JP2841347B2 - Manufacturing method of piezoelectric ceramics - Google Patents
Manufacturing method of piezoelectric ceramicsInfo
- Publication number
- JP2841347B2 JP2841347B2 JP2138580A JP13858090A JP2841347B2 JP 2841347 B2 JP2841347 B2 JP 2841347B2 JP 2138580 A JP2138580 A JP 2138580A JP 13858090 A JP13858090 A JP 13858090A JP 2841347 B2 JP2841347 B2 JP 2841347B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- compound
- niobium
- powder
- magnesium niobate
- 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
- 239000000919 ceramic Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011777 magnesium Substances 0.000 claims description 47
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 37
- 229910052749 magnesium Inorganic materials 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 150000002681 magnesium compounds Chemical class 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 150000002822 niobium compounds Chemical class 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 150000002611 lead compounds Chemical class 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 9
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 238000006243 chemical reaction Methods 0.000 description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 8
- 239000001095 magnesium carbonate Substances 0.000 description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910020684 PbZr Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は圧電体セラミックスの製造方法に関し、特に
ニオブ化合物、マグネシウム化合物、鉛化合物、チタニ
ウム化合物及びジルコニウム化合物を混合、仮焼、焼
成、分極するPbTiO3・PbZrO3・Pb（Mg1/3Nb2/3）O3系圧
電体セラミックスの製造方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing a piezoelectric ceramic, in particular, mixing, calcining, firing and polarizing a niobium compound, a magnesium compound, a lead compound, a titanium compound and a zirconium compound. The present invention relates to a method for producing PbTiO 3 , PbZrO 3 , Pb (Mg 1/3 Nb 2/3 ) O 3 piezoelectric ceramics.
PbTiO3・PbZrO3・Pb（Mg1/3Nb2/3）O3系材料は、高誘
電率の圧電体材料として使用されている（例えば特公昭
44−17103号明細書など）。PbTiO 3 , PbZrO 3 , Pb (Mg 1/3 Nb 2/3 ) O 3 material is used as a high dielectric constant piezoelectric material (for example,
44-17103, etc.).
この種の圧電体セラミックスは、その材料として各元
素を含む個別の化合物（例えば、酸化物、炭酸塩など）
を混合し、この混合物を仮焼後、成形し、更に焼成した
後、分極処理を行なうことにより、製造されている。Piezoelectric ceramics of this type are composed of individual compounds containing each element (eg, oxides, carbonates, etc.)
Are mixed, calcined, molded, fired, and then subjected to a polarization treatment.
しかしながら、近年、アクチュエーターや圧電スピー
カーなどの高品質の圧電セラミックス製品のために、よ
り高誘電率で変換効率の高い圧電体セラミックス材料が
要望されている。However, in recent years, there has been a demand for a piezoelectric ceramic material having a higher dielectric constant and a high conversion efficiency for high quality piezoelectric ceramic products such as actuators and piezoelectric speakers.
本発明者らは高誘電率・高変換効率の圧電体セラミッ
クスの製造について、鋭意研究を進めた結果、PbTiO3・
PbZrO3・Pb（Mg1/3Nb2/3）O3系圧電体セラミックスの製
造に際して、その原料化合物、特にニオブとマグネシウ
ムの原料を特定することにより、高品質の圧電体セラミ
ックスが得られるとの知見を得て、本発明を完成させる
に至った。The present inventors have for the preparation of a piezoelectric ceramic having a high dielectric constant and high conversion efficiency, a result of our intensive studies, PbTiO 3 -
In the production of PbZrO 3 · Pb (Mg 1/3 Nb 2/3 ) O 3 based piezoelectric ceramics, high quality piezoelectric ceramics can be obtained by specifying the raw material compounds, especially the raw materials of niobium and magnesium. With the knowledge described above, the present invention has been completed.
すなわち、本発明は、ニオブ化合物、マグネシウム化
合物、鉛化合物、チタニウム化合物及びジルコニウム化
合物を混合、仮焼、焼成、分極するPbTiO3・PbZrO3・Pb
（Mg1/3Nb2/3）O3系圧電体セラミックスの製造方法にお
いて、ニオブ及びマグネシウムの原料源として平均粒径
が２μｍ以下のニオブ酸マグネシウム（Mg1/3Nb2/3O2）
をニオブ化合物及びマグネシウム化合物と混合して用い
ることを特徴とする圧電体セラミックスの製造方法であ
る。That is, the present invention is a mixture of a niobium compound, a magnesium compound, a lead compound, a titanium compound and a zirconium compound, calcined, fired, and polarized PbTiO 3 .PbZrO 3 .Pb
In a method for producing (Mg 1/3 Nb 2/3 ) O 3 piezoelectric ceramics, magnesium niobate having an average particle size of 2 μm or less (Mg 1/3 Nb 2/3 O 2 ) is used as a raw material source for niobium and magnesium.
Is used in combination with a niobium compound and a magnesium compound.
（原料化合物） 本発明に使用する原料化合物のうち、ニオブ酸マグネ
シウム以外のニオブ化合物、マグネシウム化合物、鉛化
合物、チタニウム化合物及びジルコニウム化合物として
は、それぞれの元素の酸化物、炭酸塩、硝酸塩、塩化
物、硫化物など、焼成によって、最終的にPbTiO3・PbZr
O3・Pb（Mg1/3Nb2/3）O3系化合物を形成するものであれ
ばよく、特にその形態を限定しない。(Raw material compounds) Among the raw material compounds used in the present invention, niobium compounds other than magnesium niobate, magnesium compounds, lead compounds, titanium compounds and zirconium compounds include oxides, carbonates, nitrates and chlorides of the respective elements. PbTiO 3 · PbZr
Any material can be used as long as it forms an O 3 .Pb (Mg 1/3 Nb 2/3 ) O 3 compound, and the form is not particularly limited.
（原料組成物） 本発明の圧電体セラミックスの製造方法においては、
使用する原料組成にその特徴を有し、ニオブ及びマグネ
シウムの原料源としてニオブ酸マグネシウムを単独のニ
オブ化合物及びマグネシウム化合物と混合している。(Raw material composition) In the method for producing a piezoelectric ceramic of the present invention,
The raw material composition used has the characteristics, and magnesium niobate is mixed with a single niobium compound and magnesium compound as a raw material source of niobium and magnesium.
その混合割合は、ニオブ酸マグネシウム（MN）とのニ
オブ化合物（Ｎ）及びマグネシウム化合物（Μ）の合計
（Μ＋Ｎ）とが、ΜN:（Μ＋Ｎ）＝80:20〜60:40（重量
％）の範囲であることが好ましい。ΜＮが多くなると得
られる圧電体の変換効率は高いが誘電率は低下し、（Μ
＋Ｎ）が多くなると誘電率及び変換効率が共に低下す
る。The mixing ratio is such that the sum (Μ + N) of the niobium compound (N) and the magnesium compound (Μ) with magnesium niobate (MN) is ΔN: (Μ + N) = 80: 20 to 60:40 (% by weight). It is preferably within the range. As the N increases, the conversion efficiency of the obtained piezoelectric material is high, but the dielectric constant decreases, and (Μ
+ N) increases both the dielectric constant and the conversion efficiency.
（ニオブ酸マグネシウム） 本発明で用いられるニオブ酸マグネシウムは、市販品
を用いることができるが、圧電体セラミックスの原料配
合の際に予め合成してもよい。(Magnesium niobate) As the magnesium niobate used in the present invention, a commercially available product can be used, but it may be synthesized in advance at the time of mixing the raw materials of the piezoelectric ceramic.
ニオブ酸マグネシウムは、例えば、ニオブの化合物で
ある五酸化ニオブとマグネシウムの化合物である炭酸マ
グネシウムを等モルで混合し、800〜1000℃で反応させ
ることにより合成される。その際、必ずしも、ニオブ酸
マグネシウムは単一相でなく、主成分を構成する組成で
あればよい。Magnesium niobate is synthesized, for example, by mixing niobium pentoxide, a compound of niobium, and magnesium carbonate, a compound of magnesium, in equimolar amounts and reacting at 800 to 1000 ° C. In this case, magnesium niobate is not necessarily a single phase, and may have a composition constituting a main component.
本発明においては、この様にして得られたニオブ酸マ
グネシウムを、ボールミルやビーズミルなどで粉砕し、
微細で反応性の高い粉末として使用することが必要であ
る。粉砕して得られた粉末の平均粒径は２μｍ以下、望
ましくは、１μｍ以下のサブミクロン粒子である。２μ
ｍ以上の平均粒径の粉末では反応性が乏しく、特性の向
上があまり認められない。In the present invention, the magnesium niobate thus obtained is pulverized by a ball mill, a bead mill, or the like,
It must be used as a fine and highly reactive powder. The average particle size of the powder obtained by pulverization is 2 μm or less, preferably 1 μm or less, submicron particles. 2μ
With a powder having an average particle size of m or more, the reactivity is poor, and little improvement in properties is observed.
反応性が高く、微細であるニオブ酸マグネシウムとし
ては、水や溶媒に可溶性のニオブとマグネシウムの塩を
加水分解して得られた湿式合成の粉末、該塩を熱分解し
て得られた粉末などがある。この種の方法で得られた粉
末の平均粒径は１μｍ以下であり、極めて反応性に富ん
でいる。とりわけ、水熱反応で合成されたニオブ酸マグ
ネシウムは、低い温度で合成されるため特に反応性が高
く、平均粒径が1.0μｍ以下の微細な粉末が得られ、本
発明の原料としては特に好ましいものである。Highly reactive and fine magnesium niobate includes wet-synthesized powder obtained by hydrolyzing a salt of niobium and magnesium soluble in water or a solvent, powder obtained by thermally decomposing the salt, and the like. There is. The average particle size of the powder obtained by this type of method is 1 μm or less, and it is extremely reactive. In particular, magnesium niobate synthesized by a hydrothermal reaction is particularly high in reactivity because it is synthesized at a low temperature, and a fine powder having an average particle size of 1.0 μm or less is obtained, which is particularly preferable as a raw material of the present invention. Things.
水熱反応の合成によるニオブ酸マグネシウムとして
は、例えば、ニオブの化合物である五酸化ニオブとマグ
ネシウムの化合物である酸化マグネシウムとを等モルで
混合し、この混合粉末と水とを白金容器に入れ、100〜5
00kg/cm2の加圧下で、300〜600℃に保持することにより
得られる。As magnesium niobate by synthesis of a hydrothermal reaction, for example, niobium pentoxide, which is a compound of niobium, and magnesium oxide, which is a compound of magnesium, are mixed in an equimolar amount, and the mixed powder and water are put in a platinum container, 100-5
It is obtained by maintaining the temperature at 300 to 600 ° C. under a pressure of 00 kg / cm 2 .
（圧電体セラミックス組成） 上記の原料配合により製造される圧電体セラミックス
の組成としては、高性能な圧電材である以下の組成物、 ｛PbTiO3｝ｘ・｛PbZrO3｝ｙ・｛Pb（Mg1/3Nb2/3）O3｝
ｚ （ここで、ｘ、ｙ及びｚはモル％を示し、ｘ＝82〜１、
ｙ＝95〜１、ｚ＝88〜１、ｘ＋ｙ＋ｚ＝100である。） である。As the composition of the piezoelectric ceramic manufactured by (piezoelectric ceramic composition) The above raw material formulation, the following composition is high-performance piezoelectric material, {PbTiO 3} x · { PbZrO 3} y · {Pb (Mg 1/3 Nb 2/3 ) O 3 ｝
z (where x, y and z represent mol%, x = 82 to 1,
y = 95-1, z = 88-1, x + y + z = 100. ).
なお、本発明の組成物としては、上記の組成のうち、
PbがSrで１〜20原子％置換された組成物であってもよ
く、また、上記組成を基本とし、特性向上のために微量
の添加物を添加した組成物であってもよい。In addition, as the composition of the present invention, among the above compositions,
A composition in which Pb is substituted by 1 to 20 atomic% with Sr may be used, or a composition based on the above composition and to which a small amount of an additive is added for improving characteristics.
（圧電体セラミックスの製造） 上記の各原料を、最終的に必要とする組成に配合した
後の工程については、慣用の方法を用いることができ
る。(Manufacture of Piezoelectric Ceramics) For the steps after each of the above-mentioned raw materials is blended into a finally required composition, a conventional method can be used.
例えば、配合した原料粉末をボールミルなどを用いて
混合粉砕した後、得られた粉末を800〜1000℃で１〜５
時間大気雰囲気中で仮焼する。その後、仮焼粉末を必要
な形状に成形し、大気雰囲気下1100〜1350℃で１〜５時
間焼成し、焼成物を分極することにより、本発明の圧電
体セラミックスが得られる。分極の条件としては特に限
定しないが、60〜100℃で1.5〜5kV/mmの電圧を１〜30分
印加するのがその目安となる。For example, after mixing and pulverizing the compounded raw material powder using a ball mill or the like, the obtained powder is treated at 800 to 1000 ° C. for 1 to 5 times.
Calcinate in air atmosphere for hours. Thereafter, the calcined powder is formed into a required shape, fired at 1100 to 1350 ° C. in the air atmosphere for 1 to 5 hours, and the fired product is polarized to obtain the piezoelectric ceramic of the present invention. The condition of the polarization is not particularly limited, but a rule of thumb is to apply a voltage of 1.5 to 5 kV / mm at 60 to 100 ° C. for 1 to 30 minutes.
本発明において、原料組成としてニオブ化合物とマグ
ネシウム化合物に加えてニオブ酸マグネシウムを併用す
ることによる作用は必ずしも明らかではないが、この併
用により、得られた焼結体は適度に粒成長し、且つ、粒
形が整っており、このことが圧電体として高誘電率及び
高変換効率の特性向上をもたらして入るものと考えられ
る。In the present invention, the effect of using magnesium niobate in addition to the niobium compound and the magnesium compound as the raw material composition is not necessarily clear, but by this combination, the obtained sintered body is appropriately grain-grown, and It is considered that the grain shape is uniform, and this leads to the improvement of the characteristics of the piezoelectric body with high dielectric constant and high conversion efficiency.
すなわち、ニオブ酸マグネシウムを用いない場合に
は、焼結による粒成長が見られず、その粒形もいびつな
ものが多い。また、第二相としてパイロクロア相を生成
しやすく、圧電体としての特性を低下させる。That is, when magnesium niobate is not used, no grain growth due to sintering is observed, and the grain shape is often distorted. Further, a pyrochlore phase is easily generated as the second phase, and the characteristics as a piezoelectric substance are deteriorated.
一方、ニオブ及びマグネシウム源としてニオブ酸マグ
ネシウムのみを用いた場合には、粒成長によって粒が大
きく、かつ、粒形も整っており、前記したように、圧電
体の変換効率は高くなるが、誘電率は低下する。On the other hand, when only magnesium niobate is used as the niobium and magnesium sources, the grains are large due to grain growth, and the grain shape is also adjusted. As described above, the conversion efficiency of the piezoelectric body is increased, but the dielectric efficiency is increased. The rate drops.
本発明の方法において、ニオブ酸マグネシウムを併存
させることにより、ペロブスカイト単一相化が促進され
ると共に、適度の粒成長による大小の粒子の共存により
圧電体が緻密化し、高い変換効率で優れた誘電率が得ら
れるものと考えられる。In the method of the present invention, the coexistence of magnesium niobate promotes the formation of a single phase of perovskite, and the coexistence of large and small particles due to moderate grain growth densifies the piezoelectric material, thereby achieving high conversion efficiency and excellent dielectric properties. It is thought that the rate can be obtained.
実施例１ 五酸化ニオブ（Nb2O5）と炭酸マグネシウム（MgCO3）
と等モルづつ樹脂ボール及びミルを用いて混合した。こ
の混合物を白金ルツボに入れ、大気雰囲気中900℃で２
時間焼成して、ニオブ酸マグネシウムの粉末を得た。得
られた粉末を樹脂ボール及びミルを用いて16時間粉砕
し、ニオブ酸マグネシウムの原料粉末とした。セデイグ
ラフを用いて測定したこの粉末の平均粒径は1.6μｍで
あった。Example 1 Niobium pentoxide (Nb 2 O 5 ) and magnesium carbonate (MgCO 3 )
And equimolar amounts were mixed using a resin ball and a mill. This mixture is placed in a platinum crucible and placed in an air atmosphere at 900 ° C. for 2 hours.
After calcining for a time, a powder of magnesium niobate was obtained. The obtained powder was pulverized for 16 hours using a resin ball and a mill to obtain a raw material powder of magnesium niobate. The average particle size of the powder measured using a sedigraph was 1.6 μm.
酸化鉛、炭酸ストロンチウム、酸化ジルコニウム、酸
化チタン、炭酸マグネシウム、五酸化ニオブ及び上記の
ニオブ酸マグネシウムをPb0.95Sr0.05（Mg1/3Ｎ2/3）
0.375Ti0.375Zr0.25O3の組成となるように配合し、樹脂
ボール及びミルを用いて混合粉砕した。得られた混合粉
末をアルミナツボに入れ、大気雰囲気中950℃で２時間
仮焼し、得られた仮焼粉末を乳ばちを用いて解砕し、直
径15mmの厚さ3mmの円板を、350kg/cm2の圧力でプレス成
形した。Lead oxide, strontium carbonate, zirconium oxide, titanium oxide, magnesium carbonate, niobium pentoxide and the above magnesium niobate are Pb 0.95 Sr 0.05 (Mg 1/3 N 2/3 )
It was mixed so as to have a composition of 0.375 Ti 0.375 Zr 0.25 O 3 and mixed and pulverized using a resin ball and a mill. The obtained mixed powder is placed in an alumina pot, and calcined in an air atmosphere at 950 ° C. for 2 hours, and the obtained calcined powder is crushed using a squeeze to form a disk having a diameter of 15 mm and a thickness of 3 mm. And press-formed at a pressure of 350 kg / cm 2 .
アルミナルツボニに入れた白金板上に上記の成形体を
置き、1250℃で２時間焼成して焼結体を得た。The above-mentioned molded body was placed on a platinum plate placed in an alumina tube and calcined at 1250 ° C. for 2 hours to obtain a sintered body.
得られた焼結体を厚さ2mmに研磨し、両面に電極とし
て銀ペーストを焼きつけ、80℃で2.5KV/mmの電圧を５分
間印加して分極せしめ、圧電体セラミックスを得た。The obtained sintered body was polished to a thickness of 2 mm, silver paste was baked on both sides as electrodes, and a voltage of 2.5 KV / mm was applied at 80 ° C. for 5 minutes to polarize, thereby obtaining a piezoelectric ceramic.
得られた圧電体セラミックスの1MHzでの誘電率
（εｒ）と変換効率である電気機械結合係数（Kr）をイ
ンピーダンス・ゲインフェイズ・アナライザ（YHP社
製、4194A）を用いて測定した。得られた結果を第１表
に示す。The dielectric constant (ε r ) at 1 MHz and the electromechanical coupling coefficient (K r ) as the conversion efficiency of the obtained piezoelectric ceramics were measured using an impedance gain phase analyzer (4194A, manufactured by YHP). Table 1 shows the obtained results.
実施例２ 実施例１と同様にして五酸化ニオブと炭酸マグネシウ
ムとから合成したニオブ酸マグネシウムを、ジルコニア
ビーズ及び樹脂ミルを用いて10時間粉砕したもの（平均
粒径0.9μｍ）を原料粉末のニオブ酸マグネシウムとし
た以外、実施例１と同様に行なった。Example 2 Magnesium niobate synthesized from niobium pentoxide and magnesium carbonate in the same manner as in Example 1 was pulverized for 10 hours using zirconia beads and a resin mill (average particle size: 0.9 μm), and niobium as a raw material powder was used. The procedure was performed in the same manner as in Example 1 except that magnesium acid was used.
得られた圧電体セラミックスの特性測定結果を第１表
に示す。Table 1 shows the measurement results of the characteristics of the obtained piezoelectric ceramics.
実施例３〜７ 水熱合成で製造された市販のニオブ酸マグネシウム
（堺化学工業（株）製、平均粒径0.6μｍ）を用い、ニ
オブ酸マグネシウム量（MN）と炭酸マグネシウム及び五
酸化ニオブの合計量（Μ＋Ｎ）との比率を第１表に示す
ように変化させ、それ以外は実施例１と同様に行なっ
た。Examples 3 to 7 Using commercially available magnesium niobate produced by hydrothermal synthesis (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.6 μm), the amount of magnesium niobate (MN) and the amount of magnesium carbonate and niobium pentoxide were measured. The procedure was the same as in Example 1 except that the ratio to the total amount (合計 + N) was changed as shown in Table 1.
得られた圧電体セラミックスの特性測定結果を第１表
に示す。Table 1 shows the measurement results of the characteristics of the obtained piezoelectric ceramics.
比較例１ ニオブ酸マグネシウムを用いず、五酸化ニオブ、炭酸
マグネシウム、酸化鉛、炭酸ストロンチウム、酸化ジル
コニウム及び酸化チタンを直接原料として、実施例１と
同様に行なった。Comparative Example 1 The procedure of Example 1 was repeated, except that magnesium niobate was not used, and niobium pentoxide, magnesium carbonate, lead oxide, strontium carbonate, zirconium oxide and titanium oxide were directly used as raw materials.
得られた圧電体セラミックスの特性測定結果を第１表
に示す。Table 1 shows the measurement results of the characteristics of the obtained piezoelectric ceramics.
比較例２ 実施例１と同様にして五酸化ニオブと炭酸マグネシウ
ムとから合成したニオブ酸マグネシウム粉末（平均粒径
3.5μｍ）を、粉砕せずに原料粉末として用いた以外、
実施例１と同様に行なった。Comparative Example 2 Magnesium niobate powder (average particle size) synthesized from niobium pentoxide and magnesium carbonate in the same manner as in Example 1
3.5 μm) was used as raw material powder without pulverization,
Performed in the same manner as in Example 1.
得られた圧電体セラミックスの特性測定結果を第１表
に示す。Table 1 shows the measurement results of the characteristics of the obtained piezoelectric ceramics.
比較例３ 実施例３で用いた市販のニオブ酸マグネシウムを用
い、炭酸マグネシウム及び五酸化ニオブを用いないで、
酸化鉛、炭酸ストロンチウム、酸化ジルコニウム及び酸
化チタンを、実施例１と同じ組成になるように原料配合
し、以下実施例１と同様に行なった。Comparative Example 3 Using the commercially available magnesium niobate used in Example 3, without using magnesium carbonate and niobium pentoxide,
Lead oxide, strontium carbonate, zirconium oxide, and titanium oxide were blended as raw materials so as to have the same composition as in Example 1, and the same procedure as in Example 1 was performed.
得られた圧電体セラミックスの特性測定結果を第１表
に示す。Table 1 shows the measurement results of the characteristics of the obtained piezoelectric ceramics.
〔発明の効果〕 第１表に示す結果から明らかなように、原料として平
均粒径が２μｍ以下のニオブ酸マグネシウムを原料組成
に併用することにより、得られる圧電体セラミックスの
特性は従来のものと比較して大幅に向上する。本発明に
より、従来の製造工程、設備を変えることなく、高品質
の圧電体セラミックスを製造することができる。 [Effects of the Invention] As is clear from the results shown in Table 1, the characteristics of the piezoelectric ceramic obtained by using magnesium niobate having an average particle diameter of 2 µm or less as a raw material in combination with the raw material composition are different from those of the conventional piezoelectric ceramic. It is greatly improved in comparison. According to the present invention, high quality piezoelectric ceramics can be manufactured without changing conventional manufacturing processes and equipment.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−214506（ＪＰ，Ａ) 特開 昭62−197315（ＪＰ，Ａ) 特開 平１−96973（ＪＰ，Ａ) 特開 昭61−242951（ＪＰ，Ａ) 特開 昭51−59400（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01B 3/12 C04B 35/00 - 35/49 H01L 41/18──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-214506 (JP, A) JP-A-62-197315 (JP, A) JP-A-1-96973 (JP, A) JP-A 61-19763 242951 (JP, A) JP-A-51-59400 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H01B 3/12 C04B 35/00-35/49 H01L 41/18
Claims (2)
合物、チタニウム化合物及びジルコニウム化合物を混
合、仮焼、焼成、分極するPbTiO3・PbZrO3・Pb（Mg1/3N
b2/3）O3系圧電体セラミックスの製造方法において、ニ
オブ及びマグネシウムの原料源として平均粒径が２μｍ
以下のニオブ酸マグネシウム（Mg1/3Nb2/3O2）をニオブ
化合物及びマグネシウム化合物と混合して用いることを
特徴とする圧電体セラミックスの製造方法。1. PbTiO 3 .PbZrO 3 .Pb (Mg 1/3 N) in which a niobium compound, a magnesium compound, a lead compound, a titanium compound and a zirconium compound are mixed, calcined, fired and polarized.
b 2/3 ) In the method for producing O 3 -based piezoelectric ceramics, the average particle size is 2 μm as a raw material source for niobium and magnesium.
A method for producing a piezoelectric ceramic, comprising using the following magnesium niobate (Mg 1/3 Nb 2/3 O 2 ) in combination with a niobium compound and a magnesium compound.
より合成された平均粒径が1.0μｍ以下の粉末を用いる
請求項１に記載の方法。2. The method according to claim 1, wherein a powder having an average particle diameter of 1.0 μm or less synthesized by a hydrothermal reaction is used as the magnesium niobate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2138580A JP2841347B2 (en) | 1990-05-30 | 1990-05-30 | Manufacturing method of piezoelectric ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2138580A JP2841347B2 (en) | 1990-05-30 | 1990-05-30 | Manufacturing method of piezoelectric ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0433383A JPH0433383A (en) | 1992-02-04 |
| JP2841347B2 true JP2841347B2 (en) | 1998-12-24 |
Family
ID=15225443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2138580A Expired - Lifetime JP2841347B2 (en) | 1990-05-30 | 1990-05-30 | Manufacturing method of piezoelectric ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841347B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2665106B2 (en) * | 1992-03-17 | 1997-10-22 | 日本碍子株式会社 | Piezoelectric / electrostrictive film element |
| JP3161261B2 (en) * | 1994-11-28 | 2001-04-25 | 株式会社村田製作所 | Piezoelectric ceramic composition |
| CN115894020B (en) * | 2022-12-23 | 2023-12-19 | 佛山仙湖实验室 | PMNZT-based piezoelectric ceramic with high piezoelectric coefficient and preparation method and application thereof |
-
1990
- 1990-05-30 JP JP2138580A patent/JP2841347B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0433383A (en) | 1992-02-04 |
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