JP6353912B2 - Ta−Nb合金粉末および固体電解コンデンサ用陽極素子 - Google Patents
Ta−Nb合金粉末および固体電解コンデンサ用陽極素子 Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims description 136
- 229910001257 Nb alloy Inorganic materials 0.000 title claims description 60
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000010407 anodic oxide Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
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Description
C=(ε・S)/t
ここで、S:電極面積(m2)、t:電極間距離(m)、ε:誘電率(F/m)、ε=εs・ε0、εs:誘電体の比誘電率(Taの酸化皮膜:約25)、ε0:真空誘導率(8.855×10−12F/m)
で表わされ、電極面積Sが大きいほど、電極間距離tが小さいほど、また、誘電率εが高いほど、大きくなる。したがって、CV値を高めるためには、陽極面積S、即ち、陽極を構成しているTa粉末の表面積を大きくするか、電極間距離t、即ち、陽極酸化皮膜Ta2O5の膜厚を薄くするか、誘電率εの高い材料を利用する必要がある。
ρc(g/cm3)=−0.012RNb+3.57 ・・・(1)
ここで、RNb:合金中のNb含有量(mass%)
で定義されるρcの陽極素子としたときの値である。
<実験1>
熱CVD法で、Ta粉末、Nb粉末およびNb含有量を種々に変えたTa−Nb合金粉末(以降、上記3種類の粉末を「金属粉末」と総称する)を製造した。なお、上記金属粉末の製造するに際しては、一次粒子の平均粒径が60〜120nmの範囲内となるよう製造条件を調整した。次いで、上記金属粉末を加圧成形して直径3mmφ×長さ4mmのペレットとした。この際、上記加圧成形後のペレットの成形密度ρ(g/cm3)は、Ta−Nb合金中のNbの含有量RNb(mass%)に応じて、下記(1)式;
ρc=−0.012RNb+3.57 ・・・(1)
から求められるρcに対して±0.10g/cm3の範囲に収まるよう調整した。なお、上記成形密度は、ワイヤを除いた値である。
実際、上記実験における成形において、上記(1)式から得られるρcに対して+0.20g/cm3を超えると、成形後や焼結後にクラック(割れ)が発生し易くなり、逆に、上記(1)式から得られるρcに対して−0.20g/cm3を下回ると、成形体としての強度を確保することが困難であった。また、より好ましい成形密度は、(1)式から得られるρcに対して±0.10g/cm3の範囲であった。
次いで、上記素子に、温度が80℃の0.05mass%のリン酸溶液中で、電圧10Vで2hrの化成処理を施して金属粒子表面に誘電体となる陽極酸化被膜を形成した後、EIAJ RC−2361Aに記載の方法に準拠して、静電容量CVおよび漏れ電流LCを測定した。なお、静電容量CVの測定は、40mass%の硫酸溶液中で、電圧1V,バイアス電圧1.5Vdc、周波数120Hzで測定した。また、漏れ電流LCの測定は、7V電圧を印加し、2min経過後の漏れ電流を測定した。
また、参考として、Ta粉末およびNb粉末をNb含有量が30mass%となるよう配合したTa−Nb混合粉末についても、上記と同じ条件で、静電容量CVおよび漏れ電流LCを測定した。
上記の測定結果を、表1に示した。なお、漏れ電流は、単位容量当たりの漏れ電流(nA/μF・V)で示した。
この図から、単位体積当たりのCV値(μF・V/mm3)では、Ta粉末素子とNb粉末素子の差は大きく縮まり、9%弱の差しかない。この差は、体積サイズが一定としてTa粉末およびNb粉末をそれぞれ同条件で充填して素子を作製したときの静電容量の差に相当し、実用上、コンデンサを設計する上で重要な指標となる。また、この場合でも、Ta−Nb混合粉末素子のCV値は、Ta粉末素子とNb粉末素子のCV値を結ぶ直線上にあり、Nb粉末素子およびTa粉末素子のCV値から得られる内挿値と同じである。
なお、熱CVD法で製造したTa−Nb合金粉末は、微粉であるが故に、流動性が悪いという問題点を有するが、この点については、後述する造粒技術の改善によって解決可能である。
次に、発明者らは、Ta−Nb合金粉末の熱的安定性を調査するため、上記実験に用いた化成処理後の素子に、実装時のリフロー処理を模擬して、260℃×30分の熱処理をアルゴンガス雰囲気中で施し、CV値(μF・V/mm3)および漏れ電流LCの変化を調査した。なお、CV値および漏れ電流LCの測定は、前述した<実験1>と同条件で行った。なお、参考として、Ta−Nb混合粉末についても同様の調査を行った。
また、バインダとして水、リン酸水などの無機物を使用して造粒した後、加熱して焼結し、粉砕し、その後、酸素等の不純物を除去する熱造粒法も適宜用いることができる。
また、陽極素子の作製には、上記の乾式成形プロセスを用いずに、一次粉末から直接成形する方法を採用してもよい。例えば、一次粉末にバインダや水等の溶媒を添加し、混練して練土とし、押し出し成形機でシートに成形した後、該シートを脱バインダし、真空焼成し、その後、ワイヤを溶接等で接合して陽極素子としてもよい。
次いで、上記造粒粒子を、日本電子機械工業会規格EIAJ RC−2361A「タンタル電解コンデンサ用タンタル焼結素子の試験方法」附属書の表1に規定された100kCV粉末の試験条件に準拠して焼結素子を作製した。この際、素子(ペレット)の成形密度は、前述した(1)式で得られるρcに対して±0.10g/cm3以内に収まるように調整し、また、一般に、素子の最適焼結温度は粒径に依存し、粒径が大きくなるほど高くなるため、950〜1150℃の温度範囲で予備実験し、最も高い静電容量が得られる温度を採用した。
さらに、上記測定後の素子に対して、Arガス雰囲気中で、260℃×30minのリフロー処理を模した熱処理を施し、上記と同条件で、静電容量CVおよび漏れ電流LCを測定した。
Claims (5)
- 熱CVD法で製造したTa−Nb合金粉末であって、
Nbの含有量が1〜40mass%で、一次粒子の平均粒径が30〜200nmであるTa−Nb合金粉末。 - 陽極素子としたときの単位質量当たりのCV値(μF・V/g)が250kμF・V/g以上であることを特徴とする請求項1に記載のTa−Nb合金粉末。
- 陽極素子としたときの単位体積当たりのCV値(μF・V/mm3)が900μF・V/mm3以上であることを特徴とする請求項1または2に記載のTa−Nb合金粉末。ここで、上記CV値は、成形密度ρ(g/cm3)を下記(1)式で定義されるρcの陽極素子としたときの値である。
記
ρc(g/cm3)=−0.012RNb+3.57 ・・・(1)
ここで、RNb:合金中のNb含有量(mass%) - 陽極素子とした後、Ar雰囲気下で260℃×30分間保持するリフロー処理を施したときの漏れ電流が、リフロー処理前の8倍以下であることを特徴とする請求項1〜3のいずれか1項に記載のTa−Nb合金粉末。
- 請求項1〜4のいずれか1項に記載のTa−Nb合金粉末を用いた固体電解コンデンサ用陽極素子。
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JPS6473009A (en) * | 1987-09-11 | 1989-03-17 | Showa Denko Kk | Production of high purity tantalum or niobium powder |
JPH02310301A (ja) | 1989-05-24 | 1990-12-26 | Showa Kiyabotsuto Suupaa Metal Kk | タンタル粉末及びその製造法 |
DE4214722C2 (de) | 1992-05-04 | 1994-08-25 | Starck H C Gmbh Co Kg | Feinteilige Metallpulver |
US6165623A (en) | 1996-11-07 | 2000-12-26 | Cabot Corporation | Niobium powders and niobium electrolytic capacitors |
AU6495398A (en) | 1997-02-19 | 1998-09-09 | H.C. Starck Gmbh & Co. Kg | Tantalum powder, method for producing same powder and sintered anodes obtained from it |
WO2000067936A1 (en) | 1998-05-06 | 2000-11-16 | H.C. Starck, Inc. | Metal powders produced by the reduction of the oxides with gaseous magnesium |
CZ303685B6 (cs) * | 1998-05-06 | 2013-03-06 | H. C. Starck Inc. | Práskový niob ve forme aglomerovaných primárních cástic, anoda kondenzátoru z tohoto práskového niobu a kondenzátor |
EP1144147B8 (en) | 1998-05-06 | 2012-04-04 | H.C. Starck GmbH | METHOD FOR PRODUCING METAL POWDERS BY REDUCTION OF THE OXIDES, Nb AND Nb-Ta POWDERS AND CAPACITOR ANODE OBTAINED THEREWITH |
JP2000226607A (ja) * | 1999-02-03 | 2000-08-15 | Showa Kyabotto Super Metal Kk | タンタル又はニオブ粉末とその製造方法 |
ATE304734T1 (de) | 1999-07-15 | 2005-09-15 | Showa Denko Kk | Niob pulver, gesinterter körper und daraus bestehender kondensator |
US6521173B2 (en) * | 1999-08-19 | 2003-02-18 | H.C. Starck, Inc. | Low oxygen refractory metal powder for powder metallurgy |
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JP4828016B2 (ja) | 2000-08-09 | 2011-11-30 | キャボットスーパーメタル株式会社 | タンタル粉末の製法、タンタル粉末およびタンタル電解コンデンサ |
AU1851002A (en) | 2000-11-30 | 2002-06-11 | Showa Denko Kk | Powder for capacitor, sintered body thereof and capacitor using the sintered body |
US6398125B1 (en) * | 2001-02-10 | 2002-06-04 | Nanotek Instruments, Inc. | Process and apparatus for the production of nanometer-sized powders |
JP3624898B2 (ja) | 2002-04-26 | 2005-03-02 | 昭和電工株式会社 | ニオブ粉、それを用いた焼結体及びそれを用いたコンデンサ |
JP4107898B2 (ja) | 2002-07-18 | 2008-06-25 | 石原薬品株式会社 | 純金属・合金超微粉末の製造方法 |
JP2004360043A (ja) * | 2003-06-06 | 2004-12-24 | Sumitomo Metal Mining Co Ltd | ニオブおよび/またはタンタル粉末の製造方法 |
EP1736261B1 (en) * | 2004-04-15 | 2008-12-17 | JFE Mineral Company, Ltd. | Tantalum powder and solid electrolytic capacitor utilizing the same |
WO2006062234A1 (ja) * | 2004-12-10 | 2006-06-15 | Cabot Supermetals K.K. | 金属粉末および多孔質焼結体の製造方法、金属粉末、およびコンデンサ |
JP2009007675A (ja) | 2008-07-03 | 2009-01-15 | Cabot Supermetal Kk | 窒素含有金属粉末およびそれを用いた多孔質焼結体および固体電解コンデンサ |
JP2009275289A (ja) | 2009-07-10 | 2009-11-26 | Cabot Supermetal Kk | 窒素含有金属粉末の製造方法 |
JP2010265549A (ja) * | 2010-06-11 | 2010-11-25 | Showa Denko Kk | コンデンサ用ニオブ粉 |
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JPWO2016038711A1 (ja) | 2017-06-29 |
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