WO2015127613A1 - 一种高纯钽粉及其制备方法 - Google Patents

一种高纯钽粉及其制备方法 Download PDF

Info

Publication number
WO2015127613A1
WO2015127613A1 PCT/CN2014/072597 CN2014072597W WO2015127613A1 WO 2015127613 A1 WO2015127613 A1 WO 2015127613A1 CN 2014072597 W CN2014072597 W CN 2014072597W WO 2015127613 A1 WO2015127613 A1 WO 2015127613A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
purity
ppm
minutes
tantalum powder
Prior art date
Application number
PCT/CN2014/072597
Other languages
English (en)
French (fr)
Inventor
李仲香
程越伟
陈学清
王葶
师德军
童泽堃
闫燕
田小玉
赵忠环
Original Assignee
宁夏东方钽业股份有限公司
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 宁夏东方钽业股份有限公司 filed Critical 宁夏东方钽业股份有限公司
Priority to PCT/CN2014/072597 priority Critical patent/WO2015127613A1/zh
Priority to CN201480016668.3A priority patent/CN105377481B/zh
Priority to EP14883916.0A priority patent/EP3112059B1/en
Priority to US15/111,632 priority patent/US10737320B2/en
Priority to JP2016554604A priority patent/JP2017512897A/ja
Priority to TW104101358A priority patent/TWI611025B/zh
Publication of WO2015127613A1 publication Critical patent/WO2015127613A1/zh

Links

Classifications

    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/023—Hydrogen absorption
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • 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

Definitions

  • the invention relates to a high-purity strontium powder and a preparation method thereof. More specifically, the tantalum powder has a purity greater than 99.995%, an average particle diameter of ⁇ 50 ⁇ 25 ⁇ , an oxygen content of not more than 1000 ppm, a nitrogen content of not more than 50 ppm, a hydrogen content of not more than 20 ppm, and a magnesium content of not more than 5 ppm. Background technique
  • germanium is placed as a diffusion barrier between the silicon and copper conductors.
  • Production methods for sputum sputtering targets include ingot metallurgy (I/M) method and powder metallurgy (P/M) method.
  • I/M ingot metallurgy
  • P/M powder metallurgy
  • Lower target ruthenium targets are generally made from ruthenium ingots.
  • the I/M method cannot be used, and it can only be produced by powder metallurgy.
  • the I/M method cannot produce a gold alloy target because of the difference in melting point of germanium and silicon, and the low toughness of silicon compounds.
  • the performance of the target directly affects the properties of the sputtered film. There is no material that is contaminated by the semiconductor device in the formation of the film.
  • impurities are present in the target of the bismuth (alloy, compound)
  • impurities are introduced into the sputtering chamber, causing coarse particles to adhere to the substrate and short-circuiting the thin film loop.
  • impurities can also be a cause of an increase in the number of protrusion particles in the film.
  • impurities such as gaseous oxygen, carbon, hydrogen, and nitrogen present in the target are more harmful because they cause abnormal discharge and cause problems in the uniformity of the formed film.
  • the uniformity of the deposited film is a function of the grain size in the target, and the finer the crystal grains in the target, the more uniform the resulting film. Therefore, there is a need in the art for high quality tantalum powder and tantalum targets.
  • the metal ruthenium powder having a relatively small particle size is relatively active, and reacts with oxygen, nitrogen, etc. at a normal temperature to increase the content of impurities such as oxygen and nitrogen in the bismuth powder.
  • reducing the particle size of the tantalum powder may also be necessary to improve the quality of the tantalum powder and the tantalum target. It is desirable in the art to obtain high purity tantalum powder having an average particle size of ⁇ 50 ⁇ 25 ⁇ m.
  • Chinese Patent No. CN101182602A discloses a powder metallurgy and a preparation method thereof, characterized in that the powder has an oxygen content of less than 1500 ppm and a nitrogen content of less than 1,500 ppm.
  • the powder has a high content of metal impurities and a high hydrogen content, and the particles are relatively coarse, and the particle size D50 is about 70 ⁇ m.
  • the process temperature is relatively high when dehydrogenation and deoxidation are simultaneously performed.
  • the antimony powder before dehydrogenation and deoxidation is not subjected to high temperature treatment, and its activity is relatively strong, which tends to cause the magnesium or magnesia particles to be encapsulated inside the crucible particles, which is difficult to remove in the subsequent pickling process, resulting in a high magnesium content in the final product.
  • the invention is not subjected to heat treatment after pickling, and impurities such as H, F and the like which are retained in the final tantalum powder due to residual magnesium after deoxidation and pickling may not be removed. Therefore, this method is difficult to achieve a hydrogen content of less than 20 ppm and a magnesium content of less than 5 ppm. The highest purity obtained by this method is reported to be 99.9%.
  • Chinese patent CN103447544A discloses a preparation method of high-purity strontium powder with controllable particle size distribution, which is characterized in that: the hydrogenation of high-purity bismuth ingot into swarf, sequential pulverization, classification, and grading of bismuth powder
  • the low-temperature vacuum drying and dehydrogenation treatment are sequentially performed: wherein at least in the pulverization and classification process, the apparatus in contact with the tantalum powder is made of tantalum having a purity of 99.99% or more.
  • the disadvantage of this method is that: First: Since the equipment used is made of high-purity germanium, it is highly demanding and expensive.
  • the oxygen content of the obtained product is extremely unstable, and the difference is large, and it is difficult to completely less than 1000 ppm.
  • the availability of materials is greatly reduced, and the particle size of the tantalum powder is difficult to refine.
  • the production process of metallurgical grade tantalum powder is generally carried out by means of dehydrogenation and deoxidation simultaneously, which causes limitations of the design process parameters. Specifically, if the temperature is set too low, dehydrogenation is incomplete and the hydrogen content of the final product is high. At the same time, changes in properties (such as lattice constant, electrical resistance, hardness, etc.) that occur after hydrogen absorption are not completely eliminated.
  • the temperature is set too high, hydrogen can be fully dried, but it will cause the sintering of the cerium particles to grow, and at the same time, the magnesium or magnesium oxide particles are encapsulated inside the cerium particles, which are difficult to remove during the subsequent pickling process.
  • the particle size controllability is poor, and it is difficult to achieve an oxygen content of less than 1000 ppm while ensuring an average particle size of ⁇ 50 ⁇ 25 ⁇ . More unfortunately, it also leads to excessive magnesium.
  • the tantalum powder is acid-washed, dried, and sieved, which is the final product without subsequent heat treatment, which leads to residual magnesium after deoxidation, and H brought by pickling. Impurities such as F and F can not be removed, so that the content of magnesium, hydrogen, etc. in the final product is too high.
  • the present invention has been made in view of the deficiencies of the above methods.
  • the present invention provides a high purity S having a GDMS analytical purity of greater than 99.995%, preferably greater than 99.999%.
  • the cerium has a low content of oxygen, nitrogen, hydrogen, and magnesium, for example, an oxygen content of not more than 1000 ppm; and a nitrogen content of not higher than
  • the niobium powder has a particle size of ⁇ 50 ⁇ 25 ⁇ m, preferably ⁇ 50 < 20 ⁇ m.
  • the tantalum powder can also be used for other applications such as medical, surface coating, and the like.
  • the invention also provides a method for manufacturing the tantalum powder, which in turn comprises the following steps:
  • the cerium powder obtained in the previous step is subjected to low-temperature heat treatment, and then cooled, passivated, baked, and sieved to obtain a finished product a.
  • high-purity antimony ingot refers to antimony ingots having a niobium content of 99.995% or more.
  • antimony ingots can be obtained in various ways, for example, tantalum powders which can be produced by various processes are used as raw materials, and are obtained by high-temperature sintering impurity removal or electron bombardment. Such antimony ingots are also commercially available.
  • the manner of crushing the hydrogenated crumb for example, it can be crushed by a jet mill or a ball mill, but it is preferred that the crushed niobium particles should all pass through a screen of 400 mesh or higher, for example: 500 mesh. , 600 mesh, 700 mesh.
  • the sieving in step 2) preferably means passing through a 400-700 mesh screen.
  • ball milling fractures are employed in embodiments of the invention.
  • the present invention preferably performs high temperature dehydrogenation by heating the tantalum powder under an inert gas atmosphere at about 800 to 1000.
  • C e.g., about 900 C, about 950 C, about 980 C, about 850 C, about 880 C
  • 60-300 minutes e.g., about 120 minutes, about 150 minutes, about 240 minutes, about 200 minutes
  • the inventors have found that dehydrogenation at the higher temperatures described can achieve dehydrogenation while reducing surface activity.
  • the tantalum powder is subjected to low temperature deoxidation treatment in step 4), that is, the maximum temperature of the process is preferably not higher than the dehydrogenation temperature, and the maximum temperature of the deoxidation treatment process is generally lower than the dehydrogenation temperature by about 50-300. . C (such as about 100 ° C, about 150 ° C, about 180 ° C, about 80 ° C, about 200 ° C), can achieve the purpose of deoxidation while ensuring that the bismuth particles do not grow, do not grow, to avoid magnesium or oxidation
  • the magnesium particles are entrapped inside the crucible particles and are not easily removed during the subsequent pickling process, resulting in a high magnesium content in the finished product.
  • deoxygenation is carried out by adding a reducing agent to the tantalum powder.
  • the deoxidation treatment is generally carried out under inert gas protection.
  • the reducing agent has a greater affinity for oxygen than hydrazine with oxygen.
  • Such reducing agents are, for example, alkaline earth metals, rare earth metals and their hydrides, the most commonly used being magnesium powder. As a specific preferred embodiment, it can be mixed into the tantalum powder by weight of the tantalum powder.
  • 0.2-2.0% of the metal magnesium powder is loaded by the method described in Chinese Patent No. CN 102120258A, and then heated under the protection of an inert gas, at about 600-750.
  • C for example, about 700 e C
  • C is kept for about 2-4 hours, then vacuumed, and then kept under vacuum for about 2-4 hours, then cooled, passivated, and baked to obtain deoxidized a.
  • the heat treatment is also called thermal agglomeration, and the main purpose is to improve the physical properties, increase the particle size of the tantalum powder, the bulk density, and improve the fluidity and particle size distribution.
  • the heat treatment of the present invention plays a more important role in ensuring the avoidance of the increase in the particle size and the bulk density of the tantalum powder, that is, to remove as much as possible the residual magnesium metal after pickling and pickling. Impurities such as H and F brought in.
  • the present invention is carried out in a vacuum heat treatment furnace which requires a high degree of vacuum, especially at a heat treatment temperature of greater than about 600.
  • the degree of vacuum is required to be about 1.0 x 10 3 Pa or higher
  • the heat treatment temperature is a lower temperature of about 600 to 1200 ° C, for example, about 800 ° C, about 950 ° C, about 1,000. C, about 850. C, about 1100. C)
  • the maximum heat preservation time of the heat treatment is about 15-90 minutes, for example 60 minutes.
  • it can be carried out by the method described in Chinese Patent No. CN 102120258A.
  • An advantage of the method of the present invention is the combination of high temperature dehydrogenation, low temperature deoxidation, and low temperature heat treatment. Since the cerium powder raw material contains a hydride formed by inevitably absorbing hydrogen gas, its properties (such as lattice constant, electric resistance, etc.) have changed, and conventional low-temperature dehydrogenation cannot completely eliminate these changes. According to the general theory, it is believed that the high-temperature dehydrogenation used here completely eliminates the change of the enthalpy property and completely restores the bismuth powder to the original state. The purpose of using low temperature deoxidation is to avoid the excessive deoxidation temperature. The particles are sintered and grown.
  • the inventors have surprisingly found that the above-mentioned high-temperature dehydrogenation, low-temperature deoxidation and low-temperature heat treatment avoid the sintering and growth of the tantalum powder particles due to excessive temperature in the conventional process (ie, simultaneous dehydrogenation and deoxidation). At the same time, the particles of magnesium or magnesia are wrapped in the ruthenium particles, resulting in poor controllability of the final product particle size and high magnesium content; and avoiding hydrogen caused by incomplete dehydrogenation due to low temperature. High content The problem.
  • the low temperature heat treatment is mainly to remove the residual magnesium metal after deoxidation and pickling
  • the process of the present invention yields a high purity S having a GDMS analytical purity greater than 99.995%.
  • a sodium reduction gas potassium niobate process was used as a raw material (abbreviated as "sodium reduced niobium powder").
  • the tantalum powder obtained by other processes can also serve the purpose of the invention.
  • the "pressing strip” described hereinafter refers to pressing the slab into a slab by means of isostatic pressing.
  • Example 1 Sodium reduction strontium powder was selected as a raw material, subjected to beading, sintering, electron beam smelting into a bismuth ingot, and the bismuth ingot was subjected to hydrogenation treatment. The crumbs obtained by hydrogenating the ingot were crushed by a ball mill and passed through a 500 mesh sieve.
  • the ball milled sieved powder is pickled with a mixed acid of HN0 3 and HF (HN0 3 , HF and water in a volume ratio of 4:1:20) to remove metal impurities, and dried and sieved (the above tantalum powder is placed in The closed furnace was heated to 900 ° C for 180 minutes, then cooled and then sieved. After sieving, the oxygen content was analyzed. The results are shown in Table 1. Then the powder was 1% magnesium by weight of tantalum powder. Mix the powder, then heat it to 700 ° C in a closed oven, heat it for 2 hours, then cool it out, wash it with nitric acid to remove excess magnesium and magnesium oxide, then wash it with neutralized deionized water to dry the powder.
  • Example 2 Sodium-reduced strontium powder was selected as a raw material for beading, sintering, electron beam smelting into bismuth ingots, and then bismuth ingots. Hydrogenation treatment. The crumbs obtained by hydrogenation of the ingot are passed through the ball.
  • Example 3 The sodium reduced niobium powder was selected as a raw material for beading, sintering, electron beam melting into a niobium ingot, and the niobium ingot was subjected to hydrogenation treatment.
  • the crumbs obtained by hydrogenating the ingot were crushed by a ball mill and passed through a 500 mesh sieve.
  • the ball milled sieved powder was pickled with a mixed acid of HN0 3 and HF (HN0 3 , HF and water in a volume ratio of 4:1:20) to remove metal impurities, and dried and sieved.
  • the above crucible powder was placed in a closed oven and heated to 900 with argon. C is kept for 180 minutes, then cooled out of the furnace and sieved.
  • the oxygen content was analyzed after sieving, and the analysis results are shown in Table 1.
  • the tantalum powder was then mixed with 1% of the magnesium powder by weight of the tantalum powder, and then heated to 700 in an enclosed furnace in an argon atmosphere. C, kept for 2 hours, then cooled out of the furnace, washed with nitric acid to remove excess magnesium and magnesium oxide, then washed with deionized water to neutral, dried and sieved.
  • the above tantalum powder was further heated to 1100 under a vacuum of 10 ⁇ 3 Pa. C is kept for 30 minutes, cooled, passivated, baked, sieved to obtain sample C, and analyzed by Glow Discharge Mass Spectrometry (GDMS).
  • the particle size distribution test is carried out using Malvern laser particle size.
  • Comparative Example The sodium reduced niobium powder was selected as the raw material for beading, sintering, electron beam melting into a niobium ingot, and then the niobium ingot was subjected to hydrogenation treatment.
  • the crumbs obtained by hydrogenating the ingot were crushed by a ball mill and passed through a 500 mesh sieve.
  • the ball milled sieved powder was pickled with a mixed acid of HN0 3 and HF (HN0 3 , HF and water in a volume ratio of 4:1:20) to remove metal impurities, and dried and sieved.
  • the ruthenium powder treated by the method of the present invention has a particle size of ⁇ 50 ⁇ 25 ⁇ m and a purity of at least 99.999%.
  • the analysis equipment and models of each of the applications referred to in the present application are shown in the following table.
  • Analytical project Analytical equipment name Model Manufacturer Average particle size Mastersizer Malvern Instruments has Malvern

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

本发明涉及一种高纯钽粉及其制备方法，该钽粉的GDMS分析纯度大于99.995%。优选地，该钽粉的氧含量不高于1000ppm，氮含量不高于50ppm，氢含量不高于20ppm，镁含量不大于5ppm，且粒径D50＜25μm。

Description

一种高纯钽粉及其制备方法 技术领域
本发明涉及一种高纯钽粉及其制备方法。 更特别的， 该钽粉的纯 度大于 99.995%， 平均粒径 ϋ50<25μπι， 氧含量不高于 lOOOppm, 氮 含量不高于 50ppm， 氢含量不高于 20ppm， 镁含量不高于 5ppm。 背景技术
近年来， 半导体技术飞跃发展， 用作溅射膜的钽的需求量逐渐增 加。 在集成电路中， 钽作为扩散阻挡层置于在硅和铜导体之间。 钽溅 射靶的生产方法包括锭冶金（I/M )法和粉末冶金（P/M )法。 较低 要求的钽靶一般选用钽锭制成。 但在某些较高要求的情况下 I/M法不 能使用， 只能用粉末冶金法生产担 。 例如， I/M法不能生产 ^合 金靶， 这是因为钽和硅的熔点不同， 及硅化合物的韧性低等原因。
靶的性能直接影响到溅射膜的性能。 在膜的形成中不能存在对半 导体装置有污染的物质。 在溅射膜形成时， 钽（合金、 化合物）靶中 若有杂质存在， 则在溅射腔内会引入杂质， 导致粗大的粒子附在基片 上， 使薄膜回路发生短路。 同时， 杂质也会成为薄膜中突起物粒子增 多的原因。 特别地， 靶中存在的气体氧、 碳、 氢、 氮等杂质更加有 害， 因为它们会引起异常放电， 使形成的膜的均匀性出现问题。 另 外， 对于粉末冶金方法， 沉积膜的均匀性与靶中的晶粒尺寸成函数关 系， 靶中的晶粒越细， 得到的膜越均匀。 因此， 现有技术中存在对于 高品质钽粉和钽靶的需要。
因此， 为了得到高品质钽粉和钽靶， 必须首先降低钽粉中的杂质 含量， 提高钽粉的纯度。 然而， 众所周知， 虽然金属钽性能比较稳 定， 但是粒径比较细的金属钽粉末比较活泼， 在常温下与氧、 氮等反 应， 使钽粉中氧、 氮等杂质含量提高。 虽然一些金属钽制品例如一些 可商购钽锭的纯度可以达到 99.995%， 甚至更高， 但 越细， 相应 的活性越高， 吸附氧、 氮、 氢、 碳的能力也随之增加， 因而将钽粉纯 度提高到 99.99%以上一直被认为是相当困难和难以实现的。 甚至认 为进一步降低有害杂质氧、 碳、 氢、 氮中的一种的含量都是困难的， 同时降低这四种有害杂质的 H I困难。
其次， 降低钽粉的粒径对于提高钽粉和钽靶的品质也可为必要 的。 本领域希望得到平均粒径 ϋ50 < 25μπι的高纯钽粉。
很多技术人员进行了广泛的研究以试图得到更高纯度和较细粒径 的高纯钽粉， 但结果都不够理想。
例如， 中国专利 CN101182602A公开了一种粉末冶金用 及其 制备方法， 其特征在于钽粉的氧含量低于 1500ppm， 氮含量低于
200ppm。 但该粉末的金属杂质含量、 氢含量较高， 且颗粒较粗， 其 粒度 D50均在 70μπι左右。
中国专利 CN 102909365公开了一种医用 S ， 所述 的氧
<1000ppm, 95%以上的粒度为 1-50.0μπι。 但其采用脱氢脱氧同时进行 的方式， 由于低温不能有效脱除 中的氢含量， 因此脱氢脱氧同时 进行时， 其过程温度比较高。 而且， 在脱氢脱氧之前的钽粉未经过高 温处理， 其活性比较强， 容易导致镁或氧化镁颗粒被包裹在钽颗粒内 部， 在后续酸洗过程中不易除去， 导致最终产品镁含量偏高， 且该发 明在酸洗后不再进行热处理， 其最终钽粉中由于脱氧后残余的金属 镁、 酸洗带入的 H、 F等杂质不能被除去。 因此， 该方法很难达到氢 含量小于 20ppm， 镁含量小于 5ppm的水平。 据报道， 该方法获得的 最高纯度可为 99.9%。
中国专利 CN103447544A公开了一种粒度分布集中可控的高纯钽 粉的制备方法， 其特征在于包括： 将高纯钽锭氢化成钽碎屑， 依次进 行粉碎、 分级， 再将分级后的钽粉依次进行低温真空干燥和脱氢处 理： 其中至少在粉碎、 分级过程中， 与钽粉接触的器具均采用纯度在 99.99%以上的钽制成。 该方法的缺点在于， 第一： 由于其采用的设 备为高纯钽制成， 因此对设备要求高， 同时成本昂贵。 第二， 由于其 方法中没有脱氧的步骤， 因而所得产品的氧含量极不稳定， 差别很 大， 很难完全都小于 1000ppm。 第三， 由于其采用分级处理， 物料的 可利用率大大降低， 而且钽粉的粒径细化困难。 目前， 冶金级钽粉的生产工艺一般采用脱氢脱氧同时进行的方 式， 这会造成设计工艺参数的局限性。 具体地， 如果温度设定过低， 会造成脱氢不彻底， 并导致最终产品氢含量偏高。 同时， 钽在吸氢后 发生的性质 （如晶格常数、 电阻、 硬度等）变化不能完全消除。 如果 温度设定过高， 氢气可以充分幹放， 但会造成钽颗粒的烧结长大， 同 时^ t成镁或氧化镁颗粒被包裹在钽颗粒内部， 在后续酸洗过程中很 难被除去， 从而导致粒径可控性差， 很难达到氧含量低于 lOOOppm的 同时确保其平均粒径 ϋ50<25μπι的要求。 更遗憾的是， 还会导致镁含 量过高。 另外， 目前的工艺在脱氢脱氧后钽粉经过酸洗、 烘干、 过筛 后即为最终产品， 而未进行后续的热处理， 这会导致脱氧后残余的金 属镁、 酸洗带入的 H、 F等杂质不能被除去， 使最终产品的镁、 氢等 含量过高。
显然， 现有技术难以满足半导体技术中溅射膜的需求。
针对以上方法存在的缺陷， 提出了本发明。
发明内容
本发明提供了一种高纯 S ， 其 GDMS分析纯度大于 99.995%， 优选大于 99.999%的钽粉。
在本发明的一个优选实施方案中， 该钽 具有低的氧、 氮、 氢、 和镁的含量， 例如氧含量不高于 lOOOppm; 氮含量不高于
50ppm, 优选不高于 40ppm; 氢含量不高于 20ppm， 优选不高于
15ppm, 更优选不高于 lOppm; 镁含量不高于 5ppm。
在本发明的一个优选实施方案中， 该钽粉末的粒径 ϋ50<25μπι， 优选 ϋ50<20μπι。
除了半导体技术中的溅射膜， 该钽粉末也可以用于其它用途， 例 如医用、 表面喷涂等。
本发明还提供了该钽粉的制造方法， 其依次包括如下步骤：
1 )将高纯钽锭进行氢化处理；
2 )将钽锭氢化后所得的钽屑进行破碎， 并过筛， 然后对其 进行酸洗纯化处理， 以除去球磨过程带入的杂质污染；
3 )对上一步厥得到钽粉末进行高温脱氢处理； 4 )对上一步厥得到的钽粉末进行脱氧处理；
5 ) 将上一步骤得到的钽粉末进行酸洗、 水洗、 烘干、 过 筛，
6 )将上一步骤得到的钽粉末进行低温热处理， 然后进行降 温、 钝化、 出炉、 过筛得到成品 a 。
在本文中， 高纯钽锭是指钽含量达到 99.995%以上的钽锭。 目前 可以以多种方法得到这种钽锭， 例如可以以各种工艺生产的钽粉为原 料， 通过高温烧结除杂或电子轰击除杂得到。 这种钽锭也可以从市场 购得。
对于氢化钽屑的破碎方式没有限制， 例如可以通过气流粉碎 i殳备 或球磨设备进行破碎， 但是优选破碎后的钽粉颗粒应全部能通过 400 目或更高筛目的筛网， 比如： 500目、 600目、 700目。 筛网目数越 高、 钽粉越细， 但是如果钽粉太细， 比如大于 -700目， 则较难以控制 钽粉的氧含量。 因此， 步骤 2 ) 中的过筛优选是指过 400-700目筛。 出 于说明而非限制的目的， 在本发明实施例中采用的是球磨破碎。
不同于本领域中为了节能而采用的低温脱氢， 本发明优选通过如 下方式进行高温脱氢： 将钽粉在在惰性气体保护下加热， 在约 800- 1000。C (比如约 900。C、 约 950。C、 约 980。C、 约 850。C、 约 880。C ) 下 保温约 60-300分钟 (比如约 120分钟、 约 150分钟、 约 240分钟、 约 200 分钟） ， 然后进行降温、 出炉、 过筛得到脱氢的 a 。 出乎意料地， 发明人发现， 采用所述的较高温度进行脱氢， 可以实现在脱氢的同时 降低 表面活性。
在本发明的一个优选实施方案中， 在步骤 4 ) 中对钽粉进行低温 脱氧处理， 即过程最高温度优选不高于脱氢温度， 一般脱氧处理过程 最高温度低于脱氢温度约 50-300。C (比如约 100。C、 约 150。C、 约 180。C、 约 80。C、 约 200。C ) ， 能达到脱氧目的的同时保证钽颗粒不烧 结不长大即可， 以免镁或氧化镁颗粒被包裹在钽颗粒内部， 在后续酸 洗过程中不易除去， 导致成品 § 中镁含量偏高。
在本发明的一个优选实施方案中， 通过向钽粉加入还原剂进行脱 氧。 优选地， 所述的脱氧处理通常在惰性气体保护的情况下进行。 一 般来说， 所述还原剂与氧的亲和力比钽与氧的亲和力更大。 这样的还 原剂例如为碱土金属、 稀土金属及其氢化物， 最常用的是镁粉。 作为 一个具体的优选实施方案， 可以通过在钽粉中混入以钽粉重量计为
0.2-2.0%的金属镁粉， 采用中国专利 CN 102120258A中所述的方法进 行装盘， 然后在惰性气体保护的情况下加热， 在约 600-750。C (例如 约 700eC )保温约 2-4小时， 然后再抽真空， 在抽真空条件下再保温约 2-4小时， 然后降温、 钝化、 出炉从而获得脱氧的 a 。
本行业一般技术人员认为， 的热处理又称之为热团聚， 主要 目的是为了改善 物理性能， 提高钽粉粒径、 松装密度， 改善流动 性、 粒度分布等作用。 但是， 不束缚于一般理论， 认为本发明的热处 理在确保避免钽粉粒径、 松装密度增大的同时， 还具有更重要的作 用， 即： 尽可能除去脱氧后残余的金属镁、 酸洗带入的 H、 F等杂 质。 本发明在真空热处理炉中进行， 过程要求真空度较高， 尤其是在 热处理温度高于约 600。C以后， 要求真空度为约 1.0xl03Pa或更高， 热 处理温度采用约 600-1200°C的较低温度， 比如约 800°C、 约 950°C、 约 1000。C、 约 850。C、 约 1100。C ) ， 热处理最高保温时间约 15-90分钟，例 如 60分钟。 例如， 可采用中国专利 CN 102120258A中所述的方法进 行。
本发明的方法的优势在于采用高温脱氢、 低温脱氧和低温热处理 的组合方式。 由于钽粉原料中含有因不可避免地吸收氢气而生成的氢 化物， 因此其性质 （如晶格常数、 电阻、 等发生了变化， 而采 用常规的低温脱氢尚不能完全消除这些变化。 不束缚于一般理论， 认 为这里采用的高温脱氢在使氢气充分幹放的同时， 还完全消除钽性质 的变化， 使钽粉恢复到原来的状态。 采用低温脱氧的目的在于避免脱 氧温度过高造成的颗粒烧结长大。
发明人出人意料地发现， 采用上述的高温脱氢、 低温脱氧和低温 热处理的方式， 既避免了传统工艺 （即脱氢脱氧同时进行） 中由于温 度过高而带来的钽粉颗粒烧结、 长大， 同时使镁或氧化镁的颗粒被包 裹在钽颗粒内部， 从而造成的最终产品粒度可控性差， 镁含量偏高的 问题； 又避免了因为温度过低而导致的脱氢不彻底造成的氢含量偏高 的问题。 低温热处理主要是除去脱氧后残余的金属镁、 酸洗带入的
H、 F等杂质， 同时确保颗粒不长大， 在达到粒度要求的同时， 使杂 质含量得到了很好的控制。 最终， 本发明的方法得到了 GDMS分析纯 度大于 99.995%的高纯 S 。 具体实施方式：
出于说明而非限制性目的， 提供如下实施例。
在各实施例中均采用钠还原氣钽酸钾工艺得到的 为原料（简 称为"钠还原钽粉"） 。 然而， 应当理解， 采用其它工艺得到的钽粉也 能满 ^发明的目的。
如本领域技术人员所理解的那样， 下文所述的"压条"是指将 末通过等静压的方式压制成钽坯条。 实施例 1: 选用钠还原钽粉为原料， 进行压条、 烧结、 电子束熔 炼成钽锭， 将钽锭进行氢化处理。 将钽锭氢化后所得的钽屑经球磨破 碎， 并过 500目筛。 将球磨过筛后的钽粉用 HN03和 HF的混合酸 ( HN03、 HF和水的体积比是 4:1:20 )酸洗去除金属杂质， 烘干过筛 (将上述钽粉末放置在密闭炉里充氩加热到 900。C保温 180分钟， 然后 冷却出炉后过筛。 过筛后进行氧含量分析， 分析结果见表 1。 然后将 钽粉与以钽粉重量计的 1%的镁粉混合，然后在密闭炉里充氩气加热到 700。C，保温 2小时，然后冷却出炉，用硝酸洗涤去掉多余的镁及氧化镁，然 后用去离子水洗到中性，将钽粉烘干过筛。 再将上述钽粉在 10·3 Pa真空 下加热到 700。C保温 60分钟、 冷却、 钝化、 出炉、 过筛得到样品 A，用 辉光放电质镨仪 (Glow Discharge Mass Spectrometry, GDMS)进行分 析，用马尔文激^度^其进行粒度分布测试，结果见表 1。 实施例 2: 选用钠还原钽粉为原料进行压条、 烧结、 电子束熔炼 成钽锭， 再将钽锭进行氢化处理。 将钽锭氢化后所得的钽屑经球磨破 碎， 并过 500目筛。 球磨过筛后的粉用 HN03和 HF的混合酸（HN03、 HF和水的体积比是 4:1:20 )酸洗去除金属杂质， 烘干过筛。 将上述钽 粉末放置在密闭炉里充氩加热到 900。C保温 180分钟， 然后冷却出炉后 过筛。 过筛后进行氧含量分析， 分析结果见表 1。 然后将钽粉与钽粉 重量的 1 %的镁粉混合，然后在密闭炉里充氩气加热到 750。C，保温 2小时， 然后冷却出炉，用硝酸洗涤去掉多余的镁及氧化镁，然后用去离子水洗 到中性，将钽粉烘干过筛。 再将上述钽粉在 10·3 Pa真空下加热到 800。C 保温 60分钟、 冷却、 钝化、 出炉、 过筛得到样品 B，用辉 ^^电质 ^1 (Glow Discharge Mass Spectrometry, GDMS)进行分析，.用马尔文激光 粒度^其进行粒度分布测试，结果见表 1。 实施例 3: 选用钠还原钽粉为原料进行压条、 烧结、 电子束熔炼 成钽锭， 再将钽锭进行氢化处理。 将钽锭氢化后所得的钽屑经球磨破 碎， 并过 500目筛。 球磨过筛后的粉用 HN03和 HF的混合酸（HN03、 HF和水的体积比是 4:1:20 )酸洗去除金属杂质， 烘干过筛。 将上述钽 粉末放置在密闭炉里充氩加热到 900。C保温 180分钟， 然后冷却出炉后 过筛。 过筛后进行氧含量分析， 分析结果见表 1。 然后将钽粉与钽粉 重量的 1 %的镁粉混合，然后在密闭炉里充氩气加热到 700。C，保温 2小时， 然后冷却出炉，用硝酸洗涤去掉多余的镁及氧化镁，然后用去离子水洗 到中性，将钽粉烘干过筛。 再将上述钽粉在 10·3 Pa真空下加热到 1100。C 保温 30分钟、 冷却、 钝化、 出炉、 过筛得到样品 C，用辉 ^^电质 ^1 (Glow Discharge Mass Spectrometry, GDMS)进行分析，.用马尔文激光 粒度^其进行粒度分布测试，结果见表 1。 对比例： 选用钠还原钽粉为原料进行压条、 烧结、 电子束熔炼成 钽锭， 再将钽锭进行氢化处理。 将钽锭氢化后所得的钽屑经球磨破 碎， 并过 500目筛。 球磨过筛后的粉用 HN03和 HF的混合酸（HN03、 HF和水的体积比是 4:1:20 )酸洗去除金属杂质， 烘干过筛。 将上述钽 粉与钽粉重量的 1%的镁粉混合，然后在密闭炉里充氩气加热到 850°C， 保温 2小时，然后冷却出炉，用硝酸洗涤去掉多余的镁及氧化镁，然后用 去离子水洗到中性，将钽粉烘干过筛得到样品 D,用辉光放电质傅仪 (Glow Discharge Mass Spectrometry, GDMS)进行分析，.用马尔文激光 粒度^其进行粒度分布测试，结果见表 1。 表 1: 钽粉性能对比
Figure imgf000009_0001
由上述数据可以看出， 采用本发明的方法所处理钽粉末的粒径 ϋ50<25μπι，纯度至少达到 99.999%以上。 本申请中所涉及的各个^ t的分析设备及型号如下表所示。 分析项目 分析设备名称 型号 生产厂家 平均粒径 Mastersizer 英国马尔文仪器有 马尔文激^^度仪
( μιη ) 2000 司
0、 Ν、 Η 氧氮分析仪 LECO CS-436 美国力可公司
Thermo Fisher
Mg(pPm)/纯度 辉光放电质傳仪 Element GD
Scientific

Claims

权 利 要 求 书
1.一种高纯 S ， GDMS分析纯度大于 99.995%。
2. 如权利 1所述高纯钽粉， 其中该钽粉的氧含量不高于 lOOOppm; 氮含量不高于 50ppm， 优选不高于 40ppm; 氢含量不高于 20ppm , 优选不高于 15ppm， 更优选不高于 lOppm; 镁含量不高于 5ppm。
3.如权利 1所述高纯钽粉， 其中该钽粉的粒径 ϋ50<25μπι， 优选 D50 < 20μπι。
4.一种制备如权利要求 1、 2或 3所述的高纯钽粉的方法， 该方法 依次包括如下步骤：
1 )将高纯钽锭进行氢化处理；
2 )将钽锭氢化后所得的钽屑进行破碎， 然后对其进行酸洗 纯化处理， 以除去球磨过程带入的杂质污染；
3)对上一步厥得到钽粉末进行高温脱氢处理；
4 )对上一步厥得到的钽粉末进行脱氧处理；
5 ) 将上一步骤得到的钽粉末进行酸洗、 水洗、 烘干、 过 筛。
6 )将上一步骤得到的钽粉末进行低温热处理， 然后进行降 温、 钝化、 出炉、 过筛得到成品 a 。
5.如权利要求 4所述的方法， 其中高纯钽锭是指钽含量达到 99.995%以上的钽锭。
6.如权利要求 4或 5所述的方法， 其中通过如下方式进行高温脱 氢： 将钽粉在约 800-1000。C (比如约 900。C、 约 950。C、 约 980。C、 约 850。C、 约 880。C ) 下保温约 60-300分钟 （比如约 120分钟、 约 150分 钟、 约 240分钟、 约 200分钟） ， 然后进行降温、 出炉、 过筛得到脱氢 的 。
7.如权利要求 4或 5或 6所述的方法， 其中脱氧处理的温度低于脱 氢温度， 例如低于约 50-300°C (比如约 100°C、 约 150°C、 约 180°C、 约 80。C、 约 200。C ) 。
8.如权利要求 4-7中任一项所述的方法， 其中所述的低温热处理 温度通过在约 600-1200°C保温约 15-90分钟 (例如 60分钟)进行， 优选其 间真空度为 10-3Pa或更高真空度。
9.如权利要求 4-8中任一项所述的方法， 其中在步骤 2)中将钽屑破 碎到通过 400目 -700目筛网。
10.权利要求 1或 2所述的钽粉， 在半导体、 医药和 /或表面喷涂中 的用途。
PCT/CN2014/072597 2014-02-27 2014-02-27 一种高纯钽粉及其制备方法 WO2015127613A1 (zh)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PCT/CN2014/072597 WO2015127613A1 (zh) 2014-02-27 2014-02-27 一种高纯钽粉及其制备方法
CN201480016668.3A CN105377481B (zh) 2014-02-27 2014-02-27 一种高纯钽粉及其制备方法
EP14883916.0A EP3112059B1 (en) 2014-02-27 2014-02-27 Preparation of high-purity tantalum powder
US15/111,632 US10737320B2 (en) 2014-02-27 2014-02-27 High-purity tantalum powder and preparation method thereof
JP2016554604A JP2017512897A (ja) 2014-02-27 2014-02-27 高純度タンタル粉末及びその調製方法
TW104101358A TWI611025B (zh) 2014-02-27 2015-01-15 一種高純鉭粉及其製備方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/072597 WO2015127613A1 (zh) 2014-02-27 2014-02-27 一种高纯钽粉及其制备方法

Publications (1)

Publication Number Publication Date
WO2015127613A1 true WO2015127613A1 (zh) 2015-09-03

Family

ID=54008132

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/072597 WO2015127613A1 (zh) 2014-02-27 2014-02-27 一种高纯钽粉及其制备方法

Country Status (6)

Country Link
US (1) US10737320B2 (zh)
EP (1) EP3112059B1 (zh)
JP (1) JP2017512897A (zh)
CN (1) CN105377481B (zh)
TW (1) TWI611025B (zh)
WO (1) WO2015127613A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106735254A (zh) * 2016-12-28 2017-05-31 宁夏东方钽业股份有限公司 一种金属粉末及其制备方法和应用

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2015311708A1 (en) * 2014-09-07 2017-02-02 Selecta Biosciences, Inc. Methods and compositions for attenuating exon skipping anti-viral transfer vector immune responses
US20180144874A1 (en) * 2016-10-21 2018-05-24 Global Advanced Metals, Usa, Inc. Tantalum Powder, Anode, And Capacitor Including Same, And Manufacturing Methods Thereof
CN106756826A (zh) * 2016-11-25 2017-05-31 东莞市联洲知识产权运营管理有限公司 一种高纯度钽钌合金靶材及其制备方法
CN109622941A (zh) * 2018-12-28 2019-04-16 宁夏东方钽业股份有限公司 一种低氧铌粉及其制造方法
CN110947976A (zh) * 2019-11-06 2020-04-03 中航迈特粉冶科技（北京）有限公司 低氧球形钽粉及其制备方法
CN113981390A (zh) * 2021-10-29 2022-01-28 宁波江丰半导体科技有限公司 一种高纯低氧钽靶材的制备方法
CN114749655B (zh) * 2022-04-29 2023-10-24 宁夏东方钽业股份有限公司 高纯钽粉及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090067121A1 (en) * 2006-05-05 2009-03-12 Cabot Corporation Tantalum Powder and Methods Of Manufacturing Same
CN101808770A (zh) * 2007-10-15 2010-08-18 高温特殊金属公司 利用回收的废料作为源材料制备钽粉末的方法
CN102909365A (zh) * 2012-11-20 2013-02-06 重庆润泽医药有限公司 一种医用钽粉及其制备方法
CN103447544A (zh) * 2013-09-24 2013-12-18 泰克科技(苏州)有限公司 粒度分布集中可控的高纯钽粉制备方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3295951A (en) 1965-02-02 1967-01-03 Nat Res Corp Production of metals
US3418106A (en) 1968-01-31 1968-12-24 Fansteel Inc Refractory metal powder
US4017302A (en) 1976-02-04 1977-04-12 Fansteel Inc. Tantalum metal powder
DE3130392C2 (de) * 1981-07-31 1985-10-17 Hermann C. Starck Berlin, 1000 Berlin Verfahren zur Herstellung reiner agglomerierter Ventilmetallpulver für Elektrolytkondensatoren, deren Verwendung und Verfahren zur Herstellung von Sinteranoden
JPH02310301A (ja) 1989-05-24 1990-12-26 Showa Kiyabotsuto Suupaa Metal Kk タンタル粉末及びその製造法
US6323055B1 (en) 1998-05-27 2001-11-27 The Alta Group, Inc. Tantalum sputtering target and method of manufacture
US6348113B1 (en) 1998-11-25 2002-02-19 Cabot Corporation High purity tantalum, products containing the same, and methods of making the same
US6261337B1 (en) 1999-08-19 2001-07-17 Prabhat Kumar Low oxygen refractory metal powder for powder metallurgy
US6521173B2 (en) 1999-08-19 2003-02-18 H.C. Starck, Inc. Low oxygen refractory metal powder for powder metallurgy
JP2004360043A (ja) 2003-06-06 2004-12-24 Sumitomo Metal Mining Co Ltd ニオブおよび／またはタンタル粉末の製造方法
US20080011124A1 (en) * 2004-09-08 2008-01-17 H.C. Starck Gmbh & Co. Kg Deoxidation of Valve Metal Powders
PT2169086E (pt) * 2005-09-16 2015-02-17 Starck H C Gmbh Pó de metal refratário
CN101182602B (zh) 2006-11-14 2010-04-14 宁夏东方钽业股份有限公司 粉末冶金用钽和/或铌粉末及其制备方法
CN102120258B (zh) 2011-02-14 2012-12-26 宁夏东方钽业股份有限公司 钽粉的热处理方法
CN102554215B (zh) * 2011-12-29 2014-01-29 中国兵器工业第五二研究所 一种纳米级钽粉的热处理方法
CN103600086B (zh) 2013-12-03 2016-05-04 宁夏东方钽业股份有限公司 粉末冶金用钽和/或铌粉及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090067121A1 (en) * 2006-05-05 2009-03-12 Cabot Corporation Tantalum Powder and Methods Of Manufacturing Same
CN101808770A (zh) * 2007-10-15 2010-08-18 高温特殊金属公司 利用回收的废料作为源材料制备钽粉末的方法
CN102909365A (zh) * 2012-11-20 2013-02-06 重庆润泽医药有限公司 一种医用钽粉及其制备方法
CN103447544A (zh) * 2013-09-24 2013-12-18 泰克科技(苏州)有限公司 粒度分布集中可控的高纯钽粉制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3112059A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106735254A (zh) * 2016-12-28 2017-05-31 宁夏东方钽业股份有限公司 一种金属粉末及其制备方法和应用
CN106735254B (zh) * 2016-12-28 2019-08-16 宁夏东方钽业股份有限公司 一种金属粉末及其制备方法和应用

Also Published As

Publication number Publication date
TW201533248A (zh) 2015-09-01
EP3112059B1 (en) 2020-01-15
JP2017512897A (ja) 2017-05-25
CN105377481B (zh) 2018-02-06
EP3112059A4 (en) 2017-11-15
CN105377481A (zh) 2016-03-02
TWI611025B (zh) 2018-01-11
US20160354838A1 (en) 2016-12-08
US10737320B2 (en) 2020-08-11
EP3112059A1 (en) 2017-01-04

Similar Documents

Publication Publication Date Title
WO2015127613A1 (zh) 一种高纯钽粉及其制备方法
KR102490248B1 (ko) 분말 야금 스퍼터링 표적 및 그의 생성 방법
CN109108273B (zh) NbZrTiTa难熔高熵合金粉末制备方法及NbZrTiTa难熔高熵合金粉末
CN103600086B (zh) 粉末冶金用钽和/或铌粉及其制备方法
CN104841929B (zh) 一种微细铌粉及其制造方法
EP3467142B1 (en) Sputtering target and production method therefor
TWI596215B (zh) A fine tantalum powder and its preparation method
JP2004100000A (ja) 珪化鉄スパッタリングターゲット及びその製造方法
TWI636148B (zh) 鉭濺鍍靶
EP4364871A1 (en) Tantalum-tungsten alloy powder and preparation method therefor
WO2016186070A1 (ja) 銅合金スパッタリングターゲット及びその製造方法
CN111676410B (zh) 一种高强高韧CoFeNiTiV高熵合金及其制备方法
CN112251659B (zh) 一种AlCrFe2Ni2C0.24高熵合金及其制备方法
JP6649430B2 (ja) 高純度タンタル粉末及びその調製方法
JP2015516512A (ja) 乾式法を利用した酸化物分散強化型白金−金合金粉末の製造方法
CN112962069B (zh) 一种含金属间化合物的铝合金靶材及其制备方法
EP3705588B1 (en) Method for purifying titanium material
CN117265489A (zh) 一种钛铝合金靶材及其制备方法
JPH04190959A (ja) 水素吸蔵合金の製造方法
CN115259854A (zh) 一种半导体α-GeTe靶材及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14883916

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15111632

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016554604

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2014883916

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014883916

Country of ref document: EP