WO2011036306A2 - Protection contre la corrosion à base d'alliage au zinc - Google Patents

Protection contre la corrosion à base d'alliage au zinc Download PDF

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Publication number
WO2011036306A2
WO2011036306A2 PCT/EP2010/064368 EP2010064368W WO2011036306A2 WO 2011036306 A2 WO2011036306 A2 WO 2011036306A2 EP 2010064368 W EP2010064368 W EP 2010064368W WO 2011036306 A2 WO2011036306 A2 WO 2011036306A2
Authority
WO
WIPO (PCT)
Prior art keywords
corrosion protection
zinc
steel
protection layer
layer
Prior art date
Application number
PCT/EP2010/064368
Other languages
German (de)
English (en)
Other versions
WO2011036306A3 (fr
Inventor
Hermann Kronberger
Alexander Tomandl
Original Assignee
Voestalpine Stahl Gmbh
Technische Universität Wien
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
Priority claimed from DE102009045074A external-priority patent/DE102009045074A1/de
Priority claimed from DE102009045076A external-priority patent/DE102009045076A1/de
Application filed by Voestalpine Stahl Gmbh, Technische Universität Wien filed Critical Voestalpine Stahl Gmbh
Publication of WO2011036306A2 publication Critical patent/WO2011036306A2/fr
Publication of WO2011036306A3 publication Critical patent/WO2011036306A3/fr

Links

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
    • 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
    • C23C2/06—Zinc or cadmium 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the invention relates in particular to electrolytically produced anticorrosion coatings, in particular those based on zinc, for metallic substrates.
  • steel is electrolytically coated with a layer of zinc or a zinc alloy-based alloy in the art, the less noble zinc acting as a surface sacrificial anode in the event of corrosive attack.
  • the electrolytic coating process or in other chemical reactions during steel processing such.
  • an unavoidable chemical side reaction namely the hydrogen formation on the steel surface.
  • electrolytic zinc galvanizing can only be reduced by optimizing the process parameters, the hydrogen formation, but never completely ⁇ prevented from a thermodynamic point of view.
  • This atomic water present ⁇ material able to diffuse into the steel work into and partly preferably store therein at defects, grain boundaries and interstitial sites of the steel grid.
  • EP discloses 0566121 Bl a process for producing a with a zinc-chromium alloy electroplated steel sheet having excellent adhesiveness to the protective layer and elekt ⁇ rolytisch prepared Corrosion resistant ⁇ ness, which (using an acidic electrolytic bath, the addition of a nonionic organic additive zinc ions Zn 2+ ) and chromium ions (Cr 3+ ) in a molar concentration ratio of 0.1 ⁇ Cr 3+ / (Zn 2+ + Cr 3+ ) ⁇ 0.9 in a total amount of at least 0.5 mol / l.
  • a corrosion-resistant electromagnetic ⁇ lytic coated steel strip which consists of the sub ⁇ strat and comprises at least one basic coating ⁇ layer which is formed on at least one surface side of the steel strip substrate which a simultaneous electrolytic plating on Zinc-chromium-based alloy includes chromium in an amount of 5 wt .-% to 40 wt .-%, the balance being zinc.
  • EP 0607452 Al discloses a steel sheet coated with a zinc-chromium alloy having different phases ⁇ compositions.
  • Zinc-nickel-based anti-corrosion layers are further likely to be limited in the future due to carcinogenic properties of Ni-dusts only applications where no dust generating Nachbear ⁇ processing, eg, carried out by grinding.
  • the hydrogen absorption has a particularly disturbing effect on Zn-based electrolytic plating of high-strength and high-strength steel materials because, unlike conventional steel, it can lead to delayed crack formation there.
  • Zn-based corrosion protection coatings As a guideline for the maximum strength which steels may have for the electrolytic coating, the DIN 50969 specifies 1,000 MPa.
  • the risk of hydrogen embrittlement is too high.
  • Steels must be coated electrolytically ⁇ table with higher strength than 1,000 MPa, so 50969 consuming heat treatments are carried out according to DIN.
  • the steel is coated in the first step with a thin Zn layer ( ⁇ 2ym). This thin-layer Zn allowed by their porosity the off ⁇ drive of the hydrogen introduced through a subsequent thermal treatment. Thereafter, the required layer thickness is adjusted with a new electrolytic coating. This process is very complex and practically impractical in the electrolytic coating of strip steel.
  • the object of the present invention is to provide a corrosion protection layer ⁇ to provide zinc-based, which bility improves the paint and lacquer in particular avoids craters and blisters.
  • Such a hydrogen permeable corrosion protection layer is achieved with the zinc-chromium alloy system.
  • the inventors have found that electrolytically deposited zinc-chromium alloy layers are permeable to hydrogen even at chromium contents of greater than 1%. This is quite überra ⁇ prevalent, since it is known from the prior art that greater than 10%, there is a phase change only with chromium contents. Up to a content of 10%, the electrolytic burn ⁇ different zinc-chromium layer is located as well as a layer of pure zinc present in a hexagonal phase. The phases which are produced via an electrodeposited path differ markedly from the thermodynamically stable phases with the same composition.
  • the hexagonal zinc lattice can also be altered by alloying chromium so that it is permeable to hydrogen.
  • the ratio of the lattice parameters c / a ⁇ 1.75 must be set, which is already the case in the case of an electrolytic coating with chromium content> 1%. It is assumed that the zinc-chromium alloy according to the invention is permeable to hydrogen when the hexagonal lattice is changed such that the ratio of c / a shifts from 1.86 (as in the case of Reinzink) to less than 1.75.
  • a significant advantage of the invention is that for the first time high-strength and high-strength steel materials can be coated electrolytically ⁇ table with a corrosion protection layer based on zinc-chromium, without risking the risk of hydrogen embrittlement.
  • the proportion of chromium in the alloy layer changes the lattice parameters of the hexagonal phase, which is called the delta phase.
  • the delta phase In order to obtain a hydrogen-permeable layer, it is not necessary to deposit a cubic ⁇ - (Zn, Cr) phase, but it is sufficient to set the chromium content just high enough so that the ratio of the lattice parameters in the hexagonal lattice is c / a ⁇ 1.75.
  • the coating is carried out by conventional coating methods such as electrolytic coating with a corrosion protection layer which is permeable to hydrogen.
  • This hydrogen permeability ensures that hydrogen diffused into the material can escape through the alloy layer as far as possible before painting, so that a subsequently applied lacquer layer is not damaged by breaking the anti-corrosion layer. In this way, a Lackkrater- or blistering can be effectively prevented.
  • the concentra ⁇ onshunt of zinc and chromium ions is adjusted such that respect. Chromium supersaturated alloy phases form, the befin outside of thermodynamic equilibrium are the and the processing properties and the corrosion protection in the optimal ratio for use ⁇ .
  • the invention particularly relates to a corrosion protection ⁇ layer comprising primarily zinc, especially for steel ⁇ materials, said corrosion protective layer has a crystalline structure which is permeable to hydrogen.
  • the invention particularly relates to a corrosion- ⁇ onstik für that contains as an alloy component with chromium ei ⁇ nem chromium content> 1%.
  • the invention relates in particular to a corrosion ⁇ protective layer consisting wholly or partially of a hexagonal phase, the ratio of the lattice parameter c / a ⁇ 1.75 is.
  • the invention relates in particular to a corrosion protection layer which contains a zinc gamma phase in addition to the hexagonal phase.
  • the invention further particularly relates to a corrosion ⁇ protective layer is applied electrolytically or by Schmelztauchbe ⁇ layers.
  • the invention furthermore relates, in particular, to a steel component with a corrosion protection layer according to the invention.
  • the invention particularly applies to the use ⁇ dung of a steel component according to the invention for outer skin panels of automobiles.
  • the invention relates in particular to a method for producing a steel component according to the invention, in particular an outer skin sheet, wherein in a first step on the steel electrolytically or by hot dip coating a corrosion protection layer according to the invention is applied and then in a second step by conventional La ⁇ ckiermethoden a one or multilayer paint system is applied.
  • the invention particularly relates to a high- and hö ⁇ herfestes steel component with a corrosion protective layer according to the invention ⁇ .
  • the invention further relates to the use of a steel component fiction, contemporary ⁇ for particularly stressed parts of Au ⁇ tomobilen.
  • the invention further relates, in particular, to a process for producing a high-strength and high-strength steel component according to the invention with an anticorrosive layer of the invention applied electrolytically to the steel.
  • Figure 1 is a pure zinc layer (one side) is applied to a steel substrate, wherein the non-coated Be ⁇ te 10 min long loaded with a current density of 42 mA / cm 2;
  • FIG. 2 shows the zinc-chromium layer according to the invention (one-sided) on a steel substrate, wherein the uncoated side was charged for 25 minutes with a current density of 42 mA / cm 2 ;
  • Figure 3 the zinc-chromium layer of the invention on a
  • Figure 4 the inventive zinc-chromium layer of Figure 3 with an over-galvanized 7 ⁇ thick layer of pure zinc and then re-loading for 20 minutes the uncoated side with a current density of 42 mA / cm 2 .
  • Figure 1 shows a 10 min loaded with pure zinc layer with egg ⁇ ner current density of 42 mA / cm 2 steel sample. In addition to the fine-grained, original origina To see the zinc surface structure 3 the newly added many small bubbles 1.
  • FIG. 2 shows a steel sample coated with the zinc-chromium layer according to the invention and then loaded for 25 minutes with a current density of 42 mA / cm 2 . It is shown here that even at 15 minutes of charging time longer than that of the pure zinc layer, the zinc-chromium layer has no bubbles, son ⁇ countries retains its coarse surface structure. 4
  • Figure 3 shows the zinc-chromium layer of the invention on egg ⁇ ner steel sample, not loaded the Part A and Part B is loaded with egg ⁇ ner current density of 42 mA / cm 2. There are no differences in the surface condition between part A and part B.
  • the steel sample with the zinc-chromium layer according to the invention from FIG. 3 is provided with a 7 ⁇ m thick and thus hydrogen-impermeable zinc layer and then again with a current density of 42 mA for 20 minutes. cm 2 loaded.
  • a considerable number of lacquer craters 2 which only occur in part B '(loaded part), can be seen. It can be concluded indirectly that he ⁇ -making contemporary zinc-chromium layer for hydrogen must and it is not damaged for this reason be transparent. The damage only occurs in the case of the water-permeable zinc layer.

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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)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne une couche de protection contre la corrosion contenant principalement du zinc et destinée notamment à des matériaux en acier, la couche de protection contre la corrosion étant perméable à l'hydrogène. L'invention porte également sur un élément en acier pourvu que cette couche et sur un procédé pour fabriquer un élément en acier.
PCT/EP2010/064368 2009-09-28 2010-09-28 Protection contre la corrosion à base d'alliage au zinc WO2011036306A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102009045074.2 2009-09-28
DE102009045074A DE102009045074A1 (de) 2009-09-28 2009-09-28 Korrosionsschutz auf Zink-Legierungsbasis
DE102009045076A DE102009045076A1 (de) 2009-09-28 2009-09-28 Korrosionsschutz auf Zink-Legierungsbasis
DE102009045076.9 2009-09-28

Publications (2)

Publication Number Publication Date
WO2011036306A2 true WO2011036306A2 (fr) 2011-03-31
WO2011036306A3 WO2011036306A3 (fr) 2011-07-07

Family

ID=43638708

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/064368 WO2011036306A2 (fr) 2009-09-28 2010-09-28 Protection contre la corrosion à base d'alliage au zinc

Country Status (1)

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WO (1) WO2011036306A2 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0285931A1 (fr) 1987-03-31 1988-10-12 Nippon Steel Corporation Bande d'acier résistant à la corrosion et procédé de fabrication
EP0607452A1 (fr) 1992-07-10 1994-07-27 Kawasaki Steel Corporation Tole en acier resistant a la rouille et presentant des caracteristiques ameliorees y compris la resistance a la corrosion
EP0566121B1 (fr) 1992-04-16 1997-07-02 Kawasaki Steel Corporation Procédé de production d'une feuille d'acier recouverte d'un alliage zinc-chrome d'une excellente adhérence
US20080131721A1 (en) 2005-05-11 2008-06-05 Tran Luong Louie M Low hydrogen embrittlement zinc/nickel plating for high strength steels

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0885897A (ja) * 1994-09-20 1996-04-02 Kawasaki Steel Corp 塗装後耐食性に優れたＺｎ−Ｃｒ−Ｃ系めっき鋼板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0285931A1 (fr) 1987-03-31 1988-10-12 Nippon Steel Corporation Bande d'acier résistant à la corrosion et procédé de fabrication
EP0566121B1 (fr) 1992-04-16 1997-07-02 Kawasaki Steel Corporation Procédé de production d'une feuille d'acier recouverte d'un alliage zinc-chrome d'une excellente adhérence
EP0607452A1 (fr) 1992-07-10 1994-07-27 Kawasaki Steel Corporation Tole en acier resistant a la rouille et presentant des caracteristiques ameliorees y compris la resistance a la corrosion
US20080131721A1 (en) 2005-05-11 2008-06-05 Tran Luong Louie M Low hydrogen embrittlement zinc/nickel plating for high strength steels

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JAMES H. LINDSAY: "The Systems View in Automotive Finishes - Essential but Overlooked", PLATING AND SURFACE FINISHING, 1997, pages 14 - 21
JOURNAL OF ALLOYS AND COMPOUNDS, vol. 480, no. 2, 8 July 2008 (2008-07-08), pages 259 - 264

Also Published As

Publication number Publication date
WO2011036306A3 (fr) 2011-07-07

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