JP5372181B2 - 微粒チタン酸バリウム系粉末 - Google Patents
微粒チタン酸バリウム系粉末 Download PDFInfo
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- JP5372181B2 JP5372181B2 JP2011553961A JP2011553961A JP5372181B2 JP 5372181 B2 JP5372181 B2 JP 5372181B2 JP 2011553961 A JP2011553961 A JP 2011553961A JP 2011553961 A JP2011553961 A JP 2011553961A JP 5372181 B2 JP5372181 B2 JP 5372181B2
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- Prior art keywords
- barium titanate
- based powder
- powder according
- dielectric constant
- niobium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
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Description
(BaxR1 r1R2 r2)(TiyR3 r3R4 r4)O3
0.85×ε0≦εT≦1.15×ε0
(前記ε0は、25℃での比誘電率である。)
a)炭酸バリウム、チタン塩、水を混合して懸濁液を製造する段階と、
b)前記a)段階の混合懸濁液を湿式で粉砕及び乾燥して炭酸バリウム及びチタン塩が含まれた混合粉末を製造した後、300〜900℃で一次熱処理を施す段階と、
c)前記b)段階の一次熱処理を施した混合粉末、イットリウム(Y)、ランタン族元素、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)、リン(P)、ニオブ(Nb)、アルミニウム(Al)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、コバルト(Co)、ジルコニウム(Zr)及びタンタル(Ta)からなる群から選択された1種以上の元素を含む酸化物、塩化物、炭酸塩、リン酸塩、窒酸塩、硫酸塩、酢酸塩またはこれらの混合物、水を混合して懸濁液を製造する段階と、
d)前記c)段階の混合懸濁液を湿式で粉砕及び乾燥して混合粉末を製造した後、700〜1,100℃で二次熱処理を施してチタン酸バリウム系粉末を製造する段階と、を含む。
TiO2・n(H2O)
(前記nは、範囲が0〜2である実数である。)
a)炭酸バリウム及びチタン塩が含まれた懸濁液の製造
反応槽に純水422Lを投与して、チタン塩(Millennium Inorganic Chemicals製、TiO2.0.84(H2O))104.0kgと、炭酸バリウム(BaCO3)216.3kgを投与して攪拌し、懸濁液を製造した。
前記a)段階の懸濁液を二酸化ジルコニウムを主原料とする直径0.3mmの球状ビーズを装入したビーズミルを用いて充分に粉砕及び混合し、懸濁液を少量取って乾燥した後、XRF法でモル比を測定した結果、Ba/Tiモル比が1.001であった。粉砕及び混合が完了した前記懸濁液を噴霧乾燥して炭酸バリウム及びチタン塩が含まれた混合粉末を製造した。この混合粉末に、500℃で4時間の大気雰囲気下で一次熱処理を施した。
前記b)段階の熱処理粉末に、三酸化イットリウム(Y2O3)、炭酸マグネシウム(MgCO3)、五酸化ニオブ(Nb2O5)、五酸化リン(P2O5)、三酸化アルミニウム(Al2O3)、五酸化バナジウム(V2O5)、三酸化クロム(Cr2O3)及び二酸化マンガン(MnO2)を下記表1のような構成を有するようにそれぞれ秤量して添加し、純水を投与して懸濁液を製造した。
前記c)段階の懸濁液をb)段階のように湿式ビーズミルで充分に粉砕及び混合して、噴霧乾燥した後、電気炉に装入して大気雰囲気下で950℃で2時間か焼してチタン酸バリウム系粉末を製造した。XRF法でモル比を測定した結果、下記表1と同一の構成であることを確認した。製造したチタン酸バリウム系粉末の物性を分析して下記表2に示した。BET法で比表面積を測定し、5万倍の倍率のSEMイメージを用いて粒子の平均大きさを測定し、この際、粒子の大きさは面積が等しい円の直径で計算した。また、リートベルト法を用いた多相解釈により正方晶相の割合を分析した。
前記実施例1と同一に行うが、前記c)段階で添加元素の添加量を下記表1のように異にして行い、その他の工程は、前記実施例1と同様に行った。添加元素の添加量に応じてそれぞれ製造したチタン酸バリウム系粉末を実施例1のように物性を分析して下記表2に示した。
前記実施例1〜9から得られたチタン酸バリウム系粉末に、炭酸バリウムと二酸化ケイ素粉末をチタン酸バリウム系粉末100モル当たりそれぞれ1モル、1.5モルになるように添加した。また、エタノール及びトルエンを体積基準1:1に混合した混合液を溶媒とし、直径3mmの二酸化ジルコニウムビーズを用いたボールミルで15時間湿式混合し、前記固形粉が充分に分散した懸濁液を製造した。この懸濁液に、ポリビニル系バインダーとしてポリビニルブチラルを前記チタン酸バリウム系粉末の10wt%になるように添加した後、また、ボールミルで10時間湿式混合し、テープキャスト法を用いて厚さ20μmのシートを製造した。製造されたシートを積層して加圧し、横10mm、縦10mm、高さ1mmの成形体を製造した。前記成形体を窒素雰囲気下の450℃で12時間脱バインダーした後、10−11の水素分圧雰囲気下の1200℃で2時間維持した後、50ppmの酸素雰囲気下の1,000℃で3時間の再酸化して焼成試片を製作した。前記焼成試片の上面と下面にガリウム−インジウム固溶体ペースト(Sigma−Aldrich Corporation製、Gallium−Indium EUTECTIC、99.99+%)を塗布して乾燥した後、25℃で誘電率、誘電損失、絶縁抵抗を測定し、温度を変化させて温度による容量の変化率を測定した。前記電気特性の測定条件及び装置は、下記表3に示し、その結果を下記表4に示しており、EIAで規定したセラミックコンデンサの規格のうち、CLASSII規格コードによるX7R特性を満すことが確認できた。
Claims (9)
- 下記化学式1で表されるチタン酸バリウム系粉末。
[化学式1]
(BaxR1 r1R2 r2)(TiyR3 r3R4 r4)O3
(式中R1は、イットリウム(Y)、ランタン族元素からなる群から選択される1又は2種以上の元素であり、R2は、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)からなる群から選択される1又は2種以上の元素であり、R3は、リン(P)及びニオブ(Nb)からなり、R4は、アルミニウム(Al)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、コバルト(Co)、ジルコニウム(Zr)、タンタル(Ta)からなる群から選択される1種以上であり、r1とr3は、互いに独立して0より大きく0.05以下の実数であり、r2とr4は、互いに独立して0より大きく0.1以下の実数であり、R 3 のニオブとリンのモル比は1:0.1〜2.0であり、(x+r1+r2)/(y+r3+r4)は、0.85以上1.15以下である実数である。) - r1、r2、r3及びr4は、互いに独立して0より大きく0.03以下である請求項1に記載のチタン酸バリウム系粉末。
- R1はイットリウム(Y)であり、R2はマグネシウム(Mg)であり、R3はリン(P)及びニオブ(Nb)であり、R4はアルミニウム(Al)、バナジウム(V)、クロム(Cr)及びマンガン(Mn)である請求項1に記載のチタン酸バリウム系粉末。
- バリウム元素は、チタン元素1モル当たり0.995〜1.005モル含まれることを特徴とする請求項1に記載のチタン酸バリウム系粉末。
- 正方晶相の割合が全体の60〜100wt%であることを特徴とする請求項1に記載のチタン酸バリウム系粉末。
- 粒子の大きさが10〜500nmであり、比表面積が2〜35m2/gであることを特徴とする請求項1に記載のチタン酸バリウム系粉末。
- 25℃での比誘電率が1,500〜3,000であることを特徴とする請求項1に記載のチタン酸バリウム系粉末。
- 比誘電率εTが、−55〜125℃において下記式1を満たす請求項1に記載のチタン酸バリウム系粉末。
[式1]
0.85×ε0≦εT≦1.15×ε0
(前記ε0は、25℃での比誘電率である。) - 誘電体材料用、セラミック電子部品用であることを特徴とする請求項1〜8の何れか一項に記載のチタン酸バリウム系粉末。
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| KR1020090021198A KR100921352B1 (ko) | 2009-03-12 | 2009-03-12 | 미립 티탄산바륨계 분말의 제조방법 |
| KR10-2009-0021198 | 2009-03-12 | ||
| KR1020090066243A KR100955802B1 (ko) | 2009-07-21 | 2009-07-21 | 미립 티탄산바륨계 분말의 제조방법 |
| KR10-2009-0066243 | 2009-07-21 | ||
| PCT/KR2010/001564 WO2010104358A2 (ko) | 2009-03-12 | 2010-03-12 | 미립 티탄산바륨계 분말 |
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| JP6245222B2 (ja) * | 2015-06-05 | 2017-12-13 | 株式会社村田製作所 | 積層セラミックコンデンサの製造方法 |
| JP6870432B2 (ja) * | 2016-03-31 | 2021-05-12 | 三菱ケミカル株式会社 | 複合金属酸化物粒子、並びに、これを用いた分散液、ハイブリッド複合粒子、ハイブリッド複合材及び光学材料 |
| JP7122118B2 (ja) * | 2018-01-24 | 2022-08-19 | 太陽誘電株式会社 | セラミックコンデンサおよびその製造方法 |
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| JP3751304B2 (ja) * | 2002-12-18 | 2006-03-01 | 昭和電工株式会社 | チタン酸バリウムおよびそれを用いた電子部品 |
| JP2005075650A (ja) * | 2003-08-29 | 2005-03-24 | Sumitomo Chemical Co Ltd | バリウム含有金属酸化物粉末の製造方法 |
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| WO2010104358A2 (ko) | 2010-09-16 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |