JPS6324948B2 - - Google Patents
Info
- Publication number
- JPS6324948B2 JPS6324948B2 JP55130939A JP13093980A JPS6324948B2 JP S6324948 B2 JPS6324948 B2 JP S6324948B2 JP 55130939 A JP55130939 A JP 55130939A JP 13093980 A JP13093980 A JP 13093980A JP S6324948 B2 JPS6324948 B2 JP S6324948B2
- Authority
- JP
- Japan
- Prior art keywords
- porcelain
- barium titanate
- plane
- barium
- sintered
- 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
Links
- 229910052573 porcelain Inorganic materials 0.000 claims description 20
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 16
- 229910002113 barium titanate Inorganic materials 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- -1 Bi 2 O 2 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は特定の結晶方位が一定面内に配向した
チタン酸バリウム磁器の製造方法を提供しようと
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for manufacturing barium titanate porcelain in which a specific crystal orientation is oriented in a constant plane.
チタン酸バリウムを主成分とする焼結磁器は、
コンデンサや圧電部品材料として広汎に使用され
ており、それぞれの用途に応じて種々の添加物や
工程条件の検討を加えることにより、電気的諸特
性の改善がなされている。電気的諸特性を向上す
る方法として、結晶の電気的特性の異方性を利用
することも可能である。チタン酸バリウムの場
合、周知のごとく、正方晶相のａ軸方向とｃ軸方
向とで誘電率や圧電特性が著しく異なる。従つて
結晶粒子の結晶方位を制御することにより、チタ
ン酸バリウム焼結磁器の電気的性質の制御が可能
である。しかしながらチタン酸バリウム焼結磁器
の作製において、出発原料として、特定の粒子形
状および結晶方位を有する二酸化チタン（TiO2）
や酸化バリウム（BaO）、炭酸バリウム
（BaCO3）等のバリウム化合物の粉末が得られて
いなかつたため、結晶方位の制御された配向性焼
結磁器を作製することは不可能であつた。 Sintered porcelain whose main component is barium titanate is
It is widely used as a material for capacitors and piezoelectric parts, and its electrical properties have been improved by examining various additives and process conditions depending on each application. It is also possible to utilize the anisotropy of the electrical properties of crystals as a method of improving electrical properties. In the case of barium titanate, as is well known, the dielectric constant and piezoelectric properties are significantly different between the a-axis direction and the c-axis direction of the tetragonal phase. Therefore, by controlling the crystal orientation of crystal grains, it is possible to control the electrical properties of barium titanate sintered porcelain. However, in the production of barium titanate sintered porcelain, titanium dioxide (TiO 2 ) with a specific grain shape and crystal orientation is used as a starting material.
Because barium compound powders such as barium oxide (BaO), barium carbonate (BaCO 3 ), etc., had not been obtained, it was impossible to produce oriented sintered porcelain with controlled crystal orientation.
本発明はこのような欠点を除去し、特定の結晶
方位が一定面内に配向したチタン酸バリウム磁器
の製造方法を提供するものである。具体的には例
えばチタン酸バリウムを作製するにあたり、板状
の粒子形状を有する二酸化チタンに着目した。す
なわち四塩化チタン（TiCl4）―酸素（O2）―窒
素（N2）からなる混合ガスを高温中で反応させ
ることにより、Ｃ面が発達した板状形状を有する
アナターゼ型の結晶構造を有する二酸化チタン粒
子を得ることができる。かかる二酸化チタンとバ
リウムを含有する化合物、有機結合剤、可塑剤、
溶剤を混練した後、押出成形法あるいは、ロール
成形法を用いて一軸性の加圧下で成形した成形体
を焼結することにより、特定の結晶方位が一定面
内に配向したチタン酸バリウム焼結磁器が得られ
るものである。このようにして得られたチタン酸
バリウム焼結磁器においては、成形時の加圧方向
に垂直な方向と平行な方向とで誘電率が異なるな
どの電気的異方性を示すことが確認された。かか
る磁器ないしは、これに微量の添加物を含有する
磁器を用いることにより、コンデンサ材料の容量
の向上等をはかることが可能となるなど、本発明
による実用上の効果は、きわめて大なるものがあ
る。 The present invention eliminates these drawbacks and provides a method for manufacturing barium titanate porcelain in which specific crystal orientations are oriented in a constant plane. Specifically, when producing barium titanate, for example, we focused on titanium dioxide having a plate-like particle shape. In other words, by reacting a mixed gas consisting of titanium tetrachloride (TiCl 4 ), oxygen (O 2 ), and nitrogen (N 2 ) at high temperatures, it has an anatase crystal structure with a plate-like shape with a developed C-plane. Titanium dioxide particles can be obtained. Compounds containing such titanium dioxide and barium, organic binders, plasticizers,
After kneading a solvent, the molded body is sintered under uniaxial pressure using an extrusion molding method or a roll molding method, resulting in barium titanate sintered with a specific crystal orientation oriented in a constant plane. Porcelain is what you get. It was confirmed that the barium titanate sintered porcelain obtained in this way exhibits electrical anisotropy such that the dielectric constant is different in the direction perpendicular to and parallel to the direction of pressure applied during molding. . By using such porcelain or porcelain containing a small amount of additives, the practical effects of the present invention are extremely large, such as the ability to improve the capacity of capacitor materials. .
以下実施例にもとづいて詳細に説明する。 A detailed explanation will be given below based on examples.
実施例
四塩化チタン（TiCl4）―酸素（O2）―窒素
（N2）の各濃度が3.9vol％、49.0vol％、47.1vol％
となるよう配合した混合ガスを200ml／minの速
度で980℃の加熱部を通過させ、白色粉体を得た。
この粉体をＸ線回折により相解折を行なうととも
に、その粒子形状を走査型電子顕微鏡により観察
した。その結果、この粉体はアナターゼ型の結晶
構造をもち、一辺が0.5〜1.0μmの板状形状を有し
ていることがわかつた。また電子線回折測定の結
果から、Ｃ面が発達した板状形状粒子であること
が確認された。この二酸化チタンと、平均粒径が
0.2μm以下の微細な酸化バリウムが等モル比とな
るよう秤量した後、混合した。かかる混合粉100
重量部に対して、ブチラール樹脂10重量部、フタ
ル酸ジ―ｎ―ブチル（DBP）10重量部及びイソ
プロピルアルコール15重量部を添加し、ミキシン
グロールで充分に混練した後、押出成形法によ
り、600Kg/cm2の圧力で、厚さ0.6mm、巾1.5cmの生
シートのテープを作製した。かかる生シートテー
プを、3.0cmの長さに切断して、1.5×3.0cm2のシー
トを多数作製し、これらを30枚重ねあわせた後、
金型に入れ、100℃で50Kg/cm2の圧力で圧着成形を
行ない、縦1.5cm、横3.0cm、厚さ約1.3cmの角型成
形体を作製した。この成形体を400℃で10時間保
持して、有機結合剤等を飛散させ、しかる後、
1300℃で２時間焼結することにより、角型の焼結
磁器を作製した。この焼結磁器の一番面積の大き
い面、すなわち、押出成形時において、押出方向
に垂直な面（今後Ａ面と呼ぶ）についてＸ線回折
を行つた結果、（001）（002）などのＣ面の回折強
度が著しく大きくなり、一方他の面の回折強度が
著しく小さくなつた。正方晶系の全回折強度の積
分強度の総和Itに対するＣ面の回折線の積分強度
の総和Icの比Ic／Itは、従来のチタン酸バリウム
焼結磁器に比べて６倍以上の値を示した。このこ
とは、本実施例に示したチタン酸バリウム焼結磁
器のＡ面はＣ面配向していることを示している。Example The respective concentrations of titanium tetrachloride (TiCl 4 ), oxygen (O 2 ), and nitrogen (N 2 ) are 3.9 vol%, 49.0 vol%, and 47.1 vol%.
A mixed gas blended so that
This powder was subjected to phase analysis using X-ray diffraction, and its particle shape was observed using a scanning electron microscope. As a result, it was found that this powder had an anatase crystal structure and a plate-like shape with a side of 0.5 to 1.0 μm. Further, from the results of electron beam diffraction measurement, it was confirmed that the particles were plate-shaped particles with a developed C-plane. This titanium dioxide and the average particle size are
Fine barium oxide particles of 0.2 μm or less were weighed and mixed in an equimolar ratio. Mixed powder takes 100
Based on the weight part, 10 parts by weight of butyral resin, 10 parts by weight of di-n-butyl phthalate (DBP) and 15 parts by weight of isopropyl alcohol were added, and after sufficiently kneading with a mixing roll, it was extruded to produce 600 kg. A green sheet tape with a thickness of 0.6 mm and a width of 1.5 cm was produced under a pressure of /cm 2 . The raw sheet tape was cut to a length of 3.0 cm to produce a large number of 1.5 x 3.0 cm 2 sheets, and 30 of these were stacked together.
It was placed in a mold and pressure-molded at 100° C. with a pressure of 50 kg/cm 2 to produce a rectangular molded product measuring 1.5 cm long, 3.0 cm wide and about 1.3 cm thick. This molded body was held at 400℃ for 10 hours to scatter the organic binder, and then
Square sintered porcelain was produced by sintering at 1300°C for 2 hours. As a result of performing X-ray diffraction on the surface with the largest area of this sintered porcelain, that is, the surface perpendicular to the extrusion direction during extrusion molding (hereinafter referred to as A surface), it was found that C The diffraction intensity of one surface became significantly larger, while the diffraction intensity of the other surfaces became significantly smaller. The ratio Ic/It of the total integrated intensity Ic of the C-plane diffraction lines to the total integrated intensity It of the total diffraction intensity of the tetragonal system is more than 6 times that of conventional barium titanate sintered porcelain. Ta. This indicates that the A-plane of the barium titanate sintered porcelain shown in this example is oriented in the C-plane.
次に焼結体磁器のＡ面に銀を0.5μmの厚みに蒸
着し、誘電率を測定した結果、室温での誘電率は
500であり、無配向のチタン酸バリウム磁器に比
べて約1/3となることがわかつた。一方Ａ面と垂
直な面の一つと、それに相対する面にも同様に銀
電極を設け、室温での誘電率を測定した結果、そ
の値は約2800であり、無配向のチタン酸バリウム
磁器に比べて約1.8倍以上も大きくなることがわ
かつた。 Next, silver was evaporated to a thickness of 0.5 μm on the A side of the sintered porcelain, and the dielectric constant was measured. As a result, the dielectric constant at room temperature was
500, which is approximately 1/3 that of non-oriented barium titanate porcelain. On the other hand, silver electrodes were similarly placed on one of the planes perpendicular to the A plane and on the opposite plane, and the dielectric constant was measured at room temperature.The value was approximately 2800, which is the same as that of non-oriented barium titanate porcelain. It was found that the size is about 1.8 times larger than that of the previous one.
また誘電的及び圧電的性質を制御するために従
来から用いられているMgO、SiO2、SrO、
La2O3、Bi2O2、MnO2、CoO、Cr2O3などの微量
成分を添加しても何らさしつかえないことは言う
までもない。さらに一軸性の加圧法として本実施
例では、押出成形法を用いたが、この他、ロール
法を用いても、同様の配向性の制御が可能である
ことも明らかである。 In addition, MgO, SiO 2 , SrO, which has been traditionally used to control dielectric and piezoelectric properties,
It goes without saying that there is no harm in adding trace components such as La 2 O 3 , Bi 2 O 2 , MnO 2 , CoO, Cr 2 O 3 . Furthermore, although an extrusion molding method was used in this example as a uniaxial pressing method, it is clear that similar control of orientation is also possible by using a roll method.
以上の実施例からも明らかなように、本発明に
よればＣ面が発達した板状形状を有する二酸化チ
タンとバリウムを含有する化合物（たとえば酸化
バリウムあるいは炭酸バリウム等）、有機結合剤、
可塑剤、及び溶剤を混練した後、一軸性の加圧下
で成形体ないしは、これをさらに任意形状に再生
形した成形体を焼結することにより、正方晶相の
Ｃ面配向したチタン酸バリウム焼結磁器を作るこ
とが可能である。このような磁器においては、結
晶粒子の配向度を調節することにより、誘電率を
制御できるという大きな特徴がある。またこの結
果、かかるチタン酸バリウム焼結磁器を用いるこ
とにより、従来得ることの出来なかつた種々の誘
電性を有するコンデンサや圧電応用部品の作製が
可能になるほど、本発明の効果は非常に大きいも
のである。 As is clear from the above examples, according to the present invention, a compound containing titanium dioxide and barium (such as barium oxide or barium carbonate) having a plate-like shape with a developed C-plane, an organic binder,
After kneading the plasticizer and the solvent, the molded product or the molded product further regenerated into an arbitrary shape is sintered under uniaxial pressure to produce barium titanate sintered with a C-plane orientation in the tetragonal phase. It is possible to make porcelain ware. A major feature of such ceramics is that the dielectric constant can be controlled by adjusting the degree of orientation of crystal grains. Furthermore, as a result, the effects of the present invention are so great that by using such barium titanate sintered porcelain, it is possible to manufacture capacitors and piezoelectric application parts having various dielectric properties that could not be obtained conventionally. It is.
Claims (1)
ン、バリウムを含有する化合物、有機結合剤、可
塑剤及び溶剤を混練した後、一軸性の加圧下で成
形した成形体を焼成することを特徴とするチタン
酸バリウム磁器の製造方法。1. After kneading titanium dioxide having a plate-like shape with a developed C-plane, a barium-containing compound, an organic binder, a plasticizer, and a solvent, the molded product is fired under uniaxial pressure. A method for manufacturing barium titanate porcelain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55130939A JPS5756380A (en) | 1980-09-19 | 1980-09-19 | Manufacture of barium titanate ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55130939A JPS5756380A (en) | 1980-09-19 | 1980-09-19 | Manufacture of barium titanate ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5756380A JPS5756380A (en) | 1982-04-03 |
| JPS6324948B2 true JPS6324948B2 (en) | 1988-05-23 |
Family
ID=15046211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55130939A Granted JPS5756380A (en) | 1980-09-19 | 1980-09-19 | Manufacture of barium titanate ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5756380A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021043990A1 (en) | 2019-09-04 | 2021-03-11 | Tarsia Antonio | A teat |
-
1980
- 1980-09-19 JP JP55130939A patent/JPS5756380A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021043990A1 (en) | 2019-09-04 | 2021-03-11 | Tarsia Antonio | A teat |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5756380A (en) | 1982-04-03 |
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