[go: up one dir, main page]

WO2014131149A1 - Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé - Google Patents

Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé Download PDF

Info

Publication number
WO2014131149A1
WO2014131149A1 PCT/CN2013/071874 CN2013071874W WO2014131149A1 WO 2014131149 A1 WO2014131149 A1 WO 2014131149A1 CN 2013071874 W CN2013071874 W CN 2013071874W WO 2014131149 A1 WO2014131149 A1 WO 2014131149A1
Authority
WO
WIPO (PCT)
Prior art keywords
tantalum
niobium
alloy wire
electrolytic capacitor
powder
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.)
Ceased
Application number
PCT/CN2013/071874
Other languages
English (en)
Chinese (zh)
Inventor
万庆峰
解永旭
韩鹏
刘云峰
张晓�
马跃忠
陈林
郭林波
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.)
Ningxia Orient Tantalum Industry Co Ltd
Original Assignee
Ningxia Orient Tantalum Industry Co Ltd
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 Ningxia Orient Tantalum Industry Co Ltd filed Critical Ningxia Orient Tantalum Industry Co Ltd
Priority to PCT/CN2013/071874 priority Critical patent/WO2014131149A1/fr
Priority to CN201380063104.0A priority patent/CN104823253A/zh
Publication of WO2014131149A1 publication Critical patent/WO2014131149A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/008—Terminals
    • H01G9/012—Terminals specially adapted for solid capacitors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • 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
    • H01G9/008—Terminals
    • 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
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • the present invention relates to the field of electrolytic capacitors, and more particularly to a tantalum alloy wire for an anode lead of an electrolytic capacitor and a method of manufacturing the same. Background technique
  • the manufacturing process of the tantalum electrolytic capacitor generally comprises the following steps: loading the tantalum powder into a stamper and embedding the twisted wire, then pressing to form a compact, and sintering the compact in a vacuum furnace to form a porous body interconnected between the particles, and then The porous sintered body is anodized in a suitable electrolyte to form a uniform dielectric oxide film on the surface of the porous body to form an anode block, and then the cathode material is coated on the surface of the oxide film of the anode block, and finally the package is coated.
  • the seal is made into an electrolytic capacitor.
  • the main parameters for evaluating tantalum electrolytic capacitors are capacitance, DC (direct current) leakage current, and equivalent series resistance (ESR).
  • the trend in capacitors is to require high capacitance, low leakage current and low equivalent series resistance.
  • As the anode lead of tantalum electrolytic capacitors silk is mainly used to extract the capacity of tantalum electrolytic capacitors from the anode block.
  • the performance requirements of the capacitor for the twisted wire are mainly low leakage current, good brittle resistance and good welding performance.
  • There are generally two types of methods for manufacturing capacitor-grade twisted wires one of which is produced by electron beam melting of bismuth ingots or arc-melting bismuth ingots by processes such as forging, heat treatment, and drawing.
  • Another method is to use the traditional powder metallurgy method to produce pure tantalum powder through molding, sintering, rolling, annealing, drawing and other processes.
  • Tantalum wires are commonly used as anode leads in the field of tantalum electrolytic capacitors.
  • base metal is a precious metal and has a high density. Therefore, the use of base metal to make an anode lead of an electrolytic capacitor is relatively expensive, and the length of the twisted wire produced at a unit weight is short. There is therefore a need in the art for a less expensive alternative to anode leads that can be used in electrolytic capacitors. Summary of the invention
  • the present invention satisfies the above needs by providing a niobium alloy wire for an anode lead of an electrolytic capacitor and a method of manufacturing the same.
  • the present invention provides a tantalum alloy wire for an anode lead of an electrolytic capacitor, the composition of the tantalum alloy wire being: 0. 1-99. 9 wt% of niobium, and the balance of niobium and unavoidable impurities .
  • the composition of the niobium alloy wire of the present invention is: 30 to 70% by weight of niobium, and the balance of niobium and unavoidable impurities.
  • the niobium alloy wire of the present invention consists of 40 to 60% by weight of niobium and 60 to 40% by weight of niobium. 2 ⁇
  • the diameter of the bismuth alloy is preferably between 0. 1-1. 2mm.
  • the density of the metal ruthenium is 16.65 g/cm 3 , and the density of the metal ruthenium is only 8.57 g/cm 3 ; therefore, the density of the ruthenium alloy is usually between the metal ruthenium and the metal ruthenium. Since the density of the niobium alloy is less than that of the niobium metal, the length of the niobium alloy filament per unit weight will be significantly higher than that of the pure tannin wire per unit weight of the pure tannin wire in the case where the filament diameter is the same.
  • the price of metal ruthenium is significantly higher than that of metal ruthenium (for example, shortly before the filing date of this application, the price of base metal in China is 3000-4000 RMB/kg, while the price of metal ruthenium is only 600-900 RMB/kg. Therefore, the material cost of niobium alloys will be significantly lower than that of niobium. Therefore, for at least the above two reasons, the use of the niobium alloy wire according to the present invention as the anode lead of the tantalum/niobium electrolytic capacitor will significantly reduce the cost of the anode lead.
  • the present invention also provides a method of producing a niobium alloy wire for an anode lead of an electrolytic capacitor. Specifically, the method of the present invention includes the following steps:
  • the obtained niobium alloy wire is optionally cleaned and finally annealed to obtain a niobium alloy wire suitable for an electrolytic capacitor.
  • the method of the invention involves the preparation of niobium alloy filaments by powder metallurgy.
  • Metallurgical grade tantalum powder and tantalum powder are used as raw materials, wherein the weight ratios of tantalum powder and tantalum powder are shown in Table 1; in addition, the impurity contents of tantalum powder and tantalum powder are shown in Table 2 and Table 3; The bulk specific gravity and particle size of the tantalum powder and tantalum powder used.
  • the weight of bismuth powder and bismuth powder in step (1) is preferably from 30:70 to 70:30, and more preferably from 40:60 to 60:40.
  • the pressure for press forming in step (2) is from 100 to 250 MPa and the dwell time is from 10 to 60 minutes.
  • the press-formed compact is first pre-sintered at a temperature of from 1 000 to 1900 ° C, and the sintering technique is performed by vacuum sintering, and the degree of vacuum is preferably greater than 5.0 ⁇ 10 - 3 Pa, and the leak rate is preferably less than 0. 5 Pa/min.
  • the sintered alloy rod is brought into fusion with the tantalum powder particles and the tantalum powder particles to ensure that the sintered rod does not break.
  • holding time is preferably a sintered 180min vacuum sintering technology, with the proviso that the degree of vacuum is preferably greater than 5.
  • 0 ⁇ 10_ 3 Pa preferably less than the leakage rate of 0. 5 Pa / mi n 0 0 ⁇ / ⁇
  • the density of the sintered barium alloy bar is preferably greater than 9. 0g / cm 3 .
  • the sintered niobium alloy rod is rolled into a billet having a diameter of 3.0 mm or less by a processing amount of 5 to 30% per pass.
  • the billet since a large amount of heat is generated during the rolling of the niobium alloy rod, the billet may be oxidized, and therefore lubricating with a lubricating oil is preferred.
  • the rolled niobium alloy billet needs to be annealed under vacuum in an intermediate product, and the annealing temperature is 1 000-1600 ° C, and the holding time is 30-120 minutes.
  • the drawing of the bismuth alloy wire is carried out on a wire drawing machine, and in order to prevent scratching of the surface of the crepe and deformation of the high temperature oxidation, lubrication and cooling are carried out using a liquid lubricating oil.
  • the pass processing rate of the niobium alloy wire in order to prevent the processing rate of the niobium alloy wire from being unsuitable for breaking, the pass processing rate of 5-30% is employed, and the total processing ratio is 50-99%.
  • the drawn finished niobium alloy wire is cleaned; for example, with a degreaser and rinsed with water while applying ultrasonic waves.
  • the finished ruthenium alloy wire after cleaning is subjected to final annealing.
  • final annealing is employed in which heating is above the recrystallization temperature while inert gas protection is employed to prevent oxidation of the wire.
  • the final bismuth alloy wire has a final annealing temperature of 1400-2000 ° C and a line speed of 5-50 m/min.
  • the curvature of the reel according to the present invention cannot be too large, otherwise the finished product of the niobium alloy wire will be greatly bent on the reel, which cannot meet the requirements for use.
  • the usual diameter of the reel is ⁇ 200mm - ⁇ 400mm.
  • the niobium alloy wire of the present invention is suitable for use as an anode lead in tantalum electrolytic capacitors. Further, the niobium alloy wire of the present invention is also suitable for use as an anode lead in a tantalum electrolytic capacitor.
  • FIG. 1 is a flow chart showing a method for producing a niobium alloy wire of the present invention
  • FIG. 2 is a scanning electron micrograph (200 times magnification) of a cross section of the niobium alloy wire of the present invention
  • Figure 3 is a schematic view showing the multi-wheel straightening of the bismuth alloy wire of the present invention.
  • Figure 4 is a schematic illustration of the bending requirements for tantalum wire. detailed description
  • the process of the method for producing a niobium alloy wire of the present invention can be seen in FIG.
  • the tantalum powder and niobium powder are processed into a desired size of niobium alloy wire by mixing, pressing, pre-sintering, sintering, rolling, intermediate annealing, drawing, cleaning, final annealing, etc. in a certain ratio. It is preferred to use a particle size of less than 100 mesh powder and strontium powder, and uniformly mix the two in a predetermined ratio.
  • the uniform mixing of the tantalum powder and the tantalum powder was carried out in a V-type mixer, and the mixed powder mixture was placed in a latex sheath and tied with a metal splint.
  • the intermediate annealing is performed at a temperature of 1300 ° C, and the vacuum in the annealing furnace is maintained greater than 5.0 x 1 0 - 3 Pa; then a continuous wire drawing machine is used Drawn into product ⁇ alloy wire, the pass processing rate is 20%; cleaned with degreaser, rinsed with water, and applied with ultrasonic wave; finished product adopts continuous wire annealing, annealing temperature is 300-800° higher than recrystallization temperature C, the line speed is 10m/min.
  • the invention uses a metallurgical grade tantalum powder and tantalum powder to prepare a tantalum alloy wire suitable for an anode lead of an electrolytic capacitor by a powder metallurgy method.
  • Base metal density is higher than gold It is smaller, so the length of the niobium alloy wire produced under unit weight is longer; on the other hand, the price of niobium is significantly lower than that of niobium, so the cost of using niobium alloy wire as the anode lead of electrolytic capacitor is lower. . Therefore, the implementation of the present invention has a certain protection effect on the national resources.
  • the proportion of the powder is 60%, the particle size is -100 mesh 100%, and the bulk specific gravity is 5. lg/cm 3 ; the proportion of the powder is 40%, the particle size is -150 mesh 100%, and the pine The specific gravity is 2.8 g/cm 3 .
  • the vacuum in the furnace reaches 5.0 ⁇ 10— 3 Pa, the temperature is raised to 1380 ° C, and the temperature is kept for 60 minutes.
  • the power is cut off with the furnace, and then drawn into a ⁇ 0.6 mm alloy wire through a continuous drawing process, and then ultrasonically cleaned again.
  • ICP-MS Inductively coupled plasma mass spectrometry
  • Item leakage current ( ⁇ A/mm 2 ) Diameter deviation ( mm ) Detected value 0. 00041 ⁇ 0. 002 Using a leakage current tester, bismuth alloy wire is carried out in a 0.1% phosphoric acid aqueous solution at a temperature of 25 °C. Electrical performance test. In addition, the diameter tester is used to test the diameter deviation. Table 8 Bending value test results
  • the ratio of the powder to the powder is 60%, and the proportion of the powder is 40%.
  • the dimensions of the products processed are as follows:
  • the crucible rod After sintering, the crucible rod is rolled into ⁇ 3. 0 leg and then pickled, annealed, and drawn into ⁇ 0. 70 mm; then ultrasonically cleaned, annealed, and drawn into a ⁇ 0. 24 mm ⁇ ⁇ alloy wire.
  • the rest of the process is the same as in Embodiment 1.
  • the properties of the bismuth alloy wire were tested, and the detection method was the same as in Example 1; and the results are summarized as follows. Table 9 Chemical composition (Ta and Nb in weight percent, others in ppm)
  • the proportion of the powder is 70%, and the proportion of the powder is 30%.
  • the dimensional changes of the products are as follows:
  • the crucible rod After sintering, the crucible rod is rolled into a strip of ⁇ 3.0 mm; then it is pickled, intermediate annealed, drawn into ⁇ 0.90 mm and then ultrasonically cleaned, intermediate annealed, and drawn into a ⁇ 0.5 leg bismuth alloy wire. A continuous trace final annealing is then performed. The rest of the process is the same as in Embodiment 1.
  • the properties of the bismuth alloy wire were tested, and the detection method was the same as in Example 1; and the results are summarized as follows. Table 13 chemical composition (Ta and Nb in weight percent, others in ppm)

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention se rapporte à un fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et à un procédé de fabrication associé. La composition du fil en alliage de tantale et de niobium comprend : du tantale en une quantité comprise entre 0,1 et 99,9 % en poids ainsi que du niobium et des impuretés inévitables pour le contenu restant. Le procédé comprend les étapes suivantes : le mélange des matériaux, le moulage par compression, le frittage, le laminage, le recuit, l'étirage et un nettoyage facultatif et un recuit continu de manière à obtenir un fil en alliage de tantale et de niobium qui peut être appliqué à un condensateur électrolytique. Comparé à un fil métallique classique à base de tantale, le fil en alliage de tantale et de niobium réduit les coûts de manière significative.
PCT/CN2013/071874 2013-02-26 2013-02-26 Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé Ceased WO2014131149A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2013/071874 WO2014131149A1 (fr) 2013-02-26 2013-02-26 Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé
CN201380063104.0A CN104823253A (zh) 2013-02-26 2013-02-26 电解电容器阳极引线用钽铌合金丝及其制造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2013/071874 WO2014131149A1 (fr) 2013-02-26 2013-02-26 Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé

Publications (1)

Publication Number Publication Date
WO2014131149A1 true WO2014131149A1 (fr) 2014-09-04

Family

ID=51427454

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/071874 Ceased WO2014131149A1 (fr) 2013-02-26 2013-02-26 Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé

Country Status (2)

Country Link
CN (1) CN104823253A (fr)
WO (1) WO2014131149A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111524707A (zh) * 2020-04-28 2020-08-11 北京安邦特资源技术有限公司 钽电容器阳极引线用复合丝材及制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111044603A (zh) * 2020-01-14 2020-04-21 北京工业大学 一种高纯钼中非金属杂质元素的分析方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6358625B1 (en) * 1999-10-11 2002-03-19 H. C. Starck, Inc. Refractory metals with improved adhesion strength
CN1545712A (zh) * 2001-08-22 2004-11-10 昭和电工株式会社 电容器
CN101409150A (zh) * 2008-11-18 2009-04-15 菏泽海龙新能源科技发展有限公司 电容器级钽丝及其制备方法
CN101477897A (zh) * 2009-01-20 2009-07-08 宁夏东方钽业股份有限公司 钽电容器阳极引线用钽丝及其制造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6358625B1 (en) * 1999-10-11 2002-03-19 H. C. Starck, Inc. Refractory metals with improved adhesion strength
CN1545712A (zh) * 2001-08-22 2004-11-10 昭和电工株式会社 电容器
CN101409150A (zh) * 2008-11-18 2009-04-15 菏泽海龙新能源科技发展有限公司 电容器级钽丝及其制备方法
CN101477897A (zh) * 2009-01-20 2009-07-08 宁夏东方钽业股份有限公司 钽电容器阳极引线用钽丝及其制造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111524707A (zh) * 2020-04-28 2020-08-11 北京安邦特资源技术有限公司 钽电容器阳极引线用复合丝材及制备方法

Also Published As

Publication number Publication date
CN104823253A (zh) 2015-08-05

Similar Documents

Publication Publication Date Title
CN102816963B (zh) 一种钨铼合金以及制备方法
CN103906850B (zh) 形成烧结的镍‑钛‑稀土（Ni‑Ti‑RE）合金的方法
CN103740994B (zh) 纳米结构钨合金及其制备方法
JP5460312B2 (ja) 金属間相および金属とからの複合材
CZ20011740A3 (cs) Těľko tavitelný kovový práąek s nízkým obsahem kyslíku pro práąkovou metalurgii, způsob jeho výroby a výrobky z něj vyrobené
CN104169448B (zh) 铜合金线材及其制造方法
EP3445281B1 (fr) Alliages nickel-titane-yttrium avec inclusions d'oxyde réduites
CN105063394A (zh) 一种钛或钛合金材料的制备方法
CN108682509A (zh) 一种制备铁基超导复合带材的方法
CN108913973A (zh) 一种钨镍铜合金箔片的制备方法
JP5711668B2 (ja) タンタルキャパシタのアノードリード線用に用いるタンタル線及びその製造方法
WO2014131149A1 (fr) Fil en alliage de tantale et de niobium utilisé pour un conducteur d'anode d'un condensateur électrolytique et procédé de fabrication associé
CN107217171A (zh) 一种液液掺杂稀土氧化物铜基复合材料及其制备方法
JP2017502170A (ja) 分散強化白金組成物を加工する方法
TWI592962B (zh) 用於生產電解電容之陽極的方法及由該方法所得到的陽極、適合使用當作鉭電解電容的陽極及包含該陽極的電解電容及包含該電解電容的電子電路、及由閥金屬粉末生產電解電容之陽極的用途
CN104878266A (zh) 一种具有高温稳定性的钨-碳化锆-铼合金及其制备方法
WO2014131151A1 (fr) Fil en alliage de tantale et de niobium dans un condensateur et procédé de fabrication associé
CN104209511B (zh) 一种耐高压钽粉及其制备方法
JP2005264330A (ja) 高温安定性ニオブワイヤ
CN111524707B (zh) 钽电容器阳极引线用复合丝材及制备方法
WO2016070303A1 (fr) Poudre de tantale et son procédé de préparation, et anode frittée fabriquée par ce dernier
JP2019527300A (ja) 薄片状タンタル粉末およびその調製方法
CN118127434A (zh) 一种耐强氧化性锆基非晶合金及其制备方法
JPH0224883B2 (fr)
TW201446361A (zh) 鈮電容器陽極用化學合成體及其製造方法

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: 13876224

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13876224

Country of ref document: EP

Kind code of ref document: A1