EP1546427B1 - Ferritische stahllegierung - Google Patents

Ferritische stahllegierung Download PDF

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Publication number
EP1546427B1
EP1546427B1 EP03798852A EP03798852A EP1546427B1 EP 1546427 B1 EP1546427 B1 EP 1546427B1 EP 03798852 A EP03798852 A EP 03798852A EP 03798852 A EP03798852 A EP 03798852A EP 1546427 B1 EP1546427 B1 EP 1546427B1
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EP
European Patent Office
Prior art keywords
percent
weight
steel
alloy
steel alloy
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.)
Expired - Lifetime
Application number
EP03798852A
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German (de)
English (en)
French (fr)
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EP1546427A1 (de
Inventor
Karl-Heinz Kramer
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 AG
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FIRTH AG
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Publication date
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Publication of EP1546427A1 publication Critical patent/EP1546427A1/de
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Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • 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

  • the precipitated carbide particles in the order of 5-10 microns are not removed during mechanical polishing and protrude as so-called craters from the surrounding, better polished surface. There are so-called polishing tails, ie deposits of polishing paste in the polishing shadow of the carbide, with the naked eye are perceived as extremely disturbing.
  • the stabilization of the steel structure by addition of Ti or Nb is therefore not applicable because of the negative impact on the polishability in a polishable ferritic chromium steel.
  • the precipitation of chromium carbides at the grain boundaries by the diffusion rate higher by 2 powers of 2 for ferritic steels is so fast that it can not be prevented even by rapid quenching from the solution annealing temperature.
  • the chromium carbides form hard inclusions, which in turn nullify the polishability of a steel.
  • the polishability of a steel is also decisively influenced by the grain size. Coarse-grained steels cause a so-called "orange peel" during polishing, which is unacceptable for polished surfaces. This is due to the different properties of the randomly arranged grains (crystals) in the different directions. If the grain size measured according to ASTM E 112 is less than 4 ( ⁇ 80 ⁇ m), the human eye can recognize the differently removed crystal surfaces during the polishing process as punctiform particles and the result is the image of an "orange peel".
  • steel alloys can be controlled by alloying of metallic and non-metallic elements in their chemical and mechanical properties.
  • N-additives are said to significantly retard the onset of M 23 C 6 excretion in austenitic steels (Levey PR, van Bennekom, A., Corrosion 51, 911-921 (1995)).
  • the presence of nitrogen is troublesome when an alloy with soft magnetic properties is desired (see, for example, "Ullmann's Encyclopedia of Industrial Chemistry” Fifth Edition, Volume A16, page 26, left column, 2nd section).
  • a rudimentary estimation of the resistance of a Cr / Mo steel to pitting corrosion can also be obtained from a two-dimensional plot (Gräfen, H., Chem. Ing. Techn. 54, pp. 108-119 (1982)).
  • the dependence of the current potential-potential curves on the limit of the beginning of the pitting corrosion (Y-axis) against the Cr-content (X-axis) is plotted.
  • the content of molybdenum is thereby taken into account in the form of chromium equivalents (ibid., And Lorenz, K., Medawar, G., Thyssen Research 1, pp. 97-108 (1969)).
  • An approximately linear correlation between the limit potential and the Cr (Mo) content is observed.
  • the diagram does not take into account any other alloying elements, and it does not allow conclusions as to whether it is a ferritic alloy or its workability, polishability and magnetic properties.
  • Table 1 gives an overview of eight previously known concrete steels (indicated by their material numbers) and their contents of important alloying elements in weight percentages. The steel specified there No. 1.4521 is to the knowledge of the Applicant no watch steel. Table 1 1.4521 DIN 10088 1.4523 steel-iron-L.
  • the steel alloys according to the invention are soft-magnetic CrMoN steel alloys.
  • high-alloy in the context of the present application has the usual meaning in the art, i. It refers to a steel in which the alloying elements occur in total of 5 weight percent or more.
  • ferritic in the context of the present application has the meaning that at least 98 percent by volume, preferably at least 99.5 percent by volume and particularly preferably 100 percent by volume of the iron present in the alloys according to the invention are present as ferrite, the determination being made by metallography.
  • soft magnetic is used in the context of the present application for inventive steel alloys, which cause at least as strong magnetic shielding as soft iron.
  • the metallic alloying elements chromium and molybdenum can be added to the alloys according to the invention by alloying suitable amounts of the pure elements to a pig iron or to a crude steel by customary methods.
  • chromium is present in 18.0 to 22.0 percent by weight, preferably in 19.5 to 20.5 percent by weight and particularly preferably in about 20 percent by weight, based on the finished alloy.
  • molybdenum is present in about 1.80 to about 2.50 percent by weight, preferably in about 1.90 to 2.10 percent by weight and more preferably in about 2 percent by weight, based on the finished alloy, available.
  • Silicon may be present as SiO 2 (for example from the above deoxidation) in the alloy. Its content can be reduced by mechanically moving or shaking the molten steel under inert gas. As a result, the SiO 2 coagulates and increases due to the lower density of the slag surface.
  • the content of silicon is according to the invention at most about 1 weight percent, preferably about 0.7 to 0.9 weight percent, and more preferably about 0.8 weight percent, based on the alloy.
  • Carbon is noticeable from the smelting process as admixture in the pig iron itself (4 to 4.5%) and can then, as usual in the art, by adding oxygen or suitable amounts of iron oxides to molten steel (conversion of carbon to carbon monoxide) virtually arbitrary be reduced. According to the invention, it is preferably present in at most 0.025 percent by weight, particularly preferably in the highest 0.01 percent by weight, based on the alloy.
  • Sulfur comes from the smelting process (content of iron ore to iron sulphides) and is mainly in pig iron present as manganese sulfide.
  • the alloys according to the invention it is preferably present in amounts of at most about 0.03 percent by weight, more preferably in at most 0.002 percent by weight. Achieving so low levels of sulfur can be achieved by desulfurizing the melt with, for example, mixtures of CaO and metallic magnesium.
  • the sulfur content at the upper limit of 0.03 weight percent, preferably about 0.015 to 0.03 weight percent, based on the alloy are (so-called IMA grades), what can be done for a regulated addition of sulfur.
  • a melt metallurgy with the addition of Ca-Si powder can be used, which converts the hard alumina inclusions into relatively soft mixed oxides of the type CaSiAl and forms finely divided manganese sulfides through which the chip is broken during machining and thus the service life of the tools is extended.
  • a controlled sulfur addition only slightly reduces the corrosion resistance of these embodiments of the steel alloy according to the invention.
  • manganese is preferably not more than about 1.00 weight percent, more preferably at most about 0.40 weight percent, based on the finished alloy.
  • Phosphorus is originally derived from apatite or other phosphate-containing minerals found in iron ore. During smelting, phosphate can be reduced to iron phosphide (mainly Fe 2 P) and as such occur in pig iron or later steel.
  • the inventively preferred low content of phosphorus of at most 0.04 percent by weight and preferably at most 0.02 percent by weight can be reduced in the production of the novel alloys as customary in the art, for example, by adding in the smelting of the ore CaO, whereby the phosphate-containing minerals be separated in the slag.
  • inventive aluminum content of at most about 0.01 percent by weight, preferably at most about 0.005 percent by weight can be achieved if the deoxidation required in the melting process is not carried out with aluminum but with silicon or in the AOD or VOD process (see below).
  • Nickel is preferably present in at most 0.10 weight percent, more preferably at most 0.05 weight percent, based on the finished alloy.
  • the term "remainder essentially iron” in the context of the present application is intended to mean that the remaining weight percentages of the alloy according to one of claims 1 to 7, i. the percentages by weight which are not contributed by elements named by name in the corresponding claim originate almost exclusively from iron (typically at least 90 percent by weight, preferably at least 95 percent by weight and more preferably at least 99 percent or more).
  • the elements of the radical other than iron should be chosen in such an amount that the finished steel alloy according to the invention is ferritic.
  • the Schaeffler diagram mentioned above with the aid of the nickel and chromium equivalents of further elements set up by Briggs and Parker, can provide first clues.
  • the obtained alloy is actually ferritic according to the invention or not.
  • novel alloys can be prepared by conventional methods.
  • the alloys according to the invention are preferably subjected to annealing at temperatures of 750 to 850 ° C., preferably about 800 ° C. for about 0.5 to 2 hours, and subsequent water cooling. This takes place due to diffusion processes a concentration compensation of the chromium in the matrix in the region of the finely precipitated chromium nitride particles instead. By optimizing the nitrogen content, however, the chromium nitride precipitation can be largely suppressed.
  • the steel alloys according to the invention can be polished in a reproducible manner by the methods customary in the watch industry and would therefore be accepted as starting material in the watch industry.
  • the alloyed in the order of up to 0.1% nitrogen is at the annealing temperatures, which are preferably used in the inventive steel alloys, either dissolved or in the form of finely precipitated chromium, typically in the order of about 1 micron, and leads therefore no negative influence on the polishability.
  • the steel alloys according to the invention typically have the following mechanical properties (6 mm thick sheet, hot rolled, annealed at 800 ° C. for 30 minutes, quenched in water): Yield strength R p0.2 420 MPa Tensile strength R m 603 MPa Elongation at break A 0 28% Hardness HB 30 188
  • novel alloys are thus comparable to the standard steel grade No. 1.4521.
  • the alloying according to the invention of nitrogen instead of niobium or titanium makes the precipitation relatively large niobium or titanium carbides, which destroy the polishability excluded. Furthermore, the precipitation of chromium carbides at the grain boundaries is suppressed. This is done by changing the precipitation kinetics, which causes an energetically preferred precipitation of the chromium nitrides instead of chromium carbides. If the solubility limit for nitrogen in the steel alloy is exceeded, very finely dispersed chromium nitride particles with diameters of less than 1 ⁇ m and smaller precipitate, but because of their fineness they do not adversely affect the polishing behavior.
  • novel steel alloys are soft magnetic in the sense of the definition mentioned above.
  • inventively preferred steel alloys of claims 3 to 7 exceed with their effective sum, as defined above, the minimum value for implant steels of 26 required by the medical field.
  • the alloys according to the invention Due to the good polishability and soft magnetic properties of the alloys according to the invention, these can be used in the watch industry for the production of magnetically shielding housing parts, for example for watches or for other watches in which magnetic shielding of the movement is important.
  • the steel alloys according to the invention, in particular those of claim 7, are also suitable for the production of components for limb bracelets.
  • housing part in the context of the present application comprises the components usually used for the manufacture of a watch case, in particular a watch case, e.g. the housing bottom and the housing shell.
  • housing part includes in the context of the present application but also the dial.
  • housing part includes both the component, as occurs in the finished watch, as well as any blank or semi-finished thereof, which further processed by further use of other materials or semi-finished products from the inventive alloy or other materials to the finished component become.
  • Magnetically shielding watch cases according to the invention may consist of a housing bottom, a housing shell and a dial, all of which are in accordance with the invention Steel alloy are made.
  • the inventive steel alloys can thus be used simultaneously as a material for the components as well as a shielding cage against magnetic fields.
  • the elaborate to be manufactured additional soft iron cage, which would have to be provided within the usual housing of non-magnetic stainless steel and which would lead to a higher overall height of the clock, can be omitted.
  • the binder is preferably evaporated by applying a vacuum and the powder residue remaining in the mold is sintered.
  • a nitrogen atmosphere of appropriate pressure is applied so that the alloy still receives nitrogen during sintering.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Soft Magnetic Materials (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Powder Metallurgy (AREA)
EP03798852A 2002-10-04 2003-09-30 Ferritische stahllegierung Expired - Lifetime EP1546427B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH16592002 2002-10-04
CH165902 2002-10-04
PCT/CH2003/000651 WO2004031430A1 (de) 2002-10-04 2003-09-30 Ferritische stahllegierung

Publications (2)

Publication Number Publication Date
EP1546427A1 EP1546427A1 (de) 2005-06-29
EP1546427B1 true EP1546427B1 (de) 2007-04-18

Family

ID=32046629

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03798852A Expired - Lifetime EP1546427B1 (de) 2002-10-04 2003-09-30 Ferritische stahllegierung

Country Status (8)

Country Link
US (1) US20060130938A1 (zh)
EP (1) EP1546427B1 (zh)
JP (1) JP2006501368A (zh)
CN (1) CN1325687C (zh)
AT (1) ATE360103T1 (zh)
AU (1) AU2003264228A1 (zh)
DE (1) DE50307092D1 (zh)
WO (1) WO2004031430A1 (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007248397A (ja) * 2006-03-17 2007-09-27 Seiko Epson Corp 装飾品および時計
JP5212602B2 (ja) * 2007-09-14 2013-06-19 セイコーエプソン株式会社 機器およびハウジング材の製造方法
EP2813906A1 (fr) * 2013-06-12 2014-12-17 Nivarox-FAR S.A. Pièce pour mouvement d'horlogerie
US10063074B2 (en) 2016-04-01 2018-08-28 Hewlett-Packard Development Company, L.P. Electronic wearable device electrode pad with collection well
JP7413685B2 (ja) 2019-09-05 2024-01-16 セイコーエプソン株式会社 金属材料、時計用部品および時計
JP7404721B2 (ja) 2019-09-05 2023-12-26 セイコーエプソン株式会社 金属材料、時計用部品および時計
JP7272233B2 (ja) 2019-10-30 2023-05-12 セイコーエプソン株式会社 時計用部品および時計
JP7294074B2 (ja) 2019-11-11 2023-06-20 セイコーエプソン株式会社 オーステナイト化フェライト系ステンレス鋼、時計用部品、および、時計
JP2021096076A (ja) * 2019-12-13 2021-06-24 セイコーエプソン株式会社 時計用外装部品、時計、および、時計用外装部品の製造方法
JP2021096079A (ja) 2019-12-13 2021-06-24 セイコーエプソン株式会社 ハウジングおよび機器

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848323A (en) * 1955-02-28 1958-08-19 Birmingham Small Arms Co Ltd Ferritic steel for high temperature use
GB1359629A (en) * 1971-10-26 1974-07-10 Deutsche Edelstahlwerke Gmbh Corrosion-resistant ferritic chrome steel
US3953201A (en) * 1974-03-07 1976-04-27 Allegheny Ludlum Industries, Inc. Ferritic stainless steel
US4340424A (en) * 1974-04-23 1982-07-20 Daido Tokushuko Kabushiki Kaisha Ferritic stainless steel having excellent machinability and local corrosion resistance
JPS5188413A (en) * 1975-02-01 1976-08-03 Kotaishokuseifueraitosutenresuko
EP0379061B1 (fr) * 1989-01-18 1992-12-23 Eta SA Fabriques d'Ebauches Pièce extérieure d'habillement pour montre et procédé pour la fabrication d'une telle pièce
FR2705596B1 (fr) * 1993-05-24 1995-07-13 Impac Technologies Procédé de moulage par injection de barbotines et dispositif pour sa mise en Óoeuvre.
KR0169172B1 (ko) * 1994-02-15 1999-01-15 아키모토 유우미 철-크롬계 합금
JPH07244172A (ja) * 1994-03-03 1995-09-19 Seiko Instr Inc 時計部品の製造方法
JP3205162B2 (ja) * 1994-03-10 2001-09-04 新日本製鐵株式会社 切削性と耐食性に優れたフェライト系ステンレス鋼
JP3589036B2 (ja) * 1997-08-05 2004-11-17 Ｊｆｅスチール株式会社 深絞り性と耐リジング性に優れたフェライト系ステンレス鋼板およびその製造方法
JPH11323502A (ja) * 1998-05-12 1999-11-26 Sumitomo Metal Ind Ltd 加工性と靭性に優れたフェライト系ステンレス鋼およびその鋳片
EP0964071A1 (fr) * 1998-06-12 1999-12-15 Asulab S.A. Acier inoxydable ferritique et pièce extérieure d'habillement pour montre réalisée en un tel acier

Also Published As

Publication number Publication date
DE50307092D1 (de) 2007-05-31
EP1546427A1 (de) 2005-06-29
US20060130938A1 (en) 2006-06-22
ATE360103T1 (de) 2007-05-15
WO2004031430A1 (de) 2004-04-15
AU2003264228A1 (en) 2004-04-23
JP2006501368A (ja) 2006-01-12
CN1325687C (zh) 2007-07-11
CN1688734A (zh) 2005-10-26

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