CN1607197A - 基于低氧化铌的烧结体 - Google Patents

基于低氧化铌的烧结体 Download PDF

Info

Publication number
CN1607197A
CN1607197A CNA2004100900035A CN200410090003A CN1607197A CN 1607197 A CN1607197 A CN 1607197A CN A2004100900035 A CNA2004100900035 A CN A2004100900035A CN 200410090003 A CN200410090003 A CN 200410090003A CN 1607197 A CN1607197 A CN 1607197A
Authority
CN
China
Prior art keywords
sintered compact
moles
niobium
nbo
sintered
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.)
Granted
Application number
CNA2004100900035A
Other languages
English (en)
Other versions
CN100404463C (zh
Inventor
C·施尼特尔
G·维廷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HC Starck GmbH
Original Assignee
HC Starck 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34353397&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1607197(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by HC Starck GmbH filed Critical HC Starck GmbH
Publication of CN1607197A publication Critical patent/CN1607197A/zh
Application granted granted Critical
Publication of CN100404463C publication Critical patent/CN100404463C/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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
    • C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/053—Fine ceramics
    • 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
    • C04B35/64—Burning or sintering processes
    • 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
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides 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
    • 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
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 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
    • 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
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • 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
    • C04B2235/612—Machining
    • 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
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/6582—Hydrogen containing atmosphere
    • 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
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • Y10T29/00—Metal working
    • Y10T29/43—Electric condenser making
    • 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
    • Y10T29/00—Metal working
    • Y10T29/43—Electric condenser making
    • Y10T29/435—Solid dielectric type

Abstract

具有高耐化学性的烧结体,含有30到100摩尔％的NbOx和70到0摩尔％的MgO，其中0.5＜x＜1.5，以及它们在生产固体电解质电容器中的用途，特别是在生产由低氧化铌制成的烧结阳极中的用途，在生产低氧化铌和在化学仪器中的用途。

Description

基于低氧化铌的烧结体
技术领域
本发明涉及一种基于低氧化铌的烧结体，特别是烧结成形体，由于他们耐化学性，因而用于化学仪器上，并优选用于生产固体电解质电容器的阳极，特别是由低氧化铌制成的烧结阳极。
背景技术
由烧结的低氧化铌细颗粒形成表面积极大的海绵状结构来生产这种类型的阳极。通过电解氧化在此表面上形成介电五氧化二铌层，并且在五氧化二铌层上形成可由二氧化锰或高分子电解质组成的电容器阴极。用于生产此类型的阳极或电容器的方法，以及电容器前体粉末的生产方法，包括在真空或反应气体和/或保护气体中进行一系列的机械和热处理步骤，这必然要承担被某些元素污染的风险，而这些元素对电容器性能有副作用。因此，根据WO02/086923A2，有人提出用于生产阳极的机械处理或热处理的全部设备由铌金属制成或至少用铌金属涂覆。
这种技术的一个缺点是铌金属是一种高温下会吸收氧的获氧材料。因此，在生产低氧化铌阳极的高温处理步骤中，其可能涉及高达1600℃的温度，特别是在此高温下如果低氧化铌和铌金属直接接触时，带来的高风险是以无法控制的方式从低氧化铌中取出氧。而且，当重复使用时，由于摄入氧，铌金属变得愈加脆弱，因此具有较短的使用寿命。
发明内容
根据本发明，现建议用于生产此类阳极的装置应由基于低氧化铌和，如果适当，氧化镁的烧结体形成。
此类装置的例子包括：容器、反应器、反应器衬里、磨机衬里、磨球、磨辊、压模、压力机滑块等。
因此，本发明的主题是提供一种低氧化铌基烧结体，这种烧结体包含30到100摩尔％NbOx和高达70摩尔％氧化镁，其中0.5＜x＜1.5。
该烧结体优选含有分子式为NbOx的低氧化铌，其中0.7＜x＜1.3。
除不可避免的外来元素杂质之外，低氧化铌和氧化镁的摩尔百分数总量特别优选为100％。特别是，该烧结体应该基本上不含铁、铬、镍、碱金属和卤素。铁、镍、铬、钠、钾、氯和氟杂质的各自量应优选小于10ppm，特别优选小于5ppm，且总计优选小于30ppm。另一方面，杂质或钒、钽、钼和钨的搀杂元素含量为最多几摩尔％，例如5摩尔％以下，是无害的。
本发明的烧结体优选由35到100摩尔％的NbOx和65到0摩尔％的MgO组成。本发明的烧结体更优选地由30到60摩尔％的NbOx和70到40摩尔％的MgO组成，特别优选由45到60摩尔％的NbOx和55到40摩尔％的MgO组成。
本发明优选的烧结体的孔隙率小于30体积％，特别优选小于20体积％。
根据本发明，含有氧化镁的烧结体优选包括基本上包含均匀富低氧化铌区和富氧化镁区的微观结构，其在至少一个方向上延伸最多1.5μm，优选最多1.0μm。富低氧化铌区优选含有至少95％，特别优选至少99％的低氧化铌。富氧化镁区优选含有最多达99％的氧化镁。
可以利用普通的陶瓷工艺生产本发明的烧结体。例如，可以用轴压和/或等静压法、挤压法、常规无压法或加压粉浆浇铸法或通过注射模塑法进行成形。根据使用的方法，可以利用烧结技术中本来已知的方式向粉末中加入合适的有机助剂，例如PVA、PEG等(用于压制法)，市场上可买到的用于此目的的蜡或塑化剂(用于注射模塑法等)，其在模制之后可以被排出(粘结剂排出)，在空气、保护气体下或在真空中进行热处理而不会留下任何残渣，不会改变无机碱粉末的基本性能。在空气中，处理温度不应该超过250℃，优选150℃，以免低氧化铌发生氧化。
在压力成形的情况下，为了改善粉末的流动性，优选在粒化步骤中加入有机助剂。
在粉浆浇铸的情况下，在脱模之后和排出粘结剂之前，必须优选在空气中进行预干燥。而且，在成形步骤之后和排出粘结剂之前，可以利用切屑成形方法例如车削、研磨、钻屑等进行(仔细的)机械处理，以便把坯体制成尽可能接近烧结体要求的最终形状。为了固结成形体，在排出粘结剂和任何预烧结步骤之后，也可以进行此类的处理，而在这种情况下，也可以使用机械加工的方法例如干磨或湿磨。
在保护气氛例如氩气或氩气和通常3到10体积％氢气等的气体混合物下，在气密的炉子中进行烧结，以便平衡掉低氧化铌氧化态的变化。在烧结开始以前，用保护气体吹扫加热炉或抽空，并充满保护气体。为避免要烧结的成形体与炉衬之间的直接接触，将成形体固定在支架/垫片(“烧结辅助装置”)上，该支架/垫片是由在烧结温度下是热稳定和化学稳定的并且不与低氧化物起任何反应的材料制成。已经证明由致密的或多孔的碳化硅制成的烧结辅助装置是特别适合的材料。烧结优选在小于1700℃，特别优选在1550和1650℃之间的温度下进行，以小于10K/分钟的缓慢加热速度加热到烧结温度，在1100℃到烧结温度的较高温度范围优选1到3K/分钟的加热速度，同时在烧结温度下优选保温小于10小时的时间，烧结条件根据成形体要求的致密化和使用的低氧化铌和任选的氧化镁的颗粒大小来定。
用于生产本发明烧结体的原料优选是市场上可买到的比表面积为5到20m2/g的高纯度五氧化二铌。可将这样的五氧化二铌本身或者在流动的氢气中还原形成二氧化铌之后，借助镁蒸汽在950到1150℃温度下还原成低氧化物。这样形成了含有氧化镁杂质的团聚粉末。
将此种粉末研磨之后，可以用来生产本发明的烧结体。如果原料是二氧化铌，则获得含有大约50摩尔％MgO的烧结体。另一方面，如果原料是五氧化二铌，则获得含有大约67摩尔％氧化镁的烧结体。
生产不含有任何氧化镁的烧结体的原料同样优选为具有高比表面积的五氧化二铌细颗粒。五氧化二铌在流动的氢气中在1100到1400℃温度下还原形成二氧化铌。一些二氧化铌在镁蒸气中进一步还原形成铌金属。然后，用酸，例如硫酸，洗掉铌金属中形成的氧化镁。然后在含氢气的气氛中将铌金属与化学计量的二氧化铌一起加热到1100至1600℃，使其转化为低氧化铌NbO。通过相应地改变各个反应组分或混合物的量比可以获得本发明其它组成的烧结粉末。
为了获得比较高密度的烧结体，优选使用细颗粒的团聚粉末，特别优选筛分部分为38μm以下，更优选20μm以下的粉末。
而且，可以用于生产本发明烧结体的粉末非常适合于借助于高温或等离子喷涂来生产涂料，而在这种情况下可以在金属例如铌、钽、钼和/或钨上形成类似于烧结体结构的表面层。在这种情况下，如果合适，可以另外使用在20重量％以下，优选在10和18重量％之间的作为粘结剂的金属铌粉。根据本发明，由铌、钽、钼或钨制成的此类涂覆装置也适合于生产基于低氧化铌的固体电解质电容器。具有涂层的此类金属装置也列入本发明的术语“烧结体”之内，所述涂层的结构与烧结体的结构类似。
具体实施方式
生产实施例
以下通过本发明烧结体的例子来说明用于固体电解质电容器阳极的烧结板的生产。
使用组成为NbO的低氧化铌粉末，其颗粒大小小于38μm，并且按照ASTMB822(Malvem Mastersizer)的粒度分布相当于D10值为2.8μm，D50值为11.4μm和D90值为25.2μm。通过筛选粒化和滚光处理可以改善粉末的流动性，而不需要其它的添加剂就能均匀装入压模中。使用边长为125毫米的正方形孔的硬金属压模。将粒化的粉末输入模具中并且在2kN/cm2下压实。在脱模之后，将外形尺寸大约为125×125×15mm3的压制体与塑料薄膜熔接并且进一步在200兆帕下等压压实。获得大约为122×122×13mm3的压制体。在常规的铣机上加工此压制体，将其加工成带有底部和边缘的盘状部件，其周边高度为13毫米，且壁厚为5毫米。
不需要在SiC容器内进一步预处理，将加工的坯体部件放入用石墨电阻加热的气密加热炉中，并烧结。在烧结开始时，抽空加热炉，并充满含有97体积％的氩气和3体积％的氢气的气体混合物。加热程序按照10K/分钟的加热速度加热到500℃，以5K/分钟的加热速度加热到1100℃，然后以2.5K/分钟的加热速度加热到1600℃，在1600℃下保温3小时，以5K/分钟的可控冷却速度降至800℃，接着自由冷却至低于150℃。这时从加热炉中移出的成形部件的密度为6.9克/厘米3，且维氏硬度HV10为14Gpa。可以任选地对内部和/或外部再加工，以便获得预定的几何尺寸和表面结构。

Claims (12)

1.烧结体，含有30到100摩尔％的NbOx和70到0摩尔％的MgO，其中0.5＜x＜1.5。
2.根据权利要求1的烧结体，由35到100摩尔％的NbOx和65到0摩尔％的MgO组成，其中0.5＜x＜1.5。
3.根据权利要求1的烧结体，由45到60摩尔％的NbOx和55到40摩尔％的MgO组成，其中0.5＜x＜1.5。
4.根据权利要求1到3之一的烧结体，其特征在于它含有的低氧化铌具有分子式NbOx，其中0.7＜x＜1.3。
5.根据权利要求1到4之一的烧结体，其特征在于孔隙率小于30体积％。
6.根据权利要求5的烧结体，其特征在于孔隙率小于15体积％。
7.根据权利要求1到6之一的烧结体，其特征在于含有均匀的富NbOx区和富MgO区的微观结构，其在至少一个方向上延伸最多1.5μm。
8.根据权利要求1到7之一的烧结体，其为用于固体电解质电容器阳极的烧结板形式。
9.生产具有低氧化铌阳极的固体电解质电容器的方法，其特征在于至少部分使用由权利要求1到8之一的烧结体制成的设备对电容器前体进行机械处理和热处理。
10.根据权利要求9的方法，其特征在于将以权利要求1到8之一烧结体形式的由低氧化铌粉末制成的阳极压制体放置在烧结板上并烧结。
11.根据权利要求1到8之一的烧结体的用途，用作化学仪器中的耐化学的元件。
12.根据权利要求1到8之一的烧结体的用途，作为生产电容器用的低氧化铌粉末的惰性设备。
CNB2004100900035A 2003-10-14 2004-10-14 基于低氧化铌的烧结体 Expired - Fee Related CN100404463C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10347702A DE10347702B4 (de) 2003-10-14 2003-10-14 Sinterkörper auf Basis Niobsuboxid
DE10347702.0 2003-10-14

Publications (2)

Publication Number Publication Date
CN1607197A true CN1607197A (zh) 2005-04-20
CN100404463C CN100404463C (zh) 2008-07-23

Family

ID=34353397

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100900035A Expired - Fee Related CN100404463C (zh) 2003-10-14 2004-10-14 基于低氧化铌的烧结体

Country Status (15)

Country Link
US (2) US7419926B2 (zh)
EP (1) EP1524252B2 (zh)
JP (1) JP4723224B2 (zh)
KR (2) KR101146365B1 (zh)
CN (1) CN100404463C (zh)
AU (1) AU2004220706B2 (zh)
BR (1) BRPI0406065B1 (zh)
DE (2) DE10347702B4 (zh)
HK (1) HK1075244A1 (zh)
IL (1) IL164514A (zh)
MX (1) MXPA04009964A (zh)
RU (1) RU2378226C2 (zh)
SV (1) SV2004001904A (zh)
TW (1) TWI360532B (zh)
ZA (1) ZA200408188B (zh)

Families Citing this family (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080310080A1 (en) * 2005-08-19 2008-12-18 Martin Biler Solid State Capacitors and Method of Manufacturing Them
GB0517952D0 (en) * 2005-09-02 2005-10-12 Avx Ltd Method of forming anode bodies for solid state capacitors
GB0622463D0 (en) * 2006-11-10 2006-12-20 Avx Ltd Powder modification in the manufacture of solid state capacitor anodes
US7760487B2 (en) * 2007-10-22 2010-07-20 Avx Corporation Doped ceramic powder for use in forming capacitor anodes
US7768773B2 (en) * 2008-01-22 2010-08-03 Avx Corporation Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor
US7852615B2 (en) 2008-01-22 2010-12-14 Avx Corporation Electrolytic capacitor anode treated with an organometallic compound
US7760488B2 (en) * 2008-01-22 2010-07-20 Avx Corporation Sintered anode pellet treated with a surfactant 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
DE102008026304A1 (de) * 2008-06-02 2009-12-03 H.C. Starck Gmbh Verfahren zur Herstellung von Elektrolytkondensatoren mit niedrigem Leckstrom
US8199462B2 (en) * 2008-09-08 2012-06-12 Avx Corporation Solid electrolytic capacitor for embedding into a circuit board
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
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
US8514547B2 (en) 2010-11-01 2013-08-20 Avx Corporation Volumetrically efficient wet electrolytic capacitor
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
US8514550B2 (en) 2011-03-11 2013-08-20 Avx Corporation Solid electrolytic capacitor containing a cathode termination with a slot for an adhesive
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
US8947857B2 (en) 2011-04-07 2015-02-03 Avx Corporation Manganese oxide capacitor for use in extreme environments
US8300387B1 (en) 2011-04-07 2012-10-30 Avx Corporation Hermetically sealed electrolytic capacitor with enhanced mechanical stability
US9767964B2 (en) 2011-04-07 2017-09-19 Avx Corporation Multi-anode solid electrolytic capacitor assembly
US8379372B2 (en) 2011-04-07 2013-02-19 Avx Corporation Housing configuration for a solid electrolytic capacitor
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
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
US9824826B2 (en) 2013-05-13 2017-11-21 Avx Corporation Solid electrolytic capacitor containing conductive polymer particles
GB2514486B (en) 2013-05-13 2018-08-29 Avx Corp 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
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
US9892860B2 (en) 2014-11-24 2018-02-13 Avx Corporation Capacitor with coined lead frame
US10290430B2 (en) 2014-11-24 2019-05-14 Avx Corporation Wet Electrolytic Capacitor for an Implantable Medical Device
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
US9928963B2 (en) 2015-03-13 2018-03-27 Avx Corporation Thermally conductive encapsulant material for a capacitor assembly
US9754730B2 (en) 2015-03-13 2017-09-05 Avx Corporation Low profile multi-anode assembly in cylindrical housing
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
US9842704B2 (en) 2015-08-04 2017-12-12 Avx Corporation Low ESR anode lead tape for a solid electrolytic capacitor
US9905368B2 (en) 2015-08-04 2018-02-27 Avx Corporation Multiple leadwires using carrier wire for low ESR electrolytic capacitors
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
US10535471B2 (en) 2016-09-22 2020-01-14 Avx Corporation Electrolytic capacitor containing a valve metal sourced from a conflict-free mine site and a method of forming thereof
US10431389B2 (en) 2016-11-14 2019-10-01 Avx Corporation Solid electrolytic capacitor for high voltage environments
WO2019060303A1 (en) 2017-09-21 2019-03-28 Avx Corporation ELECTRONIC PART CONTAINING A METALLIC CONSTITUENT FROM A CONFLICT-FREE MINING SITE AND METHOD OF FORMING THE SAME
CA3092989A1 (en) * 2018-03-12 2019-09-19 Omega Energy Systems, Llc Solid-state energy harvester of transition metal suboxides
US11081288B1 (en) 2018-08-10 2021-08-03 Avx Corporation Solid electrolytic capacitor having a reduced anomalous charging characteristic
US11380492B1 (en) 2018-12-11 2022-07-05 KYOCERA AVX Components Corporation Solid electrolytic capacitor
KR20210148365A (ko) 2019-04-25 2021-12-07 로무 가부시키가이샤 고체 전해 콘덴서
CN113661551B (zh) 2019-05-17 2023-04-04 京瓷Avx元器件公司 固体电解电容器
WO2021097051A1 (en) 2019-11-13 2021-05-20 Omega Energy Systems, Llc Three-electrode solid-state energy harvester of transition metal suboxides
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 (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0745123A (ja) * 1993-07-28 1995-02-14 Tdk Corp 誘電体材料
JP4008997B2 (ja) * 1997-12-26 2007-11-14 京セラ株式会社 半導電性セラミックス及びこれを用いた治工具、磁気ディスク基板用保持部材並びに磁気ディスク装置
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
US6416730B1 (en) * 1998-09-16 2002-07-09 Cabot Corporation Methods to partially reduce a niobium metal oxide oxygen reduced niobium oxides
US6391275B1 (en) * 1998-09-16 2002-05-21 Cabot Corporation Methods to partially reduce a niobium metal oxide and oxygen reduced niobium oxides
US6462934B2 (en) 1998-09-16 2002-10-08 Cabot Corporation Methods to partially reduce a niobium metal oxide and oxygen reduced niobium oxides
US6322912B1 (en) 1998-09-16 2001-11-27 Cabot Corporation Electrolytic capacitor anode of valve metal oxide
DE19847012A1 (de) * 1998-10-13 2000-04-20 Starck H C Gmbh Co Kg Niobpulver und Verfahren zu dessen Herstellung
KR100650621B1 (ko) * 1999-02-16 2006-11-27 쇼와 덴코 가부시키가이샤 니오브분말, 니오브소결체, 그 소결체를 사용한 축전지 및 그 축전지의 제조방법
US6576099B2 (en) * 2000-03-23 2003-06-10 Cabot Corporation Oxygen reduced niobium oxides
DE10041901A1 (de) * 2000-08-25 2002-03-07 Starck H C Gmbh Kondensatoranode auf Basis Niob
JP4521849B2 (ja) * 2000-12-01 2010-08-11 昭和電工株式会社 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
US7210641B2 (en) † 2001-02-28 2007-05-01 Cabot Corporation Methods of making a niobium metal oxide
US7149074B2 (en) 2001-04-19 2006-12-12 Cabot Corporation Methods of making a niobium metal oxide
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
EP1402079B1 (en) * 2001-05-15 2014-12-03 Showa Denko K.K. Niobium 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
KR100444223B1 (ko) * 2001-11-13 2004-08-16 삼성전기주식회사 유전체 세라믹 조성물
EP1498391B1 (de) * 2003-07-15 2010-05-05 H.C. Starck GmbH Niobsuboxidpulver
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
US20050103638A1 (en) 2005-05-19
US20080260939A1 (en) 2008-10-23
ZA200408188B (en) 2006-06-28
RU2378226C2 (ru) 2010-01-10
US7419926B2 (en) 2008-09-02
EP1524252B1 (en) 2008-01-23
EP1524252B2 (en) 2011-06-01
JP2005119960A (ja) 2005-05-12
BRPI0406065B1 (pt) 2014-02-25
US7897197B2 (en) 2011-03-01
EP1524252A3 (en) 2005-11-09
KR20110123709A (ko) 2011-11-15
DE10347702A1 (de) 2005-05-19
TW200526539A (en) 2005-08-16
SV2004001904A (es) 2010-02-04
IL164514A0 (en) 2005-12-18
BRPI0406065A (pt) 2005-09-06
TWI360532B (en) 2012-03-21
AU2004220706B2 (en) 2008-10-16
DE602004011442T3 (de) 2012-04-26
HK1075244A1 (en) 2005-12-09
DE10347702B4 (de) 2007-03-29
IL164514A (en) 2007-09-20
KR20050036736A (ko) 2005-04-20
DE602004011442T2 (de) 2009-01-15
DE602004011442D1 (de) 2008-03-13
RU2004129683A (ru) 2006-03-27
MXPA04009964A (es) 2005-04-19
AU2004220706A1 (en) 2005-04-28
KR101146365B1 (ko) 2012-05-17
JP4723224B2 (ja) 2011-07-13
CN100404463C (zh) 2008-07-23
EP1524252A2 (en) 2005-04-20

Similar Documents

Publication Publication Date Title
CN100404463C (zh) 基于低氧化铌的烧结体
JP4773355B2 (ja) ニオブ酸化物及び酸素が低減したニオブ酸化物の製造方法
KR100583702B1 (ko) 가스상의 환원제로 산화물을 환원시켜 금속 분말을 제조하는 방법 및 그로부터 제조된 금속 분말
US20090185947A1 (en) Silicon alloy, alloy powder thereof, manufacturing apparatus, manufacturing process and sintered alloy thereof
CN102770391A (zh) LiCoO2烧结体的制造方法及溅射靶材
US20150110707A1 (en) Process for making chemically activated carbon
CN104129994A (zh) 碳化钒钛的制备方法
US8501050B2 (en) Titanium diboride-silicon carbide composites useful in electrolytic aluminum production cells and methods for producing the same
JP3667121B2 (ja) 炭化ホウ素焼結体およびその製造方法
JP2967094B2 (ja) 窒化アルミニウム焼結体、及び窒化アルミニウム粉末の製造方法
CN113584337B (zh) 一种低铜含量钨铜复合材料的制备方法及产品
JPH09100163A (ja) 球状窒化物
Budin et al. Effect of sintering atmosphere on the mechanical properties of sintered tungsten carbide
CA2331707C (en) Reduction of nb or ta oxide powder by a gaseous light metal or a hydride thereof
US20140056795A1 (en) Process for manufacturing high density boron carbide
WO2023190525A1 (ja) 窒化ホウ素焼結体及びその製造方法、セッター、並びに容器
JP3492648B2 (ja) ＴｉＮ−Ａｌ２Ｏ３系焼結体
JPH05246775A (ja) 多孔質窒化アルミニウム焼結体およびその製造方法
JPH0959064A (ja) 高炉炉底用炭素質耐火物

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1075244

Country of ref document: HK

C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1075244

Country of ref document: HK

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080723

Termination date: 20151014

EXPY Termination of patent right or utility model