EP2453026A1 - Warmumgeformtes Stahlprodukt und Verfahren zu dessen Herstellung - Google Patents

Warmumgeformtes Stahlprodukt und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP2453026A1
EP2453026A1 EP10190719A EP10190719A EP2453026A1 EP 2453026 A1 EP2453026 A1 EP 2453026A1 EP 10190719 A EP10190719 A EP 10190719A EP 10190719 A EP10190719 A EP 10190719A EP 2453026 A1 EP2453026 A1 EP 2453026A1
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EP
European Patent Office
Prior art keywords
hot
steel product
steel
product according
manganese
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.)
Withdrawn
Application number
EP10190719A
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German (de)
English (en)
French (fr)
Inventor
Hans Roelofs
Giovanni Mastrogiacomo
Ulrich Hugo Urlau
Francisca Garcia Caballero
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.)
Swiss Steel AG
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Swiss Steel AG
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 Swiss Steel AG filed Critical Swiss Steel AG
Priority to EP10190719A priority Critical patent/EP2453026A1/de
Priority to EP11188717.0A priority patent/EP2453027B1/de
Priority to PL11188717T priority patent/PL2453027T3/pl
Publication of EP2453026A1 publication Critical patent/EP2453026A1/de
Withdrawn legal-status Critical Current

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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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the invention relates to a method for producing a steel product according to the preamble of claim 1 and to a hot-formed product producible therewith.
  • the tempering treatment aims at a tempered martensitic steel structure and allows the setting of a high level of toughness with still good strength.
  • a broadly used tempered steel is the material 42CrMo4. At a tensile strength of about 1000 MPa, this steel still achieves a Charpy impact work (ISO-V at room temperature) of 200 J.
  • Annealing steels with a martensite and bainite mixed structure can also have good property combinations.
  • the WO 2007/017161 describes such a steel for thick-walled seamless tubes (with up to 30 mm wall thickness). After quenching (cooling rate> 30 K / s) from the forming heat, a dominant martensitic microstructure with up to 40% bainite is formed. Irrespective of the original austenite grain size (primary structure), the martensitic structure has a good notched impact strength as soon as the martensite grain size is ⁇ 3 ⁇ m.
  • EP 0 845 544 describes such a microalloyed bainitic steel with C ⁇ .12%, which has a tensile strength of more than 1000 MPa at room temperature.
  • the steel is austenitized again after rolling and then quenched at a cooling rate> 17 K / s. This cooling rate is still significantly higher than that of the air-cooled long products in conventional rolling mills.
  • EP 0 775 756 describes another bainitic-martensitic steel for the production of forgings.
  • the tensile strength should be>1'000 MPa and the Charpy notched impact strength ISO-U is> 50 j / CM 2 (or notched impact strength ISO-U> 25 J).
  • the described steel composition necessarily requires an accelerated cooling from the forming heat, so that these values can be achieved.
  • the exemplary embodiments show that the cooling rate should be> 14 K / s.
  • This technical teaching can not be applied in conventional forging and hot rolling processes.
  • the implementation is limited to small components in which even in the core still large cooling rates can be achieved.
  • GB 2 297 094 describes a carbide-free bainitic steel that can be made from the forming heat cooled in air.
  • the steel is designed for the production of rails and is characterized by a good wear resistance and a good fatigue behavior.
  • the notched impact strength of the material was not the focus of this development.
  • the Charpy impact work ISO-V at room temperature is only at 20 to 40 years.
  • the in CN 1 477 226 steel described after air cooling may contain the following mixed structure: granular bainite, lower bainite, martensite, retained austenite. It achieves a tensile strength of 850 to over 1,400 MPa. In order for good toughness to result, however, the steel must be heat treated again after hot working (tempered). The carbon present then migrates into the present austenite films, and at a tensile strength of about 900 MPa, a Charpy impact toughness ISO-U greater than 110 J / cm 2 (or> 55 J) can be achieved.
  • the object of the invention is to provide an improved hot-worked steel product and a method for its production, with which in particular the above disadvantages are avoided.
  • the mass number Bs used in the above condition corresponds to a known empirical approach for the bainite start temperature in Kelvin [ W. Steven, and AJ Haynes, JISI 183, pp. 349-359 (1956 )].
  • the alloy components are chosen so that at usual cooling rates from the rolling heat of 0.3 to 8.0 K / s (from 800 ° C to 500 ° C) always a bainitic-martensitic microstructure with tensile strength of 900 to 1400 MPa results without having to use expensive alloying elements and / or special equipment for accelerated cooling from the rolling heat.
  • the lower limit of the carbon content to 0.03 wt .-% is ensured in combination with manganese, chromium and molybdenum that there are no ferrite in the structure. Ferrite levels affect both the strength level and the impact strength of the product.
  • the upper limit of the carbon to 0.20 wt .-% ensures that the tensile strength does not rise above 1400 MPa. Higher strength values degrade machinability in the downstream drawing or machining process. Higher carbon contents also promote the formation of carbides, which adversely affects ductility.
  • the lower limit of 2.00% by weight in manganese ensures that a bainite start temperature below 800 K can be achieved without expensive alloying additions.
  • This deep bainite start temperature ensures a fine steel structure, which consists predominantly of lower bainite.
  • Molybdenum suppresses the grain boundary segregation of embrittling elements such as phosphorus.
  • An addition of at least 0.15 wt .-% molybdenum thus improves the tempering resistance of the steel. If no downstream heat treatment takes place, the addition of molybdenum is not mandatory.
  • a molybdenum content above 0.5% by weight promotes the formation of carbon-rich martensite islands. These lead to a marked deterioration of the toughness of the steel. For this reason, the molybdenum content should be at most 0.5% by weight.
  • Chromium may be alloyed in place of manganese to adjust the bainite start temperature.
  • the use of chromium is more expensive than the use of manganese. Since manganese segregates strongly, it may nevertheless make sense for certain applications to replace part of the manganese with chromium. Since chromium increases the risk for the formation of chromium-rich nitrides and carbides, which can lead to a deterioration of the toughness, the chromium content is limited to 2.0% by weight.
  • the addition of silicon is not necessary to achieve the desired properties.
  • a metered addition of silicon suppresses carbide formation.
  • a preferred embodiment of the product according to the invention therefore contains 0.40 to 0.80% by weight of silicon.
  • Nickel improves Charpy impact strength at low temperatures. In general, the properties are sufficient without addition of nickel. For cost reasons, the nickel content is limited to 1.0 wt .-%.
  • Phosphorus is a steel pest. It goes to the Austenitkorngrenzen and weakens the structure. For this reason, the phosphorus content was limited to 0.035 wt .-%.
  • ferrite formation should be avoided as far as possible. This can be ensured by a sufficiently rapid cooling of the hot-formed product. If the cooling rate is insufficient, addition of boron may additionally be provided. Boron goes to the austenite grain boundaries and suppresses ferrite formation. In this case, a boron content of 10 to 50 ppm is sufficient.
  • titanium carbonitrides An addition of 0.03 to 0.10% by weight of titanium ensures that the nitrogen dissolved in the liquid steel of up to 0.02% by weight is precipitated during the solidification of the steel in the form of titanium carbonitrides. This is the prerequisite for the fact that elemental boron can reach the austenite grain boundaries and is not present in the form of boron nitrides. If no boron is alloyed, no titanium addition must be provided.
  • the chemical composition of the steel should be chosen such that, after cooling in air, a structure is created which is predominantly composed of lower bainite. This is preferably achieved by setting the bainite start temperature Bs low enough. For this reason, the Bs temperature should not be more than 800 K. The low transformation temperature ensures a very fine microstructure, which is decisive for achieving the high notched impact strength.
  • a sufficiently fine microstructure is achieved if the mean grain size of the dominant bainitic secondary microstructure is less than 5 ⁇ m.
  • the grain size is defined by the linear distance between grain boundaries.
  • the crystallographic orientation at the grain boundary should change by more than 15 °.
  • a too low selected Bs temperature slows the kinetics of bainite formation. It produces significantly less bainite and the structure becomes dominant martensitic.
  • the Bs temperature should therefore be above 700 K.
  • the bainite start temperature should preferably be between 750 and 800 K.
  • Austenite is not completely transformed into bainite during structural transformation. In order to dominate the properties of the lower bainite, however, should be at least 60% of the structure of lower bainite.
  • Austenite which does not convert to bainite during hot-dip cooling, is either stabilized to a sufficient carbon content or converts to martensite at lower temperatures. At an average carbon content in the steel of 0.05 wt .-% is expected to be present in the structure no retained austenite and the resulting martensite may be up to 40%.
  • the manganese content of the steel is more than 2.0% by weight, a microscopically uneven manganese distribution in the industrially produced product is to be expected (segregation zones). For this reason, the transformation behavior of austenite during cooling from hot working may vary locally. Thus, isolated grains of ferrite, granular bainite or upper bainite can not be completely excluded. As long as their ingredients are small, they will not affect the good properties of the product. Therefore, up to 10% granular or upper bainite and up to 2% ferrite are permissible for the product produced according to the invention.
  • the room temperature Charpy impact values determined at nine melts are in Fig. 1 as a function of the bainite start temperature Bs (determined according to Steven & Hayns). It has been discovered that the melts with Bs ⁇ 800 K always have a good notched impact strength.
  • Carbon, manganese, molybdenum were used in the trial melts to adjust the Bs temperature. No chromium and nickel were alloyed. The measured chromium and nickel contents (as accompanying elements or impurities in the steel) were between 0.05 and 0.09 wt .-%.
  • the three steels according to the invention are compared with the six non-inventive steels in Tables 1 and 2.
  • the properties and the microstructure of the non-inventive steel 2 are similar to steel 1.
  • the bainite start temperature is slightly lower and the microstructure is accordingly somewhat finer ( Fig. 3 ).
  • the structure consists predominantly of a carbide-free granular bainite.
  • the quantitative microstructure analysis (by means of X-ray diffraction for austenite and quantitative SEM analysis for ferrite, bainite and M / A phase fractions) revealed the following structural composition: 80% bainite (dominant granular), 17% martensite and 3% retained austenite.
  • the microstructure changes from granular bainite to pale lower bainite.
  • LOM micrograph
  • the much finer microstructure can be seen ( Fig. 5 ).
  • the strength increases markedly compared to steels 1 and 2, but the impact value remains low.
  • Reason for the unsatisfactory toughness are coarse grains of granular, upper bainite, which are embedded in a matrix of fine lower bainite.
  • the structure consists of 87% bainite, 10% martensite and 3% retained austenite.
  • the microstructure Due to the grains of granular bainite present, the microstructure is not as fine as it appears in the LOM or in the scanning electron microscope. To visualize the fineness of the structure, EBSD studies were performed. This method measures the crystallographic orientations in the microstructure. A grain boundary exists when the crystallographic orientation changes by more than 15 °. The average linear extent of the grains can thus be determined. For steel 6, the mean grain size is 10.1 ⁇ m ( ⁇ 0.93 ⁇ m).
  • Fig. 7 shows the structure of the inventive steel 7 compared to the steel 6.
  • the structure has become even finer in steel 7.
  • the quantitative analysis gives the following structure composition: 70 to 72% lower bainite and 28 to 30% self-tempered martensite. Rough structural components such as ferrite or granular upper bainite are missing.
  • the mean grain size determined by EBSD is correspondingly small. It is 4.51 ⁇ m ( ⁇ 1.09 ⁇ m) and thus only half the size of steel 6.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
EP10190719A 2010-11-10 2010-11-10 Warmumgeformtes Stahlprodukt und Verfahren zu dessen Herstellung Withdrawn EP2453026A1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10190719A EP2453026A1 (de) 2010-11-10 2010-11-10 Warmumgeformtes Stahlprodukt und Verfahren zu dessen Herstellung
EP11188717.0A EP2453027B1 (de) 2010-11-10 2011-11-10 Warmumgeformtes Produkt und Verfahren zu dessen Herstellung
PL11188717T PL2453027T3 (pl) 2010-11-10 2011-11-10 Produkt przekształcony termicznie i sposób jego wytwarzania

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10190719A EP2453026A1 (de) 2010-11-10 2010-11-10 Warmumgeformtes Stahlprodukt und Verfahren zu dessen Herstellung

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EP2453026A1 true EP2453026A1 (de) 2012-05-16

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EP10190719A Withdrawn EP2453026A1 (de) 2010-11-10 2010-11-10 Warmumgeformtes Stahlprodukt und Verfahren zu dessen Herstellung
EP11188717.0A Not-in-force EP2453027B1 (de) 2010-11-10 2011-11-10 Warmumgeformtes Produkt und Verfahren zu dessen Herstellung

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022110466A1 (de) 2022-04-29 2023-11-02 Hirschvogel Holding GmbH Verfahren zur Herstellung eines Massivumformbauteils und Massivumformbauteil hergestellt mit einem solchen Verfahren

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2297094A (en) 1995-01-20 1996-07-24 British Steel Plc Improvements in and relating to carbide-free bainitic steels and methods of producing such steels
EP0775756A1 (fr) 1995-11-27 1997-05-28 ASCOMETAL (Société anonyme) Acier pour la fabrication d'une pièce forgée ayant une structure bainitique et procédé de fabrication d'une pièce
EP0845544A1 (fr) 1996-11-26 1998-06-03 Ascometal Produit sidérurgique en acier ayant une structure bainitique et procédé pour la fabrication du produit sidérurgique
CN1477226A (zh) 2003-08-01 2004-02-25 清华大学 中低碳锰系空冷贝氏体钢
WO2007017161A1 (en) 2005-08-04 2007-02-15 Tenaris Connections Ag High-strength steel for seamless, weldable steel pipes
JP2007284774A (ja) * 2006-04-20 2007-11-01 Jfe Bars & Shapes Corp 耐遅れ破壊特性および冷間加工性に優れる線材およびその製造方法
EP2103704A1 (de) * 2008-03-10 2009-09-23 Swiss Steel AG Warmgewalztes Langprodukt und Verfahren zu dessen Herstellung

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2297094A (en) 1995-01-20 1996-07-24 British Steel Plc Improvements in and relating to carbide-free bainitic steels and methods of producing such steels
EP0775756A1 (fr) 1995-11-27 1997-05-28 ASCOMETAL (Société anonyme) Acier pour la fabrication d'une pièce forgée ayant une structure bainitique et procédé de fabrication d'une pièce
EP0845544A1 (fr) 1996-11-26 1998-06-03 Ascometal Produit sidérurgique en acier ayant une structure bainitique et procédé pour la fabrication du produit sidérurgique
CN1477226A (zh) 2003-08-01 2004-02-25 清华大学 中低碳锰系空冷贝氏体钢
WO2007017161A1 (en) 2005-08-04 2007-02-15 Tenaris Connections Ag High-strength steel for seamless, weldable steel pipes
JP2007284774A (ja) * 2006-04-20 2007-11-01 Jfe Bars & Shapes Corp 耐遅れ破壊特性および冷間加工性に優れる線材およびその製造方法
EP2103704A1 (de) * 2008-03-10 2009-09-23 Swiss Steel AG Warmgewalztes Langprodukt und Verfahren zu dessen Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
W. STEVEN; A.J. HAYNES, JISI, vol. 183, 1956, pages 349 - 359

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022110466A1 (de) 2022-04-29 2023-11-02 Hirschvogel Holding GmbH Verfahren zur Herstellung eines Massivumformbauteils und Massivumformbauteil hergestellt mit einem solchen Verfahren

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Publication number Publication date
PL2453027T3 (pl) 2019-05-31
EP2453027B1 (de) 2018-10-24
EP2453027A1 (de) 2012-05-16

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