JPH08157216A - Production of barium oxide-titanium oxide-rate earth metal oxide dielectric material - Google Patents
Production of barium oxide-titanium oxide-rate earth metal oxide dielectric materialInfo
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- JPH08157216A JPH08157216A JP6298095A JP29809594A JPH08157216A JP H08157216 A JPH08157216 A JP H08157216A JP 6298095 A JP6298095 A JP 6298095A JP 29809594 A JP29809594 A JP 29809594A JP H08157216 A JPH08157216 A JP H08157216A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、BaO-TiO2-M2O3 系誘電
体材料の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a BaO-TiO 2 -M 2 O 3 system dielectric material.
【０００２】[0002]
【発明の背景】BaO-TiO2-M2O3 系材料を誘電体材料とし
て用いることの有望性がＫ．Ｗａｋｉｎｏ等によって提
案されてから１０年程経過している。このBaO-TiO2-M2O
3 系誘電体材料の作製方法は、当該酸化物や炭酸化物に
焼結助剤を加えて混合・粉砕・仮焼し、再粉砕後、成形
して焼成するものである。この際の仮焼温度は１２５０
〜１３５０℃、焼成温度は１３５０〜１５００℃であ
る。BACKGROUND OF THE INVENTION The promise of using BaO-TiO 2 -M 2 O 3 based materials as dielectric materials is described in K. It has been about 10 years since it was proposed by Wakino and others. This BaO-TiO 2 -M 2 O
The method for producing a 3- based dielectric material is to add a sintering aid to the oxide or carbonate, mix, pulverize, and calcine, re-pulverize, and then form and fire. The calcination temperature at this time is 1250.
˜1350 ° C., firing temperature 1350˜1500 ° C.
【０００３】ところで、現在、これらの材料に求められ
ている高機能化の為には積層化が必須である。この積層
化は、前記材料にガラス成分及び有機樹脂（バインダ）
を混合したペーストを塗布し、焼成することによって行
われる。尚、ガラス成分は低温焼結を可能にする為に添
加され、その量が多い程、焼成温度を低く出来る。例え
ば、仮焼して得られる従来の粉末にガラスを２０〜３０
ｖｏｌ％程度混合すると、１１００℃程度での焼成で緻
密な焼結体が得られる。しかし、ガラスを２０〜３０ｖ
ｏｌ％程度も混合して焼成して得た焼結体は、ガラス量
が多い為に誘電特性が低下し、誘電体材料としての実用
的価値はない。逆に、ガラス量を減らすと、従来のもの
では、焼成温度を高くしなければ緻密な焼結体が得られ
ない。By the way, in order to achieve the high functionality required for these materials at present, lamination is essential. This lamination is made by adding a glass component and an organic resin (binder) to the above materials.
It is carried out by applying a paste in which is mixed and firing. The glass component is added to enable low temperature sintering, and the higher the amount, the lower the firing temperature. For example, glass is added to conventional powder obtained by calcination for 20 to 30
When mixed at about vol%, a dense sintered body can be obtained by firing at about 1100 ° C. However, 20-30v glass
The sinter obtained by mixing and firing about 1% of ol% has a large amount of glass and thus has poor dielectric properties and is not of practical value as a dielectric material. On the other hand, if the amount of glass is reduced, in the conventional case, a dense sintered body cannot be obtained unless the firing temperature is raised.
【０００４】しかし、高温での焼成が必要な材料を用い
て積層体を得る場合には様々な困難が有る。例えば、電
極としてはPdが多く含まれたPd−Ag電極が用いられてい
る。このPd−Ag電極は、Pdが多くなるほど高価になる
為、Agの含有量が多い電極を用いるのが実状である。こ
うしたコストを考えると、積層化に際して使用できる電
極組成中のPd量は最大でも３０ｗｔ％であり、この場合
の焼成温度としては最高でも１１５０℃である。すなわ
ち、Pd−Ag電極が用いられた場合には、１１５０℃以下
の温度で焼成可能なことが望まれる。However, there are various difficulties in obtaining a laminate by using a material that needs to be fired at a high temperature. For example, a Pd-Ag electrode containing a large amount of Pd is used as the electrode. This Pd-Ag electrode becomes more expensive as the amount of Pd increases, so the actual situation is to use an electrode with a high Ag content. Considering such costs, the maximum amount of Pd in the electrode composition that can be used for lamination is 30 wt%, and the firing temperature in this case is 1150 ° C. at the maximum. That is, when a Pd-Ag electrode is used, it is desired that the Pd-Ag electrode can be fired at a temperature of 1150 ° C or lower.
【０００５】この為、低温での焼成が可能なBaO-Nd2O3-
TiO2系誘電体粉末が求められている。このような観点か
ら、Bi2O3 やPbO を添加し、１１００℃程度での低温焼
成が試みられている。しかし、Bi2O3 はPdと容易に反応
して化合物を生成したり、Pbは蒸気圧が高い為に焼成時
に焼結体自身や電極を汚染し、特性劣化が引き起こされ
る等の問題が多い。Therefore, BaO-Nd 2 O 3 -which can be fired at a low temperature
There is a demand for TiO 2 -based dielectric powder. From such a viewpoint, low temperature firing at about 1100 ° C. has been attempted by adding Bi 2 O 3 or PbO. However, there are many problems that Bi 2 O 3 easily reacts with Pd to form a compound, and Pb has a high vapor pressure, which contaminates the sintered body itself and the electrode during firing and causes characteristic deterioration. .
【０００６】[0006]
【発明の開示】本発明は前記の問題点に鑑みてなされた
ものであり、本発明の第１の目的は、低温での焼結が可
能で、焼結性は良好であり、誘電体材料として有望なBa
O-TiO2-M2O3 系誘電体粉末の製造方法を提供することで
ある。本発明の第２の目的は、仮焼が不要で、誘電体材
料として有望なBaO-TiO2-M2O 3 系誘電体粉末の製造方法
を提供することである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems.
The first object of the present invention is to enable sintering at low temperature.
, Which has good sinterability and is a promising dielectric material.
O-TiO2-M2O3By providing a method for producing a dielectric powder
is there. A second object of the present invention is to eliminate the need for calcination and to provide a dielectric material.
Promising BaO-TiO2-M2O 3Of producing dielectric powder
Is to provide.
【０００７】この本発明の目的は、酸化バリウム(BaO)
源と、希土類酸化物(M2O3)源と、二酸化チタン(TiO2)源
と、塩化カリウム(KCl) 源との混合物を加熱することを
特徴とするBaO-TiO2-M2O3 系誘電体材料の製造方法によ
って達成される。又、酸化バリウム(BaO) 源と、希土類
酸化物(M2O3)源と、二酸化チタン(TiO2)源と、塩化カリ
ウム(KCl) 源との混合物を加熱溶融し、得られた溶融物
を水で洗浄し、含有されている塩化カリウムを除去する
ことを特徴とするBaO-TiO2-M2O3系誘電体材料の製造方
法によって達成される。The object of the present invention is barium oxide (BaO).
Source, a rare earth oxide (M 2 O 3 ) source, a titanium dioxide (TiO 2 ) source, and a mixture of potassium chloride (KCl) source, characterized by heating BaO-TiO 2 -M 2 O 3 This is achieved by a method of manufacturing a dielectric material based on a metal. Also, a mixture of a barium oxide (BaO) source, a rare earth oxide (M 2 O 3 ) source, a titanium dioxide (TiO 2 ) source, and a potassium chloride (KCl) source is heated and melted, and the obtained melt is obtained. Is washed with water to remove the contained potassium chloride, and a method for producing a BaO-TiO 2 -M 2 O 3 -based dielectric material is achieved.
【０００８】尚、上記の本発明において、希土類酸化物
(M2O3)源は酸化バリウム(BaO) 源１モルに対して０．５
〜２モル、二酸化チタン(TiO2)源は酸化バリウム(BaO)
源１モルに対して１〜５モル、塩化カリウム(KCl) 源は
酸化バリウム(BaO) 源と希土類酸化物(M2O3)源と二酸化
チタン(TiO2)源との総量１０重量部に対して１〜１００
重量部の割合であることが好ましい。そして、原料混合
物中に塩化ナトリウムを添加しないことが望ましい。す
なわち、塩化ナトリウムを添加していた場合には、本発
明が目的とする誘電体材料が得られない。In the present invention, the rare earth oxide is used.
The (M 2 O 3 ) source is 0.5 per mol of the barium oxide (BaO) source.
~ 2 mol, titanium dioxide (TiO 2 ) source is barium oxide (BaO)
1 to 5 mol per mol of source, potassium chloride (KCl) source is barium oxide (BaO) source, rare earth oxide (M 2 O 3 ) source and titanium dioxide (TiO 2 ) source in a total amount of 10 parts by weight. To 1 to 100
It is preferably a part by weight ratio. And it is desirable not to add sodium chloride to the raw material mixture. That is, when sodium chloride is added, the dielectric material intended by the present invention cannot be obtained.
【０００９】又、酸化バリウム(BaO) 源と希土類酸化物
(M2O3)源と二酸化チタン(TiO2)源と塩化カリウム(KCl)
源との混合物の加熱温度は９００〜１２００℃（望まし
くは１０００〜１２００℃）であることが好ましい。そ
して、上記のような溶融塩法によって得られたBaO-TiO2
-M2O3 系誘電体粉末は、高誘電率、高Ｑ、ＮＰ０（容量
の温度係数が零）の特長を奏し、衛星通信、衛星放送、
携帯電話、自動車電話などの通信機器に用いられるマイ
クロ波誘電体セラミックス材料として好適なものであ
る。Further, a barium oxide (BaO) source and a rare earth oxide
(M 2 O 3 ) source and titanium dioxide (TiO 2 ) source and potassium chloride (KCl)
The heating temperature of the mixture with the source is preferably 900 to 1200 ° C (desirably 1000 to 1200 ° C). And BaO-TiO 2 obtained by the molten salt method as described above
-M 2 O 3 -based dielectric powder has the characteristics of high dielectric constant, high Q, and NP0 (zero temperature coefficient of capacity), and can be used for satellite communication, satellite broadcasting,
It is suitable as a microwave dielectric ceramic material used in communication devices such as mobile phones and car phones.
【００１０】特に、低温での焼成を行う為にガラスを５
％程度添加して得た焼結体でも誘電特性が優れており、
かつ、緻密である。更には、融液中で合成される為に、
得られる粉末に凝集が起き難く、微細な粉末が得られ
る。しかも、仮焼が不要である為、コスト的にも有利で
ある。以下、具体的な実施例を挙げて本発明を説明す
る。In particular, glass is used for firing at low temperature.
%, The sintered body obtained by adding about 100% also has excellent dielectric properties.
And it is precise. Furthermore, because it is synthesized in the melt,
Aggregation hardly occurs in the obtained powder, and a fine powder is obtained. Moreover, since calcination is unnecessary, it is advantageous in terms of cost. Hereinafter, the present invention will be described with reference to specific examples.
【００１１】[0011]
〔実施例１〕出発原料として、純度９９．０％以上のＢ
ａＣＯ3 粉末、Ｎｄ2 Ｏ3 粉末、ＴｉＯ2 粉末を用い
た。上記ＢａＣＯ3 粉末とＮｄ2 Ｏ3 粉末との等量混合
物にＴｉＯ2 粉末を、前記等量混合物２モルに対して１
〜５モル（例えば、４モル）加え、ボールミルで湿式混
合した後、乾燥した。[Example 1] As a starting material, B having a purity of 99.0% or more
aCO 3 powder, Nd 2 O 3 powder, and TiO 2 powder were used. TiO 2 powder was added to an equal mixture of the BaCO 3 powder and Nd 2 O 3 powder, and 1 mole was added to 2 moles of the equal mixture.
~ 5 mol (for example, 4 mol) was added, and the mixture was wet mixed with a ball mill and then dried.
【００１２】この乾燥混合物１０重量部に対して塩化カ
リウム（ＫＣｌ）粉末を１〜１００重量部（例えば、５
０重量部）配合した。このようにして得た混合物をアル
ミナルツボ中にて９００〜１２００℃で１０時間以内か
けて加熱した。加熱後、常温まで徐々に冷却し、取り出
して熱水により洗浄した。すなわち、洗浄により含まれ
ている塩化カリウムを溶解除去し、濾過によって粉末を
得た。得た粉末を、再び、熱水中に分散して濾過し、こ
の分散・濾過の操作をＣｌ- イオンが検出されなくなる
まで繰り返した。1 to 100 parts by weight of potassium chloride (KCl) powder (for example, 5 parts by weight) relative to 10 parts by weight of this dry mixture.
0 parts by weight) was blended. The mixture thus obtained was heated in an alumina crucible at 900 to 1200 ° C. for 10 hours or less. After heating, it was gradually cooled to room temperature, taken out and washed with hot water. That is, potassium chloride contained was removed by dissolution by washing, and powder was obtained by filtration. The obtained powder was again dispersed in hot water and filtered, and this dispersion / filtration operation was repeated until Cl − ions were not detected.
【００１３】このようして得られた粉末には様々な相が
確認された。例えば、BaO:Nd2O3:TiO2＝１：１：４で、
加熱条件が１０００℃で１０時間、１１００℃で５時
間、１２００℃で２時間の場合には、BaNd2Ti4O12 の単
一相粉末が生成していた。そして、このセラミックス焼
結材料の誘電特性は優れたものであった。 〔実施例２〕実施例１において、ＢａＣＯ3 粉末とＮｄ
2 Ｏ3 粉末とＴｉＯ2 粉末との混合割合をＢａＯ：Ｎｄ
2 Ｏ3 ：ＴｉＯ2 ＝１：１：３（モル比）とした以外は
同様に行った。Various phases were confirmed in the powder thus obtained. For example, BaO: Nd 2 O 3 : TiO 2 = 1: 1: 4,
When the heating conditions were 1000 ° C. for 10 hours, 1100 ° C. for 5 hours and 1200 ° C. for 2 hours, a single-phase powder of BaNd 2 Ti 4 O 12 was formed. And, the dielectric characteristics of this ceramic sintered material were excellent. Example 2 In Example 1, the BaCO 3 powder and Nd were used.
The mixing ratio of 2 O 3 powder and TiO 2 powder is BaO: Nd.
The same procedure was performed except that 2 O 3 : TiO 2 = 1: 1: 3 (molar ratio).
【００１４】１０００℃で１０時間、１１００℃で５時
間、１２００℃で２時間加熱することによって、BaNd2T
i3O10 の単一相粉末が生成していた。そして、このセラ
ミックス焼結材料の誘電特性は優れたものであった。 〔実施例３〕実施例１において、Ｎｄ2 Ｏ3 粉末の代わ
りにＳｍ2 Ｏ3 粉末を用いた以外は同様に行った。By heating at 1000 ° C. for 10 hours, 1100 ° C. for 5 hours, 1200 ° C. for 2 hours, BaNd 2 T
A single phase powder of i 3 O 10 was formed. And, the dielectric characteristics of this ceramic sintered material were excellent. In Example 3 Example 1, it was carried out as but using Sm 2 O 3 powder instead of the Nd 2 O 3 powder.
【００１５】９００℃で１０時間、１０００℃で５時
間、１１００℃で２時間、１２００℃で１時間加熱する
ことによって、BaSm2Ti4O12 の単一相粉末が生成してい
た。そして、このセラミックス焼結材料の誘電特性は優
れたものであった。 〔実施例４〕実施例３において、ＢａＣＯ3 粉末とＳｍ
2 Ｏ3 粉末とＴｉＯ2 粉末との混合割合をＢａＯ：Ｓｍ
2 Ｏ3 ：ＴｉＯ2 ＝１：１：３（モル比）とした以外は
同様に行った。By heating at 900 ° C. for 10 hours, 1000 ° C. for 5 hours, 1100 ° C. for 2 hours, and 1200 ° C. for 1 hour, a single phase powder of BaSm 2 Ti 4 O 12 was produced. And, the dielectric characteristics of this ceramic sintered material were excellent. [Example 4] In Example 3, BaCO 3 powder and Sm were added.
The mixing ratio of 2 O 3 powder and TiO 2 powder is BaO: Sm.
The same procedure was performed except that 2 O 3 : TiO 2 = 1: 1: 3 (molar ratio).
【００１６】９００℃で１０時間、１０００℃で５時
間、１１００℃で２時間、１２００℃で１時間加熱する
ことによって、BaSm2Ti3O10 の単一相粉末が生成してい
た。そして、このセラミックス焼結材料の誘電特性は優
れたものであった。 〔比較例１〕実施例１において、塩化カリウムの代わり
に塩化ナトリウムを用いた以外は同様に行った。By heating at 900 ° C. for 10 hours, 1000 ° C. for 5 hours, 1100 ° C. for 2 hours, and 1200 ° C. for 1 hour, a single phase powder of BaSm 2 Ti 3 O 10 was produced. And, the dielectric characteristics of this ceramic sintered material were excellent. [Comparative Example 1] The same procedure as in Example 1 was repeated except that sodium chloride was used instead of potassium chloride.
【００１７】しかし、BaNd2Ti4O12 の単一相粉末は得ら
れなかった。 〔比較例２〕実施例１において、塩化カリウムの代わり
に塩化ナトリウムと塩化カリウムとの混合物を用いた以
外は同様に行った。しかし、BaNd2Ti4O12 の単一相粉末
は得られなかった。However, a single-phase powder of BaNd 2 Ti 4 O 12 was not obtained. [Comparative Example 2] The same procedure as in Example 1 was repeated except that a mixture of sodium chloride and potassium chloride was used instead of potassium chloride. However, a single-phase powder of BaNd 2 Ti 4 O 12 was not obtained.
【００１８】〔特性〕実施例１〜実施例４で得たBaO-Ti
O2-M2O3 系誘電体材料の単一相粉末を１２００〜１４０
０℃で焼成した。この焼結体の密度を測定すると、理論
密度の９５％以上であった。又、実施例１で得たBaNd2T
i4O12 の単一相粉末に５ｖｏｌ％のガラスを添加し、１
０５０℃で焼成して得た緻密な焼結体の誘電特性を測定
した処、これはガラスを添加しないで焼成して得た上記
焼結体の誘電特性と同程度なものであった。[Characteristics] BaO-Ti obtained in Examples 1 to 4
O 2 -M 2 O 3 based dielectric material single phase powder is
Baked at 0 ° C. When the density of this sintered body was measured, it was 95% or more of the theoretical density. Also, BaNd 2 T obtained in Example 1
Add 5 vol% glass to i 4 O 12 single-phase powder,
When the dielectric properties of the dense sintered body obtained by firing at 050 ° C. were measured, it was similar to the dielectric properties of the above sintered body obtained by firing without adding glass.
【００１９】[0019]
【効果】本発明によれば、高誘電率、高Ｑ、ＮＰ０の特
長を奏し、通信機器に用いられるマイクロ波誘電体セラ
ミックスとして好適で、低温焼成が可能なBaO-TiO2-M2O
3 系誘電体材料が得られる。[Effect] According to the present invention, the characteristics of high dielectric constant, high Q and NP0 are obtained.
Microwave dielectric ceramic that has a long length and is used for communication equipment
BaO-TiO suitable as a mix and capable of low temperature firing2-M2O
3A dielectric material is obtained.
Claims (5)
(M2O3)源と、二酸化チタン(TiO2)源と、塩化カリウム(K
Cl) 源との混合物を加熱することを特徴とするBaO-TiO2
-M2O3 系誘電体材料の製造方法。1. A barium oxide (BaO) source and a rare earth oxide
(M 2 O 3 ) source, titanium dioxide (TiO 2 ) source, potassium chloride (K
BaO-TiO 2 characterized by heating a mixture with a Cl) source
-M 2 O 3 system manufacturing method of a dielectric material.
(M2O3)源と、二酸化チタン(TiO2)源と、塩化カリウム(K
Cl) 源との混合物を加熱溶融し、得られた溶融物を水で
洗浄し、含有されている塩化カリウムを除去することを
特徴とするBaO-TiO2-M2O3 系誘電体材料の製造方法。2. A barium oxide (BaO) source and a rare earth oxide
(M 2 O 3 ) source, titanium dioxide (TiO 2 ) source, potassium chloride (K
Cl) source is melted by heating, the obtained melt is washed with water, the potassium chloride contained is removed, characterized in that BaO-TiO 2 -M 2 O 3 -based dielectric material Production method.
(BaO) 源１モルに対して０．５〜２モル、二酸化チタン
(TiO2)源は、酸化バリウム(BaO) 源１モルに対して１〜
５モル、塩化カリウム(KCl) 源は、酸化バリウム(BaO)
源と希土類酸化物(M2O3)源と二酸化チタン(TiO2)源との
総量１０重量部に対して１〜１００重量部の割合である
ことを特徴とする請求項１又は請求項２のBaO-TiO2-M2O
3 系誘電体材料の製造方法。3. The rare earth oxide (M 2 O 3 ) source is barium oxide.
(BaO) source 0.5 mol to 2 mol per mol, titanium dioxide
The (TiO 2 ) source is 1 to 1 mol of barium oxide (BaO) source.
5 mol, potassium chloride (KCl) source is barium oxide (BaO)
The ratio of 1 to 100 parts by weight to the total amount of 10 parts by weight of the source, the rare earth oxide (M 2 O 3 ) source and the titanium dioxide (TiO 2 ) source. BaO-TiO 2 -M 2 O
Method for manufacturing 3- based dielectric material.
2O3)源と二酸化チタン(TiO2)源と塩化カリウム(KCl) 源
との混合物の加熱温度が、９００〜１２００℃であるこ
とを特徴とする請求項１又は請求項２のBaO-TiO2-M2O3
系誘電体材料の製造方法。4. A barium oxide (BaO) source and a rare earth oxide (M
The heating temperature of the mixture of the 2 O 3 ) source, the titanium dioxide (TiO 2 ) source and the potassium chloride (KCl) source is 900 to 1200 ° C. 3. BaO-TiO 2 according to claim 1 or claim 2, 2 -M 2 O 3
Of manufacturing a dielectric ceramic material.
酸化物(M2O3)源がNd 2O3 、二酸化チタン(TiO2)源がTi
O2、塩化カリウム源がKCl であり、得られた材料がBaO-
TiO2-Nd2O3系のものであることを特徴とする請求項１又
は請求項２のBaO-TiO2-M2O3 系誘電体材料の製造方法。5. The barium oxide (BaO) source is BaCO.3,rare earth
Oxide (M2O3) Source is Nd 2O3 , Titanium dioxide (TiO2) The source is Ti
O2, The source of potassium chloride is KCl, and the obtained material is BaO-
TiO2-Nd2O3A system according to claim 1, characterized in that
Is the BaO-TiO of claim 2.2-M2O3Of manufacturing a dielectric ceramic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6298095A JPH08157216A (en) | 1994-12-01 | 1994-12-01 | Production of barium oxide-titanium oxide-rate earth metal oxide dielectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6298095A JPH08157216A (en) | 1994-12-01 | 1994-12-01 | Production of barium oxide-titanium oxide-rate earth metal oxide dielectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08157216A true JPH08157216A (en) | 1996-06-18 |
Family
ID=17855103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6298095A Pending JPH08157216A (en) | 1994-12-01 | 1994-12-01 | Production of barium oxide-titanium oxide-rate earth metal oxide dielectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08157216A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002326868A (en) * | 2001-05-01 | 2002-11-12 | Samsung Electro Mech Co Ltd | Dielectric ceramic composition and ceramics capacitor using it and method of manufacturing them |
| JP2006347820A (en) * | 2005-06-16 | 2006-12-28 | Ntn Corp | Dielectric ceramic and method of manufacturing the same |
| CN114394828A (en) * | 2022-01-10 | 2022-04-26 | 湖南省美程陶瓷科技有限公司 | Electronic ceramic material with medium dielectric constant and preparation method thereof |
-
1994
- 1994-12-01 JP JP6298095A patent/JPH08157216A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002326868A (en) * | 2001-05-01 | 2002-11-12 | Samsung Electro Mech Co Ltd | Dielectric ceramic composition and ceramics capacitor using it and method of manufacturing them |
| JP2006347820A (en) * | 2005-06-16 | 2006-12-28 | Ntn Corp | Dielectric ceramic and method of manufacturing the same |
| CN114394828A (en) * | 2022-01-10 | 2022-04-26 | 湖南省美程陶瓷科技有限公司 | Electronic ceramic material with medium dielectric constant and preparation method thereof |
| CN114394828B (en) * | 2022-01-10 | 2022-10-18 | 湖南省美程陶瓷科技有限公司 | Electronic ceramic material with medium dielectric constant and preparation method thereof |
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