JPH0196973A - Manufacture of piezoelectric porcelain - Google Patents
Manufacture of piezoelectric porcelainInfo
- Publication number
- JPH0196973A JPH0196973A JP62254916A JP25491687A JPH0196973A JP H0196973 A JPH0196973 A JP H0196973A JP 62254916 A JP62254916 A JP 62254916A JP 25491687 A JP25491687 A JP 25491687A JP H0196973 A JPH0196973 A JP H0196973A
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric
- calcination
- piezoelectric porcelain
- baking
- lead oxide
- 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.)
- Pending
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 9
- -1 ZvO2 Chemical compound 0.000 claims abstract 2
- 238000001354 calcination Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 abstract description 12
- 238000010168 coupling process Methods 0.000 abstract description 12
- 238000005859 coupling reaction Methods 0.000 abstract description 12
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 4
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 1
- 229910004158 TaO Inorganic materials 0.000 abstract 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 abstract 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 abstract 1
- 229910001934 tungsten pentoxide Inorganic materials 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940110676 inzo Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明はＰｂＴｉＯｓ ＰｂＺｒＯｓ−Ｍｅ （但
し、Ｍｅ＝ＰｂＯ。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention is directed to PbTiOs PbZrOs-Me (where Me=PbO).
ＮｂｔＯｓ、 ＭｎＯ，ｓｂ！ｏ、、 ＳｎＯ＋ Ｂｉ
ｔ’３． ＭｇＯ＋ ＷｚＯｓ＋ＦｅｚＯ５＋ Ｃｒｔ
Ｏ＊＋ Ｎｉ０ｔ Ｃｏｏ、 ＺｎＯ，Ｔａｇ、 ｒｎ
ｚｏｓ＋またはＣｕ０Ｏ内少なくとも１種）からなる圧
電性磁器の製造方法に関する。NbtOs, MnO,sb! o,, SnO+ Bi
t'3. MgO+ WzOs+FezO5+ Crt
O*+ Ni0t Coo, ZnO, Tag, rn
The present invention relates to a method for producing piezoelectric porcelain made of at least one of zos+ and Cu0O.
ＰｂＴｉＯｓ ＰｂＺｒ０ｉ圧電性磁器はチタン酸ジ
ルコン酸鉛という圧電性磁器として知られて久しい。PbTiOs PbZrOi piezoelectric porcelain has long been known as a piezoelectric porcelain called lead zirconate titanate.
また、このチタン酸ジルコン酸鉛に圧電特性の向上のた
めにＭｅ ＝ＰｂＯ，Ｎｂ２Ｏ５，ＭｎＯ、５ｂｉＯｓ
、 ＳｎＯ。In addition, to improve piezoelectric properties, Me = PbO, Nb2O5, MnO, 5biOs was added to this lead zirconate titanate.
, SnO.
ＢｉｚＯｉ、ＭｇＯ，ＷｚＯｓ、ＦｅｚＯ１＋ Ｃｒ
ｚＯｆｆ、Ｎｉｐ、Ｃｏｄ、ＺｎＯ。BizOi, MgO, WzOs, FezO1+ Cr
zOff, Nip, Cod, ZnO.
Ｔａｇ、 ＩｎｚＯ＝、またはＣｕＯなどを適量添加す
るという多くの発明がなされてきた。この種の磁器を製
造するにあたっては、前記各組成を構成する各成分原料
であるｐｂｆｆｏ４． Ｚｒ０ｚ＋ Ｔ１０２１ Ｍｅ
を所定の組成が得られるように秤量し、秤量原料を調合
したのち、脱水、乾燥していた。通常この調合済みの原
料は、仮焼工程に移行する。Many inventions have been made in which appropriate amounts of Tag, InzO=, CuO, etc. are added. In manufacturing this type of porcelain, each component raw material constituting the above-mentioned compositions, pbffo4. Zr0z+ T1021 Me
was weighed to obtain a predetermined composition, and the weighed raw materials were prepared, then dehydrated and dried. Usually, this blended raw material is transferred to a calcination step.
しかしながら、仮焼段階でパイロクロア相などの中間生
成相が残り、焼成段階で完全な化合物が得られないため
、所定の圧電特性が得られないという問題があった。However, an intermediate phase such as a pyrochlore phase remains in the calcination stage, and a complete compound cannot be obtained in the calcination stage, resulting in a problem in that desired piezoelectric properties cannot be obtained.
中間生成相を減少させるには、その製造過程中、仮焼温
度を上昇させる必要がある。しかし、仮焼温度を上げて
中間生成相の減少を図ろうとすれば、仮焼された粉末が
固くなり、これを粉砕するときに粉砕メディアから仮焼
粉末に不純物の混入があるため、特性の劣化につながっ
ていた。To reduce the intermediate phase, it is necessary to increase the calcination temperature during the manufacturing process. However, if an attempt is made to reduce the intermediate phase by increasing the calcination temperature, the calcined powder will become hard, and when it is crushed, impurities may be mixed into the calcined powder from the crushing media, resulting in poor characteristics. This led to deterioration.
そこで、調合原料を仮焼する段階で、その構成成分のう
ち、Ｍｅ、 ＴｉＯ□ＺｒＯ□とｐｈｏとの仮焼工程を
別々に行うことにより、中間生成相の減少が図れ、圧電
特性、すなわち、電気機械結合係数、誘電率、ならびに
他の圧電特性の改善が図れることを見い出した。Therefore, by separately performing the calcination process for Me, TiO□ZrO□ and pho among the constituent components at the stage of calcination of the blended raw material, it is possible to reduce the intermediate phase and improve the piezoelectric properties. It has been found that the electromechanical coupling coefficient, dielectric constant, and other piezoelectric properties can be improved.
この発明は、ＰｂＴｉ０＋ ＰｂＺｒ０＋ Ｍｅ
（但し、門ｅ＝ＰｂＯ，Ｎｂ２Ｏ５，ＭｎＯ、５ｂｚ０
５． ＳｎＯ，ＢｉｚＯ：＋、 ＭｇＯ。This invention provides PbTi0+ PbZr0+ Me
(However, gate e=PbO, Nb2O5, MnO, 5bz0
5. SnO, BizO: +, MgO.
ｗ、Ｏ，、ＦｅｚＯ，Ｃｒ２Ｏ３，Ｎｉｐ、 Ｃｏｏ、
ＺｎＯ，ＴａＯ＋ Ｉｎ２Ｏ３，またはＣｕＯのうち
少なくとも１種）から成る圧電性磁器の製造方法である
。w, O,, FezO, Cr2O3, Nip, Coo,
This is a method for manufacturing piezoelectric porcelain made of at least one of ZnO, TaO+In2O3, or CuO.
上記構成成分のうち酸化鉛を除いた少なくとも２種以上
の成分を所定の構成成分比となる重量またはその所定の
構成成分比となる一部を秤量、混合した後１回目の仮焼
を行なう。１回目の仮焼物に所定の構成成分比に対して
不足している成分の原料を添加し、混合・粉砕したのち
２回目の仮焼を行い、得られた仮焼物を成形したのち、
焼成する。ただし、２回目の混合時に添加する酸化鉛の
重量はｐｂ、ｏ、に換算して、酸化鉛を除く構成成分の
重量全体の１． ８〜２．３倍である。At least two or more of the above-mentioned constituents, excluding lead oxide, are weighed and mixed to give a predetermined constituent ratio, or a portion thereof to a predetermined constituent ratio, and then calcined for the first time. After adding raw materials of ingredients lacking in the predetermined component ratio to the first calcined product, mixing and pulverizing, performing the second calcining, and shaping the obtained calcined product,
Fire. However, the weight of lead oxide added during the second mixing is converted to pb, o, and is 1.0% of the total weight of the components excluding lead oxide. It is 8 to 2.3 times.
１回目の仮焼は、８００℃〜１２００″Ｃの温度で行わ
れる。これは８００℃未満では、仮焼効果カナく、Ｔｉ
Ｏ□＋ ＺｒＯ□＋ Ｍｅ の合成が進まないため、
実用上充分な圧電特性が得られにくくなるからである。The first calcination is carried out at a temperature of 800°C to 1200"C. If the temperature is lower than 800°C, the calcination effect will be poor and the Ti
Because the synthesis of O□+ ZrO□+ Me does not proceed,
This is because it becomes difficult to obtain practically sufficient piezoelectric properties.
一方、１２００℃を越えると、仮焼粉末が固くなって粉
砕が難しく 、ＰｂｚＯ４を添加した後の粉砕度、混合
度が低下し、焼成段階で低温での焼結が困難になる。On the other hand, if the temperature exceeds 1200°C, the calcined powder becomes hard and difficult to crush, and the degree of crushing and mixing after adding PbzO4 decreases, making it difficult to sinter at a low temperature in the firing stage.
また、２回目の仮焼は、７００℃−１０００℃の温度で
行われる。これは７００℃未満では、ペロブスカイト相
の合成炭が低くなるため、実用上十分な圧電特性が得ら
れにくくなるからである。Further, the second calcination is performed at a temperature of 700°C to 1000°C. This is because if the temperature is less than 700°C, the perovskite phase of the synthetic carbon becomes low, making it difficult to obtain practically sufficient piezoelectric properties.
一方、１０００℃を越えると、仮焼粉末が固くなって粉
砕が困難となり、粒度が不均一になったり、不純物が混
入したりして焼成温度が高くなり、低温での焼結が困難
になるからである。On the other hand, if the temperature exceeds 1000°C, the calcined powder becomes hard and difficult to crush, resulting in uneven particle size or contamination with impurities, which increases the firing temperature and makes it difficult to sinter at low temperatures. It is from.
さらに、構成成分のうち酸化鉛はＰｂ３０．に換算して
酸化鉛を除く構成成分の重量全体の１．８〜２、 ３ｆ
ｆｉｉｔ倍添加しているが、これは１．８倍未満では焼
結性が悪くなり、圧電性が低下するからである。また、
２．３倍以上でも同じように圧電特性は悪くなる。Furthermore, among the constituent components, lead oxide is Pb30. 1.8 to 2,3f of the total weight of the components excluding lead oxide
This is because if the amount is less than 1.8 times, the sinterability will be poor and the piezoelectricity will be reduced. Also,
Even if it is 2.3 times or more, the piezoelectric characteristics are similarly deteriorated.
上記した工程において、仮焼工程を２段階に分けて設定
したが、１回目の仮焼物としては、Ｍｅ。In the above-described process, the calcination process was divided into two stages, and the first calcination was performed using Me.
ＴｉＯ３，ＺｒＯ□を構成する材料のうち少なくとも２
種以上の成分が処理される。これらの酸化物の中で、Ｍ
ｅ、 Ｔｉ０１を所定比に秤量、混合したのち１回目の
仮焼を行ってもよく、またＴｉＯ□、 ＺｒＯ□を所定
比に秤量、混合したのち１回目の仮焼工程で仮焼されて
いないＭｅ、 Ｔｉ０１． Ｚｒ０ｔのうち何れかをＰ
ｂｘＯｎと一緒に仮焼してもよい。At least two of the materials constituting TiO3, ZrO□
More than just seeds are processed. Among these oxides, M
e. Ti01 may be weighed and mixed in a predetermined ratio and then the first calcination may be performed, or TiO□ and ZrO□ may be weighed and mixed in a predetermined ratio and then not calcined in the first calcination step. Me, Ti01. P any one of Zr0t
It may be calcined together with bxOn.
Ｍｅ、 Ｔｉ（ｈ、Ｚｒ０１の原料としては、仮焼工程
で酸化物となる炭酸物、塩化物などの原料を用いてもよ
い。As raw materials for Me, Ti(h, and Zr01), raw materials such as carbonates and chlorides that become oxides in the calcination step may be used.
この発明にかかる圧電性磁器であるＰｂＴｉ０ｚ Ｐ
ｂＺｒＯｚ−Ｍｅとしては、ｐｂの一部をＢａ、 Ｓｒ
、 Ｃａ、 Ｌａの少なくとも１種で置換したものでも
よい。このときの置換量としてはｐｂの１０モル％まで
の範囲で置換される。PbTi0zP, which is the piezoelectric porcelain according to the present invention
As bZrOz-Me, a part of pb is Ba, Sr
, Ca, and La may be substituted. The amount of substitution at this time is up to 10 mol% of pb.
また、圧電特性をさらに改善する目的で、Ｍｎ０ｚ＋Ｆ
ｅｚＯ３＋ ＣｒｚＯｆｆなどの添加物を５重量％迄添
加含有させてもよい。In addition, in order to further improve the piezoelectric properties, Mn0z+F
Additives such as ezO3+ CrzOff may be added in an amount of up to 5% by weight.
この発明の製造方法によれば、２段階の仮焼工程、具体
的には、各構成成分のうち、Ｍｅ、 ＴｉＯ２゜ＺｒＯ
□を構成する材料のうち少なくとも２種以上の成分を用
いて行う１回目の仮焼工程および、次いで、構成成分の
うち、酸化鉛をｐｂ、ｏ４に換算して酸化鉛を除く構成
成分の重量全体の１．８〜２゜３重量倍を１回目の仮焼
物に添加して行う２回目の仮焼工程を有するため、従来
のように、１回の仮焼工程で仮焼処理したものに比べて
中間生成相の生成が低域され、その結果、得られる圧電
性磁器の特性の改善、具体的には電気機械結合係数の特
性向上や、低温度での焼成においても実用上十分な圧電
特性が得られるなどの効果を有する。According to the manufacturing method of the present invention, a two-stage calcination step, specifically, among the constituent components, Me, TiO2゜ZrO
The first calcination step using at least two or more components of the materials constituting □, and then the weight of the components excluding lead oxide by converting lead oxide into PB and O4. Since there is a second calcination step in which 1.8 to 2.3 times the weight of the entire product is added to the first calcination product, it is possible to use the same method as before. In comparison, the generation of intermediate phases is lower, and as a result, the properties of the resulting piezoelectric porcelain are improved, specifically, the electromechanical coupling coefficient is improved, and piezoelectricity that is sufficient for practical use even when fired at low temperatures is improved. It has effects such as obtaining characteristics.
以下に、この発明を実施例に従って詳細に説明する。 The present invention will be described in detail below according to examples.
実施例１゜
この実施例では、０． ４７ＰｂＴｉＯｓ Ｏ，５３
ＰｂＺｒＯｓ ０ 、 ８ ＮｂｚＯｓ （割合は
重量比、以下同様）からなる圧電性磁器を製造する例に
ついて説明する。Example 1゜In this example, 0. 47PbTiOsO,53
An example of manufacturing piezoelectric porcelain made of PbZrOs 0 , 8 NbzOs (ratios are by weight; the same applies hereinafter) will be described.
まず、構成成分のうち、ＮｂｚＯｓ−Ｔｌ０ｚ＋ Ｚｒ
０ｚを上記した所定比の圧電性磁器が得られるように秤
量、調合し、ボールミルで湿式混合した。この混合材料
を脱水し、仮焼温度として７５０，８５０゜１０５０．
１１００．１３００”Ｃの４種を設定して、それぞれ仮
焼した。First, among the constituent components, NbzOs-Tl0z+ Zr
0z were weighed and mixed so as to obtain piezoelectric porcelain having the above-mentioned predetermined ratio, and wet-mixed in a ball mill. This mixed material is dehydrated and calcined at a temperature of 750,850° and 1050°.
Four types of 1100 and 1300"C were set and calcined respectively.
一方、構成成分のうち酸化鉛をｐｂ□０．に換算して酸
化鉛を除く構成成分の重量全体の１．８〜２゜３倍を１
回目の仮焼物に対して添加し２回目の仮焼を、６５０，
８００，８５０．１０５０℃の各温度で行った。On the other hand, among the constituent components, lead oxide was added to pb□0. 1.8 to 2.3 times the weight of the entire component excluding lead oxide.
Added to the second calcined product, 650,
The experiments were conducted at temperatures of 800, 850, and 1050°C.
次いで、得られた仮焼物を大きさが直径１Ｏ９０閣、厚
み１．００ａｍの円板に成形した。この円板状の成形体
を１１００〜１２００ ’Ｃで焼成した。Next, the obtained calcined product was formed into a disk having a diameter of 1090 mm and a thickness of 1.00 am. This disk-shaped compact was fired at 1100 to 1200'C.
焼結した磁器円板に焼付は銀電極を形成し、絶縁油中に
おいて、３Ｋｖ／ｍａ＋の電圧で２０分間分極した。A silver electrode was baked on the sintered porcelain disk and polarized in insulating oil at a voltage of 3 Kv/ma+ for 20 minutes.
得られた圧電性磁器について、それぞれ誘電率（Ｃｒ）
、径方向の電気機械結合係数（Ｋｐ） 、誘電損失（ｔ
ａｎ δ）、機械的品質係数（Ｑｍ）を測定し、その結
果を第１表に示した。For the obtained piezoelectric porcelain, the dielectric constant (Cr)
, radial electromechanical coupling coefficient (Kp), dielectric loss (t
an δ) and mechanical quality factor (Qm) were measured, and the results are shown in Table 1.
なお、圧電特性は、周波数ＩＫＨｚ、印加電圧はＩ Ｖ
ｒｍｓ、測定温度２５℃で測定した。第１表中＊印はこ
の発明の範囲外のものである。Note that the piezoelectric characteristics are determined at a frequency of IKHz and an applied voltage of I V
rms, measured at a measurement temperature of 25°C. Items marked with * in Table 1 are outside the scope of this invention.
（以下余白）
第 Ｉ 表
また、試量番号１−４のものにつき、その焼成温度を変
化させたときの誘電率（’９ｒ）、電気機械結合係数（
Ｋｐ）について測定した。(Left space below) Table I also shows the dielectric constant ('9r), electromechanical coupling coefficient (
Kp) was measured.
第１図Φ実線はその測定結果であり、図から明らかなよ
うに、この発明方法で得られた圧電性磁器は焼成温度が
変化しても、圧電特性の大幅な変化がない。従って、焼
成工程において焼成温度の管理が行いやすいという利点
がある。The solid line Φ in FIG. 1 shows the measurement results, and as is clear from the figure, the piezoelectric properties of the piezoelectric porcelain obtained by the method of this invention do not change significantly even when the firing temperature changes. Therefore, there is an advantage that the firing temperature can be easily controlled in the firing process.
実施例２゜
二の実施例では、０． ５０ＰｂＴｉＯｚ ０． ５
０ＰｂＺｒＣｈ −０、５ＭｎＣＯ３からなる圧電性磁
器を製造する例について説明する。Example 2 In the second example, 0. 50PbTiOz 0. 5
An example of manufacturing piezoelectric porcelain made of 0PbZrCh -0,5MnCO3 will be described.
まず、構成成分のうち、Ｔｉ０ｚ＋ Ｚｒ０ｚ、 Ｍｎ
Ｃ０＊を上記した所定重量比の圧電性磁器が得られるよ
うに秤量、調合し、ボールミルで湿式混合した。この混
合原料を脱水し、４種の仮焼温度、７５０゜８５０．１
０５０，１１．００．１３００℃でそれぞれ仮焼した。First, among the constituent components, Ti0z+ Zr0z, Mn
C0* was weighed and mixed so as to obtain piezoelectric porcelain having the above-mentioned predetermined weight ratio, and wet-mixed in a ball mill. This mixed raw material was dehydrated and heated to four different calcination temperatures: 750° and 850.1°.
Calcination was performed at 050°C, 11°C, 00°C, and 1300°C, respectively.
一方、構成成分のうち酸化鉛をＰｂ：ｔＯ，に換算して
酸化鉛を除く構成成分の重量全体の１．８〜２゜３倍を
１回目の仮焼物に対して添加し、そののち２回目の仮焼
を６５０，８５０，１０５０℃の温度にそれぞれ設定し
て行った。 −
次いで、得られた仮焼物を大きさが直径１０゜０胴、厚
み１．００ｍｍの円板に成形した。この円板状の成形体
を１１２０〜１２２０℃で焼成した。On the other hand, among the constituent components, lead oxide was converted into Pb:tO, and 1.8 to 2.3 times the weight of the entire constituent components excluding lead oxide was added to the first calcined product. The second calcination was performed at temperatures of 650, 850, and 1050°C, respectively. - Then, the obtained calcined product was formed into a disc with a diameter of 10° and a thickness of 1.00 mm. This disk-shaped molded body was fired at 1120 to 1220°C.
焼結した磁器円板に焼付は銀電極を形成し、絶縁油中に
おいて、３ Ｋｖ／ｎｕｎの電圧で２０分間分極した。A silver electrode was baked on the sintered porcelain disk and polarized in insulating oil at a voltage of 3 Kv/nun for 20 minutes.
得られた圧電性磁器について、それぞれ誘電率（Ｓｒ）
、径方向の電気機械結合係数（Ｋｐ） 、機械的品質係
数（Ｑｍ）を測定した。その結果を第２表に示した。For the obtained piezoelectric porcelain, the dielectric constant (Sr)
, radial electromechanical coupling coefficient (Kp), and mechanical quality coefficient (Qm) were measured. The results are shown in Table 2.
なお、圧電特性は、周波数１にＨｚ、印加電圧はＩＶｒ
ｍｓ、測定温度２５℃で測定した。第２表中＊印はこの
発明の範囲外のものである。In addition, the piezoelectric characteristics are as follows: Frequency 1 is Hz, and applied voltage is IVr.
ms, measured at a measurement temperature of 25°C. Items marked with * in Table 2 are outside the scope of this invention.
この実施例においても、２回の仮焼工程を経ることによ
り、圧電特性の改善が図られ、具体的には、低温度でか
つ一定の変化幅の温度で焼成しても、誘電率の低下がみ
られず、電気機械結合係数、誘電損失、および機械的品
質係数も一定となり、安定した圧電特性が得られる。In this example as well, the piezoelectric properties are improved by going through the calcination process twice, and specifically, even if the calcination is performed at a low temperature with a constant variation range, the dielectric constant decreases. is not observed, and the electromechanical coupling coefficient, dielectric loss, and mechanical quality factor are also constant, and stable piezoelectric properties are obtained.
実施例３゜
この実施例では、Ｐｂｏ、ｅｓ＋ Ｓｒａ、ｏｓ （Ｔ
ｉｏ、ｎａ。Example 3 In this example, Pbo, es+ Sra, os (T
io, na.
Ｚｒｏ、ｓｚ） ｏ３からなる圧電性磁器を製造する例
について説明する。An example of manufacturing piezoelectric porcelain made of Zro, sz) o3 will be described.
まず、構成成分のうち、ＴｉＯ□、 ＺｒＯ□を上記し
た所定比の圧電性磁器が得られるように秤量、調合し、
ボールミルで湿式混合した。この混合原料を脱水し、仮
焼温度を７５０，８５０，１０５０゜１１００．１３０
０度にそれぞれ設定して仮焼した。First, among the constituent components, TiO□ and ZrO□ were weighed and mixed so as to obtain piezoelectric porcelain with the above-mentioned predetermined ratio.
Wet mixing was performed using a ball mill. This mixed raw material is dehydrated and the calcination temperature is set to 750,850,1050°1100.130.
Each was set to 0 degrees and calcined.
一方、構成成分のうち酸化鉛をＰｂＪｎに換算して、酸
化鉛を除く構成成分の重量全体の１．８〜２．３倍なら
びに、ＳｒＯを構成する原料を５ｒＣＯｉに換算してＳ
ｒＯを上記した所定比の０．０５〜０゜１２倍を１回目
の仮焼物に対して添加してそののち２回目の仮焼を６５
０．８５０．１０５０度の温度にそれぞれ設定して行っ
た。On the other hand, lead oxide among the constituent components is converted to PbJn, which is 1.8 to 2.3 times the weight of the entire constituent components excluding lead oxide, and the raw material constituting SrO is converted to 5rCOi, which is S
Add rO to the first calcined product at 0.05 to 0.12 times the above-mentioned predetermined ratio, and then perform the second calcining at 65
The temperature was set at 0.850 and 1050 degrees.
次いで、得られた仮焼物を大きさが直径１０゜０閣、厚
み１．０Ｏｎに成形した。この円板状の成形体を１１６
０〜ｌ ２５０ ’Ｃで焼成した。Next, the obtained calcined product was molded into a size having a diameter of 10° and a thickness of 1.0 On. This disk-shaped molded body is 116
Calcined at 0-1250'C.
焼成した磁器円板に焼付は銀電極を形成し、絶縁油中に
おいて、３にｖ／ｍｓの電圧で２０分間分極した。A fired silver electrode was formed on the fired porcelain disk and polarized in insulating oil at a voltage of 3 V/ms for 20 minutes.
得られた圧電性磁器について、それぞれ誘電率（２ｒ）
、径方向の電気機械結合係数（Ｋｐ） 、機械的品質係
数（Ｑｍ）を測定した。その結果を第３表に示した。The dielectric constant (2r) of the piezoelectric porcelain obtained is
, radial electromechanical coupling coefficient (Kp), and mechanical quality coefficient (Qm) were measured. The results are shown in Table 3.
なお、圧電特性は、周波数ＩＫＨｚ、印加電圧はＩ Ｖ
ｒｍｓ、測定温度２５℃で測定した。第３表中＊はこの
発明の範囲外のものである。Note that the piezoelectric characteristics are determined at a frequency of IKHz and an applied voltage of I V
rms, measured at a measurement temperature of 25°C. In Table 3, * is outside the scope of this invention.
（以下余白）
第３表
この実施例においても、２回の仮焼工程を経ることによ
り、圧電特性の改善が図られ、具体的には、低温度でか
つ一定の変化幅の温度で焼成しても、誘電率の低下がみ
られず、電気機械結合係数、および機械的品質係数も一
定となり、安定した圧電特性が得られる。(Margins below) Table 3 In this example as well, the piezoelectric properties were improved by going through two calcination steps. Specifically, the piezoelectric properties were improved by performing calcination at a low temperature with a constant variation range. However, no decrease in dielectric constant is observed, and the electromechanical coupling coefficient and mechanical quality coefficient remain constant, resulting in stable piezoelectric properties.
比較例
実施例１と同し組織からなる圧電性磁器を得る例である
。Comparative Example This is an example of obtaining piezoelectric porcelain having the same structure as in Example 1.
この比較例では、各構成成分のＩ’ｔｌ、Ｏｎ＋ Ｎｂ
ｚＯｓ＋ＴｉＯ□＋ Ｚｒ０ｔを所定重量比に秤量、混
合したのち、８５０℃で仮焼を行った。In this comparative example, I'tl, On+Nb of each component
After weighing and mixing zOs+TiO□+Zr0t in a predetermined weight ratio, calcination was performed at 850°C.
ついで、得られた仮焼物を大きさが直径１０゜０＋ｎｍ
、厚み１．００の円板に成形した。この円板状の成形体
を１０００〜１２００ ”Ｃで焼成した。Next, the obtained calcined product is made into a material with a diameter of 10°0+nm.
, and was molded into a disk with a thickness of 1.00. This disc-shaped compact was fired at 1000 to 1200''C.
焼結した磁器円板に焼き付は銀電極を形成し、絶縁油中
において、３にν／―端の電圧で２０分間分損した。得
られた圧電性磁器について、それぞれ誘電率（５ｒ ）
、径方向の電気機械結合係数（Ｋｐ）、誘電損失（ｔ
ａｎ δ）１．Ｉｊｑ械的品質係数（ｑｍ）を測定した
。その結果を第４表に示した。A sintered porcelain disk was baked to form a silver electrode, which was placed in insulating oil at a voltage of 3 to ν/- for 20 minutes. The dielectric constant (5r) of the obtained piezoelectric porcelain is
, radial electromechanical coupling coefficient (Kp), dielectric loss (t
an δ)1. The Ijq mechanical quality factor (qm) was measured. The results are shown in Table 4.
なお、圧電特性は、周波数ＩＫＨｚ、印加電圧ＩＶｒｍ
ｓ、測定温度２５℃で測定した。Note that the piezoelectric characteristics are determined by the frequency IKHz and the applied voltage IVrm.
s, measured at a measurement temperature of 25°C.
Ｃ以下余白）
第 ４ 表
この第４表から、従来のように、各構成成分を一度の仮
焼処理により合成した場合には、低温度での焼成では、
この発明により得られた圧電性磁器に比べて十分な圧電
特性が得られておらず、高温での焼成処理が必要である
。また、焼成工程で焼成温度が低温へ変化しないように
厳密な焼成管理が必要になる。Table 4 From Table 4, when each component is synthesized by a single calcination treatment as in the past, when calcination is performed at a low temperature,
Compared to the piezoelectric porcelain obtained according to the present invention, sufficient piezoelectric properties are not obtained, and firing treatment at a high temperature is required. Furthermore, strict firing management is required to prevent the firing temperature from changing to a low temperature during the firing process.
また、焼成温度を変化させたときの誘電率（εｒ）、電
気機械結合係数（Ｋｐ）について測定した結果を破線で
第１図に併せて示した。Further, the results of measurement of dielectric constant (εr) and electromechanical coupling coefficient (Kp) when the firing temperature was varied are also shown in FIG. 1 by broken lines.
第１図は、この発明方法で得られた圧電性磁器と比較例
で得られた圧電性ｉｆｆ器の各誘電率（εｒ）、電気機
械結合係数（Ｋｐ）と焼成温度との関係を示す図である
。FIG. 1 is a diagram showing the relationship between the dielectric constant (εr), electromechanical coupling coefficient (Kp), and firing temperature of the piezoelectric porcelain obtained by the method of this invention and the piezoelectric IF device obtained in the comparative example. It is.
Claims (4)
Ｍｅ＝ＰｂＯ，Ｎｂ＿２Ｏ＿３，ＭｎＯ，Ｓｂ＿２Ｏ＿
３，ＳｎＯ，Ｂｉ＿２Ｏ＿３，ＭｇＯ，Ｗ＿２Ｏ＿３，
ＷＯ＿３，Ｆｅ＿２Ｏ＿３，Ｃｒ＿２Ｏ＿３，ＮｉＯ，
ＣｏＯ，ＺｎＯ，ＴａＯ，Ｉｎ，Ｉｎ＿２Ｏ＿３，また
はＣｕＯの内少なくとも１種）からなる圧電性磁器の製
造方法であって、 前記圧電性磁器の原料のうち、酸化鉛を除いた少なくと
も２種以上の成分を所定の構成成分比となる重量もしく
はその所定の構成成分比となる一部を秤量・混合したの
ち１回目の仮焼を行い、次いで、１回目の仮焼物に所定
の構成成分比に対して不足している成分の原料を添加し
、混合・粉砕ののち、２回目の仮焼を行い、得られた仮
焼物を成形したのち、焼成することを特徴とする圧電性
磁器の製造方法。(1) PbTio_3-PbZrO_3-Me (however,
Me=PbO, Nb_2O_3, MnO, Sb_2O_
3, SnO, Bi_2O_3, MgO, W_2O_3,
WO_3, Fe_2O_3, Cr_2O_3, NiO,
CoO, ZnO, TaO, In, In_2O_3, or CuO) A method for producing piezoelectric porcelain consisting of at least one of the following: After weighing and mixing the weight that has a predetermined component ratio or a part of it that has a predetermined component ratio, perform the first calcination, and then perform the first calcination with a predetermined component ratio A method for producing piezoelectric porcelain, characterized by adding raw materials for missing ingredients, mixing and pulverizing, performing a second calcining, shaping the resulting calcined product, and then firing.
Ｐｂ＿３Ｏ＿４に換算して酸化鉛を除く構成成分の重量
全体の１．８〜２．３倍であることを特徴とする特許請
求の範囲第１項記載の圧電性磁器の製造方法。(2) The weight of lead oxide added during the second mixing is:
2. The method for manufacturing piezoelectric porcelain according to claim 1, wherein the amount is 1.8 to 2.3 times the weight of the entire component excluding lead oxide when converted to Pb_3O_4.
度で行うことを特徴とする特許請求の範囲第１項記載の
圧電性磁器の製造方法，(3) The method for manufacturing piezoelectric porcelain according to claim 1, wherein the first calcination is performed at a temperature of 800°C to 1200°C;
度で行うことを特徴とする特許請求の範囲第１項記載の
圧電性磁器の製造方法。(4) The method for manufacturing piezoelectric porcelain according to claim 1, wherein the second calcination is performed at a temperature of 700°C to 1000°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254916A JPH0196973A (en) | 1987-10-08 | 1987-10-08 | Manufacture of piezoelectric porcelain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254916A JPH0196973A (en) | 1987-10-08 | 1987-10-08 | Manufacture of piezoelectric porcelain |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0196973A true JPH0196973A (en) | 1989-04-14 |
Family
ID=17271637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62254916A Pending JPH0196973A (en) | 1987-10-08 | 1987-10-08 | Manufacture of piezoelectric porcelain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0196973A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004210616A (en) * | 2003-01-08 | 2004-07-29 | Tamura Seisakusho Co Ltd | Piezoelectric ceramics |
| KR100462873B1 (en) * | 2001-12-27 | 2004-12-17 | 주식회사 에스세라 | Piezoelectric ceramic composition and piezoelectric device using the same |
| JP2008007335A (en) * | 2006-06-27 | 2008-01-17 | Nec Tokin Corp | Piezoelectric ceramic composition |
| CN109320242A (en) * | 2018-10-22 | 2019-02-12 | 魏赛尔 | A kind of piezoelectric transformer ceramic material and preparation method thereof |
-
1987
- 1987-10-08 JP JP62254916A patent/JPH0196973A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100462873B1 (en) * | 2001-12-27 | 2004-12-17 | 주식회사 에스세라 | Piezoelectric ceramic composition and piezoelectric device using the same |
| JP2004210616A (en) * | 2003-01-08 | 2004-07-29 | Tamura Seisakusho Co Ltd | Piezoelectric ceramics |
| JP2008007335A (en) * | 2006-06-27 | 2008-01-17 | Nec Tokin Corp | Piezoelectric ceramic composition |
| CN109320242A (en) * | 2018-10-22 | 2019-02-12 | 魏赛尔 | A kind of piezoelectric transformer ceramic material and preparation method thereof |
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