JPH0542082B2 - - Google Patents
Info
- Publication number
- JPH0542082B2 JPH0542082B2 JP61070931A JP7093186A JPH0542082B2 JP H0542082 B2 JPH0542082 B2 JP H0542082B2 JP 61070931 A JP61070931 A JP 61070931A JP 7093186 A JP7093186 A JP 7093186A JP H0542082 B2 JPH0542082 B2 JP H0542082B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- ceo
- cao
- tio
- 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 - Fee Related
Links
- 239000000203 mixture Substances 0.000 claims description 17
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
- Control Of Motors That Do Not Use Commutators (AREA)
Description
産業上の利用分野
本発明はマイクロ波誘電体共振器、マイクロ波
集積回路基板、パツケージ、マイクロ波導波線路
等の電気通信分野及びマイクロ波透過窓、マイク
ロ波積層コンデンサ等において使用されるアルミ
ナ磁器組成物に関する。
従来の技術
近年通信網の発達に伴ない、使用周波数領域が
拡大し、高周波に及んでいる。これと関連して誘
電体磁器は高周波領域に於て、誘電体共振器やマ
イクロ波集積回路基板、各種マイクロ波回路のイ
ンピーダンス整合等に応用されている。
ところでアルミナ磁器は高周波Ｑ値が7000前後
で高いが共振周波数の温度係数τが大きく、通信
分野で望まれている｜τ｜≦30ppm／℃を到底満
足することができず、約−60ppm／℃であるの
で、誘電体材料としては使用が困難であつた。
この問題を解決するためにAl2O3−CaO−TiO2
系材料についてはその高周波誘電特性を改善する
ためにLa2O3の添加が提案され、又、焼成温度の
依存性を緩和するためにCeO2の添加が提案され
ているが、これらを綜合した場合の組成物につい
ては決定的なものは未だ出現していない。
発明が解決しようとする問題点
Al2O3−CaO−TiO2にLa2O3を添加した系では
誘電特性の焼成温度依存性が強く、特性のバラツ
キが大きい。一方CeO2を添加した系では特性上
La2O3を添加した系に劣るという問題があつた。
問題点を解決するための手段
本発明はこの問題点を解決するために鋭意検討
の結果ある一定組成のAl2O3−CaO−TiO2三成分
系に対しLa2O3とCeO2を一定量同時に添加する
ことにより解決した。
その手段はAl2O3、CaO及びTiO2からなる三成
分系磁器組成の配合比が、モル分率で表わした三
成分組成図において、下記の各点を結ぶ直線で囲
まれた内にあり、かつこの組成100重量部に対し、
La2O30.03重量部以上、CeO20.02重量部以上で、
かつLa2O3とCeO2の合計量が0.05〜４重量部を含
有するアルミナ磁器組成物である。
点 Al2O3 CaO TiO2
Ａ 99.0 0.5 0.5
Ｃ 90.0 7.0 3.0
Ｄ 90.0 2.0 8.0
（モル％）
先づ図におけるAl2O3、CaO、TiO2の各成分に
ついて説明する。
Al2O3が点Ａよりもリツチ側になるとＱ値は高
くなるがτが−30ppm／℃未満となり、線分Ｃ−
Ｄよりもプアー側になると焼結不完全であり、Ｑ
値が低くなり過ぎ、τが＋30ppm／℃を超えたり
するのでいづれも実用に適さない。
又線分Ａ−Ｂ−Ｃ又は線分Ｄ−Ｉ−Ａよりも
CaOリツチ又はTiO2リツチ側ではいづれもτの
絶対値が30ppm／℃よりも大きくなり実用に適さ
ない。
従つて本発明におけるAl2O3−CaO−TiO2の組
成は図の点Ａ，Ｃ，Ｄで囲まれた三角形の範囲が
焼結体の共振周波数の温度係数τやＱ値、高周波
での誘電体損失も少なく好ましい範囲ではある
が、これのみでは高周波誘電特性の点及び焼成温
度依存性の点で不充分である。
本発明ではLa2O3の添加により高周波誘電特性
を向上させ、CeO2の添加により共振周波数の温
度係数（τ）の焼成温度依存性を大幅に低下する
ようにしたものであり、その量は前記Al2O3−
CaO−TiO2の所定の組成100重量部に対し、
La2O30.03重量部以上、CeO20.02重量部以上でか
つLa2O3とCeO2の合計量が0.05〜４重量部を含有
するようにしたものであり、La2O3が0.03重量部
未満では高周波誘電特性の向上が不充分であり、
CeO2が0.02重量部未満ではτの焼成温度依存性
が余り低下しない。
そしてLa2O3とCeO2の合計量は0.05〜４重量部
が好ましく0.05重量部未満では前記両特性の向上
が余り見られず、逆に４重量部を越えてもさ程特
性向上に寄与しない。
実施例
アルミナ（市販品 純度99.995％） 500ｇ
二酸化チタン（試薬特級） 所定量
炭酸カルシウム（試薬特級） 〃
酸化ランタン（試薬特級） 所定量
酸化セリウム（試薬特級） 〃
脱イオン水 400ml
ポリビニルアルコール 10ｇ
以上を20mmφのアルミナ球石（純度99.99％）
1.5Kgと共にポリエチレン製ボールミルへ入れ50
時間（84RPM）混合する。
得られたスラリーを冷凍乾燥した後、32メツシ
ユの篩を通し素地粉末とした。
この素地粉末を用いて圧力1500Kg／cm2でサイズ
8.4φmm×7.7Lmmのテストピースを作成し、これを
所定の温度で焼成した。
焼成品はサイズがほゞ6.8φmm×6.3Lmmとなつ
た。
次にこれをサイズ6.5φmm×6Lmmに鏡面加工し、
クロロセンと脱イオン水でそれぞれ20分超音波洗
滌し、その後自然乾燥し、シリカゲル入デシケー
タへ15時間保管し乾燥後誘電特性を測定した。
測定条件は以下のとおりである。
方法：誘電体円柱共振法
装置：横河ヒユーレツトパツカード(株)製 8408B
ネツトワークアナライザ
周波数：7.0〜8.0GHz
なお共振周波数の温度係数τは＋20℃〜＋85℃
の温度範囲で比誘電率の温度変化率τεと熱膨張係
数αとを測定し、次式に基いて算出した値であ
る。
τ＝−1/2τε−α
本発明の実施例及び比較例に相当する試料を作
成し特性を測定し、その組成と特性値等を第１表
に表示した。
測定点は下表のとおりで図にもプロツトしてあ
る。
点 Al2O3 CaO TiO2
Ａ 99.0 0.5 0.5
Ｃ 90.0 7.0 3.0
Ｄ 90.0 2.0 8.0
Ｅ 99.5 0.25 0.25
Ｆ 89.5 8.0 2.5
Ｇ 89.5 1.5 9.0
Ｈ 93.5 3.0 3.5
Ｂ 94.5 3.7 1.8
Ｉ 94.5 1.3 4.2
Ｋ 90.0 4.5 5.5
（モル％）
これにLa2O3とCeO2の添加量を変化させて特
性を測定したものが第１表に表示してある。
但し特性値は＝10GHzで測定し、好ましい特
性は以下のとおりである。
誘電率 10前後
共振周波数の温度係数｜τ｜≦30ppm／℃
無負荷 Ｑ＞4800
△τ＝１の焼成温度範囲 △τ℃≧30
である。
表中備考欄の内、外は本発明の内外を示す。
Industrial Application Fields The present invention is an alumina porcelain composition used in the telecommunications field such as microwave dielectric resonators, microwave integrated circuit boards, packages, microwave waveguides, microwave transmission windows, microwave multilayer capacitors, etc. relating to things. BACKGROUND ART With the development of communication networks in recent years, the frequency range in use has expanded to include high frequencies. In connection with this, dielectric ceramics are applied to dielectric resonators, microwave integrated circuit boards, impedance matching of various microwave circuits, etc. in the high frequency region. By the way, alumina porcelain has a high high-frequency Q value of around 7000, but the temperature coefficient τ of the resonance frequency is large, and it is impossible to satisfy |τ|≦30ppm/℃, which is desired in the communication field, and is approximately -60ppm/℃. Therefore, it was difficult to use it as a dielectric material. To solve this problem, Al 2 O 3 −CaO−TiO 2
For these materials, the addition of La 2 O 3 has been proposed to improve their high-frequency dielectric properties, and the addition of CeO 2 has been proposed to alleviate the dependence on firing temperature. A definitive composition has not yet emerged. Problems to be Solved by the Invention In a system in which La 2 O 3 is added to Al 2 O 3 -CaO-TiO 2 , the dielectric properties are strongly dependent on the firing temperature, and the properties vary widely. On the other hand, in the system with CeO 2 added, due to the characteristics
There was a problem that it was inferior to the system containing La 2 O 3 . Means for Solving the Problems In order to solve this problem, the present invention, as a result of intensive studies, has developed a system in which La 2 O 3 and CeO 2 are kept constant for a ternary system of Al 2 O 3 -CaO-TiO 2 with a certain composition. The problem was solved by adding both amounts at the same time. This means that the blending ratio of the ternary porcelain composition consisting of Al 2 O 3 , CaO and TiO 2 is within the range surrounded by the straight line connecting each point below in the ternary composition diagram expressed in mole fraction. , and for 100 parts by weight of this composition,
La 2 O 3 0.03 parts by weight or more, CeO 2 0.02 parts by weight or more,
The alumina porcelain composition contains 0.05 to 4 parts by weight of La 2 O 3 and CeO 2 in total. Point Al 2 O 3 CaO TiO 2 A 99.0 0.5 0.5 C 90.0 7.0 3.0 D 90.0 2.0 8.0 (mol %) First, each component of Al 2 O 3 , CaO, and TiO 2 in the figure will be explained. When Al 2 O 3 becomes richer than point A, the Q value becomes higher, but τ becomes less than -30 ppm/℃, and the line segment C-
If it becomes poorer than D, sintering is incomplete, and Q
Since the value becomes too low and τ exceeds +30 ppm/°C, neither of these methods is suitable for practical use. Also, from line segment A-B-C or line segment D-I-A
On the CaO-rich or TiO 2 -rich side, the absolute value of τ is larger than 30 ppm/°C, making it unsuitable for practical use. Therefore, regarding the composition of Al 2 O 3 -CaO-TiO 2 in the present invention, the triangular range surrounded by points A, C, and D in the figure corresponds to the temperature coefficient τ of the resonance frequency of the sintered body, the Q value, and the high frequency. Although the dielectric loss is also small and within a preferable range, this alone is insufficient in terms of high frequency dielectric properties and firing temperature dependence. In the present invention, the high-frequency dielectric properties are improved by adding La 2 O 3 , and the dependence of the temperature coefficient (τ) of the resonance frequency on the firing temperature is significantly reduced by adding CeO 2 . Said Al 2 O 3 −
For 100 parts by weight of the given composition of CaO- TiO2 ,
La 2 O 3 is 0.03 parts by weight or more, CeO 2 is 0.02 parts by weight or more, and the total amount of La 2 O 3 and CeO 2 is 0.05 to 4 parts by weight, and La 2 O 3 is 0.03 parts by weight. If it is less than
When CeO 2 is less than 0.02 parts by weight, the firing temperature dependence of τ does not decrease much. The total amount of La 2 O 3 and CeO 2 is preferably 0.05 to 4 parts by weight, and if it is less than 0.05 parts by weight, the above-mentioned properties will not improve much, and if it exceeds 4 parts by weight, it will not significantly improve the properties. do not. Example Alumina (commercially available, purity 99.995%) 500 g Titanium dioxide (special grade reagent) Specified amount of calcium carbonate (special grade reagent) Lanthanum oxide (special grade reagent) Specified amount of cerium oxide (special grade reagent) Deionized water 400 ml Polyvinyl alcohol 10 g or more 20mmφ alumina coccule (purity 99.99%)
Put it in a polyethylene ball mill with 1.5Kg and 50
Mixing time (84RPM). The obtained slurry was freeze-dried and then passed through a 32-mesh sieve to obtain a base powder. Using this base powder, the size is measured at a pressure of 1500Kg/ cm2.
A test piece of 8.4φmm×7.7Lmm was prepared and fired at a predetermined temperature. The size of the fired product was approximately 6.8φmm x 6.3Lmm. Next, mirror finish this to size 6.5φmm x 6Lmm,
The sample was ultrasonically washed with chlorocene and deionized water for 20 minutes each, then air-dried, stored in a desiccator containing silica gel for 15 hours, and dielectric properties were measured after drying. The measurement conditions are as follows. Method: Dielectric cylindrical resonance method Equipment: 8408B manufactured by Yokogawa Heuretsu Card Co., Ltd.
Network analyzer frequency: 7.0 to 8.0 GHz Temperature coefficient τ of resonance frequency is +20°C to +85°C
The temperature change rate τε of the relative dielectric constant and the thermal expansion coefficient α were measured in the temperature range of , and the value was calculated based on the following equation. τ=−1/2τε−α Samples corresponding to Examples and Comparative Examples of the present invention were prepared and their characteristics were measured, and their compositions, characteristic values, etc. are shown in Table 1. The measurement points are shown in the table below and are also plotted in the figure. Point Al 2 O 3 CaO TiO 2 A 99.0 0.5 0.5 C 90.0 7.0 3.0 D 90.0 2.0 8.0 E 99.5 0.25 0.25 F 89.5 8.0 2.5 G 89.5 1.5 9.0 H 93.5 3.0 3.5 B 94.5 3.7 1.8 I 94.5 1.3 4.2 K 90.0 4.5 5.5 (mol %) Table 1 shows the properties measured by varying the amounts of La 2 O 3 and CeO 2 added. However, the characteristic values are measured at =10 GHz, and the preferable characteristics are as follows. Dielectric constant: Temperature coefficient of resonance frequency around 10 |τ|≦30ppm/℃ No load Q>4800 Firing temperature range for △τ=1 △τ℃≧30. The inside and outside of the remarks column in the table indicates the inside and outside of the present invention.
【表】【table】
【表】
発明の効果
以上の比較試験から判るように本発明による
Al2O3−CaO−TiO2−La2O3−CeO2からなる磁
器組成物は誘電率が10内外と優れ、共振周波数の
温度係数が−30〜＋30の範囲内（実施例では−29
〜＋20）であり△τ＝１の焼成温度範囲は30℃以
上（実施例では34〜71）という値にして、更に無
負荷Q02800以上である。
即ち本発明によれば高周波誘電特性を向上させ
ながら共振周波数の温度係数（τ）の焼成温度依
存性を大幅に低下することができたものである。[Table] Effects of the invention As can be seen from the above comparative tests, the present invention
The ceramic composition consisting of Al 2 O 3 −CaO−TiO 2 −La 2 O 3 −CeO 2 has an excellent dielectric constant of around 10, and a temperature coefficient of resonance frequency within the range of −30 to +30 (−29 in the example).
~+20), and the firing temperature range for Δτ=1 is set to 30° C. or higher (34 to 71 in the example), and the no-load Q 0 is 2800 or higher. That is, according to the present invention, it is possible to significantly reduce the firing temperature dependence of the temperature coefficient (τ) of the resonance frequency while improving the high frequency dielectric properties.
図は本発明の磁器組成物の成分Al2O3、CaO、
TiO2の含有量を表わす三成分系組成図である。
The figure shows the components of the porcelain composition of the present invention: Al 2 O 3 , CaO,
It is a three-component system composition diagram showing the content of TiO 2 .
Claims (1)
組成の配合比がモル分率で表わした三成分組成図
において、下記の各点を結ぶ直線で囲まれた内に
あり、かつこの組成100重量部に対し、
La2O30.03重量部以上、CeO20.02重量部以上で、
かつLa2O3とCeO2の合計量が0.05〜４重量部を含
有することを特徴とするアルミナ磁器組成物。 点 Al2O3 CaO TiO2 Ａ 99.0 0.5 0.5 Ｃ 90.0 7.0 3.0 Ｄ 90.0 2.0 8.0 （モル％） [Claims] 1. In a ternary composition diagram in which the compounding ratio of a ternary porcelain composition consisting of Al 2 O 3 , CaO and TiO 2 is expressed in mole fraction, the following points are surrounded by straight lines connecting each point: and for 100 parts by weight of this composition,
La 2 O 3 0.03 parts by weight or more, CeO 2 0.02 parts by weight or more,
An alumina porcelain composition characterized in that the total amount of La 2 O 3 and CeO 2 is 0.05 to 4 parts by weight. Point Al 2 O 3 CaO TiO 2 A 99.0 0.5 0.5 C 90.0 7.0 3.0 D 90.0 2.0 8.0 (mol%)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61070931A JPS62229711A (en) | 1986-03-31 | 1986-03-31 | Alumina porcelain compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61070931A JPS62229711A (en) | 1986-03-31 | 1986-03-31 | Alumina porcelain compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62229711A JPS62229711A (en) | 1987-10-08 |
| JPH0542082B2 true JPH0542082B2 (en) | 1993-06-25 |
Family
ID=13445750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61070931A Granted JPS62229711A (en) | 1986-03-31 | 1986-03-31 | Alumina porcelain compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62229711A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68909665T2 (en) * | 1988-04-26 | 1994-02-10 | Toto Ltd | Method of manufacturing dielectric ceramics for electrostatic chucks. |
| JPH0345555A (en) * | 1989-07-11 | 1991-02-27 | Nippon Cement Co Ltd | Alumina porcelain composition |
| US5521332A (en) * | 1992-08-31 | 1996-05-28 | Kyocera Corporation | High dielectric layer-containing alumina-based wiring substrate and package for semiconductor device |
| CN106938920A (en) * | 2017-03-28 | 2017-07-11 | 华东理工大学 | A kind of low-dielectric loss alumina ceramic material |
-
1986
- 1986-03-31 JP JP61070931A patent/JPS62229711A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62229711A (en) | 1987-10-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |