していることがわかる。すなわち、Pb
（Zn1/3Nb2/3）O3、PbTiO3、PbZrO3の比率には特に関係
なく、Ba及びSrの比率で特性が決まるのである。Fig. 2 shows [Pb 0.875 (Ba 1-a Sr a ) 0.125 ] [(Zn 1/3 N
The curve a shows the change in d 33 when a is changed in the composition system of b 2/3 ) 0.125 Ti 0.405 Zr 0.47 ] O 3 . Also, [Pb 0.92
(Ba 1-a Sr a ) 0.08 ] [(Zn 1/3 Nb 2/3 ) 0.25 Ti 0.36 Z
The case of r 0.39 ] O 3 is shown as a curve b. In both cases, a = 0.6
It can be seen that the maximum is shown at ~ 0.8. That is, Pb
The characteristics are determined by the ratio of Ba and Sr, regardless of the ratio of (Zn 1/3 Nb 2/3 ) O 3 , PbTiO 3 , and PbZrO 3 .
なお、前記A,B,C,D点で囲まれた領域（第１図）とした
のは、この範囲をはずれると、|d33|＜350（×10-12C/
N）、|d31|＜160（×10-12C/N）となり、大きな変位が
要求されるアクチュエータ用素子として適さなくなって
しまうからである。The area surrounded by the points A, B, C and D (Fig. 1) is defined as | d 33 | <350 (× 10 -12 C /
N), | d 31 | <160 (× 10 -12 C / N), which makes it unsuitable as an actuator element that requires large displacement.
以上説明したように本発明によれば、圧電歪特性の良好
な酸化物圧電材料を得ることができる。As described above, according to the present invention, it is possible to obtain an oxide piezoelectric material having good piezoelectric strain characteristics.
従って大きな変位量の要求されるアクチュエータ用とし
て有効である。Therefore, it is effective for an actuator that requires a large amount of displacement.
以下に本発明の実施例を説明する。 Examples of the present invention will be described below.
PbO（またはPb3O4）,TiO2,ZrO2,ZnO,Nb2O5,BaCO3,SrCO3
を所定の量比となるように秤量し混合の後、800〜900℃
で１〜８時間焙焼し、再度粉砕した。この粉末を0.8ton
/cm3の圧力で25φ×1.5mm及び8.5φ×20mmに成形し、10
80〜1280℃１〜３時間で焼成した。この焼結体を加工し
20φ×1.0mmの円板状試料と、７φ×15mmの棒状試料と
し、両面にAgペーストを700℃で焼付けた。その後、100
℃のシリコーンオイル中で10〜30kV/cmの電界を印加し
ながら常温で冷却した。PbO (or Pb 3 O 4 ), TiO 2 ,, ZrO 2 ,, ZnO, Nb 2 O 5 ,, BaCO 3 , SrCO 3
Are weighed so that the specified amount ratio is achieved and mixed, then 800-900 ° C
It was roasted for 1 to 8 hours and then pulverized again. 0.8 tons of this powder
Molded into 25φ × 1.5mm and 8.5φ × 20mm at a pressure of / cm 3 ,
It was baked at 80 to 1280 ° C for 1 to 3 hours. Processing this sintered body
A disc-shaped sample of 20φ × 1.0 mm and a rod-shaped sample of 7φ × 15 mm were prepared, and Ag paste was baked at 700 ° C. on both sides. Then 100
It was cooled at room temperature while applying an electric field of 10 to 30 kV / cm in silicone oil at ℃.
これらの試料を用いてIRE標準回路により共振周波数
ｒ、反共振周波数ａを測定し、結合係数Kp,K33を求め
た。なお誘電率は分極後24時間後の1KHzでの値である。
これらの値から圧電歪定数ｄを算出した。Using these samples, the resonance frequency r and the anti-resonance frequency a were measured by the IRE standard circuit, and the coupling coefficients K p and K 33 were obtained. The dielectric constant is a value at 1 KHz 24 hours after polarization.
The piezoelectric strain constant d was calculated from these values.
この結果を第１表に示す。The results are shown in Table 1.
第１表から明らかなように本発明の材料はd33が極めて
大きいことがわかる。 As is clear from Table 1, d 33 of the material of the present invention is extremely large.
参考例−３はba＋Sr量は実施例−１と同じであるがBaと
Srの比率が本発明範囲外のものであるが、d33の値が大
きく違うことがわかる。Reference Example-3 has the same amount of ba + Sr as that of Example-1,
It can be seen that although the Sr ratio is out of the range of the present invention, the value of d 33 is greatly different.
又、実施例６に示された試料を用いて17m×5m×0.1mmの
両端支持型バイモルフアクチュエータを作成し、その変
位量を時間とともに測定した。その結果を参考例２の試
料とともに第３図に示す。参考例２の試料ではその変位
量が1000時間動作後では10％以上も低下するのに比べて
本発明の試料ではその変位量がほとんど見られない。Also, using the sample shown in Example 6, a double-sided support type bimorph actuator of 17 m × 5 m × 0.1 mm was prepared, and its displacement amount was measured with time. The results are shown in FIG. 3 together with the sample of Reference Example 2. In the sample of Reference Example 2, the amount of displacement decreases by 10% or more after 1000 hours of operation, whereas in the sample of the present invention, the amount of displacement is hardly seen.
この様に本発明の磁器は従来の圧電材料と比べてその圧
電歪定数が極めて大きいのみならず、その動作時の経時
変化も少ない。又焼成温度も組成によっては1100℃以下
と低く、積層型のアクチュエーター素子を作成する場合
には内部電極に安価な銀を主体とした合金が使用出来る
等工業的に価値のある有用な磁器組成物である。As described above, the porcelain of the present invention has not only a very large piezoelectric strain constant as compared with the conventional piezoelectric material but also a small change with time during its operation. Also, depending on the composition, the firing temperature is as low as 1100 ° C or less, and an industrially valuable useful porcelain composition, such as the use of inexpensive silver-based alloys for the internal electrodes when making laminated actuator elements. Is.
第１図は本発明の組成範囲で示す三元図、第２図はd33
と組成の関係を示す特性曲線図、愛３図は変位量と時間
の関係を示す特性曲線図。FIG. 1 is a ternary diagram showing the composition range of the present invention, and FIG. 2 is d 33.
Is a characteristic curve diagram showing the relationship between composition and Ai 3 is a characteristic curve diagram showing the relationship between displacement amount and time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 孝 神奈川県川崎市幸区小向東芝町１ 株式会 社東芝総合研究所内 (56)参考文献 特公 昭45−39977（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takashi Takahashi 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa 1st, Toshiba Research Institute, Inc. (56) References Japanese Patent Publication No. 45-39977 (JP, B1)
Claims (1)
bZrO3で表され、Pb（Zn1/3Nb2/3）O3,PbTiO3およびPbZr
O3を項点とする三角図表で、 Ａ（x,y,z）＝（0.05,0.35,0.60） Ｂ（x,y,z）＝（0.05,0.45,0.50） Ｃ（x,y,z）＝（0.40,0.35,0.25） Ｄ（x,y,z）＝（0.40,0.25,0.35） の各点を結ぶ線内の領域で、かつPbの11mol％以上、20m
ol％以下をBa1-aSra（0.6≦ａ≦0.8）で置換したことを
特徴とする酸化物圧電材料。1. A general formula xPb (Zn 1/3 Nb 2/3 ) O 3 -yPbTiO 3 -zP
Represented by bZrO 3 , Pb (Zn 1/3 Nb 2/3 ) O 3 , PbTiO 3 and PbZr
A trigonometric chart with O 3 as the points, A (x, y, z) ＝ (0.05,0.35,0.60) B (x, y, z) ＝ (0.05,0.45,0.50) C (x, y, z ) ＝ (0.40,0.35,0.25) D (x, y, z) ＝ (0.40,0.25,0.35) The area inside the line connecting the points, and 11 mol% or more of Pb, 20m
An oxide piezoelectric material characterized in that ol% or less is replaced by Ba 1-a Sr a (0.6 ≦ a ≦ 0.8).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59250486A JPH0788252B2 (en) | 1984-11-29 | 1984-11-29 | Oxide piezoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59250486A JPH0788252B2 (en) | 1984-11-29 | 1984-11-29 | Oxide piezoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61129888A JPS61129888A (en) | 1986-06-17 |
| JPH0788252B2 true JPH0788252B2 (en) | 1995-09-27 |
Family
ID=17208573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59250486A Expired - Lifetime JPH0788252B2 (en) | 1984-11-29 | 1984-11-29 | Oxide piezoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788252B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527480A (en) * | 1987-06-11 | 1996-06-18 | Martin Marietta Corporation | Piezoelectric ceramic material including processes for preparation thereof and applications therefor |
| JP4721507B2 (en) * | 2000-11-29 | 2011-07-13 | 京セラ株式会社 | Piezoelectric ceramic composition and ink jet recording head using the same |
| JP4688301B2 (en) * | 2001-01-23 | 2011-05-25 | 京セラ株式会社 | Piezoelectric ceramic composition and ink jet recording head using the same |
| WO2002081404A1 (en) | 2001-03-30 | 2002-10-17 | Tdk Corporation | Piezoelectric porcelain and method for preparation thereof, and piezoelectric element |
| JP2004002069A (en) | 2002-05-30 | 2004-01-08 | Tdk Corp | Processes for manufacturing piezoelectric ceramic and piezoelectric element |
| US7264744B2 (en) | 2004-03-26 | 2007-09-04 | Tdk Corporation | Piezoelectric ceramic and piezoelectric device |
| JP2006096626A (en) | 2004-09-30 | 2006-04-13 | Tdk Corp | Method of manufacturing piezoelectric ceramic, method of manufacturing piezoelectric element, and piezoelectric element |
-
1984
- 1984-11-29 JP JP59250486A patent/JPH0788252B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61129888A (en) | 1986-06-17 |
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