EP2839049A1 - Stahlblech mit einer beschichtung mit einem kathodenopferschutz, verfahren zur herstellung eines bauteils mit einem solchen blech und in diesem verfahren hergestelltes bauteil - Google Patents

Stahlblech mit einer beschichtung mit einem kathodenopferschutz, verfahren zur herstellung eines bauteils mit einem solchen blech und in diesem verfahren hergestelltes bauteil

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Publication number
EP2839049A1
EP2839049A1 EP12722750.2A EP12722750A EP2839049A1 EP 2839049 A1 EP2839049 A1 EP 2839049A1 EP 12722750 A EP12722750 A EP 12722750A EP 2839049 A1 EP2839049 A1 EP 2839049A1
Authority
EP
European Patent Office
Prior art keywords
weight
coating
cathodic protection
steel
steel sheet
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.)
Granted
Application number
EP12722750.2A
Other languages
English (en)
French (fr)
Other versions
EP2839049B1 (de
Inventor
Christian Allely
Julie Chassagne
Beril CORLU
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.)
ArcelorMittal SA
Original Assignee
ArcelorMittal Investigacion y Desarrollo SL
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 ArcelorMittal Investigacion y Desarrollo SL filed Critical ArcelorMittal Investigacion y Desarrollo SL
Priority to SI201231186T priority Critical patent/SI2839049T1/en
Priority to HUE12722750A priority patent/HUE037303T2/hu
Priority to PL12722750T priority patent/PL2839049T3/pl
Priority to RS20171316A priority patent/RS56715B1/sr
Priority to PT127227502T priority patent/PT2839049T/pt
Publication of EP2839049A1 publication Critical patent/EP2839049A1/de
Application granted granted Critical
Publication of EP2839049B1 publication Critical patent/EP2839049B1/de
Priority to HRP20171855TT priority patent/HRP20171855T1/hr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12Electrodes characterised by the material
    • C23F13/14Material for sacrificial anodes
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    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
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    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals

Definitions

  • the present invention relates to a steel sheet provided with a sacrificial cathodic protection coating, more particularly intended for the manufacture of automotive parts, without being limited thereby.
  • the other family of metal coatings commonly used for the production of automobile parts is the family of aluminum and silicon-based coatings. These coatings do not generate microcracking in the steel when deformed due to the presence of an Al-Si-Fe intermetallic layer and have good paintability. Although they provide barrier protection and are weldable, they do not provide cathodic protection.
  • the present invention therefore aims to overcome the disadvantages of the coatings of the prior art by providing coated steel sheets having a reinforced protection against corrosion, before and after implementation by stamping, in particular.
  • the sheets When the sheets are intended to be hardened in press, in particular hot-stamped, it also seeks a resistance to the propagation of microcracks in the steel and, preferably, a window of the widest possible use in time and temperature during the heat treatment preceding the curing in press.
  • sacrificial cathodic protection it is sought to achieve an electrochemical potential at least 50 mV more negative than that of steel, a minimum value of -0.75 V compared to a saturated calomel electrode (ECS).
  • ECS saturated calomel electrode
  • the subject of the invention is a steel sheet provided with a sacrificial cathodic protection coating comprising from 5% to 50% by weight of zinc, from 0.1% to 15% by weight of silicon and optionally up to 10% by weight of magnesium and up to 0.3% by weight, in aggregated contents, of elements additional, and further comprising a protective member to be selected from tin in a weight percentage of between 0.1% and 5%, indium in a percentage by weight of between 0.01 and 0.5% and their combinations, the balance consisting of aluminum and residual elements or unavoidable impurities.
  • a sacrificial cathodic protection coating comprising from 5% to 50% by weight of zinc, from 0.1% to 15% by weight of silicon and optionally up to 10% by weight of magnesium and up to 0.3% by weight, in aggregated contents, of elements additional, and further comprising a protective member to be selected from tin in a weight percentage of between 0.1% and 5%, indium in a percentage by weight of between 0.01 and 0.5% and their combinations, the balance consisting of aluminum
  • the sheet according to the invention may further incorporate the following characteristics, taken separately or in combination:
  • the protective element of the coating is tin in a percentage by weight of between 1% and 3%
  • the protective element of the coating is indium in a percentage by weight of between 0.02% and 0.1%
  • the coating comprises 20 to 40% by weight of zinc, and optionally magnesium in a content of 1 to 10% by weight,
  • the coating comprises from 20 to 30% by weight of zinc and optionally magnesium in a content of 3 to 6% by weight,
  • the coating comprises from 8% to 12% by weight of silicon
  • the coating comprises, as a residual element, a content of 2 to 5% by weight of iron,
  • the steel of the sheet comprises, in percent by weight, 0.15% ⁇ C ⁇ 0.5%, 0.5% ⁇ Mn ⁇ 3%, 0.1% ⁇ silicon ⁇ 0.5%, Cr ⁇ 1%, Ni ⁇ 0, 1%, Cu ⁇ 0, 1%,
  • Another object of the invention is constituted by a method of manufacturing a steel part provided with a sacrificial cathodic protection coating comprising the following steps, taken in this order and consisting of:
  • the temperature Tm, the time tm, the thickness of the preliminary coating and its contents of protective element, zinc and optionally magnesium being chosen so that the final average iron content in the upper part of the coating of said part is less than 75% by weight.
  • the thickness of the primer coating is greater than or equal to 27 ⁇ , its tin content is greater than or equal to 1% by weight and its zinc content is greater than or equal to 20% by weight.
  • Another subject of the invention consists of a part provided with a sacrificial cathodic protection coating obtainable by the method according to the invention or by cold stamping of a sheet according to the invention, and which is more particularly intended for the automotive industry.
  • the invention relates to a steel sheet provided with a coating first of all necessarily comprising a protective element to be chosen from tin, indium, and combinations thereof.
  • tin in a percentage of between 0.1% and 5%, preferably between 0.5% and 4% by weight, more particularly preferably between 1 and 3%. % by weight or between 1 and 2% by weight.
  • indium which has a stronger protective power than tin. It may be used alone or in addition to tin, at contents of between 0.01 and 0.5%, preferably between 0.02 and 0.1% and more preferably between 0.05 and 0, 1% by weight.
  • the coatings of the sheets according to the invention also comprise from 5 to 50% by weight of zinc and optionally up to 10% of magnesium.
  • the present inventors have found that these elements make it possible, in combination with the protection elements mentioned above, to reduce the electrochemical potential of the coating with respect to the steel, in media containing or not containing chloride ions.
  • the coatings according to the invention thus have sacrificial cathodic protection.
  • zinc whose protective effect is greater than that of magnesium and which is easier to implement because less oxidizable.
  • the coatings of the sheets according to the invention also comprise from 0.1 to 15%, preferably from 0.5 to 15% and more preferably from 1 to 15%, or even from 8 to 12% by weight of silicon, element which makes it possible in particular to give the sheets high resistance to oxidation at high temperature.
  • silicon allows their use up to 650 ° C without risk of flaking coating.
  • silicon can prevent the formation of a thick layer of iron-zinc intermetallic during a hot dip coating, intermetallic layer that reduces the adhesion and formability of the coating.
  • the presence of a silicon content greater than 8% by weight makes them more particularly capable of being hardened in press and in particular to be shaped by hot stamping. It is preferred to use for this purpose a quantity of between 8 and 12% of silicon. A content greater than 15% by weight is undesirable since primary silicon is formed which could degrade the properties of the coating, in particular the properties of corrosion resistance.
  • the coatings of the sheets according to the invention can also comprise, in cumulated contents, up to 0.3% by weight, preferably up to 0.1% by weight, or even less than 0.05% by weight of elements. additional such as Sb, Pb, Ti, Ca, n, La, Ce, Cr, Ni, Zr or Bi. These various elements may allow, among other things, to improve the corrosion resistance of the coating or its fragility or adhesion, for example. Those skilled in the art who know their effects on the characteristics of the coating will be able to use them according to the complementary aim sought, in the proportion adapted for this purpose which will generally be between 20 ppm and 50 ppm. It was further verified that these elements did not interfere with the main properties sought in the context of the invention.
  • the coatings of the sheets according to the invention may also comprise unavoidable residual elements and impurities resulting, in particular, from the pollution of hot dip galvanizing baths by passage of the steel strips or impurities from the ingots of the same baths or ingots of vacuum deposition processes.
  • a residual element mention may be made of iron which may be present in amounts of up to 5% by weight and in general from 2 to 4% by weight in hot dip coating baths.
  • the coatings of the sheets according to the invention finally comprise aluminum, the content of which may range from about 20% to about 90% by weight. This element makes it possible to provide protection against corrosion of the plates by a barrier effect.
  • the coating may be predominantly composed of zinc or aluminum.
  • the thickness of the coating will preferably be between 10 and 50 ⁇ m. Indeed, below 10 pm, protection against corrosion of the band might be insufficient. Above 50 pm, the corrosion protection exceeds the required level, especially in the automotive field. In addition, if a coating of such thickness is subjected to a significant rise in temperature and / or for long periods, it may melt in the upper part and come to flow on the oven rolls or in the stamping tools , which would deteriorate them.
  • the nature of it is not critical as long as the coating can adhere sufficiently.
  • the steel has a composition that allows the part to reach a tensile strength of 500 to 1600 MPa, depending on the conditions. of use.
  • a steel composition comprising, in% by weight 0, 15% ⁇ C ⁇ 0.5%, 0.5% ⁇ Mn ⁇ 3%, 0, 1% ⁇ Si ⁇ 0.5%, Cr ⁇ 1%, N / ⁇ 0.1%, Cu ⁇ 0.1%, Ti ⁇ 0.2%, Al ⁇ 0.1%, P ⁇ 0.1%, S ⁇ 0 , 05%, 0.0005% ⁇ B ⁇ 0.08%, the balance being iron and unavoidable impurities from steel making.
  • An example of a commercially available steel is 22MnB5.
  • a steel composition comprising: 0.040% ⁇ C ⁇ 0.100%, 0.80% ⁇ Mn ⁇ 2.00%, Si ⁇ 0.30 %, S ⁇ 0.005%, P ⁇ 0.030%, 0.010% ⁇ Al ⁇ 0.070%, 0.015% ⁇ Nb ⁇ 0, 100%, 0.030% ⁇ Ti ⁇ 0.080%, N ⁇ 0.009%, Cu ⁇ 0, 100%, Ni ⁇ 0, 100%, Cr ⁇ 0.100%, Mo ⁇ 0, 100%, Ca ⁇ 0.006%, the balance being iron and unavoidable impurities resulting from the production of steel.
  • the steel sheets can be made by hot rolling and can optionally be re-cold rolled, depending on the final thickness referred to, which can vary, for example, between 0.7 and 3 mm.
  • They may be coated by any suitable means such as an electroplating process or by a deposition process under vacuum or under pressure close to atmospheric pressure, such as deposition by magnetron sputtering, by cold plasma or by evaporation under vacuum, for example, but it will be preferred to obtain them by a hot dipping method in a molten metal bath. It is observed that the superficial cathodic protection is more important for coatings obtained by hot quenching than for coatings obtained by other coating processes.
  • the sheets according to the invention can then be shaped by any method adapted to the structure and shape of the parts to be manufactured, such as for example cold stamping.
  • the sheets according to the invention are more particularly suitable for the manufacture of hardened parts in press, in particular by hot stamping.
  • This method consists of supplying a steel sheet according to the previously coated invention, then cutting the sheet to obtain a blank.
  • This blank is then heated in an oven under a non-protective atmosphere to an austenitization temperature Tm of between 840 and 950 ° C, preferably between 880 and 930 ° C, and then to keep the blank at this temperature Tm for a duration tm between 1 and 8 minutes, preferably between 4 and 6 minutes.
  • the temperature Tm and the holding time tm depend on the nature of the steel but also on the thickness of the sheets to be stamped, which must be entirely in the austenitic field before they are shaped.
  • the speed of rise in temperature also affects these parameters, a high speed (greater than 30 ° C / s for example) to also reduce the holding time tm.
  • the blank is then transferred to a hot stamping tool and then stamped.
  • the resulting part is then cooled either in the stamping tool itself or after transfer to a specific cooling tool.
  • the cooling rate is in all cases controlled according to the composition of the steel, so that its final microstructure after the hot stamping comprises at least one component selected from martensite and bainite, in order to achieve the desired level of mechanical strength.
  • An essential point to ensure that the hot-stamped and hot-stamped part will indeed have a sacrificial cathodic protection is to regulate the temperature Tm, the time tm, the thickness of the preliminary coating and its contents of element (s) of protection, zinc and optionally magnesium such that the final average iron content in the upper part of the coating of the part is less than 75% by weight, preferably less than 50% by weight or even less than 30% by weight.
  • This upper part has a thickness of at least 5 ⁇ . Indeed, under the effect of heating up to the austenitization temperature Tm, iron from the substrate diffuses into the primer coating and increases its electrochemical potential. To maintain a satisfactory cathodic protection, it is therefore necessary to limit the average iron content in the upper part of the final coating of the room.
  • the temperature Tm and / or the holding time tm it is possible to limit the temperature Tm and / or the holding time tm. It is also possible to increase the thickness of the pre-coating to prevent the diffusion front of the iron from reaching the surface of the coating. In this respect, it is preferable to use a sheet having a pre-coating thickness greater than or equal to 27 ⁇ m, preferably greater than or equal to 30 ⁇ or even 35 ⁇ m.
  • Tests were carried out with cold-rolled sheets of 22MnB5 of thickness 1.5 mm, provided with hot-dip coatings comprising, in% by weight, 20% of zinc, 10% of silicon, 3% of iron, 0 , 1% indium, the remainder being made of aluminum and unavoidable impurities, and whose thicknesses are about 15 pm. These sheets were the subject of conventional electrochemical measurements in 5% NaCl medium, with reference to a saturated calomel electrode.
  • the electrochemical potential of the coated sheet is -0.95 V / ECS.
  • the sheet according to the invention thus has a sacrificial cathodic protection. Under the same conditions of measurement, it has been verified that an identical plate but provided with a coating comprising neither zinc nor indium has an electrochemical potential of -0.70 V / SCE, which does not provide cathodic protection to steel.
  • EXAMPLE 2 Al-Si-Zn-Mg-Sn-Fe Coating Tests were carried out with cold-rolled, 1.5 mm thick, 22MnB5 sheets provided with hot-dip coatings comprising in% by weight % silicon, 10% zinc, 6% magnesium, 3% iron and 0.1% tin, the remainder being made of aluminum and unavoidable impurities, and having an average thickness of 17 pm . These sheets were the subject of conventional electrochemical measurements in 5% NaCl medium, with reference to a saturated calomel electrode.
  • the electrochemical potential of the coated sheet is -0.95 V / SCE, while the electrochemical potential of an identical sheet provided with a coating comprising 10% silicon, the rest being made of aluminum and aluminum. unavoidable impurities, is -0.70 V / ECS.
  • the sheet according to the invention thus has a sacrificial cathodic protection.

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  • Chemical & Material Sciences (AREA)
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  • Heat Treatment Of Articles (AREA)
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EP12722750.2A 2012-04-17 2012-04-17 Stahlblech mit kathodischen schutz beschichtung und herstellungsverfahren eines artikels davon Active EP2839049B1 (de)

Priority Applications (6)

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SI201231186T SI2839049T1 (en) 2012-04-17 2012-04-17 Steel sheet, equipped with a cathodic protective sacrificial lining, a process for the manufacture of a product using such sheet metal and the resulting piece
HUE12722750A HUE037303T2 (hu) 2012-04-17 2012-04-17 Acéllemez elfogyó katódos védõbevonattal és eljárás abból egy tárgy elõállítására
PL12722750T PL2839049T3 (pl) 2012-04-17 2012-04-17 Blacha stalowa zaopatrzona w katodową protektorową powłokę ochronną, sposób produkcji wyrobu przez zastosowanie takiej blachy i wyrób tak otrzymany
RS20171316A RS56715B1 (sr) 2012-04-17 2012-04-17 Čelični lim sa žrtvenom katodnom zaštitnom prevlakom i postupak za izradu proizvoda polazeći od tog čeličnog lima
PT127227502T PT2839049T (pt) 2012-04-17 2012-04-17 Chapa de aço dotada com um revestimento de proteção catódica sacrificial, método de fabrico de uma peça utilizando uma tal chapa e peça resultante
HRP20171855TT HRP20171855T1 (hr) 2012-04-17 2017-11-28 Čelični lim s žrtvenom katodnom zaštitnom prevlakom i postupak za izradu proizvoda počevši od navedenog čeličnog lima

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PCT/FR2012/000149 WO2013156688A1 (fr) 2012-04-17 2012-04-17 Tôle d'acier munie d'un revêtement à protection cathodique sacrificielle, procédé de fabrication d'une pièce par mise en oeuvre d'une telle tôle et pièce ainsi obtenue

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WO2015181581A1 (fr) * 2014-05-28 2015-12-03 ArcelorMittal Investigación y Desarrollo, S.L. Tôle d'acier munie d'un revêtement à protection cathodique sacrificielle comprenant du lanthane
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RS56715B1 (sr) 2018-03-30
EA201401136A1 (ru) 2015-03-31
MX2014012626A (es) 2015-05-11
HUE037303T2 (hu) 2018-08-28
NO2839049T3 (de) 2018-03-17
JP2015520797A (ja) 2015-07-23
AU2012377741B2 (en) 2016-03-17
JP6348105B2 (ja) 2018-06-27
AU2012377741A1 (en) 2014-12-04
KR20180017229A (ko) 2018-02-20
PT2839049T (pt) 2018-01-08
US20150284861A1 (en) 2015-10-08
SI2839049T1 (en) 2018-02-28
CA2870532C (fr) 2016-12-13
KR101667131B1 (ko) 2016-10-17
PL2839049T3 (pl) 2018-03-30
BR112014025697B1 (pt) 2020-10-20
EP2839049B1 (de) 2017-10-18
KR101886611B1 (ko) 2018-08-09
ZA201407327B (en) 2017-08-30
WO2013156688A1 (fr) 2013-10-24
EA030016B1 (ru) 2018-06-29
UA112688C2 (uk) 2016-10-10
CN104302802A (zh) 2015-01-21
MX358552B (es) 2018-08-23
HRP20171855T1 (hr) 2018-01-12
KR20150008114A (ko) 2015-01-21
KR20160114735A (ko) 2016-10-05
CN104302802B (zh) 2017-04-12
CA2870532A1 (fr) 2013-10-24
DK2839049T3 (da) 2017-11-20
US10253418B2 (en) 2019-04-09

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