JPH0325955B2 - - Google Patents
Info
- Publication number
- JPH0325955B2 JPH0325955B2 JP15623281A JP15623281A JPH0325955B2 JP H0325955 B2 JPH0325955 B2 JP H0325955B2 JP 15623281 A JP15623281 A JP 15623281A JP 15623281 A JP15623281 A JP 15623281A JP H0325955 B2 JPH0325955 B2 JP H0325955B2
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric ceramic
- fine particles
- piezoelectric
- particles
- ceramic fine
- 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 claims description 44
- 239000002245 particle Substances 0.000 claims description 41
- 239000010419 fine particle Substances 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 6
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VJPLIHZPOJDHLB-UHFFFAOYSA-N lead titanium Chemical compound [Ti].[Pb] VJPLIHZPOJDHLB-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- 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
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は圧電セラミツク微粒子の製造方法に係
り、個々の圧電セラミツク微粒子の形状が球状で
単一の焼結粒子から成る微粒子の製造方法に関す
るもので、特に高分子等との複合圧電体材料の製
造に適するものである。
圧電セラミツク材料は電気エネルギー機械エネ
ルギーの変換素子として広く用いられているが、
近年、特に著しく進歩して来たのがPVF2等の高
分子と圧電セラミツク微粒子との複合圧電体材料
がある。この複合圧電体材料は高分子と圧電セラ
ミツク微粒子との複合率（圧電セラミツク重量
％／高分子重量％＋圧電セラミツク重量％）を変
化させることにより可撓性に富み圧電効果の大き
な複合圧電体材料が製造でき、キーボード用のス
イツチング素子、超音波トランスジユーサーとし
て応用されている。
これらの用途に用いる圧電セラミツク微粒子は
従来まで焼結または焙焼を終えた焼結体、焙焼粉
体をアルミナ製、ポリエチレン製のポツトでアル
ミナ、メノウ、ステンレス又はこれらに樹脂加工
した玉石を用いて機械的に１〜50μmまで粉砕し、
粒径によるふるい分けを行ないこれを高分子と混
合し、複合圧電体材料の製造に用いていた。
しかしながら従来の機械的な粉砕では得られた
圧電セラミツク粒子の形状は多種多様であり、そ
の粒度分布が大きいためふるい分けを行わないと
粒度の揃つた圧電セラミツク粒子が得られないと
いう欠点が存在した。又、玉石、ポツトからの不
純物の混入が圧電特性を低下させることがさけら
れなかつた。
特に焼結体粒子径が2μm以下の圧電セラミツク
粒子を得るためには長時間の粉砕を必要とし、工
業的ではなかつた。又、機械的粉砕方法を用いる
ため焼結体粒子が粒界から分離されず焼結体粒子
が一部破断された様な形状の粒子が混入すること
がさけられなかつた。このため圧電性の向上に寄
与しない焼結体微粒子を高分子と複合させること
になり実用上有効なものではなかつた。又、公開
特許公報55−153381には圧電セラミツク焼結体を
機械的に焼結体粒子に近い粒径までポツトミルを
用いて粉砕し、その後にH2O，HF，HNO3の混
合液に十数秒浸してエツチングして微粒子を得
て、それらを再び焼成する方法が記されている
が、これらの方法においても前に述べた様な欠
点、すなわち、不純物の混入、微粒子形状の不整
い、ふるい分けの必要性、焼結体粒子の一部破断
がさけられず、これらの方法により製造した微粒
子を用いても複合率の割合には圧電性がさほど向
上しないという問題は解決出来なかつた。
本発明は前記の欠点を改良し、個々の圧電セラ
ミツク粒子の形状がほぼ球状であり、粒度分布の
揃つた、不純物を含まない単一の焼結体粒子から
なる微粒子が得られ特に高分子等との複合圧電体
として用いた際に大きな圧電性が得られる圧電セ
ラミツク微粒子の製造方法である。
本発明は従来のごとく機械的粉砕法を用いるこ
となく、上記の目的を達成するものであり、焼結
体粒子および酸化鉛を主成分とする粒界層からな
る圧電セラミツク焼結体に酸処理を施し前記粒界
層をエツチング除去する圧電セラミツク微粒子の
製造方法である。
つまり本発明は従来の機械的に焼結体、焙焼粉
体を粉砕するのではなく、酸に対してエツチング
速度の大きい粒界層成分を焼結体粒子の回りに積
極的に折出させ、粒界層を酸により化学的に取り
除き、焼結体粒子のみを取り出すことにより製造
するものである。
この様な本発明に係る圧電セラミツク微粒子は
例えば第１図に示す如く製造される。
例えばPbO，TiO2，ZrO2，CoO，WO3，MnO
等の原料を用いてPb〔（Co1/2W1/2）0.08Ti0.47Zr0.45
〕
O3＋0.8wt％MnOの組成になる様に正確に評量(1)
を行つた。それらをボールミル等によつて混合(2)
する尚、この際用いる原料は加熱によつて酸化物
に転ずる化合物、例えば水酸化物、炭酸塩などで
あつても良い。
次いで前記混合物を例えば700〜1100℃程度で
仮焼（焙焼）(3)する。仮焼（焙焼）(3)を終えた粉
体に粒界層成分としてPbOを好ましくは重量比で
0.5〜10wt％添加する(4)。それらを再びボールミ
ル等によつて混合(5)する。しかる後にこの調整粉
末に水、あるいはポリビニルアルコールなどの粘
結剤を添加配合し、0.1〜2ton／cm3程度の圧力で
金型等を用いて成形(6)する。又、成形は、ロール
方法、ドクターグレード方法による薄板でも可能
である。成形体を1000〜1270℃程度の温度で１〜
10時間焼成(7)する。焼結を終えた試料をガラス、
又はテフロン製の密閉出来る容器に入れ、５〜30
％の塩酸で１〜24時間粒界層のPbOを溶かし出す
酸処理(8)を施す。
得られた焼結体粒子は水酸化カリウム等で中和
(9)した後に充分に水洗い(10)を行い、乾燥(11)させて
圧電セラミツク微粒子を得る。
なお粒界層を溶かし出す酸は塩酸のみならず、
硝酸、硫酸等、およびそれらの混合物を用いても
さしつかえない。又、化学的エツチングの速度を
早めるために加熱する方法を用いても良い。又、
圧電セラミツク材料はチタンジルコン酸鉛系圧電
材料、チタン酸鉛系圧電材料、複合三成分系圧電
材料、タングステンブロンズ型圧電セラミツク材
料いずれを用いても本発明の方法は適用出来る。
又、焼成温度、焼成時間、添加物を変化させるこ
とにより１〜50μmの所望の単一の焼結粒子から
成る圧電セラミツク微粒子が得られる。
なお本発明における粒界層成分としては、PbO
を圧電セラミツク焼結体に対し0.5％〜10wt％と
する事が好ましい。これは0.5％未満では酸によ
るエツチング工程の際に圧電セラミツク微粒子
（焼結体粒子）も侵されてしまうためであり、又、
10wt％以下としたのは10wt％を越えると粒界層
を取り除くのにエツチング時間が長くなり実用的
でないためである。
本発明により得られた圧電セラミツク微粒子が
特に高分子との複合圧電体において良好な圧電特
性を示すことを確認するために本発明により得ら
れた圧電セラミツク微粒子（平均粒径6μm）と従
来のボールミル等の機械的粉砕方法により得られ
た圧電セラミツク微粒子（平均粒径6μm）をそれ
ぞれ用意した。高分子マトリツクスとしてPVDF
の粉末と可塑剤として弗素ゴムを用い上記圧電セ
ラミツク微粒子との混合物を180〜200℃の混練ロ
ール機で複合化(12)した後、200℃の熱プレス（150
Kg／cm3）で30分間プレスし、冷水を通じて冷却
し、100〜300μmの複合シートを得た。
シートの表面にAu，Ag等を真空蒸着し、次い
で120℃の恒温槽中で所定の電圧下で分極を施し
た。分極を終えた試料から圧電定数を測定するた
めに40mm×10mmを切り出した。測定の結果を従来
の機械的粉砕方法により製造した圧電セラミツク
微粒子と比較して第１表に示す。
第１表の結果より明らかな様に本発明により製
造した圧電セラミツク微粒子を用いた複合圧電体
の圧電定数は従来の機械的粉砕方法により得られ
た圧電セラミツク微粒子を用いたものより同量の
複合率において大きい値を示した。又、従来の方
法により得られた圧電セラミツク微粒子を用いた
場合、95体積％以上の複合圧電材料を製造するこ
とが困難であつたが本発明により得られた圧電セ
ラミツク微粒子を用いることにより95体積％の複
合圧電材料の製造が可能となつた。これらの結果
は実施例５，６、参考例５，６で示された様に
PbTiO3を主成分とする材料系においても同様で
あつた。
The present invention relates to a method for producing piezoelectric ceramic particles, and more particularly to a method for producing piezoelectric ceramic particles each having a spherical shape and consisting of a single sintered particle, and particularly to a method for producing composite piezoelectric materials with polymers, etc. It is suitable for Piezoelectric ceramic materials are widely used as electrical and mechanical energy conversion elements.
In recent years, a composite piezoelectric material made of polymers such as PVF 2 and piezoelectric ceramic particles has made remarkable progress. This composite piezoelectric material is highly flexible and has a large piezoelectric effect by changing the composite ratio of polymer and piezoelectric ceramic fine particles (piezoelectric ceramic weight %/polymer weight % + piezoelectric ceramic weight %). can be manufactured and used as switching elements for keyboards and ultrasonic transducers. Piezoelectric ceramic fine particles used for these applications have conventionally been produced by sintering or roasting sintered bodies or roasted powders in alumina or polyethylene pots using alumina, agate, stainless steel, or cobblestones treated with resin. mechanically crushed to 1-50μm,
The particles were sieved by particle size, mixed with polymers, and used to manufacture composite piezoelectric materials. However, the piezoelectric ceramic particles obtained by conventional mechanical grinding have a wide variety of shapes, and the particle size distribution is large, so piezoelectric ceramic particles with uniform particle size cannot be obtained unless sieving is performed. In addition, impurities from cobbles and pots inevitably deteriorate the piezoelectric properties. In particular, obtaining piezoelectric ceramic particles with a sintered particle size of 2 μm or less requires grinding for a long time, which is not industrially practical. Furthermore, since the mechanical crushing method is used, the sintered particles are not separated from the grain boundaries, and it is unavoidable that particles in a shape where the sintered particles are partially broken are mixed in. For this reason, the sintered fine particles, which do not contribute to the improvement of piezoelectricity, are combined with the polymer, which is not practically effective. Furthermore, in Japanese Patent Publication No. 55-153381, a piezoelectric ceramic sintered body is mechanically ground using a pot mill to a particle size close to that of the sintered body particles, and then thoroughly soaked in a mixed solution of H 2 O, HF, and HNO 3 . A method is described in which fine particles are obtained by dipping and etching for a few seconds, and then calcined again, but these methods also have the disadvantages mentioned above, such as contamination with impurities, irregularity in the shape of fine particles, and problems with sieving. However, the problem that the piezoelectricity is not significantly improved in proportion to the composite ratio cannot be solved even if fine particles produced by these methods are used. The present invention improves the above-mentioned drawbacks, and provides fine particles consisting of a single sintered particle, in which each piezoelectric ceramic particle is approximately spherical in shape, has a uniform particle size distribution, and does not contain any impurities. This is a method for producing piezoelectric ceramic fine particles that exhibit great piezoelectricity when used as a composite piezoelectric material with The present invention achieves the above object without using conventional mechanical crushing methods, and involves acid treatment of a piezoelectric ceramic sintered body consisting of sintered body particles and a grain boundary layer mainly composed of lead oxide. This is a method for producing piezoelectric ceramic fine particles in which the grain boundary layer is removed by etching. In other words, the present invention does not mechanically crush a sintered body or roasted powder as in the conventional method, but actively precipitates grain boundary layer components that have a high etching rate with acid around the sintered body particles. It is manufactured by chemically removing the grain boundary layer with acid and taking out only the sintered particles. Such piezoelectric ceramic fine particles according to the present invention are manufactured, for example, as shown in FIG. For example, PbO, TiO 2 , ZrO 2 , CoO, WO 3 , MnO
Using raw materials such as Pb[(Co 1/2 W 1/2 ) 0.08 Ti 0.47 Zr 0.45
]
Accurately evaluate the composition to obtain a composition of O 3 +0.8wt%MnO (1)
I went to Mix them using a ball mill etc.(2)
However, the raw material used at this time may be a compound that converts into an oxide by heating, such as a hydroxide or a carbonate. Next, the mixture is calcined (roasted) (3) at, for example, about 700 to 1100°C. Add PbO as a grain boundary layer component to the powder after calcination (roasting) (3), preferably in a weight ratio.
Add 0.5-10wt% (4). They are mixed again using a ball mill or the like (5). Thereafter, water or a binder such as polyvinyl alcohol is added to the prepared powder and molded using a mold or the like at a pressure of about 0.1 to 2 ton/cm 3 (6). Further, forming a thin plate by a roll method or a doctor grade method is also possible. The molded body is heated at a temperature of about 1000 to 1270℃.
Bake for 10 hours (7). The sample after sintering is made into glass,
Or put it in an airtight Teflon container for 5 to 30 minutes.
% hydrochloric acid for 1 to 24 hours to dissolve PbO in the grain boundary layer (8). The obtained sintered particles are neutralized with potassium hydroxide etc.
After (9), it is thoroughly washed with water (10) and dried (11) to obtain piezoelectric ceramic fine particles. The acid that dissolves the grain boundary layer is not only hydrochloric acid, but also
Nitric acid, sulfuric acid, etc., and mixtures thereof may also be used. Alternatively, a heating method may be used to speed up the chemical etching. or,
The method of the present invention can be applied to any of the piezoelectric ceramic materials, including lead titanium zirconate-based piezoelectric materials, lead titanate-based piezoelectric materials, composite three-component piezoelectric materials, and tungsten bronze type piezoelectric ceramic materials.
Furthermore, by changing the firing temperature, firing time, and additives, piezoelectric ceramic fine particles consisting of a desired single sintered particle of 1 to 50 μm can be obtained. Note that the grain boundary layer component in the present invention is PbO
is preferably 0.5% to 10wt% of the piezoelectric ceramic sintered body. This is because if it is less than 0.5%, the piezoelectric ceramic fine particles (sintered body particles) will also be attacked during the acid etching process.
The reason for setting it below 10 wt% is that if it exceeds 10 wt%, the etching time will be long to remove the grain boundary layer, which is not practical. In order to confirm that the piezoelectric ceramic fine particles obtained according to the present invention exhibit good piezoelectric properties especially in a composite piezoelectric material with a polymer, piezoelectric ceramic fine particles obtained according to the present invention (average particle size 6 μm) and a conventional ball mill were used. Piezoelectric ceramic fine particles (average particle size 6 μm) obtained by a mechanical crushing method such as the above were prepared. PVDF as polymer matrix
A mixture of the above powder and the piezoelectric ceramic fine particles using fluororubber as a plasticizer was compounded using a kneading roll machine at 180 to 200°C (12), followed by a heat press at 200°C (150°C).
Kg/cm 3 ) for 30 minutes and cooled through cold water to obtain a composite sheet of 100-300 μm. Au, Ag, etc. were vacuum-deposited on the surface of the sheet, and then polarization was performed under a predetermined voltage in a constant temperature bath at 120°C. After polarization, a 40 mm x 10 mm piece was cut out to measure the piezoelectric constant. The measurement results are shown in Table 1 in comparison with piezoelectric ceramic fine particles produced by a conventional mechanical crushing method. As is clear from the results in Table 1, the piezoelectric constant of the composite piezoelectric material using the piezoelectric ceramic fine particles produced according to the present invention is higher than that of the composite piezoelectric material using the same amount of piezoelectric ceramic fine particles obtained by the conventional mechanical crushing method. showed a large value in the ratio. Furthermore, when using piezoelectric ceramic fine particles obtained by the conventional method, it was difficult to produce a composite piezoelectric material with a volume of 95% or more, but by using the piezoelectric ceramic fine particles obtained by the present invention, it was difficult to produce a composite piezoelectric material with a volume of 95% or more. % of composite piezoelectric materials. These results are as shown in Examples 5 and 6 and Reference Examples 5 and 6.
The same was true for the material system containing PbTiO 3 as the main component.
【表】
次に上記実施例−１及び参考例−１について各
種比較を行い、その結果を示す。
まず実施例−１、参考例−１により得た圧電セ
ラミツク微粒子の形状をそれぞれ第２図ａ（参考
例−１）、第２図ｂ（実施例−１）として示す。こ
の結果から明らかな如く、実施例−１により得ら
れた圧電セラミツク微粒子は形状がほぼ球状であ
り、個々の圧電セラミツク微粒子が単一の焼結体
粒子（Ａ）からなるのに対し、従来法（参考例−
１）により得られる圧電セラミツク微粒子は形状
が不整いで単一の焼結体粒子が破断したもの、粒
界層（Ｂ）の一部と結合したものが数多く見られ
た。
次得られた圧電セラミツク微粒子の粒度分布を
光透過式粒度分布測定（遠心分離機付き）で求め
た結果を第３図ａ（参考例−１）、第３図ｂ（実施
例−１）として示す。この結果本発明方法で得た
圧電セラミツク微粒子では粒径分布が集中してい
るのに対し、参考例−１では1μm以下の微粒子や
20μm以上の巨大粒子が数多く存在している事が
わかる。
又、実施例２、参考例２の試料を用いて得た複
合圧電体について圧電定数の分極電圧依存性を調
べたところ第４図に示した様な結果が得られた。
なお第４図において曲線ａは参考例２を、曲線ｂ
は実施例２をそれぞれ示す。
本発明による圧電セラミツク微粒子を用いた複
合圧電体はその圧電定数が従来の方法により得ら
れたものより大きい事は明らかである。
以上述べた様に本発明により得られた圧電セラ
ミツク微粒子は優れた特性を有し、工業的に大量
生産出来る等その効果は大きいと言える。[Table] Next, various comparisons were made between the above Example-1 and Reference Example-1, and the results are shown. First, the shapes of the piezoelectric ceramic fine particles obtained in Example-1 and Reference Example-1 are shown in FIG. 2a (Reference Example-1) and FIG. 2B (Example-1), respectively. As is clear from this result, the piezoelectric ceramic fine particles obtained in Example 1 are approximately spherical in shape, and each piezoelectric ceramic fine particle is composed of a single sintered particle (A), whereas the conventional method (Reference example-
The piezoelectric ceramic fine particles obtained by 1) had irregular shapes, and many single sintered particles were broken and many were bonded to part of the grain boundary layer (B). Next, the particle size distribution of the piezoelectric ceramic fine particles obtained was determined by light transmission particle size distribution measurement (with a centrifuge). The results are shown in Figure 3a (Reference Example-1) and Figure 3B (Example-1). show. As a result, the particle size distribution of the piezoelectric ceramic fine particles obtained by the method of the present invention is concentrated, whereas in Reference Example-1, there are fine particles of 1 μm or less.
It can be seen that there are many large particles larger than 20μm. Further, when the dependence of the piezoelectric constant on the polarization voltage of the composite piezoelectric bodies obtained using the samples of Example 2 and Reference Example 2 was investigated, the results shown in FIG. 4 were obtained.
Note that in FIG. 4, curve a represents Reference Example 2, and curve b represents Reference Example 2.
indicate Example 2, respectively. It is clear that the piezoelectric constant of the composite piezoelectric body using piezoelectric ceramic fine particles according to the present invention is larger than that obtained by the conventional method. As described above, the piezoelectric ceramic fine particles obtained according to the present invention have excellent properties, and can be said to have great effects such as being able to be industrially mass-produced.
第１図は本発明の工程例を示す流れ図、第２図
は顕微鏡により観察した従来の方法により得られ
た圧電セラミツク粒子の形状図ａ、本発明により
得られた圧電セラミツク粒子の形状図ｂ、第３図
は従来の方法により得られた圧電セラミツク粒子
の粒度分布を示す図ａ、本発明により得られた圧
電セラミツク粒子の粒度分布を示す図ｂ、第４図
は複合圧電体の圧電定数と分極電圧の関係を示す
関係曲線図をそれぞれ示す。
FIG. 1 is a flowchart showing a process example of the present invention, FIG. 2 is a shape diagram a of piezoelectric ceramic particles obtained by a conventional method observed with a microscope, and a shape diagram b of piezoelectric ceramic particles obtained by the present invention. Figure 3 is a diagram showing the particle size distribution of piezoelectric ceramic particles obtained by a conventional method, diagram b is a diagram showing the particle size distribution of piezoelectric ceramic particles obtained by the present invention, and Figure 4 is a graph showing the piezoelectric constant of the composite piezoelectric material. Relationship curve diagrams showing the relationship between polarization voltages are shown, respectively.
Claims (1)
層からなる圧電セラミツク焼結体に酸処理を施し
前記粒界層をエツチング除去することを特徴とす
る圧電セラミツク微粒子の製造方法。 ２ 特許請求の範囲第１項において粒界層中の酸
化鉛が焼結体に対し、0.5〜10wt％であることを
特徴とする圧電セラミツク微粒子の製造方法。[Scope of Claims] 1. Piezoelectric ceramic fine particles characterized in that a piezoelectric ceramic sintered body consisting of sintered body particles and a grain boundary layer containing lead oxide as a main component is subjected to acid treatment to remove the grain boundary layer by etching. manufacturing method. 2. A method for producing piezoelectric ceramic fine particles according to claim 1, characterized in that lead oxide in the grain boundary layer is 0.5 to 10 wt% based on the sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56156232A JPS5857765A (en) | 1981-10-02 | 1981-10-02 | Preparation of piezoelectric ceramic fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56156232A JPS5857765A (en) | 1981-10-02 | 1981-10-02 | Preparation of piezoelectric ceramic fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5857765A JPS5857765A (en) | 1983-04-06 |
| JPH0325955B2 true JPH0325955B2 (en) | 1991-04-09 |
Family
ID=15623251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56156232A Granted JPS5857765A (en) | 1981-10-02 | 1981-10-02 | Preparation of piezoelectric ceramic fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5857765A (en) |
-
1981
- 1981-10-02 JP JP56156232A patent/JPS5857765A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5857765A (en) | 1983-04-06 |
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