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WO1997000978A1 - Procede de fabrication d'un alliage de cobalt-chrome-molybdene a haute teneur en carbone - Google Patents

Procede de fabrication d'un alliage de cobalt-chrome-molybdene a haute teneur en carbone Download PDF

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Publication number
WO1997000978A1
WO1997000978A1 PCT/GB1996/001507 GB9601507W WO9700978A1 WO 1997000978 A1 WO1997000978 A1 WO 1997000978A1 GB 9601507 W GB9601507 W GB 9601507W WO 9700978 A1 WO9700978 A1 WO 9700978A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
furnace
ingot
electrode
temperature
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/GB1996/001507
Other languages
English (en)
Inventor
Graham Berry
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.)
Firth Rixson Superalloys Ltd
Original Assignee
Firth Rixson Superalloys 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 Firth Rixson Superalloys Ltd filed Critical Firth Rixson Superalloys Ltd
Priority to AU62333/96A priority Critical patent/AU6233396A/en
Publication of WO1997000978A1 publication Critical patent/WO1997000978A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00011—Metals or alloys
    • A61F2310/00029—Cobalt-based alloys, e.g. Co-Cr alloys or Vitallium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C2007/0093—Duplex process; Two stage processes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum

Definitions

  • This invention relates to alloys, and more particularly to a novel method for the production of cobalt-chromium-molybdenum alloys, and alloys produced thereby. 5
  • Cobalt-chromium-molybdenum alloys in the form of forged or machined components, have been used, for example, for the production of medical implants, for a number of years, and such products are covered by the
  • alloys which have so far been produced have extreme surface hardness and cause rapid wear of machining tools.
  • Other such alloys are very brittle, and this is believed to be due to precipitation of carbon at the grain boundaries.
  • 25 chromium-molybdenum alloys have been produced by powder metallurgical routes, but these are extremely expensive. It has been proposed, in East German patent number 148238, to manufacture a high carbon cobalt-chromium- molybdenum alloy containing nitrogen, by vacuum melting the charge, flushing the melting vessel with nitrogen, adding a chromium nitride to the melt and casting the molten metal into ingots in a nitrogen atmosphere. The ingots are then heat treated, forged into blanks, and rolled. This process is believed likely to give inadequate compositional control for many applications.
  • high quality, high carbon, cobalt-chromium-molybdenum alloys are obtained by a melting and refining process which includes the step of electroslag remelting, followed by heat treatment and working under controlled temperature conditions.
  • the present invention provides a process for the manufacture of a high carbon cobalt- chromium-molybdenum alloy article which comprises:
  • steps 5, 6 and 7 are carried out at a temperature less than 1155°C and preferably less than 1145°C.
  • the raw material for the charge to the first furnace can comprise, for example, high purity virgin metals, and selected and processed alloy scrap. Individual charges are preferably prepared to controlled compositional specifications, and for example, suitable compositions can fall within the following preferred ranges: Composition Min ( % ) Max ( % ) Preferred
  • compositions are new materials and are accordingly included within the invention.
  • induction melting an electric current is induced into a metal charge causing heating and subsequent melting.
  • the induced current is produced, for example, by a primary current being passed through a water cooled copper coil, contained within a refractory lined furnace body.
  • vacuum induction melting is preferably conducted within a sealed chamber, from which all gases are exhausted by a vacuum pumping system.
  • the charge may be loaded into the induction furnace, for example, through a vacuum-tight bulk charging port which is an integral part of the vacuum chamber shell. In the event that the furnace is air released, for example, at the start of a lining campaign, then the furnace can be charged directly.
  • the furnace is provided with a vibratory chute system for the addition of small quantities of late additions and trimming alloys.
  • a vibratory chute system for the addition of small quantities of late additions and trimming alloys.
  • power is applied and melting commences. Completion of the charging and melting process can then be progressive, via the bulk charging port.
  • the bath of liquid metal in the furnace can be sampled, chemical analysis conducted, and the composition adjusted, by additions, for example, via the vibratory chute.
  • a period of super heating or refining may be necessary at this stage depending on the specific alloy being produced, prior to bringing the liquid charge to the precise pouring temperature.
  • the vacuum induction melting step is carried out at a pressure of 15 microns vacuum or less, for example, from 1 to 5 microns, and, towards the end of the refine, a maximum pressure rise rate of 28 microns per minute.
  • a typical melting cycle can last, for example, from 8 to 12 hours, preferably around 10 hours, and the molten bath temperature is from 1400°C to 1500°C, preferably around 1470°C.
  • the temperature of the bath is preferably raised to around 1500°C to 1600°C, for example around 1555°C, for pouring.
  • the furnace can, for example, be tilted and alloy dispensed either directly from the lip thereof, or via a "T" pot pouring tube, into a pre-cast refractory launder and tundish system, which may incorporate filters, baffles and weirs to maintain cleanliness.
  • the alloy can then travel into tubular metal moulds, for example, of 23 or 33 cms diameter.
  • the final stages of the melting and casting process are carried out under an argon atmosphere which can, for example, comprise an argon back pressure of around 20mm but preferably at least 300mm.
  • an argon atmosphere helps to prevent the loss from the liquid charge of specifically added elements such as nitrogen, manganese, and magnesium.
  • the cast ingots can be prepared into electrodes, for example, by rough dressing of the surface and welding a "stub" on to one end.
  • the prepared electrode can, for example, be suspended vertically in the second furnace, with the stub of the top forming one of the electrical contacts.
  • the bottom of the electrode forms an electrical circuit through contact with a molten slag bath contained within the second furnace, which can, for example, comprise a water- cooled copper mould.
  • the base plate of the mould can be supported on a vertical travel, and thereby complete the electrical circuit.
  • pre-mixed slag comprising various constituents such as, for example, fluorspar and lime
  • slag is arc melted, transferred into the copper mould, the electrode presented, and power applied.
  • Progressive melting then takes place with the bottom of the electrode melting, passing through the slag, and solidifying on the base plate.
  • the electrode can be continually fed into the liquid slag, and the base plate continually withdrawn, forming a remelted ingot.
  • the process can be automatically computer controlled with electrode feed, ingot withdrawal, cooling water flow and electrical current being balanced.
  • the electrode melt rate is from 3 to 4.5 kilogrammes per minute
  • the slag depth is from 80mm to 120mm
  • the slag composition is around 70% calcium fluoride CaF 2 with the balance made up of calcium oxide CaO, magnesium oxide MgO, and alumina Al 2 0 3 .
  • the refined second ingot from the second furnace can, for example, be from around 30 to 45 cms in diameter.
  • the second ingot can be transferred to a cooling station from whence it is subjected to heat treatment and working.
  • Heat treatment of the second ingot is desirably carried out at a temperature and for a time sufficient to improve the homogeneity of the alloy.
  • heat treatment is carried out at a temperature of from 1125°C to 1155°C, preferably around 1140°C for a minimum treatment time of at least 12 hours. Heat treatment may be carried out in any suitable furnace.
  • the temperature of the second ingot should not rise substantially above 1155°C, since if the temperature rises in an uncontrolled manner, this can lead to carbon precipitation at the grain boundaries. Such precipitation can lead to a very brittle end product.
  • the second ingot is subjected to mechanical working, which preferably comprises forging and/or rolling.
  • the forging process can be carried out, for example, on an open-die forging press, or using an automated reciprocating process, or a combination of both.
  • the maximum forging temperature is preferably 1140°C plus or minus 15°C
  • the minimum forging temperature is preferably 950°C plus or minus 15°C
  • the minimum reduction achieved is preferably at least 50%. Careful control of the forging conditions is necessary to avoid cracking of the second ingot.
  • the forging process can convert the second ingot into billet stock which can then be rolled if desired.
  • Rolling to finished size can be conducted, for example, on a rolling mill, to produce a final product which can, for example, be a round bar of diameter of from around 1 to 5cms, such as, for example, around 2 to 3.8 cms.
  • the rolling conditions should be carefully controlled, and preferably the maximum rolling temperature is 1140°C plus or minus 15°C, the minimum rolling temperature is preferably 950°C, plus or minus 15°C, and the minimum reduction achieved is preferably at least 50%.
  • Preferred high carbon cobalt-chromium-molybdenum alloy articles in accordance with the invention can be produced having a microstructure of fine grain size of ASTM 5, preferably ASTM 8, the grain structure comprising finally divided, discrete, primary intragranular carbide particles.
  • Preferred minimum mechanical properties for an alloy produced in accordance with the invention can be as follows: Mechanical properties (room temperature) :
  • High carbon cobalt-chromium-molybdenum alloys produced in accordance with the invention can be used, for example, for the manufacture of medical implants, either by machining directly from the rolled bar, or by using the rolled bar as forging stock to produce forged components of the required shape.
  • a particular advantage of the process of the present invention is that, in preferred embodiments, the mechanical properties referred to above can be retained in the forged product, which is not the case for presently available F799 alloys.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Ce procédé de fabrication d'un article en alliage de cobalt-chrome-molybdène à haute teneur en carbone comprend les étapes consistant: (i) à soumettre une charge de matière première dont la composition est régulée à une fusion par induction sous vide, dans un premier four; (ii) à couler le premier alliage provenant du premier four afin de produire un premier lingot; (iii) à préparer le lingot afin d'obtenir une électrode que l'on soumet, dans un second four, à une fusion sous laitier électroconducteur; (iv) à couler cet alliage affiné en fusion, de manière progressive à travers le second four, afin de produire un second lingot; (v) à traiter à chaud ce second lingot afin de favoriser l'homogénéisation de celui-ci; (vi) à forger le second lingot, afin d'obtenir une billette et (vii) éventuellement, à laminer celle-ci pour lui donner la forme voulue.
PCT/GB1996/001507 1995-06-22 1996-06-21 Procede de fabrication d'un alliage de cobalt-chrome-molybdene a haute teneur en carbone Ceased WO1997000978A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU62333/96A AU6233396A (en) 1995-06-22 1996-06-21 Process for the manufacture of a high carbon cobalt-chromium-molybdenum alloy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9512719A GB2302551B (en) 1995-06-22 1995-06-22 Improvements in or relating to alloys
GB9512719.7 1995-06-22

Publications (1)

Publication Number Publication Date
WO1997000978A1 true WO1997000978A1 (fr) 1997-01-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/001507 Ceased WO1997000978A1 (fr) 1995-06-22 1996-06-21 Procede de fabrication d'un alliage de cobalt-chrome-molybdene a haute teneur en carbone

Country Status (3)

Country Link
AU (1) AU6233396A (fr)
GB (1) GB2302551B (fr)
WO (1) WO1997000978A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0841041A3 (fr) * 1996-11-12 1999-03-17 Johnson & Johnson Medical Ltd. Prothèse de l'articulation de la hanche
WO2018192180A1 (fr) * 2017-04-17 2018-10-25 涿州新卓立航空精密科技有限公司 Articulation artificielle forgée ainsi que nouveau procédé de production et nouvelle utilisation de produit métallique
WO2021231285A1 (fr) * 2020-05-11 2021-11-18 Haynes International, Inc. Alliages à base de cobalt comportant du chrome et corroyables, présentant une résistance améliorée au grippage et aux attaques par crevasses induites par le chlorure
CN114561550A (zh) * 2022-03-04 2022-05-31 洛阳双瑞精铸钛业有限公司 一种能够防止重熔飞溅的钴铬钼合金熔炼方法
CN114703403A (zh) * 2022-06-07 2022-07-05 中国航发北京航空材料研究院 CoCrMo合金、其制备方法及其用途
CN114717449A (zh) * 2022-03-04 2022-07-08 洛阳双瑞精铸钛业有限公司 一种含碳氮锰钴铬钼合金的熔炼方法
EP4063529A1 (fr) * 2021-03-24 2022-09-28 Haynes International, Inc. Alliage cobalt-chrome résistant à l'usure par friction à grande vitesse/auto-couplée
CN115138685A (zh) * 2021-03-30 2022-10-04 泰州市新龙翔金属制品有限公司 一种高强度钴基合金的轧制加工方法
CN116160021A (zh) * 2022-12-30 2023-05-26 广东华鳌合金新材料有限公司 一种高温合金粉末重熔母合金的制造方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3951928B2 (ja) 2002-02-21 2007-08-01 株式会社日立製作所 ガスタービン用高温部材
RU2509816C1 (ru) * 2012-12-21 2014-03-20 Федеральное Государственное Унитарное Предприятие "Центральный научно-исследовательский институт черной металлургии им. И.П. Бардина" (ФГУП "ЦНИИчермет им. И.П. Бардина") Способ получения сплава на основе кобальта для металлокерамических и бюгельных зубных протезов
CN104109760A (zh) * 2014-07-18 2014-10-22 武汉钢铁(集团)公司 钢锭的中频感应炉电渣炉双联冶炼系统、冶炼方法及钢锭
CN105132703A (zh) * 2015-09-08 2015-12-09 中国航空工业集团公司北京航空材料研究院 一种电渣重熔炉冶炼外科植入用含氮钴铬钼合金的方法
CN106676444B (zh) * 2017-01-06 2018-06-26 江苏隆达超合金航材股份有限公司 一种钴铬钼超合金棒材的成型方法
CN111575539B (zh) * 2020-04-23 2021-07-23 中国科学院金属研究所 一种热加工态钴基合金棒丝材的制备方法

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EP0259660A1 (fr) * 1986-08-18 1988-03-16 Inco Alloys International, Inc. Alliage nickel-chrome à haute limite d'endurance
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SEMLITSCH, M.: "Properties of CoNiCrMo Alloy Protasul-10, a highly corrosion and fatigue resistant implant material for joint endoprostheses", ENG. MED., vol. 9, no. 4, October 1980 (1980-10-01), pages 201 - 207, XP000601566 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0841041A3 (fr) * 1996-11-12 1999-03-17 Johnson & Johnson Medical Ltd. Prothèse de l'articulation de la hanche
WO2018192180A1 (fr) * 2017-04-17 2018-10-25 涿州新卓立航空精密科技有限公司 Articulation artificielle forgée ainsi que nouveau procédé de production et nouvelle utilisation de produit métallique
WO2021231285A1 (fr) * 2020-05-11 2021-11-18 Haynes International, Inc. Alliages à base de cobalt comportant du chrome et corroyables, présentant une résistance améliorée au grippage et aux attaques par crevasses induites par le chlorure
CN115698351B (zh) * 2020-05-11 2024-11-22 海恩斯国际公司 对擦伤和氯化物引发的缝隙侵蚀具有改善耐受性的可形变的含铬的钴基合金
JP2023525530A (ja) * 2020-05-11 2023-06-16 ヘインズ インターナショナル，インコーポレーテッド 耐かじり性および塩化物誘起隙間腐食に対する耐性が改善された展伸用クロム含有コバルト基合金
CN115698351A (zh) * 2020-05-11 2023-02-03 海恩斯国际公司 对擦伤和氯化物引发的缝隙侵蚀具有改善耐受性的可形变的含铬的钴基合金
EP4063529A1 (fr) * 2021-03-24 2022-09-28 Haynes International, Inc. Alliage cobalt-chrome résistant à l'usure par friction à grande vitesse/auto-couplée
US11702724B2 (en) 2021-03-24 2023-07-18 Haynes International, Inc. Cobalt-chromium alloy resistant to high speed/self-coupled sliding wear
CN115138685A (zh) * 2021-03-30 2022-10-04 泰州市新龙翔金属制品有限公司 一种高强度钴基合金的轧制加工方法
CN114717449A (zh) * 2022-03-04 2022-07-08 洛阳双瑞精铸钛业有限公司 一种含碳氮锰钴铬钼合金的熔炼方法
CN114561550B (zh) * 2022-03-04 2023-10-03 洛阳双瑞精铸钛业有限公司 一种能够防止重熔飞溅的钴铬钼合金熔炼方法
CN114561550A (zh) * 2022-03-04 2022-05-31 洛阳双瑞精铸钛业有限公司 一种能够防止重熔飞溅的钴铬钼合金熔炼方法
CN114703403B (zh) * 2022-06-07 2023-01-24 中国航发北京航空材料研究院 CoCrMo合金、其制备方法及其用途
CN114703403A (zh) * 2022-06-07 2022-07-05 中国航发北京航空材料研究院 CoCrMo合金、其制备方法及其用途
CN116160021A (zh) * 2022-12-30 2023-05-26 广东华鳌合金新材料有限公司 一种高温合金粉末重熔母合金的制造方法

Also Published As

Publication number Publication date
GB2302551A (en) 1997-01-22
GB9512719D0 (en) 1995-08-23
AU6233396A (en) 1997-01-22
GB2302551B (en) 1998-09-16

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