EP2240622B1 - Verfahren zur herstellung eines bauteils aus einem mit einem al-si-überzug versehenen stahlprodukt und zwischenprodukt eines solchen verfahrens - Google Patents

Verfahren zur herstellung eines bauteils aus einem mit einem al-si-überzug versehenen stahlprodukt und zwischenprodukt eines solchen verfahrens Download PDF

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Publication number
EP2240622B1
EP2240622B1 EP09705444A EP09705444A EP2240622B1 EP 2240622 B1 EP2240622 B1 EP 2240622B1 EP 09705444 A EP09705444 A EP 09705444A EP 09705444 A EP09705444 A EP 09705444A EP 2240622 B1 EP2240622 B1 EP 2240622B1
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EP
European Patent Office
Prior art keywords
steel product
temperature
coating
steel
heating
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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.)
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Application number
EP09705444A
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German (de)
English (en)
French (fr)
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EP2240622A1 (de
Inventor
Friedhelm Macherey
Franz-Josef Lenze
Michael Peters
Manuela Ruthenberg
Sascha Sikora
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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Priority to PL09705444T priority Critical patent/PL2240622T3/pl
Publication of EP2240622A1 publication Critical patent/EP2240622A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/48—Aluminising
    • C23C10/50—Aluminising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/1275—Next to Group VIII or IB metal-base component
    • Y10T428/12757—Fe

Definitions

  • the invention relates to a method for producing a component from a coated with an Al-Si protective coating steel product. Moreover, the invention also relates to an intermediate product which arises in the course of such a process and can be used for the production of components of the type in question.
  • Steel products of the type in question are typically steel strips or sheets which are provided in a manner known per se, for example by means of fire aluminizing, with an Al-Si coating. However, it can also be preformed semifinished products, which are preformed, for example, from sheet metal and then molded to the respective component.
  • the component formed from the respective steel product is protected against corrosion during its practical use.
  • the Al-Si protective coating also already offers the anticorrosive effect, in particular the protection against scaling, immediately after the coating of the steel substrate and keeps it in the course of the forming process at. This is especially true when the shaping is carried out as so-called "press hardening".
  • the starting material to be formed is brought to a temperature at which a at least partly austenitic structure is present, and is deformed in a warm state prior to shaping. Either already during the thermoforming process or immediately thereafter, the resulting component is then accelerated cooled to form hardness structure.
  • a starting material for press hardening flat products such as sheet metal blanks, or already pre-or final molded semi-finished products can be used.
  • the Al-Si coating prevents tinder from forming on the steel product, which would severely hinder the molding process. In this way, it is possible to form components of high-strength, heat-treatable steels, which are exposed to particularly high loads in practice.
  • a steel grade typically used for this purpose is known in practice as "22MnB5". From steel grades of this type, for example, body parts of motor vehicles are manufactured, which must have a high strength with low flat product thickness and, consequently, comparably low weight. Likewise, however, other steel grades, such as deep-drawing steels known under the trade designation “DX55D”, according to DIN EN 10327 composite type, as well as microalloyed steels alloyed according to DIN EN 10292, under the Description "HX300 / 340 LAD" commercially available type, press-form hardened. It is also possible to use the starting products, which are composed in the manner of tailored blanks / patchwork blanks of several sheets.
  • Al-Si coating In order for the Al-Si coating to adhere to the steel substrate so strongly that it does not crack or chip during forming, it is necessary to subject the Al-Si-coated steel product to heat treatment prior to forming, in which iron is precipitated the steel substrate is alloyed into the Al-Si coating.
  • the aim is to pass through the coating over its entire thickness to ensure that there are no breaks or chips in the upper layers of the coating, which are adjacent to the free outer surface of the coated flat product.
  • the type or degree of alloying of Al-Si coatings also has an influence on the weldability and paintability of the components produced by press-hardening.
  • a method of the type described above is in the EP 1 380 666 A1 described.
  • a steel sheet coated with an Al-Si coating is first heated to 900 ° C to 950 ° C over a period of 2 to 8 minutes. Thereafter, the coated steel sheet is cooled to a temperature of 700-800 ° C and thermoformed at that temperature. Subsequently, the formed steel part is rapidly cooled to a temperature below 300 ° C to produce a martensitic structure in the obtained steel part.
  • the heat treatment of the coating provided steel substrate is carried out so that by diffusion of the iron from the steel substrate after the heat treatment, the iron content in the coating in a range between 80% and 95%. In this way, a thermoformed component is to be obtained in which a good weldability and good formability combined with a high corrosion protection.
  • a problem in the implementation of the heat treatment required for the alloying out is that in addition to the setting of a sufficient heating temperature, a certain amount of furnace time must be maintained. The duration over which the respective steel product must be kept in the oven results from the heating rate of the substrate and the required alloying of the substrate with the Al-Si layer.
  • the prior art is a bake time of five to 14 minutes.
  • heating ovens carried out prior to hot working, of the Al-Si coated steel products use radiant heaters.
  • Basic research on the heating behavior of steel products provided with Al-Si coatings has shown in this context that in such furnaces the reflection of the heat radiation at the surface of the respective coating leads to a reduced heating rate in comparison to uncoated or organically or inorganically coated materials. As a result, a relatively long period of time for the warming must be accepted.
  • This long period of time leads to the processor of the provided with an Al-Si coating flat products to long process times, which not only extends the cycle times in component manufacturing, but also increases the cost of the equipment required for the heating furnace.
  • the object of the invention was based on the background of the prior art explained above to provide a method that allows shorter processing times in the processing of Al-Si coated steel products without the risk of corrosive attacks or disadvantages in a subsequent cutting of the coated flat products must be accepted.
  • the steel product processed according to the invention can be a flat steel product, such as a steel sheet or steel strip, or a semi-finished product preformed, for example, from a steel sheet, that is finally deformed in the hot press hardening carried out according to the invention. Also can be processed according to the invention of several composite in the manner of tailored blanks / patchwork blanks sheets.
  • this first alloying step is carried out by setting an appropriate temperature and treatment time so that the Al-Si coating is only partially alloyed with iron of the steel product after the first heating step.
  • the steel product provided with the incompletely ironed-through coating according to the invention can be cooled to room temperature and stored until it is fed to the respective component for further processing. Since the Al-Si coating is only partially alloyed in the first heating step, the Al-Si coating has a low susceptibility to corrosion even after the first heating step, so that its storage, transport and other operations carried out in advance of the second heat treatment are easy can be carried out without the need for additional measures.
  • the coating which has only partially ironed out in the course of the first heating step retains a toughness which, even after the first heating step, still allows the flat products obtained to be cut or cut with simple cutting operations, without resulting in lasting damage to the coating layer ,
  • the flat product obtained after the first heating step and provided with a pre-alloyed coating according to the invention undergoes a second heating step.
  • This second heating step is usually performed at the final processor, while the first heat treatment step to be completed is usually at the producer of the steel products.
  • the second heating step is usually completed immediately before the hot forming.
  • the steel product provided in accordance with the invention with only a pre-alloyed Al-Si coating is heated to the heating temperature required for the subsequent hardening, which is above the Ac1 temperature at which the steel product has an at least partially porous structure.
  • the temperature and duration of the second heating step are to be adjusted according to the invention such that the Al-Si coating is completely alloyed with Fe of the steel product in the course of the second heating step.
  • the coating which according to the invention is only partially alloyed with the steel substrate, has a degree of reflection which, compared with the heating of flat products provided with completely alloyed Al-Si-Fe coatings, has a significantly higher heating rate when heated in radiant furnaces to the heating temperature allowed without causing the coating to drain off.
  • An obtained in accordance with the invention intermediate product is thus characterized in that it with a only with the iron of the steel substrate incompletely pre-alloyed Al-Si coating is provided.
  • the starting material which is now provided with a fully alloyed Si-Al-Fe coating, is then shaped in a manner known per se in a suitable thermoforming tool to form the desired component.
  • the resulting component may be a finished-molded component or a semi-finished product which is subsequently subjected to further deformation steps.
  • thermoforming is finally cooled controlled to produce hardness in the steel substrate.
  • the working steps “thermoforming” and “cooling” can be carried out in particular in the manner known from “compression molding”.
  • the procedure according to the invention thus makes it possible, in a cost-effective and at the same time particularly efficient manner, to provide an aluminized component produced by press-forming hardening within shorter processing times.
  • the expense for the heating step usually carried out at the producer of the steel product is not shortened due to the fact that the process time and the treatment temperature for the partial Al alloying of the Al-Si layer with the iron of the steel substrate are shortened compared with the prior art , but also the usually at the processor of the invention with only incompletely alloyed Al-Si coating carried out second heating step in a shorter process time can run at a correspondingly reduced energy consumption and minimized equipment costs.
  • the temperature of the first heating step is at least 500 ° C, but at the same time at most equal to the A C1 temperature of the steel product.
  • temperatures which are in the range from 550 to 723 ° C., in particular from 550 to 700 ° C. are therefore suitable in particular for the first heating step.
  • the mechanical technological characteristics of the steel product are not deteriorates and the basic structure remains intact in its components.
  • the time to be scheduled for the first heating step at these heating temperatures is 4 to 24 hours when heated in the hood furnace for Al-Si coating thicknesses in the starting state of 10 to 30 ⁇ m (corresponding to 80 to 150 g / m 2 ). It is also conceivable to heat in a continuous furnace or chamber furnace, the heating times in each case be less than one hour.
  • the temperature and duration of the first treatment step are in each case adjusted so that the Al-Si coating, measured starting from the steel substrate, is alloyed with Fe over at least 50%, in particular 70-99%, preferably 90-99%, of its thickness ,
  • the first heating step may be carried out in a bell annealing furnace, chamber furnace or in a continuous annealing furnace.
  • a master alloy in a continuous furnace, which is arranged directly inline at the outlet of a coating plant, similar to a system for galvannealing the case and the heating in a temperature range between 600 and 723 ° C takes place.
  • the steel product obtained according to the invention and provided with a partially alloyed Al-Si coating can be heated to the required heating temperature in a continuous furnace in the second heating step to be heated.
  • the second heating can be effected inductively, conductively or by means of thermal radiation.
  • the samples have been subjected to a heat treatment corresponding to the first heating step of the process according to the invention in a test oven simulated in a crucible annealing furnace for eight hours each time.
  • a first part of samples was annealed at 500 ° C, a second part at 550 ° C and a third part at 600 ° C.
  • further samples have passed through the continuous furnace at 950 ° C in six minutes. This is a typical heat treatment for press-hardening in which the Al-Si coating layer is alloyed. After the respective anneals, the samples were cooled to room temperature.
  • the obtained samples each had a non-fully alloyed Al-Si coating layer except for the sample heat-treated at 950 ° C.
  • the previously annealed and cooled samples are in a second heating step corresponding annealing treatment in a radiant oven to a heating temperature of 950 ° C was heated, in which the steel substrate had austenite microstructure.
  • the heating rates were recorded, ie it was monitored how quickly the samples were heated to the target temperature of 950 ° C.
  • the temperature T of the respective samples is plotted over the annealing time t.
  • the sample annealed for a not annealed in a first heating step upstream (curve "- ° C / - s").
  • the times required for the alloying in the austenitizing furnace before the hot working can be significantly reduced. It was thus shown that a time saving of at least 90 s is expected compared to the conventional procedure can be. With this time saving, the furnaces needed for heating before hot forming can be made smaller. In the maintenance of conventional size ovens cooling to room temperature in about 10 days, whereas in the possible reduction of the furnace size by the invention with a time saving of at least 2 to 3 days can be expected for the cooling.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Physical Vapour Deposition (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Articles (AREA)
EP09705444A 2008-01-30 2009-01-29 Verfahren zur herstellung eines bauteils aus einem mit einem al-si-überzug versehenen stahlprodukt und zwischenprodukt eines solchen verfahrens Active EP2240622B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09705444T PL2240622T3 (pl) 2008-01-30 2009-01-29 Sposób wytwarzania elementu konstrukcyjnego z produktu stalowego wyposażonego w powłokę al-si oraz produkt pośredni tego sposobu

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008006771A DE102008006771B3 (de) 2008-01-30 2008-01-30 Verfahren zur Herstellung eines Bauteils aus einem mit einem Al-Si-Überzug versehenen Stahlprodukt und Zwischenprodukt eines solchen Verfahrens
PCT/EP2009/050980 WO2009095427A1 (de) 2008-01-30 2009-01-29 Verfahren zur herstellung eines bauteils aus einem mit einem al-si-überzug versehenen stahlprodukt und zwischenprodukt eines solchen verfahrens

Publications (2)

Publication Number Publication Date
EP2240622A1 EP2240622A1 (de) 2010-10-20
EP2240622B1 true EP2240622B1 (de) 2011-08-17

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EP09705444A Active EP2240622B1 (de) 2008-01-30 2009-01-29 Verfahren zur herstellung eines bauteils aus einem mit einem al-si-überzug versehenen stahlprodukt und zwischenprodukt eines solchen verfahrens

Country Status (13)

Country Link
US (1) US8349098B2 (pt)
EP (1) EP2240622B1 (pt)
JP (1) JP5666313B2 (pt)
KR (1) KR101539077B1 (pt)
CN (1) CN101932747B (pt)
AT (1) ATE520798T1 (pt)
CA (1) CA2713381C (pt)
DE (1) DE102008006771B3 (pt)
ES (1) ES2368820T3 (pt)
MX (1) MX2010008390A (pt)
PL (1) PL2240622T3 (pt)
PT (1) PT2240622E (pt)
WO (1) WO2009095427A1 (pt)

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JP4860542B2 (ja) * 2006-04-25 2012-01-25 新日本製鐵株式会社 高強度自動車部品およびその熱間プレス方法
JP4725415B2 (ja) * 2006-05-23 2011-07-13 住友金属工業株式会社 熱間プレス用鋼板および熱間プレス鋼板部材ならびにそれらの製造方法
WO2009090443A1 (en) * 2008-01-15 2009-07-23 Arcelormittal France Process for manufacturing stamped products, and stamped products prepared from the same

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EP3889313A4 (en) * 2018-11-30 2021-11-17 Posco ALUMINUM BASED STEEL PLATE FOR HOT PRESSING WITH EXCELLENT RESISTANCE TO HYDROGEN INDUCED BREAKAGE AND POINT WELDABILITY AND METHOD OF MANUFACTURING IT

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CA2713381C (en) 2016-03-29
MX2010008390A (es) 2010-10-04
WO2009095427A1 (de) 2009-08-06
US20110056594A1 (en) 2011-03-10
KR101539077B1 (ko) 2015-07-23
CN101932747B (zh) 2013-02-13
ES2368820T3 (es) 2011-11-22
EP2240622A1 (de) 2010-10-20
US8349098B2 (en) 2013-01-08
ATE520798T1 (de) 2011-09-15
CN101932747A (zh) 2010-12-29
KR20100108608A (ko) 2010-10-07
PT2240622E (pt) 2011-09-30
DE102008006771B3 (de) 2009-09-10
JP2011514440A (ja) 2011-05-06
CA2713381A1 (en) 2009-08-06
PL2240622T3 (pl) 2012-01-31
JP5666313B2 (ja) 2015-02-12

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