JPH02175614A - Piezoelectric material of oxide - Google Patents
Piezoelectric material of oxideInfo
- Publication number
- JPH02175614A JPH02175614A JP1271905A JP27190589A JPH02175614A JP H02175614 A JPH02175614 A JP H02175614A JP 1271905 A JP1271905 A JP 1271905A JP 27190589 A JP27190589 A JP 27190589A JP H02175614 A JPH02175614 A JP H02175614A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- piezoelectric material
- dielectric constant
- composition
- piezoelectric
- 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
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract 4
- 230000008878 coupling Effects 0.000 abstract description 11
- 238000010168 coupling process Methods 0.000 abstract description 11
- 238000005859 coupling reaction Methods 0.000 abstract description 11
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 8
- 229910003781 PbTiO3 Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910019704 Nb2O Inorganic materials 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- 229910010253 TiO7 Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000126 substance 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
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 Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は酸化物の圧電材料に係るもので、詳しく ば、
Ｐｂ （Ａｌｌ／２ Ｎｂ＋ｚｚ）０．＋
ＰｂＺｒＣ）：＋ＰｂＴｉＯ３の３元系を基本組
成とし、高い誘電常数及び電気機械結合係数と、低い機
械品質係数とを有する新規な圧電磁気物質として、信号
受電素子等に適合した酸化物の圧電材料に関するもので
ある。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an oxide piezoelectric material.
Pb (All/2 Nb+zz)0. +
PbZrC): +PbTiO3 as a new piezoelectric magnetic material having a ternary system as its basic composition and having a high dielectric constant, electromechanical coupling coefficient, and low mechanical quality coefficient, and relating to an oxide piezoelectric material suitable for signal receiving elements, etc. It is something.
〈従来の技術並びに発明が解決しようとする課題〉最近
、酸化物圧電材料を利用して超音波振動子、音響フィル
タ及び圧電作動器等が開発されており、これらの素子に
用いる素材の代表的な例として、ＰｂＺｒ０：＋ Ｐ
ｂＴｉＯ３の２元系に圧電特性の改善のためにＮｂ２Ｏ
３やＷ Ｏｓ等の添加物を添加した形態の圧電材料が挙
げられる（Ｆ、 ＫｕＩｃｓａｒ：Ｊ、Ａｍ、Ｃｅｒ
ａｍ、Ｓｏｃ、４２ （５９５９）３４３）。<Prior art and problems to be solved by the invention> Recently, ultrasonic vibrators, acoustic filters, piezoelectric actuators, etc. have been developed using oxide piezoelectric materials, and typical materials used for these elements are As an example, PbZr0:+P
Nb2O is added to the bTiO3 binary system to improve piezoelectric properties.
Examples include piezoelectric materials in the form of additives such as 3 and W Os (F, KuIcsar: J, Am, Cer
am, Soc, 42 (5959) 343).
しかしながら、このような２元系の圧電材料は電気機械
結合係数が５０％に過ぎないので、その特性が優秀でな
いと共に誘電常数が９００を超えず、機械的品質の係数
も高く現れるので、信号受電素子用として水中聴音器、
フォノピックアンプ、音響探知器、加速度計、遅延線路
、流動検出器及び流量針等に使用するには不適合になる
問題点があった。However, such binary piezoelectric materials have an electromechanical coupling coefficient of only 50%, so their properties are not excellent, the dielectric constant does not exceed 900, and the mechanical quality coefficient appears high, making it difficult to receive signals. Hydrophone for element use,
There were problems that made it unsuitable for use in phonopic amplifiers, acoustic detectors, accelerometers, delay lines, flow detectors, flow rate needles, etc.
従って、このような信号受電素子の用途に適合させるた
めに圧電の特性を改善したＰｂ（Ｍ ｇ ＋／３Ｎ ｂ
ｚｚ＋）Ｏ：＋ Ｐ ｂ Ｚ ｒ ０３ Ｐ ｂＴ
ｉ ０３並びに多様な３元系の組成が開発されている
が（旧Ｂａｎｎｏ：Ｊｐｎ、Ｊ、Ａｐｐ−０．Ｐｈｙｓ
。Therefore, Pb (M g +/3N b
zz+)O:+ P b Z r 03 P bT
i 03 and various ternary system compositions have been developed (formerly Banno: Jpn, J, App-0. Phys
.
６ （１９７６）９５４）、このような３元系組成の圧
電材料もやはり殆どが電気機械結合係数が低かったり、
機械品質係数又は誘電常数の値が低く現れたりして、信
号受電用素子の用途としては不適合な点があった。特に
、このような信号受電用の素子に於いては外部からの微
弱な電気的信号に対応して出来る限り電気的に大きな信
号を発生しなければならないため、高い誘電率と低い機
械品質係数とが要求され、且つ、電気機械変換効率の電
気機械結合係数が高いことを要求する特性を有している
。その理由は、若し、電気機械変換効率が低い場合には
素子が機械的信号を電気的信号に変換させる時に、素子
が内部熱を発生してエネルギーの損失を招来するからで
ある。6 (1976) 954), most piezoelectric materials with such ternary compositions also have low electromechanical coupling coefficients,
The mechanical quality factor or dielectric constant value may appear low, making it unsuitable for use as a signal receiving element. In particular, such signal receiving elements must generate as large an electrical signal as possible in response to a weak electrical signal from the outside, so they must have a high dielectric constant and a low mechanical quality factor. It also has characteristics that require a high electromechanical coupling coefficient of electromechanical conversion efficiency. This is because if the electromechanical conversion efficiency is low, the device generates internal heat when converting a mechanical signal into an electrical signal, resulting in energy loss.
それで、このような問題点を解決するために創案された
本発明は、信号受電素子に適合した高い電気機械結合係
数と高い誘電常数とを有すると共に、信号帯域の幅が広
い低機械品質係数を有する新規な酸化物の圧電材料を提
供することを目的としている。Therefore, the present invention, which was created to solve these problems, has a high electromechanical coupling coefficient and a high dielectric constant suitable for a signal receiving element, as well as a low mechanical quality factor with a wide signal band. The object of the present invention is to provide a novel oxide piezoelectric material having the following characteristics.
〈課題を解決するための手段及び作用〉すなわち、本発
明に係る酸化物の圧電材料は、基本的にＰｂ （Ａｌｌ
／２ Ｎｂ＋ｚ□）０３ ＰｂＺｒＣ１Ｉ ＰｂＴｉ
Ｃ）＋の３元系で成り、酸化物の成分及び組成比を具体
的に表示すると、
ＸＰｂ （Ａｌｌ／２ Ｎｂ＋ｚｚ）（）＋ ＹＰｂ
ＺｒＯ：＋Ｚ Ｐ ｂ Ｔ ｉ Ｏ３
Ｘ ＝０．０１−０．３
Ｙ＝０．１９８−０．９０３
Ｚ＝０．０４８−０．７０２
（イ旦し、Ｘ十Ｙ＋Ｚ＝１）
で表示される酸化物の圧電材料である。<Means and effects for solving the problem> That is, the oxide piezoelectric material according to the present invention is basically Pb (All
/2 Nb+z□)03 PbZrC1I PbTi
C) It consists of a ternary system of +, and the oxide components and composition ratio are specifically expressed as: XPb (All/2 Nb+zz) () + YPb
ZrO: +Z P b T i O3 It is an oxide piezoelectric material.
また、このような組成に、添加物としてＣｒｚＯ，ｌ、
ＮｉＯ及びＭｎＯ□の中のいずれが一つの酸化物を０．
１〜１重量％含有することを特徴とする酸化物の圧電材
料である。In addition, to such a composition, CrzO,l,
Which of NiO and MnO□ has one oxide at 0.
It is an oxide piezoelectric material characterized by containing 1 to 1% by weight.
このような本発明に係る酸化物の圧電材料は次のような
一般的な酸化物の混合方法に依り容易に製造することが
できる。Such an oxide piezoelectric material according to the present invention can be easily manufactured by the following general oxide mixing method.
先ず、ｐｂｏ、Ｔ ｉ Ｏｚ 、Ｚ ｒ ０２ 、Ａ
Ｉ２０３、Ｎｂｚ ０５ 、Ｃｒ２Ｏ３、ＮｉＯ及びＭ
ｎＯ２等の酸化物を適正な比率で正確に計量し、アルミ
ナボールミルを利用して混合及び粉砕を行う。この時、
用いる原料は加熱により容易に酸化物に転換する化合物
、例えば、水酸化物及び炭酸塩等が含まれた原料の化合
物であれば良く、８００〜９゜ＯｏＣで 焼した後、再
び、ボールミルで再粉砕して合成粉末にし、以後、この
粉末は水やＰＶＡ水溶液等の結合剤の添加下で１ ｔｏ
ｎ／ｃＪの圧力で加圧成形されて１１００〜１２００°
Ｃの温度で焼結が行われる。この場合、低い揮発温度（
約８８０″Ｃ）を有するｐｂｏの揮発に因る圧電特性の
低下を防くために焼結は密閉された容器中で行われる。First, pbo, T i Oz , Z r 02 , A
I203, Nbz 05 , Cr2O3, NiO and M
Oxides such as nO2 are accurately weighed in appropriate proportions, and mixed and pulverized using an alumina ball mill. At this time,
The raw materials to be used may be compounds that are easily converted into oxides by heating, such as raw materials containing hydroxides and carbonates. The powder is ground into a synthetic powder, which is then mixed with water or a binder such as a PVA aqueous solution.
Pressure molded at n/cJ pressure to 1100~1200°
Sintering takes place at a temperature of C. In this case, a low volatilization temperature (
The sintering is carried out in a closed container to prevent deterioration of the piezoelectric properties due to volatilization of the pbo (approximately 880″C).
このように製造された焼結体は通常の方法により両面に
電極が形成されるが、９０〜１１０“Ｃ程度のシリコン
油中でその電極に直流型系３５Ｋｖ／ｃｍを３０分間印
加することにより分極が行われる。Electrodes are formed on both sides of the sintered body produced in this way by the usual method, but by applying a direct current system of 35 Kv/cm to the electrodes for 30 minutes in silicone oil at about 90 to 110"C. Polarization takes place.
このように製造することにより、従来のＰｂＺｒＯｓ
ＰｂＴｉＯ３２元系、又はＰｂ（Ｍｇ＋ｚｉＮｂｚｚ
３）０３−ＰｂＺｒＯ３−ＰｂＴｉ０３３元系の圧電材
料とは異なった組成を有する材料として優秀な圧電の特
性を具備した酸化物の圧電材料を容易に得ることができ
る。By manufacturing in this way, conventional PbZrOs
PbTiO3 binary system, or Pb(Mg+ziNbzz
3) It is possible to easily obtain an oxide piezoelectric material having excellent piezoelectric properties as a material having a composition different from that of the 03-PbZrO3-PbTi03 ternary piezoelectric material.
第１図は本発明に係る酸化物の圧電材料の組成比を表示
するＰｂ（ＡＩ＋ｚ□Ｎｂｌ７□）０．、−ＰｂＺｒＯ
３−ＰｂＴｉＯ３３元系図で、Ａ、、Ｂ、、Ｃ。FIG. 1 shows the composition ratio of the oxide piezoelectric material according to the present invention, Pb(AI+z□Nbl7□)0. , -PbZrO
3-PbTiO3 ternary family tree, A,,B,,C.
Ｄ、Ｅ及びＦにより囲まれた多角形の斜線部分は本発明
に係る酸化物の成分組成範囲を現す。又、第２図は本発
明に係る酸化物の圧電材料に於いて、一つの原料の成分
を構成するＰｂ （ＡＩＮｂ）０３の添加量の変化に因
るＣｕｒｉｅの温度変化を示したグラフである。第２図
のグラフに示したように、本発明の圧電材料に於いて、
Ｐｂ （ＡＩＮｂ）０３の組成比が増加してもＣｕｒｉ
ｅの温度が３００°Ｃ以上であるので、実際に部品とし
て適用しても圧電素子の分極破壊に依る問題点が排除さ
れ、且つ、Ｃｒ２Ｏ５やＭｎＯ□及びＮｉＯのような添
加物の微量添加に因り、電気機械結合係数の値を大いに
低下させることなく、誘電率及び機械品質係数を変化さ
せることができるので、各種の振動子及び音響フィルタ
の素材として使用することができると共に、高い電気機
械結合係数及び低い機械品質係数を要求する信号受電素
子に適用することができる。The shaded area of the polygon surrounded by D, E, and F represents the composition range of the oxide according to the present invention. Furthermore, FIG. 2 is a graph showing Curie temperature changes due to changes in the amount of Pb (AINb)03 that constitutes one raw material component in the oxide piezoelectric material according to the present invention. . As shown in the graph of FIG. 2, in the piezoelectric material of the present invention,
Even if the composition ratio of Pb (AINb)03 increases, Curi
Since the temperature of e is 300°C or higher, problems caused by polarization breakdown of the piezoelectric element can be eliminated even when it is actually applied as a component, and it is also suitable for adding trace amounts of additives such as Cr2O5, MnO□, and NiO. Therefore, the dielectric constant and mechanical quality factor can be changed without greatly reducing the value of the electromechanical coupling coefficient, so it can be used as a material for various vibrators and acoustic filters, and it also has high electromechanical coupling. It can be applied to signal receiving elements that require high coefficients and low mechanical quality coefficients.
〈実施例〉
以下、本発明に係る実施例に対して説明するが、本発明
は特許請求の範囲をはずれない限り本実施例に局限され
るものでないことは勿論である。<Examples> Examples of the present invention will be described below, but it goes without saying that the present invention is not limited to these examples unless it deviates from the scope of the claims.
ＸＰｂ（ＡＩ＋ｚｚＮｂ＋ｚｚ）（）＋ ＹＰｂＺｒ
Ｏ３ＺＰｂＴｉＯ３３元系に於いて、
χ−０．０１−０．３
Ｙ＝０．１９８−０．９０３
Ｚ＝０．０４８ −０．７０２
（但し、Ｘ −１−Ｙ ＋ Ｚ ＝ １ ）の組成範囲
になるようにＰｂＯ，、ＴｉＯ７、ＺｒＯ２、Ａｌ２Ｏ
２、Ｎｂ２Ｏ５、Ｃｒ２Ｏ３、ＮｉＯ及びＭｎＯ□等の
酸化物を各モル比に従って１０−４ｇまで正確に計量し
てアルミナボールミル中で混合粉砕した。次いで、混合
が完了した試料は８００−９００°Ｃで 焼した後ボー
ルミルで再粉砕し、その粉砕された粉末に水又はＰＶＡ
水溶液等の結合剤を微量添加して、１ ｔｏｎ／ｃ＋ｆ
ｌの圧力で加圧成形し、１１００〜１２００°Ｃの温度
で焼結を行った。XPb(AI+zzNb+zz)()+YPbZr
In the O3ZPbTiO ternary system, the composition range is χ-0.01-0.3 Y=0.198-0.903 Z=0.048-0.702 (X-1-Y + Z = 1) PbO, , TiO7, ZrO2, Al2O so that
2. Oxides such as Nb2O5, Cr2O3, NiO, and MnO□ were accurately weighed to 10-4 g according to their respective molar ratios, and mixed and ground in an alumina ball mill. Next, the mixed sample was baked at 800-900°C and re-ground in a ball mill, and the ground powder was mixed with water or PVA.
By adding a small amount of a binder such as an aqueous solution, 1 ton/c+f
Pressure molding was carried out at a pressure of 1 liter, and sintering was carried out at a temperature of 1100 to 1200°C.
焼結の場合、組成成分中の一つであるＰｂＯが揮発温度
（約８８０°Ｃ）が低いため正確な化学的等量を成し得
す圧電特性の低下を招来する憂いがあるので、実施組成
と同様な組成の粉末をＰｂＯの揮発抑制用雰囲気の粉末
にして、密閉された容器中で焼結を行い、この時の最高
温度に於いての維持時間は１時間にした。In the case of sintering, PbO, one of the compositional components, has a low volatilization temperature (approximately 880°C), so it is difficult to carry out sintering because there is a concern that the piezoelectric properties that can achieve accurate chemical equivalence may deteriorate. Powder having the same composition as the powder in an atmosphere for suppressing PbO volatilization was sintered in a sealed container, and the maximum temperature at this time was maintained for 1 hour.
焼結が完了した成形焼結体は直径１５ｍｍ、厚さ１ ｍ
ｍの円板状に加工した後、両面に電極を形成して該電極
に直流型系３５ＫＶ／Ｃｌ１１を約９０〜１１０°Ｃの
シリコン油中で３０分間印加し、分極を行った。そして
、分極が完了した試片に対してＩＲＥ、ＳＴＤ （Ｐｒ
ｏｃ、ｏｆ ｔｈｅ ＩＲＥＩ９６１、Ｐ１１６１
〜１１６９）により電気機械結合係数（Ｋｒ）、機械品
質係数（Ｑｍ）及び周波数定数等を測定し、それぞれ組
成比を異にする各焼結体の測定結果を表１に示した。The sintered body after sintering has a diameter of 15 mm and a thickness of 1 m.
After processing into a disk shape of m in diameter, electrodes were formed on both sides, and a direct current system of 35 KV/Cl11 was applied to the electrodes in silicone oil at about 90 to 110°C for 30 minutes to perform polarization. Then, IRE, STD (Pr
oc, of the IREI961, P1161
-1169), the electromechanical coupling coefficient (Kr), mechanical quality coefficient (Qm), frequency constant, etc. were measured, and the measurement results of each sintered body having different composition ratios are shown in Table 1.
表１に於いて、Ｆ、 Ｔは焼結温度を示し、Ｋ３３はｌ
ＫＨ２の周波数で２５°Ｃで測定した試片の誘電率を表
示する。In Table 1, F and T indicate the sintering temperature, and K33 indicates the sintering temperature.
The dielectric constant of the specimen measured at 25°C at the frequency of KH2 is displayed.
表１で明らかになるように、Ｐｂ （ＡＩＮｂ）０３を
３−１Ｏモル％添加すると、電気機械結合係数（Ｋｒ）
及び誘電定数（Ｋ３３”）が高くなり、機械品質係数（
Ｑｍ）が１００以下を有する優秀な特性が現れた。As is clear from Table 1, when 3-10 mol% of Pb(AINb)03 is added, the electromechanical coupling coefficient (Kr)
and the dielectric constant (K33”) become higher, and the mechanical quality factor (
Excellent properties with a Qm) of 100 or less appeared.
一方、本発明に係るＰ ｂ （Ａ ＩＮｂ） ０３
Ｐ ｂＺｒ０３−ＰｂＴｉＯ３３元系の圧電材料は、従
来のＰｂＺｒＯ３ＰｂＴｉＯ３２元系に比べて非常に広
範囲に亘って優秀な圧電特性を有しており、２元系のＰ
ｂＺｒＯ３ＰｂＴｉＣＬ＋系と本発明の３元系Ｐｂ （
ＡＩＮｂ）０３−ＰｂＺｒ０３Ｐ ｂ Ｔ ｉ Ｏ３系
との圧電特性を比べると表２のようであった。On the other hand, P b (A INb) 03 according to the present invention
The PbZr03-PbTiO3 element system piezoelectric material has excellent piezoelectric properties over a very wide range compared to the conventional PbZrO3PbTiO3 element system, and the binary system Pb
bZrO3PbTiCL+ system and the ternary system Pb of the present invention (
Table 2 shows a comparison of the piezoelectric properties with the AINb)03-PbZr03P b T i O3 system.
表２で明らかになるように、２元系のＰｂＺｒ０．−Ｐ
ｂＴ ｉ Ｏ３系の場合には、優秀な圧電特性を現す範
囲がＭ Ｐ Ｂ （Ｍｏｒｐｈｏｔｒｏｐｉｃ Ｐｈａ
ｓｅ Ｂ。As is clear from Table 2, the binary PbZr0. -P
In the case of the bT i O3 system, the range that exhibits excellent piezoelectric properties is M P B (Morphotropic Pha
seB.
ｕｎｄａｒｙ ）地域に局限している反面、本発明に係
る組成の場合には非常に広い組成範囲で優秀な特性を有
する素材の焼結体を容易に得られるごとが現れている。However, in the case of the composition according to the present invention, it has become possible to easily obtain a sintered body of material having excellent properties over a very wide composition range.
すなわち、参考例１及び参考例２に示したように２元系
組成の場合には、−点に局限して比較的優秀な特性が現
れているが、本発明の場合に於いては実施例１８〜実施
例２０並びに実施例３５〜実施例３９に示したように、
広い領域に亘って圧電特性が改善されていることが現れ
ている。That is, in the case of a binary composition as shown in Reference Examples 1 and 2, comparatively excellent characteristics appear limited to the - point, but in the case of the present invention, As shown in Examples 18 to 20 and Examples 35 to 39,
It appears that the piezoelectric properties are improved over a wide area.
特に、本発明の３元系酸化物の一つであるｐｂ（ＡＩＮ
ｂ）○、にばＡ１が含有されており、ボールミルにおけ
る原料の混合及び粉砕の過程で混入可能なＡ１□０３の
影響を殆ど受けないようになるため、所定の圧電特性を
具備する焼結体の製造を容易に行うことができる。In particular, pb (AIN
b) A sintered body that contains ○, Niva A1 and has predetermined piezoelectric properties because it is almost unaffected by A1□03 that can be mixed in during the mixing and pulverizing process of raw materials in a ball mill. can be easily manufactured.
又、本発明のＰｂ （ＡＩＮｂ）０３ ＰｂＺｒ／８
○３−ＰｂＴｉ○３３元系には添加物としてＭｎＯ２、
Ｃｒ２Ｏ３及びＮｉＯ酸化物中の一つが添加されること
により、圧電の特性が改善され、これら添加物の添加に
因る圧電特性の変化を表３に示した。In addition, the Pb (AINb)03 PbZr/8 ○3-PbTi○ 33-element system of the present invention contains MnO2,
The piezoelectric properties were improved by adding one of Cr2O3 and NiO oxide, and Table 3 shows the changes in the piezoelectric properties due to the addition of these additives.
良好な圧電特性を現した添加物の組成範囲は、ＣｒｚＯ
，、の場合０．１−０．５重量％、ＭｎＯ□は０．１−
−０．０重量％、ＮｉＯは０．１−０．５重量％であり
、この範囲以外の添加量に於いては、焼結性の低下と圧
電特性の低下とを招来した。The composition range of additives that exhibited good piezoelectric properties was CrzO
, , 0.1-0.5% by weight, MnO□ is 0.1-0.
-0.0% by weight, and 0.1-0.5% by weight for NiO. Addition amounts outside this range resulted in a decrease in sinterability and a decrease in piezoelectric properties.
表３で明らかになるように、Ｃｒ２Ｏ３やＭｎＯ□及び
ＮｉＯのような添加物を微量添加することに依り、電気
機械結合係数の大した低下無しに誘電率及び機械品質係
数を変化させることができるので、電子素子の用途に適
合した特性を有する焼結体を得ることができる。As is clear from Table 3, by adding trace amounts of additives such as Cr2O3, MnO□, and NiO, the dielectric constant and mechanical quality factor can be changed without a significant decrease in the electromechanical coupling coefficient. Therefore, a sintered body having characteristics suitable for use in electronic devices can be obtained.
一方、第１図に示したように、本発明に係る酸化物材料
の組成範囲を現す多角形のＡ点は実施例４８．８点は実
施例４７．０点は実施例４６、Ｄ点は実施例３、Ｅ点は
実施例１、Ｅ点は実施例２をそれぞれ現し、第２図は実
施例２４乃至実施例３２までのＰ ｂ （Ａ ］ Ｎ
ｂ） ０３の組成比変化に因るＣｕｒｉｃ温度の変化を
表示したものである。On the other hand, as shown in FIG. 1, point A of the polygon representing the composition range of the oxide material according to the present invention is Example 48.8, Example 47.0 is Example 46, and D is Example 3, point E represents Example 1, point E represents Example 2, and FIG. 2 shows P b (A ] N of Examples 24 to 32.
b) Changes in Curic temperature due to changes in composition ratio of 03 are displayed.
〈発明の効果〉
以」二、説明したように本発明によれば、従来に７．６
比べて高い電気機械結合係数と、高い誘電常数とを有す
ると共に、信号帯域の幅が広い低機械的品質係数を有す
る信号受電素子に適合した新規な酸化物の圧電材料を得
ることができる効果がある。<Effects of the Invention> 2. As explained above, according to the present invention, a low mechanical There is an effect that a novel oxide piezoelectric material suitable for a signal receiving element having a quality factor can be obtained.
第１図は本発明に係る酸化物の圧電材料の組成比を示し
たＰ ｂ （Ａｌｌ／２ Ｎｂ＋ｚｚ）Ｏｓ Ｐ ｂ
Ｚｒ０３ 、Ｐ ｂ Ｔ ｉ ０３３元系図、第２図
は本発明に係る酸化物圧電材料のＰ ｂ （Ａ Ｉ Ｎ
ｂ ） ０３添加量に因るＣｕｒｉｅ温度の変化を示
したグラフである。FIG. 1 shows the composition ratio of the oxide piezoelectric material according to the present invention, P b (All/2 Nb+zz)Os P b
Zr03, P b T i 03 element family tree, FIG. 2 shows the P b (A I N
b) It is a graph showing the change in Curie temperature depending on the amount of 03 added.
Claims (4)
＿３−ＹＰｂＺｒＯ＿３−ＺＰｂＴｉＯ＿３系を基本組
成とし、Ｘ＝０．０１−０．３ Ｙ＝０．１９８−０．９０３ Ｚ＝０．０４８−０．７０２ （但し、Ｘ＋Ｙ＋Ｚ＝１） の組成範囲を有する酸化物の圧電材料。(1)XPb(Al_1_/_2Nb_1_/_2)O
The basic composition is _3-YPbZrO_3-ZPbTiO_3 system, and has a composition range of Oxide piezoelectric material.
量％含有された請求項１記載の酸化物の圧電材料。(2) The oxide piezoelectric material according to claim 1, containing 0.1-0.5% by weight of Cr_2O_3 as an additive.
含有された請求項１記載の酸化物の圧電材料。(3) 0.1-1.0% by weight of MnO_2 as an additive
A piezoelectric material containing an oxide according to claim 1.
された請求項１記載の酸化物の圧電材料。(4) The oxide piezoelectric material according to claim 1, containing 0.1-0.5% by weight of NiO as an additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR15513/1988 | 1988-11-24 | ||
| KR1019880015513A KR910006710B1 (en) | 1988-11-24 | 1988-11-24 | Oxide Piezoelectric Materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02175614A true JPH02175614A (en) | 1990-07-06 |
| JPH0717382B2 JPH0717382B2 (en) | 1995-03-01 |
Family
ID=19279544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1271905A Expired - Fee Related JPH0717382B2 (en) | 1988-11-24 | 1989-10-20 | Oxide piezoelectric material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0717382B2 (en) |
| KR (1) | KR910006710B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5506404A (en) * | 1993-09-08 | 1996-04-09 | Milan-Kamski; W. J. | Retrofitting device providing automatic reading capability for metering systems |
-
1988
- 1988-11-24 KR KR1019880015513A patent/KR910006710B1/en not_active IP Right Cessation
-
1989
- 1989-10-20 JP JP1271905A patent/JPH0717382B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5506404A (en) * | 1993-09-08 | 1996-04-09 | Milan-Kamski; W. J. | Retrofitting device providing automatic reading capability for metering systems |
Also Published As
| Publication number | Publication date |
|---|---|
| KR900008710A (en) | 1990-06-03 |
| JPH0717382B2 (en) | 1995-03-01 |
| KR910006710B1 (en) | 1991-08-31 |
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