WO2004042095A1 - Procede servant a preparer de la poudre de niobium et/ou de tantale presentant une surface importante - Google Patents

Procede servant a preparer de la poudre de niobium et/ou de tantale presentant une surface importante Download PDF

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Publication number
WO2004042095A1
WO2004042095A1 PCT/BR2003/000122 BR0300122W WO2004042095A1 WO 2004042095 A1 WO2004042095 A1 WO 2004042095A1 BR 0300122 W BR0300122 W BR 0300122W WO 2004042095 A1 WO2004042095 A1 WO 2004042095A1
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WO
WIPO (PCT)
Prior art keywords
niobium
powder
surface area
production
large surface
Prior art date
Application number
PCT/BR2003/000122
Other languages
English (en)
Inventor
Solon Yasuhiko Tagusagawa
Original Assignee
Companhia Brasileira De Metalurgia E Mineração - Cbmm
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 Companhia Brasileira De Metalurgia E Mineração - Cbmm filed Critical Companhia Brasileira De Metalurgia E Mineração - Cbmm
Priority to GB0508844A priority Critical patent/GB2409466B/en
Priority to JP2004548947A priority patent/JP2006516039A/ja
Priority to DE10393407T priority patent/DE10393407T5/de
Priority to AU2003254646A priority patent/AU2003254646A1/en
Priority to US10/533,791 priority patent/US20060096418A1/en
Publication of WO2004042095A1 publication Critical patent/WO2004042095A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • NbxOy, and/or TaxOy a controlled layer of niobium and/or tantalum oxide
  • the main problem of the metallothermal reaction is its strongly exothermal and uncontrolled reaction, causing an excessive heating of the system and impairing the characteristics of the powder that is produced (increase in mean particle size and decrease of specific area).
  • One of the manners of controlling the reaction is to perform the reduction initially to a sub-oxide of niobium, such as described in some patents, since in this condition the exothermal characteristic of the reaction is less intense.
  • the sub-oxide thus produced would then be reduced to metallic niobium, again with less intense exothermal behavior, producing a powder with the recommended characteristics.
  • such procedure creates a need to conduct the process in two stages, requiring an increased consumption of energy and time.
  • the possibility of contamination of the powder is increased due to the greater number of stages under high temperatures in contact with the oven atmosphere, with the reducing agent and with the container where the reaction takes place.
  • 4,725,312 and WO 01/59166 proposes a process for the production of metals in powder form of groups IV-B and V-B of the Periodic Table of Elements (US Patent No. 4,725,312) by reducing the salts of those metals through the use of a bath of molten salts containing lithium as the reducing agent.
  • a wide range of binary mixtures of salts is mentioned, among which there should be pointed out: LiCl-KCl, CsCl-LiCl, RbCl-LiBr and KBr-LiBr, LiCl-NaCl-CsCl, LiCl-NaCl-RbCl and LiCl-KCl-KF.
  • the bath of salts is kept at a temperature between 400 and 550°C.
  • the quantity of lithium present in the bath of molten salts should at least be the stoichiometric amount required for the reduction of the chlorides of Nb, Ti and Nd, and these chlorides may be introduced in solid, liquid or gas form, this latter being preferred.
  • WO 01/59166 mention the production of niobium powders by means of the reduction of K2NbF7 using sodium as the reducing agent added to a bath of molten salts (KCl-KF or KCl-NaCl).
  • the main advantages of the use of the method of reduction in molten salts are: a) the dissipation of the heat generated in the reaction occurs in the bath of salts thus avoiding localized overheating; b) it is possible to control the reducing potential of the reducing agent by means of the dissolution thereof in a molten salt; c) it is possible to continuously feed both the reducing agent and the raw material containing Nb and/or Ta to the salts bath and thereby to control the speed of reduction and therefore the generation of heat; d) avoiding direct contact between the reducing agent and the source of Nb and/or Ta, decreasing the possibility of sintering and inadequate growth of the powder of Nb and or Ta thus reduced; e) it is possible to stir the bath of salts, and therefore to allow control over the speed of the reaction increasing or decreasing the rate of dissolution both of the reducing agent and of the source of Nb and/or Ta in the molten salt; f) it is possible to control the reaction temperature by proper selection of a salt solution which melting
  • the oxide of niobium and/or tantalum may be reduced in a controlled manner with a strong reducing agent producing a power of high purity, with a sponge-like morphology, of low apparent density and large specific surface area.
  • the raw material is a metallic niobium and/or tantalum powder and/or hydrides thereof of high purity and adequate size, that was previously oxidized in a controlled manner to have an adequate layer of oxide, the thermal energy generated in the reduction of this layer of oxide is much less than that which would be generated to obtain the same particle if the raw material was to consist entirely in oxide. This lesser generation of energy facilitates the control of the process such that the possibility of contamination by gasses and other metals is significantly reduced, which may be evidenced by the low leakage current of the powder obtained using this process.
  • the present invention comprises a process for the production of metallic powder of niobium and/or tantalum by means of metallothermal reduction in molten salts wherein the problems of overheating during the reduction, or of the need to conduct the process in more than one step, are eliminated.
  • the reaction is more controlled due to the possibility of controlling the potential of the reducing agent, due to the same being diluted in the salt at the desired concentration. In this manner, the driving force for the reduction may be controlled, allowing increased control of the process.
  • oxidized powder a raw material in the form of a powder, of adequate size, consisting basically in metallic niobium and/or tantalum and/or hydrides thereof, of high purity, previously oxidized in a controlled manner (hereinafter referred as "oxidized powder"), leads to a uniform precipitation of the Nb and or the Ta, with the aspect of a sponge, within the medium of liquid salt, producing an adequate distribution of particles without the formation of clusters of undesirable size.
  • the reducing agent is an alkali or earth alkali metal, preferably calcium or magnesium and/or a hydride of such metal. Nitrides of alkali metals or earth alkali metals may also be fed to the reactor constituting sources of N2 for the produced niobium and/or tantalum.
  • the reduction occurs at temperatures between 300 and 1200°
  • the salt may be subjected to mechanical stirring or to the injection of an inert or partially inert gas containing, for example, N2.
  • the molten salt may be comprised of mixtures of salts or of pure salts, such as fluorides and chlorides of Ca, Li, Ba, Mg, K and Na.
  • the salts evidencing greater solubility of the reducing agent are preferred, such as CaC12 when employing calcium as reducing agent.
  • the reducing agent and the oxidized Nb and/or Ta powder may be continuously fed to the molten salt using devices that allow to control the feed rate of both.
  • the temperature of the process may be kept constant by controlling the feed rate of the raw materials.
  • the quantity of reducing agent that is used should be at least the stoichiometric amount for the reduction of all the oxide of the oxidized powder of Nb and/or Ta that is fed. There may be employed a quantity up to 800% of the stoichiometric amount. Such excess depends, among other parameters, on the quantity of salts bath.
  • Both the reducing agent and the "oxidized powder" may be added together with the salt bath to the reduction reactor prior to the melting step or may be fed separately or together to the salt bath upon the prior melting thereof. This feeding may be carried out continuously or otherwise.
  • the quantity of reducing agent is substantially less in comparison to the reduction of particles of oxides, and depending on the oxygen content of the oxidized powder, the required quantity of reducing agent may be previously added to the salt bath.
  • the following salts or mixtures thereof are employed to control the reaction: CaC12, NaCl, KC1 and MgC12.
  • the mixture of salts allows the reduction to occur at a lower temperature, allowing to obtain smaller particle sizes and larger surface areas.
  • the quantity of salt or mixture of salts will have an effect on the control of the reaction temperature, the greater is the quantity of salt the easier it will be to control the temperature.
  • the quantity of salt used may vary between 5 and lOOg/g of oxidized powder fed.
  • the reaction may be carried out in stainless steel, nickel, tantalum or niobium reactors, depending on the degree of contamination that can be tolerated in the product obtained.
  • the resulting salt mixture containing metallic niobium and/or tantalum is dissolved in deionized water and is subsequently filtered and leached with a solution containing HC1 and which may also contain HF, HN03 and H2S04. After the leaching the material is rinsed and dried.
  • the amount of water for solubilization of the salt varies between 10 and 100 liters for every 5 kg of salt.
  • For the acid leaching step there are used 1 to 100 ml of solution for every gram of powder obtained from dissolution of the salt.
  • the control of the nitrogen content in the Nb and/or Ta may be effected by controlling the partial pressure of N2 in the atmosphere of the oven, by an injection of N2 gas or of mixtures of gasses containing N2 into the molten salt, or yet, by the addition of N2 carrier elements, such as nitrides soluble in the molten salt.
  • N2 carrier elements such as nitrides soluble in the molten salt.
  • a part of the nitrogen is dissolved in the solution of salts allowing that nitride ions may be available to allow the solubilization of nitrogen in the particles of Nb and/or Ta.
  • it is possible to dope with phosphorus by adding phosphorus compounds soluble in the salt bath.
  • the particles of powder of Nb and or Ta produced using the present process have a reduced size, have a large surface area and a sponge-like morphology, and are adequate for the production of capacitors.
  • the reducing procedure consists in melting the salt initially in a stainless steel, nickel, niobium or tantalum reactor, either or not in the presence of the oxidized powder, and of the reducing agent in an inert gas atmosphere.
  • the oven chamber Before the heating of the reactor, the oven chamber should be evacuated and then pressurized with the inert gas at pressures that may vary from 400 to 1200 torr.
  • the temperature is stabilized between 30 and 150° C above the melting point of the salt or of the reducing metal, whichever has the higher melting point. From this moment on there is started the stirring process of the bath using a mechanical agitator or by means of injection of an inert or reactive gas (N2 or a mixture of N2 with an inert gas). If the reducing agent and/or the "oxidized powder" have not been previously added, there is initiated the addition of both or of one of them using an adequate system that allows to control the feed rate to the salt bath.
  • the stirring is discontinued and the oven is turned off to allow the cooling of the salt containing metallic Nb and or Ta.
  • the time required for the reduction will depend on the feed rate of the reducing agent or the oxidized powder, or yet of the quantity of powder and reducer fed together with the salt prior to the beginning of the reaction.
  • the feed rate of the oxidized powder is an important parameter for the control of the process, since it may control the localized generation of heat. However, as previously explained, this amount of heat is substantially less when compared to the use of oxide of Nb and/or Ta as source of Nb and/or Ta.
  • the reduction temperature may have an influence on the surface area of the produced powder. Higher temperatures may lead to larger particles with lesser specific surfaces. Therefore, the selection of the mixture of salts is important with a view to lowering the temperature of the process.
  • Stirring the salt is also important to avoid localized overheating and to disperse the oxidized powder, avoiding its segregation in the bath.
  • Figure 1 is a schematic drawing of a reactor for reduction of the oxidized powder
  • Figure 2 depicts a detail of the support stem inside the crucible
  • Figure 3 illustrates back-scattered electrons of the typical morphology of powders produced using the processes set forth herein.
  • Figure 1 is a schematic drawing of the reactor used for the reduction in molten salts where the oxidized powder is continuously fed in a crucible containing a molten salt. In the same crucible that contains the salt, there is placed another container, submerged in the salt, containing the liquid alkali metal or earth alkali metal.
  • the identifications of Figure 1 are: 1- Crucible containing the liquid alkali metal or earth alkali metal; 2- Crucible containing the molten salt; 3- Stirring stem; 4- Molten salt; 5- Inert or reactive gas inlet; 6- "oxidized powder"; 7- Container with the "oxidized powder” contained therein; 8- Thermocouple; 9- Oven chamber and 10- Vacuum system outlet.
  • the mechanical stirring may be substituted by stirring caused by injection of an inert or reactive gas.
  • the produced material is dissolved in deionized water.
  • the solution obtained in the dissolution of the salt is filtered, and is then leached in a solution containing HC1, HN03, H2S04 and HF.
  • the amount of leaching solution employed is 1 to 100 ml/g of filtered product, preferably 10 to 40 ml/g. After this leaching, there is performed a final rinsing with deionized water, filtration and subsequently, vacuum-drying.
  • Ta obtained has contents of Mg and Ca below 500 ppm, sodium content below 50 ppm, oxygen content between 1,000 and 4,000 ppm/(m2/g), sum total of contents of Fe, Cr and Ni below 300 ppm and a specific surface area between 1 and 30 m2/g.
  • the material was removed from the reactor and subjected to dissolution in deionized water.
  • the solid phase was leached with an aqueous solution containing HCl and HF for 90 minutes. This mixture was then filtered and rinsed with 10 liters of deionized water. The cake obtained from filtration was subsequently vacuum-dried.
  • the chemical analysis of the obtained powder evidenced that the oxygen content had fallen from 18,000 ppm to 3,850 ppm.
  • the material was removed from the reactor and subjected to dissolution in deionized water.
  • the solid phase was leached with an aqueous solution containing HCl and HF for 90 minutes. This mixture was then filtered and rinsed with 10 liters of deionized water. The cake obtained from filtration was subsequently vacuum-dried.
  • the chemical analysis of the obtained powder evidenced that the oxygen content had fallen from 6,300 ppm to 785 ppm.
  • the material was removed from the reactor and subjected to dissolution in deionized water.
  • the solid phase was leached with an aqueous solution containing HCl and HF for 90 minutes. This mixture was then filtered and rinsed with 10 liters of deionized water. The cake obtained from filtration was subsequently vacuum-dried.
  • the chemical analysis of the obtained powder evidenced that the oxygen content had fallen from 52,210 ppm to 10,500 ppm (equivalent to 4,565 ppm/(m2/g)).
  • the material was removed from the reactor and subjected to dissolution in deionized water.
  • the solid phase was leached with an aqueous solution containing HCl and HF for 90 minutes. This mixture was then filtered and rinsed with 10 liters of deionized water. The cake obtained from filtration was subsequently vacuum-dried.
  • the chemical analysis of the obtained powder evidenced that the oxygen content had fallen from 39,620 ppm to 6,700 ppm (equivalent to 4,188 ppm/(m2/g)).
  • Example 5 The oxidized powder (11 g) was placed on a metallic screen, attached to the support stem (11), inside a crucible 1, as shown in Figure 2.
  • the metallic magnesium (25 g) was placed in the reducer container (Ca/Mg, NbH), also attached to the support stem (2).
  • the mixture of calcium chloride (240 g) and potassium chloride (60 g) was placed inside the crucible, together with the oxidized powder and the metallic magnesium.
  • the crucible was sealed, there being welded a cover thereon.
  • the mixture was heated to a temperature of 900° C for 2 hours. After the reduction, the mixture was cooled down to ambient temperature.
  • the material was removed from the crucible and dissolved in deionized water.
  • the solid phase was leached with an aqueous solution containing HCl and HF for 90 minutes. This mixture was then filtered and rinsed with deionized water.
  • the cake obtained from filtration was subsequently vacuum-dried.
  • the chemical analysis of the obtained powder evidenced that the oxygen content had fallen from 52,210 ppm to 5,850 ppm (equivalent to 3,250 ppm/(m2/g)).
  • the oxidized powder (11 g) was placed on a metallic screen, attached to the support stem (11), inside a crucible (1), as shown in Figure 2.
  • the metallic calcium (25 g) was placed in the reducer container (Ca/Mg, NbH), also attached to the support stem.
  • the calcium chloride (300 g) was placed inside the crucible, together with the oxidized powder and the metallic calcium.
  • the crucible was sealed, there being welded a cover thereon.
  • the mixture was heated to a temperature of 900° C for 2 hours. After the reduction, the mixture was cooled down to ambient temperature.
  • the material was removed from the crucible and dissolved in deionized water.
  • the solid phase was leached with an aqueous solution containing HCl and HF for 90 minutes. This mixture was then filtered and rinsed with deionized water.
  • the cake obtained from filtration was subsequently vacuum-dried.
  • the chemical analysis of the obtained powder evidenced that the oxygen content had fallen from 52,210 ppm to 5,520 ppm (equivalent to 3,070 ppm/(m2/g)).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un procédé servant à préparer une poudre de niobium et/ou de tantale extrêmement pure possédant une surface spécifique importante, des teneurs contrôlées en oxygène et en azote et une morphologie appropriée pour la fabrication de condensateurs. Ce procédé consiste, de façon caractéristique, en une seule étape de réduction d'une couche contrôlée d'oxyde de niobium et/ou de tantale (NbxOy, et/ou TaxOy, dans laquelle x = 1 à 2 et y = 1 à 5) déposé au-dessus de particules de niobium et/ou de tantale métallique et/ou de leurs hydrides de pureté adéquate, par des métaux alcalins ou des métaux alcalins terreux et/ou leurs hydrides dans un bain de sels en fusion, puis en une étape de dissolution du sel dans une solution aqueuse afin de récupérer la poudre de niobium et/ou de tantale. Les particules préparées au moyen de ce procédé présentent une faible dimension, une surface importante et une morphologie spongieuse, ce qui les rend appropriées pour la fabrication de condensateurs.
PCT/BR2003/000122 2002-11-04 2003-08-27 Procede servant a preparer de la poudre de niobium et/ou de tantale presentant une surface importante WO2004042095A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB0508844A GB2409466B (en) 2002-11-04 2003-08-27 A process for the production of niobium and/or tantalum powder with large surface area
JP2004548947A JP2006516039A (ja) 2002-11-04 2003-08-27 大きな表面積を有するニオブ粉末及び／又はタンタル粉末の製造方法
DE10393407T DE10393407T5 (de) 2002-11-04 2003-08-27 Ein Verfahren zur Herstellung von Niob- und/oder Tantalpulver mit großer Oberfläche
AU2003254646A AU2003254646A1 (en) 2002-11-04 2003-08-27 A process for the production of niobium and/or tantalum powder with large surface area
US10/533,791 US20060096418A1 (en) 2002-11-04 2003-08-27 Process for the production of niobium and/or tantalum powder with large surface area

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0204587-7 2002-11-04
BR0204587-7A BR0204587A (pt) 2002-11-04 2002-11-04 Processo de produção de pó de nióbio e/ou de tântalo de elevada área superficial

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Publication Number Publication Date
WO2004042095A1 true WO2004042095A1 (fr) 2004-05-21

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US (1) US20060096418A1 (fr)
JP (1) JP2006516039A (fr)
CN (1) CN1694973A (fr)
AU (1) AU2003254646A1 (fr)
BR (1) BR0204587A (fr)
DE (1) DE10393407T5 (fr)
GB (1) GB2409466B (fr)
WO (1) WO2004042095A1 (fr)

Cited By (6)

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WO2005028370A1 (fr) * 2003-09-25 2005-03-31 Companhia Brasileira De Metalurgia E Mineracão Methode de production d'une poudre d'oxyde de niobium utilisable dans des capacites
DE102004043343A1 (de) * 2004-09-08 2006-03-23 H.C. Starck Gmbh Desoxidation von Ventilmetallpulvern
WO2006101850A1 (fr) * 2005-03-22 2006-09-28 H.C. Stark Inc. Methode de preparation d’un metal refractaire de premiere fusion
US8999500B2 (en) 2006-08-16 2015-04-07 H.C. Starck Gmbh Semifinished products with a structured sinter-active surface and a process for their production
US9393623B2 (en) 2009-02-13 2016-07-19 Metalysis Limited Method for producing metal powders
US10081847B2 (en) 2012-10-17 2018-09-25 University Of Bradford Method for metal production

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JP3610942B2 (ja) * 2001-10-12 2005-01-19 住友金属鉱山株式会社 ニオブおよび／またはタンタルの粉末の製造法
EP2709784A4 (fr) * 2011-05-16 2015-11-18 Boston Electronic Materials Llc Fabrication et applications de poudres et alliages métalliques
KR101911871B1 (ko) * 2016-12-23 2018-10-29 한국기초과학지원연구원 탄탈륨 분말의 제조방법
CN108217596B (zh) * 2018-01-29 2021-03-30 吉林大学 使用非氢源溶液法制备铌氢化物和钽氢化物的方法
KR102359159B1 (ko) * 2019-12-30 2022-02-08 충남대학교산학협력단 연소 반응을 이용한 금속 나노분말 제조방법
CN113500204A (zh) * 2021-07-08 2021-10-15 安徽理工大学 一种氯化钙熔盐中钙热还原氯化铌制备细微铌粉的方法

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DE10393407T5 (de) 2005-10-06
GB2409466B (en) 2006-06-21
AU2003254646A1 (en) 2004-06-07
JP2006516039A (ja) 2006-06-15
GB2409466A (en) 2005-06-29

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