EP1341944B1 - Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details - Google Patents

Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details Download PDF

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Publication number
EP1341944B1
EP1341944B1 EP01270634A EP01270634A EP1341944B1 EP 1341944 B1 EP1341944 B1 EP 1341944B1 EP 01270634 A EP01270634 A EP 01270634A EP 01270634 A EP01270634 A EP 01270634A EP 1341944 B1 EP1341944 B1 EP 1341944B1
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EP
European Patent Office
Prior art keywords
steel
steel alloy
alloy according
max
holders
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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
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EP01270634A
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German (de)
English (en)
French (fr)
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EP1341944A1 (en
Inventor
Odd Sandberg
Magnus Tidesten
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Uddeholms AB
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Uddeholms AB
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Publication of EP1341944A1 publication Critical patent/EP1341944A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0264Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/60Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a steel alloy and particularly to a steel alloy for the manufacturing of holders and holder details for plastic moulding tools.
  • the invention also concerns holders and holder details manufactured of the steel, as well as blanks made of the steel alloy for the manufacturing of such holders and holder details.
  • Holders and holder details for plastic moulding tools are employed as clamping and/or framing components for the plastic moulding tool in tool sets, in which tool the plastic product shall be manufactured through some kind of moulding method.
  • holder details there can be mentioned bolster plates and other construction parts as well as heavy blocks with large recesses which can accommodate and hold the actual moulding tool.
  • Said holders and holder details are made of many different steel alloys, including martensitic stainless steels.
  • a steel which is manufactured and marketed by the applicant under the registered trade name RAMAX S® belongs to that group and has the following nominal composition in weight-%: 0.33 C, 0.35 Si, 1.35 Mn, 16.6 Cr, 0.55 Ni, 0.12 N, 0.12 S, balance iron and impurities from the manufacturing of the steel.
  • the closest comparable standardized steel is AISI 420F. Steels of this type have an adequate corrosion resistance, but do not have a martensitic micro-structure which is as homogenous that is desirable, but may contain ferrite and hard spots, which are due to retained, untempered martensite, which in turn can be explained by a certain segregation tendency of the steel. Therefore it exists a demand of improvements as far as holder steels are concerned. It is also desirable that the same steel, possibly with some modification of the composition, also shall be useful for the actual moulding tool.
  • Carbon and nitrogen are elements which have a great importance for the hardness and ductility of the steel. Carbon is also an important hardenability promoting element. Carbon, however, binds chromium in the form of chromium carbides (M7C3-carbides) and may therefore impair the corrosion resistance of the steel.
  • the steel therefore may contain max 0.15 % carbon, preferably max 0.13 % carbon (in this text always weight-% is referred to if not otherwise is stated). However, carbon also has some advantageous effects, such as to exist together with nitrogen as a dissolved element in the tempered martensite in order to contribute to the hardness thereof, and also acts as an austenite stabilizer and thence counteract ferrite in the structure.
  • the minimum amount of carbon in the steel therefore shall be 0.06%, preferably at least 0.07 %.
  • Nitrogen contributes to the provision of a more even, more homogenous distribution of carbides and carbonitrides by affecting the solidification conditions in the alloy system such that larger aggregates of carbides are avoided or are reduced during the solidify-cation.
  • the proportion of M23 C6-carbides also is reduced in favour of M(C,N), i.e. vanadium-carbonitrides, which has a favourable impact on the ductility/toughness.
  • nitrogen contributes to the provision of a more favourable solidification process implying smaller carbides and nitrides, which can be broken up during the working to a more finely dispersed phase.
  • nitrogen shall exist in an amount of at least 0.07 %, preferably at least 0.08 %, but not more than 0.22 %, preferably max 0.15 %, at the same time as the total amount of carbon and nitrogen shall satisfy the condition 0.16 ⁇ C + N ⁇ 0.26.
  • C + N shall be at least 0.17 % but suitably max 0.23 %.
  • the steel contains 0.20 - 0.22 (C + N).
  • nitrogen is substantially dissolved in the martensite in the form of nitrogen-martensite in solid solution and thence contributes to the desired hardness.
  • nitrogen shall exist in the said minimum amount in order to contribute to the desired corrosion resistance by increasing the so called PRE-value of the matrix of the steel, to exist as a dissolved element in the tempered martensite which contributes to the hardness of the martensite, and to form carbonitrides, M(C, N), to a desired degree together with carbon, but not exceed said maximum content, maximizing the content of carbon + nitrogen, where carbon is the most important hardness contributor.
  • Silicon increases the carbon activity of the steel and thence the tendency to precipitate more primary carbides. This is a first reason why it is desirable that the steel has a low content of silicon.
  • silicon is a ferrite stabilizing element, which is a disadventageous feature of silicon.
  • the steel also shall contain the ferrite stabilizing elements chromium and molybdenum in sufficient amounts to provide desirable effects by those elements, at the same time as the steel contains a lower content of carbon than is conventional in steels for the application in question, the content of silicon should be restricted in order not to cause the steel to contain ferrite in its matrix.
  • the steel therefore must not contain more that 1 % Si, preferably max. 0.7 % Si, suitably max.
  • the ferrite stabilizing elements shall be adapted to the austenite stabilizing ones in order to avoid formation of ferrite in the steel.
  • silicon exists as a residue from the desoxidation treatment, wherefore the optimum content of silicon lies in the range 0.05 - 0.5 %, normally in the range 0.1- 0.4 %, and is nominally about 0.2 - 0.3 %.
  • Manganese is an element which promotes austenite and hardenability, which is a favourable effect of manganese, and can also be employed for sulphur refining by forming harmless manganese sulphides in the steel. Manganese therefore shall exist in a minimum amount of 0.1 %, preferably at least 0.3 %. Manganese, however has a segregation tendency together with phosphorous which can give rise to tempering-embrittlement. Manganese therefore must not exist in an amount exceeding 2 %, preferably max. 1.5 %, suitably max. 1.3 %.
  • Chromium is the main alloying element of the steel and is essentially responsible for provision of the stainless character of the steel, which is an important feature of holders and holder details for plastic moulding tools, as well as for the plastic moulding tool itself, which often is used in damp environments, which may cause less corrosion resistant steels to rust.
  • Chromium also is the most important hardenability promoting element of the steel. However, no substantial amounts of chromium are bound in the form of carbides, because the steel has a comparatively low carbon content, wherefore the steel can have a chromium content as low as 12.5 % and nevertheless get a desired corrosion resistance.
  • the steel contains at least 13.0 % chromium. The upper limit is determined in the first place by the ferrite forming tendency of chromium. The steel therefore must not contain more than max. 14.5 % Cr, preferably max. 14.0 % Cr. Nominally, the steel should contain 13.1-13.7 % Cr.
  • Nickel should exist in the steel in a minimum amount of 0.8 %, preferably at least 1.0 %, in order to afford the steel a very high hardenability. From cost reasons, however, the content should be limited to max. 2.5 %, preferably to max. 2.0 %. Nominally, the steel contains 1.4 -1.8 % or about 1.6 % Ni.
  • the steel of the invention also may contain an active content of vanadium in order to bring about a secondary hardening through precipitation of secondary carbides in connection with the tempering operation, wherein the tempering resistance is increased.
  • Vanadium when present, also acts as a grain growth inhibitor through the precipitation of MC-carbides. If the content of vanadium is too high, however, there will be formed large primary MC-carbonitrides during the solidification of the steel, and this also occurs if the steel is subjected to ESR-remelting, which primary carbides will not be dissolved during the hardening procedure.
  • the optional content of vanadium should lie in the range 0.07 - 0.7 % V.
  • a suitable content is 0.10 - 0.30 % V, nominally about 0.2 % V.
  • the steel also contains an active content of molybdenum, e.g. at least 0.1 %, in order to give a hardenability promoting effect.
  • Molybdenum up to an amount of at least 1.0 % also promotes the corrosion resistance but may have effect also if the content is higher.
  • molybdenum also contributes to increasing the tempering resistance of the steel, which is favourable.
  • a too high content of molybdenum may give rise to an unfavourable carbide structure by causing a tendency to precipitation of grain boundary carbides and segregations.
  • molybdenum is ferrite stabilizing, which is unfavourable.
  • the steel therefore shall contain a balanced content of molybdenum in order to take advantage of its favourable effects but at the same time avoid those ones which are unfavourable.
  • the content of molybdenum should not exceed 1.7 %.
  • An optimal content may lie in the range 0.1 - 0.9 %, probably in the range 0.4 - 0.6 % Mo.
  • the steel does not contain tungsten in amounts exceeding the impurity level, but may possibly be tolerated in amounts up to 1 %.
  • the steel of the invention shall be possible to be delivered in its tough-hardened condition, which makes it possible to manufacture large sized holders and mould tools through machining operations.
  • the hardening is carried out through austenitizing at a temperature of 850 - 1000 °C, preferably at 900- 975 °C, or at about 950 °C, followed by cooling in oil or in a polymer bath, by cooling in gas in a vacuum furnace, or in air.
  • the high temperature tempering for the achievement of a tough hardened material with a hardness of 30 - 42 HRC, preferably 38 - 41 or about 40 HRC, which is suitable for machining operations, is performed at a temperature of 510 - 650 °C, preferably at 520 - 540 °C, for at least one hour, preferably through double tempering; twice for two hours.
  • the steel may, as an alternative, be low temperature tempered at 200 - 275 °C, e.g. at about 250 °C, in order obtain a hardness of 38 - 42 or about 40 HRC.
  • the steel may, according to a preferred embodiment, also contain an active content of sulphur, possibly in combination with calcium and oxygen, in order to improve the machinability of the steel in its tough hardened condition.
  • the steel should contain at least 0.07 % S if the steel does not also contain an intentionally added amount of calcium and oxygen, and at least 0.035 %, respectively, if the steel also contains an active amount of calcium and oxygen.
  • the maximum sulphur content of the steel is 0.25 %, when the steel is intentionally alloyed with a content of sulphur.
  • a suitable sulphur content in this case may be 0.12 %.
  • a non-sulphurized variant of the steel can be conceived.
  • the steel does not contain sulphur above impurity level, and nor does that steel contain any active contents of calcium and/or oxygen.
  • the steel may contain 0.035 - 0.25 % S in combination with 3 - 100 weight-ppm Ca, preferably 5 - 75 ppm Ca, suitably max. 40 ppm Ca, and 10 - 100 ppm O, wherein said calcium, which may be supplied as silicon-calcium, CaSi, in order to globulize existing sulphides to form calcium sulphides, counteracts that the sulphides get a non-desired, elongated shape, which might impair the ductility.
  • said calcium which may be supplied as silicon-calcium, CaSi, in order to globulize existing sulphides to form calcium sulphides, counteracts that the sulphides get a non-desired, elongated shape, which might impair the ductility.
  • the steel of the invention can be manufactured conventionally at a production scale by manufacturing a metal melt in the normal way, said melt having a chemical composition according to the invention, and casting the melt into large ingots or casting the melt continuously. It is also possible to cast electrodes of the molten metal and then remelting the electrodes through Electro-Slag-Remelting (ESR). It is also possible to manufacture ingots powder-metallurgically through gas-atomization of the melt to produce a powder, which then is compacted through a technique which may comprise hot isostatic pressing, so called HIPing, or, as an alternative, manufacture ingots through sprayforming.
  • ESR Electro-Slag-Remelting
  • Fig. 1 shows a holder block 1 of a typical design, which shall be possible to be manufactured of the steel according to the invention.
  • the block1 In the block1 there is a cavity 2, which shall accommodate a mould tool, usually a plastic moulding tool.
  • the block 1 has considerable dimensions and the cavity 2 is large and deep. Therefore, a number of different requirements are raised on the material according to the invention, i.a. an adequate hardenability with reference to the considerable thickness of the block, and a good ability to be machined by means of cutting tools, such as mill cutters and borers.
  • the steels Q9043 and Q9063 are reference materials.
  • Q9043 has a composition according to SIS2314 and AISI 420, while Q9063 corresponds to W.Nr. 1.2316.
  • the Q-ingots were forged to the shape of rods of size 60 x 40 mm, whereupon the rods were cooled in vermiculite.
  • Table I- Test materials chemical composition in weight-%, balance Fe and unavoidable impurities Q-ingot C N Si Mn Cr V Ni Mo S Q9043 0.36 0.026 0.83 0.47 13.9 0.32 0.18 0.12 n.a.
  • the hardness versus the austenitizing temperature is shown in Fig. 2A and Fig. 2B. It is evident from the charts of these drawings that the hardness increases with increasing austenitizing temperature for some steels having a higher carbon content, such as for Q9043, Q9063, Q9103, Q9104 and Q9135. 1030 °C is an austenitizing temperature which may be appropriate in these cases. For other steels, the hardness decreases or remains constant with increasing austenitizing temperature. In that case it may be more appropriate to choose 950 °C as an austenitizing temperature.
  • Polarization curves were established in a first test round for the steels given in Table IV in terms of critical current density, Icr, for the evaluation of the corrosion resistance of the steels. As far as this method of measurement is concerned, the rule is that the lower Irc is, the better is the corrosion resistance.
  • the investigations were performed in two test series, in which the test specimens were subjected to different cooling rates. The heat treatments of the first series are shown in Table IV. Table IV - Heat treatment of polarization test specimens.
  • Fig. 6B illustrates that best corrosion resistances were notified for samples of Q9063, 9129, 9153 and 9154.
  • the steel Besides a good machinability, the steel shall have a good ductility, a good corrosion resistance, and a good hardenability. It can be stated that it is an aim that the steel, besides a good machinability, shall have better ductility, corrosion resistance and hardenability than steel Q9063.
  • Four steels satisfy those criteria, namely Q9068, Q9129, Q9153 and Q9154, which have a rather similar composition; although steel Q9154 has a higher nitrogen content and a lower content of carbon.
  • an optimal composition could be the following, namely 0.10 C, 0.075 N, 0.16 Si, 1.1 Mn, 13.1 Cr, 0.13 V, 1.8 Ni, 0.5 Mo, balance Fe and unavoidable impurities.
  • An alternative could be a steel which contains 0.06 C and 0.14 Ni but as for the rest the same composition as the foregoing.
  • compositions could be the following ones: 0.12 C, 0.20 Si, 1.30 Mn, 0.10 S, 13.4 Cr, 1.60 Ni, 0.50 Mo, 0.20 V, 0.10 N, balance iron and unavoidable impurities, and/or 0.14 C, 0.18 Si, 1.30 Mn, 0.10 S, 13.5 Cr, 1.67 Ni, 0.50 Mo, 0.22 V, 0.10 N, balance iron and unavoidable impurities.
  • a 35 tons heat of molten metal was manufactured in an electric arc furnace. Before tapping, the melt had the following chemical composition: 0.15 C, 0.18 Si, 0.020 P, 0.08 S, 13.60 Cr, 1.60 Ni, 0.48 Mo, 0.20 V, 0.083 N, balance Fe and unavoidable impurities.
  • the melt there were manufactured ingots, which were forged to the shape of flat rods of varying dimensions. The forging did not cause any problems.
  • the forged rods were tough-hardened to a hardness of about 380 HB through austenitizing at 950 °C, holding time 2h, fast quenching in air and tempering at 540 °C, 2x2h. The thus tough-hardened rods were machined to final gauges.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Heat Treatment Of Steel (AREA)
  • Gripping Jigs, Holding Jigs, And Positioning Jigs (AREA)
  • Connection Of Plates (AREA)
EP01270634A 2000-12-11 2001-11-22 Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details Expired - Lifetime EP1341944B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0004586A SE518023C2 (sv) 2000-12-11 2000-12-11 Stål för plastformningsverktyg och detaljer av stålet för plastformningsverktyg
SE0004586 2000-12-11
PCT/SE2001/002576 WO2002048418A1 (en) 2000-12-11 2001-11-22 Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details

Publications (2)

Publication Number Publication Date
EP1341944A1 EP1341944A1 (en) 2003-09-10
EP1341944B1 true EP1341944B1 (en) 2007-02-14

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EP01270634A Expired - Lifetime EP1341944B1 (en) 2000-12-11 2001-11-22 Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details

Country Status (19)

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US (1) US20040013559A1 (zh)
EP (1) EP1341944B1 (zh)
JP (1) JP4030872B2 (zh)
KR (1) KR100831823B1 (zh)
CN (1) CN1207420C (zh)
AT (1) ATE353986T1 (zh)
AU (2) AU2427002A (zh)
BR (1) BR0116057A (zh)
CA (1) CA2425893C (zh)
DE (1) DE60126646T2 (zh)
ES (1) ES2280304T3 (zh)
HK (1) HK1060157A1 (zh)
HU (1) HU228284B1 (zh)
MX (1) MXPA03005136A (zh)
PL (1) PL196489B1 (zh)
PT (1) PT1341944E (zh)
SE (1) SE518023C2 (zh)
TW (1) TWI286576B (zh)
WO (1) WO2002048418A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8808472B2 (en) * 2000-12-11 2014-08-19 Uddeholms Ab Steel alloy, holders and holder details for plastic moulding tools, and tough hardened blanks for holders and holder details
BR0311757B1 (pt) * 2002-06-13 2011-12-27 aÇo para trabalho a frio e ferramenta para trabalho a frio.
FR2872825B1 (fr) * 2004-07-12 2007-04-27 Industeel Creusot Acier inoxydable martensitique pour moules et carcasses de moules d'injection
HUE030068T2 (en) * 2014-01-16 2017-04-28 Uddeholms Ab Stainless steel and stainless steel cutting tool body
AU2014377770B2 (en) * 2014-01-16 2018-09-20 Uddeholms Ab Stainless steel and a cutting tool body made of the stainless steel
US10975460B2 (en) 2015-01-28 2021-04-13 Daido Steel Co., Ltd. Steel powder and mold using the same
SE541151C2 (en) * 2017-10-05 2019-04-16 Uddeholms Ab Stainless steel
US11970760B2 (en) * 2021-11-10 2024-04-30 Daido Steel Co., Ltd. Metal powder

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US3362813A (en) * 1964-09-15 1968-01-09 Carpenter Steel Co Austenitic stainless steel alloy
JPS5554551A (en) * 1978-10-12 1980-04-21 Kobe Steel Ltd Stainless steel with superior rust resistance
US5939018A (en) * 1984-10-10 1999-08-17 Kawasaki Steel Corporation Martensitic stainless steels for seamless steel pipe
SE9002276D0 (sv) * 1990-06-28 1990-06-28 Abb Powdermet Ab Saett att framstaella fulltaeta kroppar av varmhaallfast martensitiskt cr-staal
DE4212966C2 (de) * 1992-04-18 1995-07-13 Ver Schmiedewerke Gmbh Verwendung eines martensitischen Chrom-Stahls
US5320687A (en) * 1992-08-26 1994-06-14 General Electric Company Embrittlement resistant stainless steel alloy
JP2962098B2 (ja) * 1993-04-09 1999-10-12 日本鋼管株式会社 110Ksi グレードの高強度耐食性マルテンサイト系ステンレス鋼管の製造法
DE4411795A1 (de) * 1994-04-06 1995-12-14 Kugelfischer G Schaefer & Co Nichtrostender Stahl für das Einsatzhärten mit Stickstoff
US6220306B1 (en) * 1998-11-30 2001-04-24 Sumitomo Metal Ind Low carbon martensite stainless steel plate
JP4252145B2 (ja) * 1999-02-18 2009-04-08 新日鐵住金ステンレス株式会社 耐遅れ破壊性に優れた高強度・高靭性ステンレス鋼

Also Published As

Publication number Publication date
PT1341944E (pt) 2007-04-30
HU228284B1 (en) 2013-02-28
WO2002048418A1 (en) 2002-06-20
HUP0301825A3 (en) 2005-10-28
SE0004586D0 (sv) 2000-12-11
HUP0301825A2 (hu) 2003-09-29
JP4030872B2 (ja) 2008-01-09
DE60126646D1 (de) 2007-03-29
HK1060157A1 (en) 2004-07-30
EP1341944A1 (en) 2003-09-10
CA2425893A1 (en) 2002-06-20
PL361985A1 (en) 2004-10-18
ES2280304T3 (es) 2007-09-16
SE518023C2 (sv) 2002-08-20
CN1478151A (zh) 2004-02-25
CN1207420C (zh) 2005-06-22
KR20030051904A (ko) 2003-06-25
MXPA03005136A (es) 2003-12-04
DE60126646T2 (de) 2007-10-31
US20040013559A1 (en) 2004-01-22
PL196489B1 (pl) 2008-01-31
AU2002224270B2 (en) 2006-09-14
KR100831823B1 (ko) 2008-05-28
BR0116057A (pt) 2004-02-03
JP2004515654A (ja) 2004-05-27
SE0004586L (sv) 2002-06-12
CA2425893C (en) 2010-09-14
AU2002224270B8 (en) 2006-10-19
AU2427002A (en) 2002-06-24
TWI286576B (en) 2007-09-11
ATE353986T1 (de) 2007-03-15

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