TWI355424B - Process for producing niobium suboxide - Google Patents

Process for producing niobium suboxide Download PDF

Info

Publication number
TWI355424B
TWI355424B TW93121672A TW93121672A TWI355424B TW I355424 B TWI355424 B TW I355424B TW 93121672 A TW93121672 A TW 93121672A TW 93121672 A TW93121672 A TW 93121672A TW I355424 B TWI355424 B TW I355424B
Authority
TW
Taiwan
Prior art keywords
patent application
temperature
reaction
nboy
metal
Prior art date
Application number
TW93121672A
Other languages
English (en)
Other versions
TW200516157A (en
Inventor
Christoph Schnitter
Original Assignee
Starck H C Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Starck H C Gmbh filed Critical Starck H C Gmbh
Publication of TW200516157A publication Critical patent/TW200516157A/zh
Application granted granted Critical
Publication of TWI355424B publication Critical patent/TWI355424B/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H01G9/0525—Powder therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6265—Thermal treatment of powders or mixtures thereof other than sintering involving reduction or oxidation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/20—Powder free flowing behaviour
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C04B2235/3253—Substoichiometric niobium or tantalum oxides, e.g. NbO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/528—Spheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C04B2235/5481—Monomodal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/549—Particle size related information the particle size being expressed by crystallite size or primary particle size
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/608—Green bodies or pre-forms with well-defined density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Description

九、發明說明： 【技術領域】
本發明涉及-㈣造近她成為腦的低氧祕的方法 低氧化鈮特別適合於固體電解質電容器陽極的生產。 L 【背景技術】 固體電解質電容器具有非常大的有效電容器表面積，因而具 較小的整體結構，適合用於移動通信電子器件，其主要是具有應 於相應導電基底上的鈮或鎢的五氧化物阻擋層的電容器，並且其 用了攻些化合物（“閥金屬”）的穩定性、相對高的介電常數以及通 過電化學方法可以製造出層厚非常均句的絕緣五氧化物層的事 實。所用的基底是金屬或相應五氧化物的導電的低氧化物（低氧化 物）前體。基底，其同時構成了電容器電極（陽極），包含通過燒 結那些已經是類海綿狀形式的極細微粒初級或次級結構而產生的 高度多孔的、類海雜的結構。基底結構的表面被電解氡化（“成 形”)來產生五氧化物，且五氧化物層厚度由最大的電解氧化電壓 (“成形電壓”）確定《»反電極通過向_雜結構注人魏猛而製 得，硝酸Μ加熱轉變成二氧條，或者注人聚合物電解質的液態前 體並接著進行聚合。對電極的電接觸—方面由在基底結構製造過程 中燒結而成驗或齡屬線來產生H面㈣所述金屬線絕緣 的金屬電容器護層構成。 電容器電容通過下列方程計算： C = (F-£)/(d-VF) 式中F表示電容器表面積，ε為介電常數，d為每乂成形電壓 的絕緣層厚度，並且Vf為成形電壓。由於五氡化二城五氧化二 銳的介電常數ε分別是27.6或4卜但其每伏特成形電壓的層厚度
Sd ::二6: Γ〜種五氧化物擁有幾乎相同的s/d 關的⑽m〜 具有相同的電容。關於與重量相 5 --〇.-"：：>:r ； ：rr'·3: 的優點，當::= 音，2 母克重量的節省都是優先的。考相費用的因 有利/%極結構的某些體積由氧來提供，因此Nb0*比Nb更為 10 =化銳粉末使用標準的冶金反應和合金方法來生產，據此通# 氧化銳和金屬銳在氫的存在下暴露於氧濃度達到平衡的溫 又下而產生平均氧化物含量，請參閱例子w〇⑻/i55m · 2Nb205+3Nb 5NbO ⑴ 15 一因此該方法包括商業上可得的高純五氧化二朗使用及其與 高純金屬銳的混合，二者皆為粉末狀且按照化學計量比例混合在 溫度為80(TC-160(rC的含氫氣氛中加工處理二者數小時，該氣氛中 優選應至多含氫1G% 〇對於五氧化物和金屬物，在氧平衡發生後， ’、有所期望的(小於或稍大於(最小）截面尺寸的初始粒度的& 優選。 零 20 在該方法中，用鈮或钽做成的坩堝内充滿了五氧化二鈮和金屬 鈮粉末，然後在含氫氣氛下在爐中被加熱到反應溫度。 需要與五氧化二鈮進行氧交換的金屬鈮最好由高純度的五氧 化一銳還原形成金屬而產生。 這可以通過鋁熱作用來實現，即點燃Nb2〇5/A1的混合物，並清 洗掉所形成的鋁的氧化物，然後用電子束淨化鈮金屬塊錠。還原以 及電子束熔化後得到的鈮金屬塊可以通過已知的方法用氫使其脆 化，並被磨細以產生薄層片晶狀粉末。 -6 - 25 1355424 Λ 依照與WOOO/67936A1相一致的生產金屬鈮的優選方法，首 先用氫在1000-16001還原高純度的五氧化二鈮粉末以形成分子式 近似為Nb〇2的銳的二氧化物，然後用鎂蒸汽在75〇_11〇(rc還原成 ，屬。在該方法中形成的氧化鎂用酸來清洗掉。上述後一種的方法 疋特別優選的，這疋由於其能量要求相當低，以及大致上保持了五 氧化二_初始粒度和被對電容H特財害的㈣污染的風險 低的事實。 依照反應方程式（1)反應的-個缺點是五氧化二銳體積收縮 在轉變成低氧化鈮的過程中大約等於50%，這導致了 一個相當鬆散 10 #低氧化物晶體微結構，該晶體微結構只能在具有加人晶體缺陷的 風險的條件下被壓實，並且因此可能最終對電容器特性產生負面影 響。低氧化物不良的晶體性質也是其流動特性不足的一個原因。〜 在電谷器生產中，電容器粉末良好的流動特性代表了一個重要 的加工參數’這是由於粉末通過自動高速擠壓機而被擠壓而要被 15擠壓的粉末是通過儲存容器供給到高速擠壓機的。良好的流動特性 2表了規定的粉末量以滿足當代要求的精度流入壓榨模具的一個 前提條件’例如+/_〇.5mg的精度。 【發明内容】 20 本發明的目的是克服現有技術的缺點。 本發明進一步的目 粉末》 的是提供具有改良的流動特性的低氧化鈮 本發明的另外一個目的是減少高純鎂的消耗和氧化鎂的 生’以及同時減少涉及氧化鎂清洗的費用。 、 此外’顯著增加爐容量也是本發明的目的。 屬 本發明另-個目的是進-步減少在生產低氧化銳所需的金 银的生產過程中發生污染的風險。 25 1355424 因此，根據本發明，近似組成為Nb〇2的鈮的二氧化物用作起 始氧化物以和金屬鈮粉末達到冶金氧平衡。優選在1〇〇(rc到 1600C的溫度下通入氫，還原五氧化二銳製備銳的二氧化物。 因此本發明的主題是一種製造Nb〇x的方法，其中〇 7<χ<1 3， 5 優選Ο·%〆1·1〗，特別優選1<χ<1·〇5，通過NbOy與按化學計量所 需的金屬銳在風的存在下反應，其中l_8<y<2.i，優選。在 能使所發生的反應基本上完全進行的前提下來確定的反應溫度和 時間。 本發明的另一個主題是分子式NbOx的低氧化鈮粉末，其中 10 0.7<x<1.3，優選〇.9<x<1.15 ’特別優選ι<χ<ι.05，此低氧化鈮粉 末具有根據ASTM B213最大60s/25g的流動特性，優選最大 50s/25g，特別優選最大4〇s/25g。 根據本發明，該方法的反應溫度優選從900°C到160(TC。反應 時間可以選擇0.5-4小時，取決於反應溫度和起始物質的成分和瀨 15 粒結構，以及最終產品的成分。 根據本發明，用於該方法的起始銳的二氧化物優選通過通入氫 還原五氧化二銳來製備。優選在5〇到u〇〇mbar的氫分壓下發生反 應。可以發現，當氫流中沒有水蒸汽時，反應已綠完成。反應完成 後，為了穩定及壓實NbOy晶格，優選地產品仍在9〇〇。〇到1600°C， 20 優選從1200°C到1600°C的溫度下保持一定的時間，如〇·ΐ-〇.5小時。 而且，在還原五氧化物以形成二氧化物時，優選地，溫度逐漸 地從950C-1100°C範圍的起始溫度增加到13〇〇。〇1600。(：範圍的最 高溫度’特別優選從l〇〇〇tM〇5〇t：範圍的起始溫度到 1350C-1600C範圍的最高溫度。並且，使還原在逐步降低的溫度 25 中繼續進行，如果適當的話，可以先在最高溫度停留一段時考 慮到在初始還原價段中氧濃度的降低’可以通過增加溫度在基本上 對還原速率加以維持，或通過使用更低的起始溫度來避免過快的還 1355424 原速率所導致的過快的晶格擴展。然後’將高的最終溫度在 1300°C-1600°C範圍内保持一段時間’這樣晶格能夠缴密化而且晶 格缺陷被在很大程度上退火。 另一方面’通過急速加熱到1450°C-1600°C的還原溫度，可能 會在初始時發生非常急速的還原，從而導致早在二氧化物產生期間 晶格就急速擴展’這樣晶格變得很不穩定，並產生相對強的初始粒 子增長。如果目的是生產30000-70000pFV/g的中容量電容器，並 用超細顆粒五氧化二銳做起始物質’這可能是令人滿意的。如果這 樣的話’為了鞏固二氧化物的晶格，將溫度保持在丨2〇〇。〇4600。0 是有益的® 所需的還原時間依賴於使用的五氧化二銳的粒度以及選擇的 還原溫度。當五氧化物的初始粒度為〇.3-〇.5μηι的情況下，20-40 分鐘的還原時間一般足夠、 由於相對高的還原溫度（包括第一個例子中的最高溫度），燒 結的帶有極高強度的跨接甚至在鈮的二氧化物中形成。· 通過鎮蒸>飞，可以在相對低的溫度下，例如90(^(0-11001，實 現二氧化物的進一步還原，以形成金屬。在這些低的溫度下，僅發 生最小的初始微粒粗化》結果，由於二氧化物和金屬的初始微粗和 團聚物的尺寸沒有差別，尤其是氧平衡後彼此幾乎相同，因此，對 於來源單一的鈮的二氧化物來說，可能一方面部分的被進一步還原 以形成金屬物，而另一方面未經進一步處理而同金屬物混合，然後 達到氧平衡以形成低氧化物。 因此’根據本發明’低氧化物依照下列方程式產生：
Nb02+Nb 2NbO ⑺ 體積收縮在Nb〇2轉變成NbO的過程中大約僅為13%。雖然 五氧化物42%的體積收縮中的多數已轉移到Nb〇2的生產中但這 沒有相反的作用，因為在氫還原期間它可能會影響作為的晶 -9- 1355424 體微結構的中間穩定。 一個另外的優勢是，依照本發明的方法，鎂的消耗、沖洗費用 以及生產金屬鈮所需產生的氧化鎂的比例均減少了 2〇%(基於Nb〇 的最終產量） 本發明另一個優勢是增加了用於形成Nb〇的反應爐的容量。 依照反應方程（1) ’從起始混合物到產品的體積收縮為23 5%，而 依照本發明的反應方程式體積的增加僅有6%(理論上），其在實際 中被燒結收縮所彌補《依照方程式（丨），溶爐掛祸最初丨被充 滿’反應結束後僅有81%被NbO充滿。 因此’就依照本發明所對應的方程式（2)的反應來說’容量 能（在理論上）增加（19%/81%=) 23% ^實際上，考慮到燒結收 縮，容量的增加甚至更大。 【具體實施方式】 15 實施例 實施例1 a)鈮的二氧化物NbOy的製造 使用部分團聚的高純度的球狀五氧化二鈮，此五氧化二鈮經過 300μιη篩格尺寸的篩子篩濾，具有直徑大約為0.7μιη的初始粒度 2〇 .以及依照BET(ASTM D 3663)測定的2.4m2/g的比表面積。 在如下所述的溫度條件下通入氫，使五氧化物被還原成鈮的二 氧化物，其中溫度在40分鐘的時間内從950°C升到1300°C，爲後 保持在1300°C下30分鐘，接下來在30分鐘内降溫至120(TC，然 後保持此溫度1小時。 25 鈮的二氧化物具有對應於式Nb02.G1的組成；初始粒度被粗化 到接近0.9μηι(從SEM圖像中觀測），並且BET表面積為l.lm2/g。 通過300μπι篩格尺寸的篩子之後，使用Malvern(ASTM B 822, -10· 1355424 濕潤劑Daxad 11)生產的MastersizerSp測量粒度分佈’得到32μιη 的 D10 值，164μπι 的 D50 值’和 247μπι 的 D90 值。 b) 金屬鈮的製造 5 在反應器中，部分在a)中獲得的鈮的二氧化物被放置在鈮線篩 子上。1.1倍於按化學反應計量所索的鎂(基於二氧化物中氧的量）， 被放置在坩堝中篩子下面》反應器用氬氣從下而上清洗。然後，反 應器被加熱到1050°C。8小時後，冷卻反應器並且空氣緩慢的進入 以鈍化金屬表面、
1〇 獲得的金屬妮粉末具有0.85μηι的初始粒度，1.32m2/g的BET 面積，並且通過300μιη篩格尺寸的篩子之後，具有33μπι的D10 值，176μιη 的 D50 值，和 263μιη 的 D90 值。 c) 低氧化銳NbOx的製造. 15 按重量計，將43份在b>中獲得的銳、粉末以及57份在a)中獲 得的鈮的二氧彳匕物粉末混合並導入坩堝令，填充到坩堝邊緣。然後-’ 在2.5小時期間内，在爐中將坩堝加熱到丨38.〇。〇，咚熔爐用含85% 體積氬氣和15%體積氫氣的混合氣清洗過。 冷卻之後’獲得對應於式Nb〇(>96的低氧化鈮粉末。此低氧化 20 物粉末具有〇·95μηι的初始粒度以及l.lm2/g的BET面積。通過 300μήι _格尺寸的篩子之後，m〇值為41卿，D5〇值為182μπι， D90 值為 258μιη。 d)電容器製造 在每個實例中’ l〇3mg根據c)所得的低氧化錕粉末被導入擠 壓模具中’以包圍銳接觸線，然後其被擠壓以形成壓制密度為2.8g/ cm3的壓縮體。 • 11 - 1355424 此壓縮體被隨意放置在銳平臺上，在10-3pa的高真空中在 1450C’皿度下燒結20分鐘。在85〇c溫度下，在含有〇 1%強度鱗酸 的電解質中形成陽極’成型電流為並且成型電愿可高達 3〇V，該成型電壓在電流衰退後維持2小時。 / 5 陽極體的電容和殘餘電流’其由通過成形而得的五氧化二銳阻 擔層所提供’並通過用18%強度的濃硫酸在坑下模擬的反電極 來加以測定。3分鐘的充電時間之後，這些測量在21V (成型電壓 的70%)電壓’ 120Hz的頻率以及1〇v的偏壓下進行^測定平均、 比電容為75 158pFV/g並且殘餘電流為〇 76ηΑ/μ]ρν。 10 實施例2 a) 鈮的二氧化物NbOy的製造： 所使用的起始物質是部分團聚的、高純度的、實際上為球狀的 Nb2〇5,經過篩濾使其小於300μιη，並且其依照BET(ASTMD3663)、 15 測定的比表面積為2.3m2/g。通入氫氣，這些Nb205部分被還原為 組成為Nb〇2〇2的氧;化物，在其中溫度在6〇分鐘的時間内從1〇〇〇。匚. 升到1450°C，然後在1450°C下保持200分鐘。此二氧化物比表面 積為0.32m2/g ’通過鐳射衍射(ASTM B 822)測定，具有D10值為 67μιη，D50值為176μπι以及D90值為284μιη的粒度分佈。 20 b) 金屬鈮的製造 部分在a)中製造的鈮的二氧化物被放置在反應器_金屬絲網 上。在金屬絲網下面，有1.2倍於按化學反應計量所需的鎂（基於 二氧化物中氧的量）。將反應器在通入氬氣下加熱4小時，到 25 900°C。在此期間，鎂蒸發並且把其上面的鈮的二氧化物還原成金 屬。冷卻和鈍化之後，通過反復的用硫酸再用水清洗，從形成的金 屬銳中移除形成的氧化鎂。 • 12· 1355424
形成的金屬銳粉末具有0·4-0.6μιη的初始粒度（從SEM圖像中 觀測）’ 3.87m2/g的比表面積以及通過鐳射衍射測定（ASTm D 3663 ’ Malvern Mastersizer)的 54μιη 的 Dl〇 值，ΐ61μπι 的 D50 值， 和 272μιη 的 D90 值。 5 ( c)低氧化鈮NbOx的製造 1·依照現有技術的程序 在b)中製造的金屬铌的一半與在a)中所描述的Nb2〇5按重量 比1 : 0.95混合。然後在67mbar的絕對氫分壓下，在爐中加熱到 10 1400°C並維持3小時◊然後使粉末通過3〇〇μιη篩格尺寸的篩子。 用該方法獲得的低氧化鈮（粉末Α)的組成為NbOui並具有 0.95-1.1μιη的初始粒度（從SEM圖像中觀測）。比表面積為 1.07m2/g，以及經鐳射衍射測定的D1O值為71μιη，D50值為 165μιη ’ D90 值為 263μιη。 15 2.依照本發明的程序 另一半在b)中製造的金屬鈮同在a)中產生的部分按重 量比1:1.34混合《然後在67mbar絕對氫分壓下，在爐中加熱2小 時，到1210°C。獲得的低氧化鈮（粉末B)具有>^〇()98的組成以_ 及1.13m/g的比表面積。從SEM圖像中觀測的初始粒度平均為 20 丨.^111’並且經鐳射衍射測定的粒度分佈為62μηι的D10值，Ι58μηι 的D50值’和269μιη的D90值。 兩種粉末的流動特性根據ASTM Β213測定。 結果如下： 粉末 A: 65s/25g 25 粉末 B: 26s/25g. 因此’與按傳統方法所得的產品相比，本發明的程序製得的低 氧化鈮的區別在於其進步的流動特性。

Claims (1)

  1. 專利申請案第93121672號 ROC Patent Application No. 93121672 修正之申請專利範圍中文本-附件（二) Amended Claims in Chinese-Encl. ΠΠ (民國100年7月20日送呈） (Submitted on July 20,2011) 年7肋日修正本 '申請專利範圍： l —種製造NbOx的方法，其中〇.7<x<1.3，優選〇 9<χ<1 15，特 別優選1<χ<1.〇5,該方法通過將NbOy與化學計量數的金屬鈮在 氫的存在下進行反應’其中1.8<y<2.1，優選，來製造 所述的NbOx。 2·根據申請專利範圍第丨項的方法，其特徵在於，反應的溫度和 時間按照使反應基本完全發生的方式來選擇。 3. 根據申請專利範圍第2項的方法，其特徵在於，反應的溫度是 9〇〇°C-1600°C ’以及反應的時間是0.5-4小時。 4. 根據申請專利範圍第丨至3項中任一項的方法，其特徵在於， 起始物質鈮的二氧化物NbOy是通過通入氫還原五氧化二鈮而 製得的。 5. 根據申請專利範圍第4項的方法，其特徵在於，所述還原是在 1〇〇0°C-1600°C的溫度下進行的。 6. 根據申請專利範圍第5項的方法，其特徵在於，反應結束後， 反應產物仍在90(rc-1600t：的溫度下保持一段時間以穩定和壓 實NbOy晶格。 〜 7. 根據申睛專利範圍第6項中任一項的方法，其特徵在於，使用 由平均最小粒度〇.4-2μιη的初始微粒的團聚物形成的粉末狀五 氧化二鈮。. .刀 8. 根據申睛專利範圍第1至3項中任一項的方法，其特汽在於， 使用按照申請專利範圍第4至6項中任一項的方法用鎮蒸汽還 原NbOy所獲得的金屬鈮粉末。 9. 根據申請專利範圍第8項的方法，其特徵在於，在75〇它_11別。c 的溫度下還原NbOy以形成所述金屬。 10. —種分子式為Nb〇x的低氧化物，其中Θ 3，優選 93320申請專利範圍 • 14· 1355424 0.9<χ<1·15，特別優選1<χ<1.05，具有依照ASTM B213最大 60s/25g的流動特性。 11.一種電容器，其包含根據申請專利範圍第10項所述燒結的粉末 狀陽極。
TW93121672A 2003-07-22 2004-07-21 Process for producing niobium suboxide TWI355424B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2003133156 DE10333156A1 (de) 2003-07-22 2003-07-22 Verfahren zur Herstellung von Niobsuboxid

Publications (2)

Publication Number Publication Date
TW200516157A TW200516157A (en) 2005-05-16
TWI355424B true TWI355424B (en) 2012-01-01

Family

ID=34042009

Family Applications (1)

Application Number Title Priority Date Filing Date
TW93121672A TWI355424B (en) 2003-07-22 2004-07-21 Process for producing niobium suboxide

Country Status (15)

Country Link
US (2) US7341705B2 (zh)
EP (2) EP2078699A1 (zh)
JP (2) JP4317091B2 (zh)
KR (1) KR101129764B1 (zh)
CN (2) CN101298340A (zh)
AU (1) AU2004203208B2 (zh)
BR (1) BRPI0402986A (zh)
DE (2) DE10333156A1 (zh)
IL (1) IL163104A (zh)
MX (1) MXPA04007024A (zh)
PH (1) PH12008000260A1 (zh)
PT (1) PT1508550E (zh)
RU (1) RU2363660C2 (zh)
TW (1) TWI355424B (zh)
ZA (1) ZA200405851B (zh)

Families Citing this family (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10333156A1 (de) * 2003-07-22 2005-02-24 H.C. Starck Gmbh Verfahren zur Herstellung von Niobsuboxid
DE10347702B4 (de) * 2003-10-14 2007-03-29 H.C. Starck Gmbh Sinterkörper auf Basis Niobsuboxid
US8362987B2 (en) * 2004-09-27 2013-01-29 Qualcomm Mems Technologies, Inc. Method and device for manipulating color in a display
US7399335B2 (en) * 2005-03-22 2008-07-15 H.C. Starck Inc. Method of preparing primary refractory metal
US7399341B2 (en) * 2005-04-26 2008-07-15 Uop Llc Gas purification process
WO2007020458A1 (en) * 2005-08-19 2007-02-22 Avx Limited Polymer based solid state capacitors and a method of manufacturing them
GB0517952D0 (en) * 2005-09-02 2005-10-12 Avx Ltd Method of forming anode bodies for solid state capacitors
JP4969233B2 (ja) * 2006-12-20 2012-07-04 三洋電機株式会社 固体電解コンデンサ及び固体電解コンデンサ用のニオブ製陽極リードの製造方法
US7760487B2 (en) * 2007-10-22 2010-07-20 Avx Corporation Doped ceramic powder for use in forming capacitor anodes
US7760488B2 (en) * 2008-01-22 2010-07-20 Avx Corporation Sintered anode pellet treated with a surfactant for use in an electrolytic capacitor
US7852615B2 (en) 2008-01-22 2010-12-14 Avx Corporation Electrolytic capacitor anode treated with an organometallic compound
US7768773B2 (en) * 2008-01-22 2010-08-03 Avx Corporation Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor
US7826200B2 (en) * 2008-03-25 2010-11-02 Avx Corporation Electrolytic capacitor assembly containing a resettable fuse
US8094434B2 (en) 2008-04-01 2012-01-10 Avx Corporation Hermetically sealed capacitor assembly
US8199462B2 (en) 2008-09-08 2012-06-12 Avx Corporation Solid electrolytic capacitor for embedding into a circuit board
DK2332429T3 (da) * 2008-09-09 2013-10-28 Ndc Corp Handske og vedhæftning dertil
DE102008048614A1 (de) * 2008-09-23 2010-04-01 H.C. Starck Gmbh Ventilmetall-und Ventilmetalloxid-Agglomeratpulver und Verfahren zu deren Herstellung
US20100085685A1 (en) * 2008-10-06 2010-04-08 Avx Corporation Capacitor Anode Formed From a Powder Containing Coarse Agglomerates and Fine Agglomerates
US8203827B2 (en) * 2009-02-20 2012-06-19 Avx Corporation Anode for a solid electrolytic capacitor containing a non-metallic surface treatment
US8405956B2 (en) * 2009-06-01 2013-03-26 Avx Corporation High voltage electrolytic capacitors
US8199461B2 (en) * 2009-05-29 2012-06-12 Avx Corporation Refractory metal paste for solid electrolytic capacitors
US8441777B2 (en) * 2009-05-29 2013-05-14 Avx Corporation Solid electrolytic capacitor with facedown terminations
US8279583B2 (en) * 2009-05-29 2012-10-02 Avx Corporation Anode for an electrolytic capacitor that contains individual components connected by a refractory metal paste
US8139344B2 (en) * 2009-09-10 2012-03-20 Avx Corporation Electrolytic capacitor assembly and method with recessed leadframe channel
US8194395B2 (en) 2009-10-08 2012-06-05 Avx Corporation Hermetically sealed capacitor assembly
US8125768B2 (en) 2009-10-23 2012-02-28 Avx Corporation External coating for a solid electrolytic capacitor
US8339771B2 (en) 2010-02-19 2012-12-25 Avx Corporation Conductive adhesive for use in a solid electrolytic capacitor
US8125769B2 (en) 2010-07-22 2012-02-28 Avx Corporation Solid electrolytic capacitor assembly with multiple cathode terminations
US8259436B2 (en) 2010-08-03 2012-09-04 Avx Corporation Mechanically robust solid electrolytic capacitor assembly
US8279584B2 (en) 2010-08-12 2012-10-02 Avx Corporation Solid electrolytic capacitor assembly
US8605411B2 (en) 2010-09-16 2013-12-10 Avx Corporation Abrasive blasted conductive polymer cathode for use in a wet electrolytic capacitor
US8199460B2 (en) 2010-09-27 2012-06-12 Avx Corporation Solid electrolytic capacitor with improved anode termination
US8514547B2 (en) 2010-11-01 2013-08-20 Avx Corporation Volumetrically efficient wet electrolytic capacitor
US8259435B2 (en) 2010-11-01 2012-09-04 Avx Corporation Hermetically sealed wet electrolytic capacitor
US8824122B2 (en) 2010-11-01 2014-09-02 Avx Corporation Solid electrolytic capacitor for use in high voltage and high temperature applications
US8355242B2 (en) 2010-11-12 2013-01-15 Avx Corporation Solid electrolytic capacitor element
US8493713B2 (en) 2010-12-14 2013-07-23 Avx Corporation Conductive coating for use in electrolytic capacitors
US8576543B2 (en) 2010-12-14 2013-11-05 Avx Corporation Solid electrolytic capacitor containing a poly(3,4-ethylenedioxythiophene) quaternary onium salt
US8451588B2 (en) 2011-03-11 2013-05-28 Avx Corporation Solid electrolytic capacitor containing a conductive coating formed from a colloidal dispersion
US8582278B2 (en) 2011-03-11 2013-11-12 Avx Corporation Solid electrolytic capacitor with improved mechanical stability
US8514550B2 (en) 2011-03-11 2013-08-20 Avx Corporation Solid electrolytic capacitor containing a cathode termination with a slot for an adhesive
US8300387B1 (en) 2011-04-07 2012-10-30 Avx Corporation Hermetically sealed electrolytic capacitor with enhanced mechanical stability
US8947857B2 (en) 2011-04-07 2015-02-03 Avx Corporation Manganese oxide capacitor for use in extreme environments
US8379372B2 (en) 2011-04-07 2013-02-19 Avx Corporation Housing configuration for a solid electrolytic capacitor
US9767964B2 (en) 2011-04-07 2017-09-19 Avx Corporation Multi-anode solid electrolytic capacitor assembly
US9275799B2 (en) 2011-12-20 2016-03-01 Avx Corporation Wet electrolytic capacitor containing an improved anode
WO2013106659A1 (en) 2012-01-13 2013-07-18 Avx Corporation Solid electrolytic capacitor with integrated fuse assembly
DE102013101443A1 (de) 2012-03-01 2013-09-05 Avx Corporation Ultrahigh voltage solid electrolytic capacitor
US8971019B2 (en) 2012-03-16 2015-03-03 Avx Corporation Wet capacitor cathode containing an alkyl-substituted poly(3,4-ethylenedioxythiophene)
JP2013219362A (ja) 2012-04-11 2013-10-24 Avx Corp 過酷な条件下で強化された機械的安定性を有する固体電解コンデンサ
US9776281B2 (en) 2012-05-30 2017-10-03 Avx Corporation Notched lead wire for a solid electrolytic capacitor
JP5933397B2 (ja) 2012-08-30 2016-06-08 エイヴィーエックス コーポレイション 固体電解コンデンサの製造方法および固体電解コンデンサ
KR101702790B1 (ko) 2012-11-13 2017-02-06 제이엑스금속주식회사 NbO2 소결체 및 그 소결체로 이루어지는 스퍼터링 타깃 그리고 NbO2 소결체의 제조 방법
GB2512480B (en) 2013-03-13 2018-05-30 Avx Corp Solid electrolytic capacitor for use in extreme conditions
US9324503B2 (en) 2013-03-15 2016-04-26 Avx Corporation Solid electrolytic capacitor
US9240285B2 (en) 2013-04-29 2016-01-19 Avx Corporation Multi-notched anode for electrolytic capacitor
US9892862B2 (en) 2013-05-13 2018-02-13 Avx Corporation Solid electrolytic capacitor containing a pre-coat layer
US9472350B2 (en) 2013-05-13 2016-10-18 Avx Corporation Solid electrolytic capacitor containing a multi-layered adhesion coating
GB2517019B (en) 2013-05-13 2018-08-29 Avx Corp Solid electrolytic capacitor containing conductive polymer particles
US9236192B2 (en) 2013-08-15 2016-01-12 Avx Corporation Moisture resistant solid electrolytic capacitor assembly
US9269499B2 (en) 2013-08-22 2016-02-23 Avx Corporation Thin wire/thick wire lead assembly for electrolytic capacitor
US9916935B2 (en) 2014-11-07 2018-03-13 Avx Corporation Solid electrolytic capacitor with increased volumetric efficiency
US9620293B2 (en) 2014-11-17 2017-04-11 Avx Corporation Hermetically sealed capacitor for an implantable medical device
US10290430B2 (en) 2014-11-24 2019-05-14 Avx Corporation Wet Electrolytic Capacitor for an Implantable Medical Device
US9892860B2 (en) 2014-11-24 2018-02-13 Avx Corporation Capacitor with coined lead frame
US9837216B2 (en) 2014-12-18 2017-12-05 Avx Corporation Carrier wire for solid electrolytic capacitors
US9620294B2 (en) 2014-12-30 2017-04-11 Avx Corporation Wet electrolytic capacitor containing a recessed planar anode and a restraint
US10014108B2 (en) 2015-03-13 2018-07-03 Avx Corporation Low profile multi-anode assembly
US10297393B2 (en) 2015-03-13 2019-05-21 Avx Corporation Ultrahigh voltage capacitor assembly
US9754730B2 (en) 2015-03-13 2017-09-05 Avx Corporation Low profile multi-anode assembly in cylindrical housing
US9928963B2 (en) 2015-03-13 2018-03-27 Avx Corporation Thermally conductive encapsulant material for a capacitor assembly
US9905368B2 (en) 2015-08-04 2018-02-27 Avx Corporation Multiple leadwires using carrier wire for low ESR electrolytic capacitors
US9842704B2 (en) 2015-08-04 2017-12-12 Avx Corporation Low ESR anode lead tape for a solid electrolytic capacitor
US9545008B1 (en) 2016-03-24 2017-01-10 Avx Corporation Solid electrolytic capacitor for embedding into a circuit board
US9907176B2 (en) 2016-03-28 2018-02-27 Avx Corporation Solid electrolytic capacitor module with improved planarity
US9870869B1 (en) 2016-06-28 2018-01-16 Avx Corporation Wet electrolytic capacitor
US9870868B1 (en) 2016-06-28 2018-01-16 Avx Corporation Wet electrolytic capacitor for use in a subcutaneous implantable cardioverter-defibrillator
MX2019003260A (es) 2016-09-22 2019-07-04 Avx Corp Capacitor electrolitico que contiene un metal de valvula proveniente de un sitio de mina libre de conflictos y un metodo para formarlo.
US10431389B2 (en) 2016-11-14 2019-10-01 Avx Corporation Solid electrolytic capacitor for high voltage environments
DE112018004392T5 (de) 2017-09-21 2020-05-14 Avx Corporation Elektronisches bauteil, enthaltend eine metallkomponente, die aus einem konfliktfreien bergwerksstandort bezogen wurde, und ein verfahren zu dessen ausbildung
US11081288B1 (en) 2018-08-10 2021-08-03 Avx Corporation Solid electrolytic capacitor having a reduced anomalous charging characteristic
CN110963529B (zh) * 2018-09-30 2021-12-07 中国科学院上海硅酸盐研究所 一种纯相的铌的低价态氧化物纳米粉体及其制备方法和应用
US11380492B1 (en) 2018-12-11 2022-07-05 KYOCERA AVX Components Corporation Solid electrolytic capacitor
CN113728408B (zh) 2019-04-25 2024-03-08 京瓷Avx元器件(曼谷)有限公司 固态电解电容器
US11328874B2 (en) 2019-05-17 2022-05-10 KYOCERA AVX Components Corporation Solid electrolytic capacitor
US11756742B1 (en) 2019-12-10 2023-09-12 KYOCERA AVX Components Corporation Tantalum capacitor with improved leakage current stability at high temperatures
US11763998B1 (en) 2020-06-03 2023-09-19 KYOCERA AVX Components Corporation Solid electrolytic capacitor

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000067936A1 (en) 1998-05-06 2000-11-16 H.C. Starck, Inc. Metal powders produced by the reduction of the oxides with gaseous magnesium
DE19831280A1 (de) * 1998-07-13 2000-01-20 Starck H C Gmbh Co Kg Verfahren zur Herstellung von Erdsäuremetallpulvern, insbesondere Niobpulvern
US6180549B1 (en) 1998-09-10 2001-01-30 The B. F. Goodrich Company Modified zeolites and methods of making thereof
US6416730B1 (en) * 1998-09-16 2002-07-09 Cabot Corporation Methods to partially reduce a niobium metal oxide oxygen reduced niobium oxides
US6322912B1 (en) 1998-09-16 2001-11-27 Cabot Corporation Electrolytic capacitor anode of valve metal oxide
US6558447B1 (en) 1999-05-05 2003-05-06 H.C. Starck, Inc. Metal powders produced by the reduction of the oxides with gaseous magnesium
DE10030387A1 (de) * 2000-06-21 2002-01-03 Starck H C Gmbh Co Kg Kondensatorpulver
WO2002037513A2 (en) * 2000-11-06 2002-05-10 Cabot Corporation Modified oxygen reduced valve metal oxides
US7149074B2 (en) 2001-04-19 2006-12-12 Cabot Corporation Methods of making a niobium metal oxide
KR100663735B1 (ko) 2001-05-15 2007-01-03 쇼와 덴코 가부시키가이샤 니오브 분말, 니오브 소결체 및 이 소결체를 사용한 콘덴서
US7737066B2 (en) * 2001-05-15 2010-06-15 Showa Denko K.K. Niobium monoxide powder, niobium monoxide sintered body and capacitor using the sintered body
US20030104923A1 (en) * 2001-05-15 2003-06-05 Showa Denko K.K. Niobium oxide powder, niobium oxide sintered body and capacitor using the sintered body
CN103219156B (zh) * 2001-05-15 2017-04-26 昭和电工株式会社 电容器电极、电容器及其生产方法、电子电路及电子仪器
JP2003147403A (ja) * 2001-11-14 2003-05-21 Sumitomo Metal Mining Co Ltd コンデンサ製造用ニオブ粉末およびその製造方法
US7655214B2 (en) * 2003-02-26 2010-02-02 Cabot Corporation Phase formation of oxygen reduced valve metal oxides and granulation methods
PT1505611E (pt) * 2003-07-22 2012-01-12 Starck H C Gmbh Método para a produção de condensadores
DE10333156A1 (de) * 2003-07-22 2005-02-24 H.C. Starck Gmbh Verfahren zur Herstellung von Niobsuboxid

Also Published As

Publication number Publication date
JP4317091B2 (ja) 2009-08-19
US20090242853A1 (en) 2009-10-01
AU2004203208A1 (en) 2005-02-10
JP5630962B2 (ja) 2014-11-26
KR20050011700A (ko) 2005-01-29
IL163104A (en) 2007-10-31
ZA200405851B (en) 2005-09-28
RU2004122053A (ru) 2006-01-27
JP2005041774A (ja) 2005-02-17
TW200516157A (en) 2005-05-16
BRPI0402986A (pt) 2005-05-24
CN101298340A (zh) 2008-11-05
EP2078699A1 (de) 2009-07-15
CN100404428C (zh) 2008-07-23
EP1508550A1 (de) 2005-02-23
DE502004009299D1 (de) 2009-05-20
RU2363660C2 (ru) 2009-08-10
AU2004203208B2 (en) 2009-07-23
JP2009143804A (ja) 2009-07-02
MXPA04007024A (es) 2005-03-23
EP1508550B1 (de) 2009-04-08
KR101129764B1 (ko) 2012-03-26
PT1508550E (pt) 2009-05-22
US7341705B2 (en) 2008-03-11
PH12008000260A1 (en) 2006-03-07
DE10333156A1 (de) 2005-02-24
CN1576234A (zh) 2005-02-09
US20050019581A1 (en) 2005-01-27

Similar Documents

Publication Publication Date Title
TWI355424B (en) Process for producing niobium suboxide
AU2010201394B2 (en) Process for producing capacitors
AU2005291557B2 (en) Tantalum powder for the production of solid electrolyte capacitors
KR102317632B1 (ko) 큰 표면적을 갖는 저 산소 밸브 금속 소결체 제조 방법
JP2004524674A (ja) 電解コンデンサ基板のためのタンタルおよび窒化タンタル粉末混合物
JP4828016B2 (ja) 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
JP2002060803A (ja) 電解コンデンサ用タンタル焼結体の製造方法
WO2002004152A1 (fr) Poudre metallique contenant de l'azote, son procede de preparation, condensateur electrolytique solide et agglomere poreux fabrique au moyen de cette poudre metallique
EP2939761B1 (en) Production method for a niobium granulated product, production method for a sintered body, production method for a chemical conversion body for nobium capacitor positive electrode and production method for a capacitor
JP4521849B2 (ja) コンデンサ用ニオブ粉と該ニオブ粉を用いた焼結体および該焼結体を用いたコンデンサ
AU2012233028A1 (en) Process for producing capacitors

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees