JPH0766691B2 - Method for manufacturing sintered body for high frequency dielectric - Google Patents
Method for manufacturing sintered body for high frequency dielectricInfo
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- JPH0766691B2 JPH0766691B2 JP2005295A JP529590A JPH0766691B2 JP H0766691 B2 JPH0766691 B2 JP H0766691B2 JP 2005295 A JP2005295 A JP 2005295A JP 529590 A JP529590 A JP 529590A JP H0766691 B2 JPH0766691 B2 JP H0766691B2
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- oxide
- sintered body
- calcined product
- complex oxide
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、高周波誘電体用焼結体の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for manufacturing a sintered body for a high frequency dielectric.
従来、マイクロ波領域において高誘電率および高Ｑ値を
もつ高周波誘電体用焼結体として、BaMg1/3Ta2/3O3（＝
Ba3MgTa2O9）であらわされるペロブスカイト型高周波誘
電体用焼結体（以下、適宜「BMT焼結体」と称すること
がある）がある。Conventionally, BaMg 1/3 Ta 2/3 O 3 (= is used as a high-frequency dielectric sintered body having a high dielectric constant and a high Q value in the microwave region.
There is a perovskite type high frequency dielectric sintered body represented by Ba 3 MgTa 2 O 9 ) (hereinafter sometimes referred to as “BMT sintered body” as appropriate).
焼結体は、原料配合物を仮焼して得た仮焼物を本焼成し
焼結させることで得られている。しかし、BMT焼結体
は、一般に、誘電特性の良い焼結体を歩留まりよく得る
ことが困難であるとされている。得られた焼結体の緻密
度が低かったり、焼結体にクラックが入っていたりする
ことが多いからである。The sintered body is obtained by calcining and calcining the calcined product obtained by calcining the raw material mixture. However, it is generally said that it is difficult to obtain a BMT sintered body having a good dielectric property with a high yield. This is because the density of the obtained sintered body is low, and the sintered body often has cracks.
緻密度を高めるために、本焼成での昇温速度を100℃／
分と急速に上げる方法が提案されているが、この急速昇
温構成では、焼成コストが高くて電子デバイス（例え
ば、共振器）の低価格化が困難であるため、量産に適さ
ず実用性が薄い。In order to increase the compactness, the temperature increase rate in the main firing is 100 ° C /
Although a method of rapidly increasing the temperature has been proposed, this rapid temperature rising configuration is not suitable for mass production because it is difficult to reduce the cost of electronic devices (for example, resonators) because the firing cost is high. thin.
上記事情に鑑み、この発明は、誘電特性の優れた高周波
誘電体用焼結体を歩留まりよく安価に製造することので
きる量産性に富む方法を提供することを課題とする。In view of the above circumstances, an object of the present invention is to provide a mass-productive method capable of manufacturing a sintered body for a high-frequency dielectric having excellent dielectric properties at a good yield and at a low cost.
発明者は、上記課題を解決するため、BMT焼結体につい
て、様々な方向から検討し、つぎのようなことを見出し
た。すなわち、1000〜1100℃程度で仮焼した粉末を焼成
して得た焼結体には、クラック発生があるために誘電特
性は十分でないが、緻密度は十分に高いということを、
他方、1300〜1400℃程度で仮焼した粉末を焼成して得た
焼結体には、、クラックの発生はないが緻密度で劣ると
いうことを見出した。そこで、その原因を詳しく検討し
た結果、仮焼温度1000〜1100℃の仮焼物では、少量のBa
Ta2O6が生成されているが、仮焼温度1300〜1400℃の仮
焼物では、BaTa2O6が事実上生成されていないことが分
かり、このBaTa2O6がBMT焼結体の緻密度を向上させてい
るのではないかと推察し、1300程度を越える温度で十分
に仮焼したBaMg1/3Ta2/3O3であらわされる難焼結性仮焼
物に、少量のBaTa2O6を積極的に添加すれば、クラック
発生を抑制しつつ、緻密度の高い焼結体とすることがで
きるのではないかと推定し、実験によってこの推定の正
しいことを確かめた結果、ここに、この発明を完成させ
ることができたのである。In order to solve the above problems, the inventor studied the BMT sintered body from various directions and found the following. That is, in the sintered body obtained by firing the powder calcined at about 1000 to 1100 ° C., the dielectric properties are not sufficient because of the occurrence of cracks, but the compactness is sufficiently high.
On the other hand, it was found that the sintered body obtained by firing the powder calcined at about 1300 to 1400 ° C does not have cracks but is inferior in compactness. Therefore, as a result of detailed examination of the cause, a small amount of Ba was found in the calcined product at a calcination temperature of 1000 to 1100 ° C.
While ta 2 O 6 is generated, the calcined product of calcining temperature 1300-1400 ° C., found that BaTa 2 O 6 is not generated effectively, dense this BaTa 2 O 6 is BMT sintered body It is speculated that the temperature may be improved, and a small amount of BaTa 2 O is added to the non-sinterable calcined product represented by BaMg 1/3 Ta 2/3 O 3 which has been sufficiently calcined at a temperature exceeding 1300. It is estimated that if 6 is positively added, it is possible to make a sintered compact with high density while suppressing crack generation, and as a result of confirming the correctness of this estimation by experiments, here, This invention has been completed.
したがって、この発明のペロブスカイト型高周波誘電体
用焼結体のＡ、Ｂ、Ｃの記号でそれぞれ表す元素または
元素団およびＯで表す酸素の構成比率がAB1/3C2/3O3で
あらわされるペロブスカイト型高周波誘電体用焼結体を
得る方法であり、AB1/3C2/3O3であらわされる仮焼物に
A,C複合酸化物を添加して1300℃以上で焼成する。Therefore, in the sintered body for perovskite type high frequency dielectric material of the present invention, the composition ratio of the element or element group represented by the symbols A, B and C and the oxygen represented by O is represented by AB 1/3 C 2/3 O 3 . Is a method for obtaining a perovskite-type high-frequency dielectric sintered body, which can be used as a calcined material represented by AB 1/3 C 2/3 O 3.
Add A and C complex oxides and fire at 1300 ℃ or higher.
AB1/3C2/3O3であらわされる仮焼物のＡ、Ｂ、Ｃと、A,C
複合酸化物のＡ、Ｃとは、下記Ａ、Ｂ、Ｃの中から適宜
選んで組み合わされる。AB 1/3 C 2/3 O 3 A, B, C and A, C
The composite oxides A and C are appropriately selected and combined from the following A, B and C.
A;Ba、Sr、Ba1-XSrX B;Mg、Zn、Ni、Mn C;Ta、Nb BMT焼結体を得るための仮焼物は、例えば、請求項２記
載のように、BaMg1/3Ta2/3O3であらわされるものが挙げ
られ、この場合における好ましい複合酸化物はBaTa2O6
である。さらには、請求項３のように、仮焼物が（Ba
1-XSrX）B1/3C2/3O3であらわされる仮焼物もあり（但
し、０＜Ｘ＜１である）、この場合、A,C複合酸化物
に、Ba,C複合酸化物およびSr,C複合酸化物の少なくとも
一方を用いるようにする。A; Ba, Sr, Ba 1-X Sr X B; Mg, Zn, Ni, Mn C; Ta, Nb The calcined material for obtaining the BMT sintered body is, for example, BaMg 1 / 3 Ta 2/3 O 3 and the preferred complex oxide in this case is BaTa 2 O 6
Is. Furthermore, as in claim 3, the calcined product is (Ba
There is also a calcined product represented by 1-X Sr X ) B 1/3 C 2/3 O 3 (provided that 0 <X <1). In this case, A, C complex oxide is mixed with Ba, C complex oxide. At least one of the oxide and the Sr, C composite oxide is used.
この発明では、請求項４のように、A,C複合酸化物に加
えて、これと合わせてAB1/3C2/3O3であらわされるペロ
ブスカイト型化合物を生成する酸化物をも添加するよう
にしてもよい。例えば、前記BMT焼結体を得る場合に
は、複合酸化物BaTa2O6に下記〜のいずれかの酸化
物を併せて添加するようにするのである。According to the present invention, as in claim 4, in addition to the A, C composite oxide, an oxide which produces a perovskite type compound represented by AB 1/3 C 2/3 O 3 is also added together with the A, C composite oxide. You may do it. For example, when obtaining the BMT sintered body, any one of the following oxides is added to the composite oxide BaTa 2 O 6 .
BaOとMgO BaCO3とMgO Ba2MgO3 すなわち、前記記号Ａ、Ｂ、Ｏで表現すると、前記仮焼
物に前記A,C複合酸化物とともに、Ａの酸化物とＢの
酸化物との組み合わせ、Ａの炭酸化物とＢの酸化物と
の組み合わせ、および、A,B複合酸化物のうちの何れ
か１組または１種をさらに添加して焼成するのである。BaO and MgO BaCO 3 and MgO Ba 2 MgO 3 That is, when expressed by the symbols A, B, and O, the calcined product together with the A, C complex oxide, a combination of an oxide of A and an oxide of B, The combination of the carbon oxide of A and the oxide of B, and any one set or one of A and B composite oxides are further added and fired.
この発明では、請求項５のように、AB1/3C2/3O3であら
わされる仮焼物1molに対しA,C複合酸化物を0.001〜0.40
molの割合で添加するのが良い。0.001molを下回ると十
分な添加効果を確保することが難しく、0.40molを上回
ると却って十分な誘電特性や緻密度の焼結体が得にくく
なるからである。In the present invention, as in claim 5, 0.001 to 0.40 of A, C complex oxide is added to 1 mol of the calcined product represented by AB 1/3 C 2/3 O 3.
It is better to add it in a mol ratio. This is because if it is less than 0.001 mol, it is difficult to secure a sufficient addition effect, and if it exceeds 0.40 mol, it is rather difficult to obtain a sintered body having sufficient dielectric properties and denseness.
なお、ペロブスカイト型高周波誘電体用焼結体を得るた
めの仮焼物と、添加される複合酸化物および併用酸化物
の他の組み合わせとしては、下記のようなものが挙げら
れる。Other combinations of the calcined product for obtaining the perovskite-type high frequency dielectric sintered body, and the added complex oxide and the combined oxide are as follows.
(a) 仮焼物；BaZn1/2Ta2/3O3の場合 複合酸化物；BaTa2O6 併用酸化物；BaOとZnO、BaCO3とZnO、Ba2ZnO3の
うちのいずれか。(a) Calcined product; in the case of BaZn 1/2 Ta 2/3 O 3 Complex oxide; BaTa 2 O 6 combined oxide; BaO and ZnO, BaCO 3 and ZnO, or Ba 2 ZnO 3 .
(b) 仮焼物：BaNi1/3Ta2/3O2の場合 複合酸化物；BaTa2O6 併用酸化物；BaOとNiO、BaCO3とNiO、Ba2NiO3の
うちのいずれか。(b) Calcined product: In the case of BaNi 1/3 Ta 2/3 O 2 Complex oxide; BaTa 2 O 6 combined oxide; BaO and NiO, BaCO 3 and NiO, or Ba 2 NiO 3 .
(c) 仮焼物；BaMn1/3Ta2/3O3の場合複合酸化物；BaTa2
O6 併用酸化物；BaO2とMnO、BaCO3とMnO、Ba2MnO3の
うちのいずれか。(c) Calcined product; BaMn 1/3 Ta 2/3 O 3 In case of complex oxide; BaTa 2
O 6 combined oxide; any one of BaO 2 and MnO, BaCO 3 and MnO, and Ba 2 MnO 3 .
(d) 仮焼物：BaMg1/3Nb2/3O3の場合 複合酸化物；BaNbO3 併用酸化物；BaOとMgO、BaCO3とMgO、Ba2MgO3の
うちのいずれか。(d) Calcined product: In the case of BaMg 1/3 Nb 2/3 O 3 Complex oxide; BaNbO 3 combined oxide; BaO and MgO, BaCO 3 and MgO, or Ba 2 MgO 3 .
(e) 仮焼物：BaZn1/3Nb2/3O3の場合 複合酸化物；BaNbO3 併用酸化物；BaOとZnO、BaCO3とZnO、Ba2ZnO3の
うちのいずれか。(e) Calcined product: In the case of BaZn 1/3 Nb 2/3 O 3 Complex oxide; BaNbO 3 combined oxide; BaO and ZnO, BaCO 3 and ZnO, or Ba 2 ZnO 3 .
(f) 仮焼物：BaMn1/3Nb2/3O3の場合 複合酸化物；BaNbO3 併用酸化物；BaOとMnO、BaCO3とMnO、Ba2MnO3の
うちのいずれか。(f) Calcined product: In the case of BaMn 1/3 Nb 2/3 O 3 Complex oxide; BaNbO 3 combined oxide; BaO and MnO, BaCO 3 and MnO, or Ba 2 MnO 3 .
(g) 仮焼物：SrMg1/3Ta2/3O3の場合 複合酸化物；SrTa2O6 併用酸化物；SrOとMgO、SrCO3とMgO、SrMgO3のう
ちのいずれかが挙げられる。(g) Calcined product: In the case of SrMg 1/3 Ta 2/3 O 3 Complex oxide; SrTa 2 O 6 combined oxide; any one of SrO and MgO, SrCO 3 and MgO, and SrMgO 3 .
(h) 仮焼物：SrZn1/3Ta2/3O3の場合 複合酸化物；SrTa2O6 併用酸化物；SrOとZnO、SrCO3とZnO、SrZnO3のう
ちのいずれかが挙げられる。(h) Calcined product: In the case of SrZn 1/3 Ta 2/3 O 3 Complex oxide; SrTa 2 O 6 combined oxide; any one of SrO and ZnO, SrCO 3 and ZnO, and SrZnO 3 .
(i) 仮焼物：SrNi1/3Ta2/3O3の場合 複合酸化物；SrTa2O6 併用酸化物；SrOとNiO、SrCO3とNiO、SrNiO3のう
ちのいずれかが挙げられる。(i) Calcined product: In the case of SrNi 1/3 Ta 2/3 O 3 Complex oxide; SrTa 2 O 6 combined oxide; SrO and NiO, SrCO 3 and NiO, or SrNiO 3 .
(j) 仮焼物：Ba1-XSrxMg1/3Ta2/3O3の場合 但し;0＜
Ｘ＜１ １−Ｘ≧Ｘの場合 複合酸化物イ；BaTa2O6 併用酸化物イ；BaOとMgO、BaCO3とMgO、Ba2MgO8
のうちのいずれか。(j) Calcined: Ba 1-X SrxMg 1/3 Ta 2/3 O 3 ;
In the case of X <11 1−X ≧ X Complex oxide a; BaTa 2 O 6 combined oxide a; BaO and MgO, BaCO 3 and MgO, Ba 2 MgO 8
One of.
１−Ｘ≦Ｘの場合 複合酸化物ロ；SrTa2O6 併用酸化物ロ；SrO2とMgO、SrCO3とMgO、Sr2MgO3
のうちのいずれか。In the case of 1-X ≦ X, composite oxide B; SrTa 2 O 6 combined oxide B; SrO 2 and MgO, SrCO 3 and MgO, Sr 2 MgO 3
One of.
さらには、比率に応じて複合酸化物イ，ロや併用酸化物
イ、ロを併せて用いるようにしてもよい。Further, the composite oxides a and b or the combined oxides a and b may be used together depending on the ratio.
(k) 仮焼物：Ba1-XSrxNi1/3Ta2/3O3の場合 但し;0＜
Ｘ＜１ １−Ｘ≧Ｘの場合 複合酸化物イ；BaTa2O6 併用酸化物イ；BaOとNiO、BaCO3とNiO、Ba2NiO3
のうちのいずれか。(k) Calcined product: Ba 1-X SrxNi 1/3 Ta 2/3 O 3 ;
In the case of X <11 1−X ≧ X, complex oxide B; oxide used in combination with BaTa 2 O 6 ; BaO and NiO, BaCO 3 and NiO, Ba 2 NiO 3
One of.
１−Ｘ≦Ｘの場合 複合酸化物ロ；SrTa2O6 併用酸化物ロ；SrO2とNiO、SrCO3とNiO、Sr2NiO3
のうちのいずれか。In the case of 1-X ≦ X, composite oxide B; oxide used in combination with SrTa 2 O 6 ; SrO 2 and NiO, SrCO 3 and NiO, Sr 2 NiO 3
One of.
さらには、比率に応じて複合酸化物イ，ロや併用酸化物
イ、ロを併せて用いるようにしてもよい。Further, the composite oxides a and b or the combined oxides a and b may be used together depending on the ratio.
このように、この発明において、Ａが複数の元素の場合
（例えばＡ＝Ａ′1-XＡ″X）には、Ａ、Ｃ複合酸化物と
して、Ａ′、Ａ″の元素のうち占有率の高い方の元素の
みの複合酸化物（Ａ′、Ｃ複合酸化物またはＡ″、Ｃ複
合酸化物）が単独で使われたり、あるいは、Ａに複数の
元素の各元素が単独で入った複合酸化物（Ａ′、Ｃ複合
酸化物およびＡ″、Ｃ複合酸化物）が元素占有比率に応
じて併せて使われたり、さらには、Ａに全ての元素が入
った複合酸化物（Ａ′Ａ″、Ｃ複合酸化物）が使われた
りする態様をとる。As described above, in the present invention, when A is a plurality of elements (for example, A = A ′ 1-X A ″ X ), the occupancy ratio of the elements A ′ and A ″ is the A and C composite oxide. A complex oxide containing only the higher element (A ', C complex oxide or A ", C complex oxide) is used alone, or a complex in which A is a mixture of multiple elements Oxides (A ', C complex oxides and A ", C complex oxides) are used together depending on the element occupancy ratio, and further, a complex oxide in which all elements are contained in A (A'A ″, C complex oxide) is used.
この発明では、例えば、BMT焼結体の場合、具体的には
以下のようにして製造する。In the present invention, for example, in the case of a BMT sintered body, it is specifically manufactured as follows.
BaMg1/3Ta2/3O5の化学量論比に従って、出発原料Ba
CO3、MgOおよびTa2O3を計算する。According to the stoichiometric ratio of BaMg 1/3 Ta 2/3 O 5 , the starting material Ba
Calculate CO 3 , MgO and Ta 2 O 3 .
BaCO3の代わりにBaOを用いてもよいが、BaCO3は高純度
で粒径の揃ったものが安価に入手できる。また、MgOの
代わりにMgCO3を用いてもよい。BaO may be used instead of BaCO 3 , but BaCO 3 with high purity and uniform particle size is available at low cost. Further, MgCO 3 may be used instead of MgO.
1000〜1100℃の温度で予備仮焼を行う。予備仮焼
は、後の仮焼や本焼成の際にMgOが揮発するのを避ける
ようにするためのものである。但し、この予備仮焼は省
いてもよい。Pre-calcination is performed at a temperature of 1000-1100 ℃. The preliminary calcination is for avoiding volatilization of MgO during the subsequent calcination or main calcination. However, this preliminary calcination may be omitted.
なお、1000〜1100℃の予備仮焼での固相反応は、 ３（BaCO3）＋MgO＋Ta2O5→αBa3MgTa2O9 ＋β〔BaTa2O6＋2BaCO3＋MgO〕＋（３−２β）CO2↑ である。Incidentally, the solid-phase reaction in the preliminary calcination of 1000 to 1100 ° C. is, 3 (BaCO 3) + MgO + Ta 2 O 5 → αBa 3 MgTa 2 O 9 + β [BaTa 2 O 6 + 2BaCO 3 + MgO ] + (3-2β) CO 2 ↑.
予備仮焼を終えた粉末は、冷却後、純粋中で24時間
程度ボール・ミルを用い粉砕し、乾燥してから、1300〜
1400℃の温度で２〜10時間仮焼する。この仮焼は、２回
以上行うことが好ましい。一回の仮焼毎に仮焼物を粉砕
するようにする。この仮焼物は、BaMg1/3Ta2/3O3であら
わされるものとなっている。The powder that has been pre-calcined is cooled, then crushed in a pure ball mill for about 24 hours, dried, and then dried at 1300-
Calcination is performed at a temperature of 1400 ° C for 2 to 10 hours. This calcination is preferably performed twice or more. The calcinated product should be crushed after each calcination. This calcined product is represented by BaMg 1/3 Ta 2/3 O 3 .
なお、1300〜1400℃の仮焼での反応は、 ３（BaCO3）＋MgO＋Ta2O5→Ba3MgTa2O9＋3CO2↑ である。The reaction in calcination at 1300 to 1400 ° C. is 3 (BaCO 3 ) + MgO + Ta 2 O 5 → Ba 3 MgTa 2 O 9 + 3CO 2 ↑.
ここで、仮焼物1molに対してBaTa2O6をP1mol（０＜
P1≦0.05の範囲）添加し、加圧成形により所定形状の圧
粉体にする。Here, BaTa 2 O 6 is added to P 1 mol (0 <
P 1 ≦ 0.05), and press-molding to obtain a green compact with a predetermined shape.
ついで、本焼成を行う。 Then, main firing is performed.
(1) 1550℃以上の温度で２〜５時間焼成する。昇温速
度には特に制限はない。この(1)の焼成は、緻密化を進
行させるためのものである。ついで、 (2) 1200〜1450℃で10〜120時間熱処理する。この(2)
の処理は、BMT結晶を理想的な六方晶とするためになさ
れる。(1) Baking at a temperature of 1550 ° C or higher for 2 to 5 hours. There is no particular limitation on the heating rate. The firing of (1) is for promoting densification. Then, (2) heat treatment at 1200 to 1450 ° C for 10 to 120 hours. This (2)
The treatment (1) is performed to make the BMT crystal an ideal hexagonal crystal.
これにより、優れたBMT焼結体が容易に得られるように
なる。This makes it possible to easily obtain an excellent BMT sintered body.
なお、上記以下を下記のようにしてもよい。The following may be performed as follows.
′ここで、仮焼物1molに対して〔BaTa2O6＋2BaO＋Mg
O〕をP2mol（0.01＜P2≦0.07の範囲）添加し、加圧成形
により所定形状の圧粉体にする。′ Here, [BaTa 2 O 6 + 2BaO + Mg
O] is added to P 2 mol (0.01 <P 2 ≦ 0.07) and pressure molding is performed to obtain a green compact having a predetermined shape.
′ついで、本焼成を行う。′ Then, main firing is performed.
(1)′1550〜1650℃の温度で２〜５時間焼成する。1100
℃までの昇温速度には特に制限はないが、それ以降は、
50℃/hr程度以上とすることが好ましい。この焼成(1)′
は緻密化を進行させるためのものである。ついで、 (2)′1300〜1650℃で10〜200時間熱処理する。この
(2)′の処理は、BaTa2O6、BaO、MgOにおける固相反応に
よりこれらの化合物をBaMg1/3Ta2/3O3として生成させ、
焼結体の母体組成物と同一にすると同時に、BMT結晶を
理想的な六方晶とするためのものである。(1) Calcination is performed at a temperature of 1550 to 1650 ° C for 2 to 5 hours. 1100
There is no particular limitation on the heating rate up to ℃, but after that,
It is preferably about 50 ° C./hr or higher. This firing (1) ′
Is for promoting densification. Then, (2) ′ is heat-treated at 1300 to 1650 ° C. for 10 to 200 hours. this
The treatment of (2) ′ produces these compounds as BaMg 1/3 Ta 2/3 O 3 by solid-state reaction in BaTa 2 O 6 , BaO and MgO,
This is for making the BMT crystal an ideal hexagonal crystal while making it the same as the matrix composition of the sintered body.
また、上記以下を下記のようにしてもよい。The following may be performed as follows.
″ここで、仮焼物1molに対して〔2BaCO3＋2MgO＋BaTa
2O6〕をP3mol（0.01＜P3≦0.40の範囲）添加し、加圧成
形により所定形状の圧粉体にする。″ Here, [2BaCO 3 ＋ 2MgO ＋ BaTa
2 O 6 ] is added to P 3 mol (0.01 <P 3 ≦ 0.40) and pressure molding is performed to obtain a green compact having a predetermined shape.
″ついで、本焼成を行う。″ Then, main firing is performed.
(1)″1550〜1650℃の温度で２〜５時間焼成する。1100
℃までの昇温速度には特に制限はないが、それ以降は、
50℃/hr程度以上とすることが好ましい。この焼成(1)′
は緻密化を進行させるためのものである。ついで、 (2)″1300〜1650℃で10〜200時間熱処理する。この
(2)″の処理は、BaTa2O6、MgO、BaCO3における固相反応
によりこれらの化合物をBaMg1/3Ta2/3O3として生成さ
せ、焼結体の母体組成物と同一にすると同時に、BMT結
晶を理想的な六方晶とするためのものである。(1) Calcination is performed at a temperature of ″ 1550 to 1650 ° C. for 2 to 5 hours.
There is no particular limitation on the heating rate up to ℃, but after that,
It is preferably about 50 ° C./hr or higher. This firing (1) ′
Is for promoting densification. Then, (2) heat treatment at 1300 to 1650 ℃ for 10 to 200 hours.
The treatment of (2) ″ produces these compounds as BaMg 1/3 Ta 2/3 O 3 by solid-state reaction in BaTa 2 O 6 , MgO, and BaCO 3 , and makes them the same as the matrix composition of the sintered body. At the same time, it is for making the BMT crystal an ideal hexagonal crystal.
この発明では、本焼成において添加されるA,C複合酸化
物は、AB1/3C2/2O3であらわされる仮焼物に対し焼結を
促す作用を発揮する。In the present invention, the A, C composite oxide added in the main firing exerts an action of promoting sintering of the calcined product represented by AB 1/3 C 2/2 O 3 .
ペロブスカイト型高周波誘電体用焼結体がBaMg1/3Ta2/3
O3であらわされるものである場合は、他の組成のものの
場合に比べ、誘電特性の優れたものが得やすい。Perovskite type high frequency dielectric sintered body is BaMg 1/3 Ta 2/3
In the case of being expressed by O 3 , it is easier to obtain a material having excellent dielectric properties than in the case of using other compositions.
前記仮焼物に前記A,C複合酸化物とともに、Ａの酸化
物とＢの酸化物との組み合わせ、Ａの炭酸化物とＢの
酸化物との組み合わせ、および、A,B複合酸化物のう
ち何れか１組または１種をも添加するようにする場合に
は、A,C複合酸化物単独の場合に比べ、高Ｑ値のものが
得やすいという利点がある。Any of a combination of an oxide of A and an oxide of B, a combination of a carbonate of A and an oxide of B, and an A, B complex oxide together with the A, C complex oxide in the calcined product. When one set or even one type is added, there is an advantage that a compound having a high Q value can be easily obtained, as compared with the case where only the A, C composite oxide is used.
A,C複合酸化物の添加量がAB1/3C2/3O3であらわされる仮
焼物1molに対し0.001〜0.40molである場合には、焼結促
進作用が確実に発揮されるようになる。When the amount of A, C complex oxide added is 0.001 to 0.40 mol per 1 mol of the calcined product represented by AB 1/3 C 2/3 O 3 , it is possible to ensure that the sintering promoting action is exhibited. Become.
以下、この発明の実施例を説明する。 Examples of the present invention will be described below.
−実施例１〜４− 上記〜に従って、BMT焼結体を得た。-Examples 1 to 4 According to the above, BMT sintered bodies were obtained.
但し、仮焼物1molに対するBaTa2O6の添加割合は、第１
表の通りとした。However, the addition ratio of BaTa 2 O 6 to 1 mol of the calcined product is the first
As shown in the table.
なお、予備仮焼工程では、1100℃、10時間の処理を行
い、仮焼工程では、1300度、10時間の処理を２回行
い、本焼成の(1)焼成工程では、1600℃、２時間の焼
成を行い、(2)焼成工程では、1450℃、100時間の処理を
行った。In the preliminary calcination process, 1100 ° C. and 10 hours were applied, in the calcination process, 1300 ° C. and 10 hours were applied twice, and in the main firing (1) firing step, 1600 ° C. and 2 hours. In (2) firing step, the treatment was performed at 1450 ° C. for 100 hours.
−比較例１− 実施例１において、BaTa2O3を添加しなかった他は、同
様にしてBMT焼結体を得た。- Comparative Example 1 Example 1, except that no addition of BaTa 2 O 3, thereby obtaining the BMT sintered body in the same manner.
−実施例５、６− 上記〜、′、′に従って、BMT焼結体を得た。-Examples 5 and 6-A BMT sintered body was obtained according to the above-, ', and'.
但し、仮焼物1molに対する〔BaTa2O6＋2BaO＋MgO〕の添
加割合は、第１表の通りとした。However, the addition ratio of [BaTa 2 O 6 + 2BaO + MgO] to 1 mol of the calcined product was as shown in Table 1.
なお、予備仮焼工程では、1100℃、10時間の焼成を行
い、′仮焼工程では、1300℃、10時間の焼成を２回行
い、′本焼成の(1)′焼成工程では1600℃、２時間の
焼成を行い、(2)′熱処理工程では、1600℃、80時間の
処理を行った。In the preliminary calcination step, calcination was performed at 1100 ° C for 10 hours, in the ′ calcination step, 1300 ° C, 10 hours calcination was performed twice, and in the ′ (main) (1) ′ calcination step, 1600 ° C, Firing was performed for 2 hours, and in the (2) ′ heat treatment step, treatment was performed at 1600 ° C. for 80 hours.
−比較例２− 〔BaTa2O6＋2BaO＋MgO〕を添加しなかった他は、実施例
５と同様にしてBMT焼結体を得た。- other was not added Comparative Example 2 [BaTa 2 O 6 + 2BaO + MgO] is to give the BMT sintered body in the same manner as in Example 5.
−実施例７〜12− 上記〜、″、″に従って、BMT焼結体を得た。-Examples 7 to 12-BMT sintered bodies were obtained in accordance with the above-, ",".
但し、仮焼物1molに対する〔BaTa2O6MgO＋2BaCO3〕の添
加割合は、第２表の通りである。However, the addition ratio of [BaTa 2 O 6 MgO + 2BaCO 3 ] to 1 mol of the calcined product is as shown in Table 2.
なお、予備仮焼工程では、1100℃、２時間の処理を行
い、″仮焼工程では、1300℃、10時間の焼成を２回行
い、″本焼成の(1)″焼成工程では、1600℃、２時間
の焼成を行い、(2)″熱処理工程では、1600℃、80時間
の処理を行った。In the preliminary calcination step, 1100 ° C. and 2 hours are applied. In the “calcination step, 1300 ° C. and 10 hours firing are performed twice. In the“ main firing (1) ”firing step, 1600 ° C. Firing was performed for 2 hours, and in the (2) ″ heat treatment step, treatment was performed at 1600 ° C. for 80 hours.
−比較例３− 〔BaTa2O6＋MgO＋2BaCO3〕を添加しなかった他は、実施
例７と同様にしてBMT焼結体を得た。- other was not added Comparative Example 3 [BaTa 2 O 6 + MgO + 2BaCO 3 ], thereby obtaining the BMT sintered body in the same manner as in Example 7.
−比較例４− 実施例１において、予備仮焼後の仮焼を行わなかっ
た他は、同様にしてBMT焼結体を得た。-Comparative Example 4-A BMT sintered body was obtained in the same manner as in Example 1 except that calcination after preliminary calcination was not performed.
実施例および比較例について、緻密度（焼結体の相対密
度）を測定するとともに、誘電率とＱ値を誘電体円柱共
振法により測定した。また、クラック発生の有無につい
ても調べた。For the examples and comparative examples, the density (relative density of the sintered body) was measured, and the dielectric constant and Q value were measured by the dielectric cylinder resonance method. Moreover, the presence or absence of cracks was also examined.
なお、クラック発生の有無に関しては、実施例１〜12、
比較例１〜３についてはクラック発生無しであり、比較
例４についてはクラック発生がみられた。 Regarding the presence or absence of cracks, Examples 1 to 12,
No cracks were generated in Comparative Examples 1 to 3, and cracks were observed in Comparative Example 4.
第１、第２表にみるように、実施例の各焼結体は、比較
例１〜４の焼結体と比べ、緻密であり、クラック発生も
なく、優れた誘電特性の誘電体となっていることが分か
る。As can be seen from Tables 1 and 2, each sintered body of the examples is denser than the sintered bodies of Comparative Examples 1 to 4 and has no cracks and has excellent dielectric properties. I understand that.
以上に述べたように、請求項１〜５記載の発明では、AB
1/3C2/3O3であらわされる仮焼物に優れた焼結促進作用
をもつA,C複合酸化物を添加し焼成するようにするた
め、クラックが入らず緻密度も高い優れた高周波誘電特
性の焼結体を歩留まりよく容易に製造することができ
る。As described above, in the inventions according to claims 1 to 5, AB
An excellent high-frequency wave that does not crack and has a high density, because the A / C complex oxide, which has an excellent sintering-promoting effect, is added to the calcined product represented by 1/3 C 2/3 O 3 and fired. A sintered body having dielectric characteristics can be easily manufactured with high yield.
請求項２記載の発明では、ペロブスカイト型高周波誘電
体用焼結体の組成がBaMg1/3Ta2/3O3であるため、誘電特
性が他の組成のものに比べてよく、利用価値が高い。In the invention according to claim 2, since the composition of the sintered body for perovskite type high frequency dielectric is BaMg 1/3 Ta 2/3 O 3 , the dielectric properties are better than those of other compositions and the utility value is high. high.
請求項４記載の発明では、前記仮焼物に前記A,C複合酸
化物とともに前記併用酸化物をも添加することで、これ
らA,C複合酸化物と併用酸化物とが合わされてAB1/3C2/3
O3であらわされるペロブスカイト型化合物となって生成
し焼結体の母体組成と同一となってしまうため、AB1/3C
2/3O3のみ添加する場合に比べてＱ値が高くなるなどの
利点がある。In the invention according to claim 4, by adding the combined oxide together with the A, C complex oxide to the calcined product, the combined oxide of the A, C complex and the combined oxide is combined to produce AB 1/3. C 2/3
As a perovskite type compound represented by O 3 is formed and has the same composition as the matrix of the sintered body, AB 1/3 C
There are advantages such as higher Q value than when only 2/3 O 3 is added.
請求項５記載の発明では、AB1/3C2/3O3であらわされる
仮焼物1molに対しA,C複合酸化物を0.001〜0.40molの割
合で添加しているため、A,C複合酸化物の焼結促進作用
がより確実に発揮される。In the invention of claim 5, since the A, C complex oxide is added in a proportion of 0.001 to 0.40 mol to 1 mol of the calcined product represented by AB 1/3 C 2/3 O 3 , the A, C complex is added. The effect of promoting the sintering of the oxide is more reliably exhibited.
Claims (5)
うちの何れか１種の元素または元素団を表すＡと、Mg、
Zn、Ni、Mnのうちの何れか１種の元素を表すＢと、Taま
たはNbの何れか１種の元素を表すＣと、酸素を表すＯと
の構成比率がAB1/3C2/3O3であらわされるペロブスカイ
ト型高周波誘電体用焼結体を得るにあたり、AB1/3C2/3O
3であらわされる仮焼物にA,C複合酸化物を添加して1300
℃以上で焼成する高周波誘電体用焼結体の製造方法。1. A, which represents any one element or element group of Ba, Sr and Ba 1-X Sr X (where 0 <X <1), and Mg,
The composition ratio of B representing any one element of Zn, Ni and Mn, C representing any one element of Ta or Nb and O representing oxygen is AB 1/3 C 2 / To obtain a perovskite type high frequency dielectric sintered body represented by 3 O 3 , AB 1/3 C 2/3 O
1300 by adding A, C complex oxide to the calcined product represented by 3
A method for producing a sintered body for high frequency dielectrics, which is fired at a temperature of ℃ or higher.
るものであり、前記A,C複合酸化物がBaTa2O6であらわさ
れるものである請求項１記載の高周波誘電体用焼結体の
製造方法。2. The high frequency wave according to claim 1, wherein the calcined product is represented by BaMg 1/3 Ta 2/3 O 3 , and the A, C complex oxide is represented by BaTa 2 O 6. Manufacturing method of sintered body for dielectric.
し、０＜Ｘ＜１）であらわされるものであって、前記A,
C複合酸化物が、Ba,C複合酸化物およびSr,C複合酸化物
の少なくとも一方である請求項１記載の高周波誘電体用
焼結体の製造方法。3. The calcined product is represented by (Ba 1-X Sr X ) B 1/3 C 2/3 O 3 (where 0 <X <1),
The method for producing a sintered body for a high frequency dielectric according to claim 1, wherein the C complex oxide is at least one of Ba, C complex oxide and Sr, C complex oxide.
に、Ａの酸化物とＢの酸化物との組み合わせ、Ａの炭酸
化物とＢの酸化物との組み合わせ、および、A,B複合酸
化物のうちの何れか１組または１種をさらに添加して焼
成する請求項１から３までのいずれかに記載の高周波誘
電体用焼結体の製造方法。4. A combination of an oxide of A and an oxide of B, a combination of a carbon oxide of A and an oxide of B, and an A, B complex together with the A, C complex oxide in the calcined product. The method for producing a sintered body for a high-frequency dielectric according to any one of claims 1 to 3, wherein any one set or one type of oxides is further added and fired.
対しA,C複合酸化物を0.001〜0.40molの割合で添加する
請求項１から４までのいずれかに記載の高周波誘電体用
焼結体の製造方法。5. The method according to any one of claims 1 to 4, wherein the A, C complex oxide is added in a ratio of 0.001 to 0.40 mol to 1 mol of the calcined product represented by AB 1/3 C 2/3 O 3. 1. A method for manufacturing a high frequency dielectric sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005295A JPH0766691B2 (en) | 1990-01-11 | 1990-01-11 | Method for manufacturing sintered body for high frequency dielectric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005295A JPH0766691B2 (en) | 1990-01-11 | 1990-01-11 | Method for manufacturing sintered body for high frequency dielectric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03210704A JPH03210704A (en) | 1991-09-13 |
| JPH0766691B2 true JPH0766691B2 (en) | 1995-07-19 |
Family
ID=11607258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005295A Expired - Fee Related JPH0766691B2 (en) | 1990-01-11 | 1990-01-11 | Method for manufacturing sintered body for high frequency dielectric |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0766691B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05182521A (en) * | 1991-12-31 | 1993-07-23 | Nikko Co | Manufacture of bzt sintered body |
| JP4494725B2 (en) * | 2003-04-18 | 2010-06-30 | 日本特殊陶業株式会社 | Dielectric ceramic composition and manufacturing method thereof |
-
1990
- 1990-01-11 JP JP2005295A patent/JPH0766691B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03210704A (en) | 1991-09-13 |
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