WO2006026982A1 - Acier lamine calme, non allie ou micro-allie a effet de durcissement par etuvage et procede de production associe - Google Patents

Acier lamine calme, non allie ou micro-allie a effet de durcissement par etuvage et procede de production associe Download PDF

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Publication number
WO2006026982A1
WO2006026982A1 PCT/DE2005/001589 DE2005001589W WO2006026982A1 WO 2006026982 A1 WO2006026982 A1 WO 2006026982A1 DE 2005001589 W DE2005001589 W DE 2005001589W WO 2006026982 A1 WO2006026982 A1 WO 2006026982A1
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WO
WIPO (PCT)
Prior art keywords
rolled steel
free
steel
values
bake
Prior art date
Application number
PCT/DE2005/001589
Other languages
German (de)
English (en)
Inventor
Klaus Freier
Original Assignee
Salzgitter Flachstahl Gmbh
Klaus Freier
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 Salzgitter Flachstahl Gmbh, Klaus Freier filed Critical Salzgitter Flachstahl Gmbh
Priority to EP05789368A priority Critical patent/EP1786937B1/fr
Publication of WO2006026982A1 publication Critical patent/WO2006026982A1/fr

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Classifications

    • 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
    • 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
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
    • C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
    • C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • 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
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling

Definitions

  • the invention relates to a calmed, unalloyed or microalloyed rolled steel with a bake hardening effect and to a process for its production.
  • unalloyed steels are those types of steels whose composition is free of alloying elements or whose proportion of alloying elements does not exceed predetermined limit values in each case.
  • microalloyed steels are unalloyed steels which contain small amounts of alloying elements (below the limit values).
  • the settling of the steel presupposes that the sedative is added in a stoichiometric excess so that the alloying element causing the calming remains in an excess proportion in the steel, while the corresponding bonded oxide (alumina in the case of aluminum) reacts with the slag the molten steel is removed.
  • the excess amount of aluminum remaining in the steel has been found to be advantageous, because aluminum is a fine grain former, which favors the formability of the formed rolled steel. All standards and draft standards for common rolled steels therefore provide for a minimum content of aluminum in the steel of 0.01 for titanium addition, otherwise 0.015 or even 0.02 wt%.
  • Well deformable rolled steels should have the property of ensuring high strength despite their good ductility. This applies, for example, to steel sheets used in the automotive industry. It has been found that certain steel grades after cold working significantly increase their yield strength values when subjected to a heat treatment such as, for example, bake coating. In the case used temperatures of about 120 ° C or 170 0 C a "aging" of the steel takes place, is significantly increased by the yield strength of the steel. This effect is due to the effect of free, gelös ⁇ tem carbon which due to The thermal action in the crystal structure resulting from the cold-forming process migrates and is thus blocked at an adjoining strain, and it is therefore known that a bake-hardening effect can be achieved at a normal C content (0.02-0).
  • 0.20% by weight can occur only when a cold-rolled steel is subjected to recrystallization in a continuous process, because in the case of the high cooling rate used, a connection of the free, dissolved carbon with iron to form cementite is prevented of the recrystallizing annealing in a crucible annealing furnace in the tight bundle arise so low cooling rates that no free carbon i n remains so that the resulting steel does not age and has no bake-hardening effect.
  • rolled steels of the type mentioned which have a bake hardening effect, basically only with a normal C content (C> 0.01 wt.%) Can be produced in a continuous annealing.
  • An alternative be ⁇ lower the C content in the vacuum process well below 0.01 wt.%. In this case, it is possible, even at low cooling rates after a recrystallizing annealing, to obtain free carbon in the forming crystal structure, because the diffusion paths of the free carbon to free iron atoms have become so great due to the low carbon concentration that a noteworthy Part of the free carbon atoms remains unbound in the crystal structure and can cause the bake hardening effect.
  • the invention has for its object to enable the production of a calmed, unalloyed or microalloyed rolled steel with an improved bake hardening effect, wherein the initial enabling a bake hardening effect for certain steel grades should be included.
  • the steel must be treated either by means other than aluminum, or the steel must be produced by "pre-soaking" with aluminum, with the addition of aluminum being somewhat substoichiometric, so that a residual sedimentation with another Alternatively, a pretreatment can also be achieved with a vacuum treatment It is possible to carry out the complete settling with silicon, but this is not preferred because of the high addition amounts required for this purpose.
  • the steel produced according to the invention is thus preferably free of aluminum, i. the aluminum content is less than 0.01% by weight, preferably less than 0.005% by weight. Should the aluminum content be higher, the amount of free nitrogen bound thereby must be taken into account, so that the molten steel must be produced with a significantly higher proportion of free, dissolved nitrogen in order to ensure the proportion of free, dissolved nitrogen provided according to the invention ,
  • a particularly suitable alloying element for this purpose is phosphorus, preferably with a proportion of> 0.015% by weight, preferably> 0.020% by weight, in particular> 0.025% by weight.
  • Another alloying element that significantly enhances the bake hardening effect is niobium, which is preferably included in addition to the one alloying element (preferably phosphorus) in an amount> 0.01% by weight.
  • the rolled steel according to the invention preferably contains a proportion of> 0.15% by weight of silicon, preferably> 0.20% by weight of silicon.
  • the present invention makes it possible for the first time to produce a hot strip for the application of a bake hardening effect for products which are formed directly (ie in particular without subsequent cold rolling) from the hot strip. Since the use of hot strips is preferred because of the elimination of the otherwise required cold rolling and heat treatment steps for cost reasons, the present invention opens up wide new fields of application for the use of hot strips.
  • the present invention allows for the first time without any special effort the production of ductile-glow-annealed cold tapes with a bake hardening effect, when the steel has a normal C content (between 0.01 or 0.02 and 0.20 wt.% ) having.
  • the present invention also makes it possible to produce those steels which are conventionally produced with a free carbon based bake hardening effect, now with a significantly improved bake hardening effect, which according to the invention has the (additional) effect of free, dissolved nitrogen is based in the crystal structure. Accordingly, it is readily possible to use the method according to the invention also in Maschinentube ⁇ annealed or vacuum-cooled rolled steels, so as to significantly increase the already known bake-hardening effect by the measures according to the invention.
  • the steels according to the invention have the remarkable property that the bake-hardening effect based on the free nitrogen occurs only at a temperature treatment after a previous deformation (BH 2).
  • the particle size can be controlled by the proportion of the further alloying element, in particular by phosphorus, in comparison with aluminum-killed steels. produce fine or even a finer grain in the steel according to the invention.
  • the total content of nitrogen in the steel according to the invention is ⁇ 0.0090% by weight, preferably ⁇ 0.075% by weight, in particular ⁇ 0.0045% by weight.
  • the existing in the preparation of the melt nitrogen content (0.0040 ⁇ N sat. ⁇ 0.0060 wt.%) Is preferably used, thus apart from one alloying N.
  • H annealing in the fixed coil in the hood furnace
  • D annealing in the continuous annealing
  • Figure 1 relates to a composite according to the invention with a normal C-content of 0.028 wt.% And negligible proportions of sulfur, phosphorus and aluminum.
  • the steel has been (finally) calmed with silicon and has a content of free, dissolved nitrogen of 0.0090% by weight. Due to its yield strength of just under 300 N / mm 2, it is already a high-strength steel and has a distinct, if not high BH 2 effect (25 to 30 N / mm 2 ) at both Haspeitemperaturen after completion of the hood.
  • FIG. 2 shows the results for a steel that is not prinicipally varied in the composition.
  • FIGS. 4 and 5 also illustrate that the influence of niobium, which increases the BH2 value, decreases as the proportion of silicon increases relatively.
  • the silicon content is almost twice as high as in comparison figures 2 and 3.
  • FIG. 6 shows that a significant increase in the BH 2 value can be achieved by adding phosphorus (in this case 0.054% by weight).
  • FIG. 7 illustrates that, after the addition of phosphorus, an increase in the silicon content has no positive effect on the BH2 value. It is merely an increase in the strength values with a simultaneous drop in the parameters which are essential for the ductility, namely Ag, A80 and n value. While the results presented so far were based on laboratory experiments, an operating melt has additionally been prepared under industrial production conditions with the following chemical composition in% by weight.
  • Figures 16 to 18 show changes in the mechanical and technological properties of the steel according to Figures 12 to 15 by a heat treatment at 250 ° C for three minutes, as typically occurs in a plastic tape coating.
  • FIGS. 19 to 22 illustrate the measured values for hot-dip galvanized steel strip produced from the same melt and FIGS. 23 to 25 illustrate the changes in the measured values by a heat treatment at 250 ° C. for three minutes, as typically occurs for a plastic strip coating.
  • the steel strip produced in the above-mentioned composition was hot-rolled in the customary manner and then cooled by cooling to a reeling temperature of 500 ° C. or 700 ° C. After cooling in the coiler cold rolling steps are carried out in a conventional manner, by which the steel sheet has been subjected to cold deformation of well over 50%.
  • the wound cold strip is in the coil in a hood furnace at a Temperature under 720 ° C (A1) was annealed recrystallizing and benofen in Hau ⁇ under quasi-isothermal conditions cooled.
  • Measured values at the beginning of the strip (A), in the middle of the strip (M) and at the end of the strip (E) are shown in FIGS. 12 et seq.,
  • the left column being a sample taken in the longitudinal direction of the strip and the right one each represents a transversal and tested sample.
  • the steel has a BH2 value of about 40 N / mm 2 at the low coiler temperature and well above 40 N / mm 2 at the higher coiler temperature, despite the bell annealing, as can be seen in FIG.
  • the BHO values, at least for the low reel temperature tend to be negligible.
  • Grain size is above ASTM 9 for the high reel temperature while well above ASTM 10 for the lower reel temperature.
  • Erkenn ⁇ bar is that a practically perfectly round grain is formed, since in the longitudinal and Quer ⁇ direction completely identical grain sizes are measured.
  • Figures 16 to 18 illustrate the changes in the specified Pa ⁇ parameters after performing a heat treatment, as in a Coating is common, so a heat treatment for about three minutes at about 25O 0 C.
  • FIGS. 19 to 22 illustrate the mechanical-technological parameters for a steel strip recrystallized in a continuous annealing annealer after the hot rolling, reeling and cold rolling as described above, which has been hot-dip galvanized.
  • a steel strip treated in this way has higher strength values and can be produced with a good BH 2 value which, depending on the strength, is usually of the order of 40 N / mm 2 .
  • the BH 2 value obtained according to the invention is considerably higher according to FIG. 21 and is between 80 and 90 N / mm 2 .
  • Such a BH2 value has hitherto not been achievable with conventional production methods.
  • the grain size is, depending on the reel temperature at ASTM 8.5 to 9.5, ie in the range of a fine-grained steel.
  • the low level of 0.0012 wt.% Free nitrogen indicated in the composition described is believed to be significant to the observed strain hardening prevention.
  • a free N content which is between 0.0010 and 0.0020% by weight is preferred.
  • the invention was able to produce a ductile-annealed steel strip which, given relatively high strength values, has very good deformation values and, at the same time, a clear BH 2 effect.
  • the result is a fine-grained structure with ASTM grain sizes 9.25 to 10.75.
  • the fine grain of unalloyed steel is comparable to the fine graininess otherwise achieved with a microalloyed steel.
  • the steels according to the invention can be produced with a bake hardening effect, which is based on the existence of free, dissolved nitrogen in the crystal structure.
  • This effect can be increased by controlling the diffusion of the free nitrogen, beispiels ⁇ example by the addition of phosphorus and / or niobium.
  • phosphorus can influence the grain size of the resulting steel.
  • niobium an adjustment of the strength can be effected.
  • the steels according to the invention have consistently high elongation, r and n values, ie good deformation properties.
  • the steels according to the invention show good BH 2 values, but very low BHO values.
  • the bake-hardening effect therefore utilizes usable only after a previous deformation.
  • the steels are almost free from aging at room temperature, so that there is only a slight amount of strain aging due to the free nitrogen.
  • the measured BH2 effect is enhanced by the addition of P, as phosphor activates nitrogen diffusion.
  • the BH2 values are obtained both at a heat treatment of 12O 0 C and 170 0 C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

L'objectif de l'invention est de produire de l'acier laminé calme, non allié ou micro-allié au moyen d'un effet de durcissement par étuvage. A cet effet, de l'azote dissous, sans effet de durcissement par étuvage est utilisé dans une quantité supérieure à 0,001% en poids.
PCT/DE2005/001589 2004-09-09 2005-09-08 Acier lamine calme, non allie ou micro-allie a effet de durcissement par etuvage et procede de production associe WO2006026982A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05789368A EP1786937B1 (fr) 2004-09-09 2005-09-08 Acier lamine calme, non allie ou micro-allie a effet de durcissement par etuvage et procede de production associe

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410044022 DE102004044022A1 (de) 2004-09-09 2004-09-09 Beruhigter, unlegierter oder mikrolegierter Walzstahl mit Bake-hardening-Effekt und Verfahren zu seiner Herstellung
DE102004044022.0 2004-09-09

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WO2006026982A1 true WO2006026982A1 (fr) 2006-03-16

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EP (1) EP1786937B1 (fr)
DE (1) DE102004044022A1 (fr)
WO (1) WO2006026982A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4050959A (en) * 1974-11-18 1977-09-27 Nippon Kokan Kabushiki Kaisha Process of making a high strength cold reduced steel sheet having high bake-hardenability and excellent non-aging property
JPH10183301A (ja) * 1996-10-31 1998-07-14 Kawasaki Steel Corp 焼付硬化性および耐室温時効性に優れた熱延鋼板およびめっき鋼板ならびに熱延鋼板の製造方法
EP1028167A2 (fr) * 1999-02-09 2000-08-16 Kawasaki Steel Corporation Tôle d'acier laminée à chaud à haute résistance à la traction et procédé de sa production
EP1193322A1 (fr) * 2000-02-29 2002-04-03 Kawasaki Steel Corporation Tole d'acier laminee a froid a haute resistance presentant d'excellentes proprietes de durcissement par vieillissement par l'ecrouissage
US20030015263A1 (en) * 2000-05-26 2003-01-23 Chikara Kami Cold rolled steel sheet and galvanized steel sheet having strain aging hardening property and method for producing the same
JP2003064446A (ja) * 2001-08-21 2003-03-05 Kawasaki Steel Corp 歪時効硬化特性に優れるとともに室温時効劣化のない冷延鋼板および冷延めっき鋼板ならびにそれらの製造方法
EP1291447A1 (fr) * 2000-05-31 2003-03-12 Kawasaki Steel Corporation Tole d'acier laminee a froid presentant d'excellentes proprietes de rheodurcissement par vieillissement, et procede de production
EP1291448A1 (fr) * 2000-05-26 2003-03-12 Kawasaki Steel Corporation Tole d'acier laminee a froid et tole d'acier galvanisee possedant des proprietes de durcissement par ecrouissage et par precipitation et procede de production associe

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4050959A (en) * 1974-11-18 1977-09-27 Nippon Kokan Kabushiki Kaisha Process of making a high strength cold reduced steel sheet having high bake-hardenability and excellent non-aging property
JPH10183301A (ja) * 1996-10-31 1998-07-14 Kawasaki Steel Corp 焼付硬化性および耐室温時効性に優れた熱延鋼板およびめっき鋼板ならびに熱延鋼板の製造方法
EP1028167A2 (fr) * 1999-02-09 2000-08-16 Kawasaki Steel Corporation Tôle d'acier laminée à chaud à haute résistance à la traction et procédé de sa production
EP1193322A1 (fr) * 2000-02-29 2002-04-03 Kawasaki Steel Corporation Tole d'acier laminee a froid a haute resistance presentant d'excellentes proprietes de durcissement par vieillissement par l'ecrouissage
US20030015263A1 (en) * 2000-05-26 2003-01-23 Chikara Kami Cold rolled steel sheet and galvanized steel sheet having strain aging hardening property and method for producing the same
EP1291448A1 (fr) * 2000-05-26 2003-03-12 Kawasaki Steel Corporation Tole d'acier laminee a froid et tole d'acier galvanisee possedant des proprietes de durcissement par ecrouissage et par precipitation et procede de production associe
EP1291447A1 (fr) * 2000-05-31 2003-03-12 Kawasaki Steel Corporation Tole d'acier laminee a froid presentant d'excellentes proprietes de rheodurcissement par vieillissement, et procede de production
JP2003064446A (ja) * 2001-08-21 2003-03-05 Kawasaki Steel Corp 歪時効硬化特性に優れるとともに室温時効劣化のない冷延鋼板および冷延めっき鋼板ならびにそれらの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 12 31 October 1998 (1998-10-31) *
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 07 3 July 2003 (2003-07-03) *

Also Published As

Publication number Publication date
EP1786937B1 (fr) 2013-02-20
DE102004044022A1 (de) 2006-03-16
EP1786937A1 (fr) 2007-05-23

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