EP2992127B1 - Procédé de traitement de surface d'un substrat métallique - Google Patents

Procédé de traitement de surface d'un substrat métallique Download PDF

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Publication number
EP2992127B1
EP2992127B1 EP14728808.8A EP14728808A EP2992127B1 EP 2992127 B1 EP2992127 B1 EP 2992127B1 EP 14728808 A EP14728808 A EP 14728808A EP 2992127 B1 EP2992127 B1 EP 2992127B1
Authority
EP
European Patent Office
Prior art keywords
solution
protective coating
corrosion
range
hydrozincite
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.)
Active
Application number
EP14728808.8A
Other languages
German (de)
English (en)
Other versions
EP2992127A1 (fr
Inventor
Gerald Luckeneder
Karl-Heinz Stellnberger
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.)
Voestalpine Stahl GmbH
Original Assignee
Voestalpine Stahl GmbH
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 Voestalpine Stahl GmbH filed Critical Voestalpine Stahl GmbH
Priority to PL14728808T priority Critical patent/PL2992127T3/pl
Publication of EP2992127A1 publication Critical patent/EP2992127A1/fr
Application granted granted Critical
Publication of EP2992127B1 publication Critical patent/EP2992127B1/fr
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Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • 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
    • 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
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon

Definitions

  • the invention relates to a method for the surface treatment of a metallic substrate, in particular steel sheet, with a protective coating based on Zn, in which a chloride-containing solution is applied to this protective coating and thereby a corrosion protection layer comprising hydrozincite and simoncollect is formed at least in some areas.
  • WO2012 / 091385A2 propose to set the weight ratios of Al and Mg in the protective coating based on Zn so that the formation of Simonkolleit is easier in the event of corrosion. It is proposed that the protective coating should have a ratio of Al to (Mg + Al) in a range from 0.38 to 0.48.
  • compositional regulations disadvantageously cause a comparatively high outlay, in particular if protective coatings are to be applied to a metal sheet by means of a hot-dip process - the reproducibility of the process is therefore difficult to ensure.
  • such regulations mostly only lead to a compromise between improved corrosion behavior on the one hand and undesirable changes in mechanical, chemical and / or electrical properties on the other. The usability of the sheet coated in this way can be significantly restricted.
  • JP 01127683A the JP 04165082A and the JP 2011168855A for steel sheets, coatings containing Zn, Mg and / or Al.
  • the invention is therefore based on the task, starting from the prior art described at the outset, of changing a method for surface treatment of a sheet coated with a protective layer based on Zn in such a way that the corrosion resistance is increased, the range of fluctuation is reduced and its production is accelerated.
  • a high reproducibility of the process should be ensured and the process should be applicable regardless of the composition of the protective coating based on Zn.
  • the invention solves the problem set by the process features of claim 1, wherein the protective coated substrate with the, adjusted with the aid of an acid to a pH in the range of 4 to 6 and having 1.8 to 18.5 wt .-% chloride Solution to form an increased proportion of Simonzolleitreact in the corrosion protection layer compared to the hydrozincite.
  • Preferred embodiments of the method are defined in claims 2 to 10.
  • the protective-coated substrate reacts with the solution which has been adjusted to a pH in the range from 4 to 6 and has from 1.8 to 18.5% by weight of chloride with the aid of an acid, a particularly advantageous corrosion protection layer can be achieved on the protective coating .
  • This solution according to the invention in particular also water-based, can considerably favor the formation of Simonkolleit on the treated or corroded surface of the protective coating.
  • the composition of the anticorrosive layer can be influenced in one direction in such a way that an increased proportion of Simoncollegium compared to the hydrozincite fraction. This means that the protective-coated substrate can be expected to be highly resistant to corrosion.
  • this directional treatment or corrosion of the protective coating can be carried out independently of the composition of a protective coating based on Zn - any compositions can therefore be improved with regard to their corrosion resistance.
  • a universally applicable and reproducible process can therefore be made available in which the influence of a hot-dip process on corrosion resistance or its fluctuation range with regard to the layer thickness, its continuity and composition can be significantly reduced.
  • the method according to the invention for increasing the corrosion resistance can be distinguished in particular if the protective coating has a Zn-Al-Mg base to which the chloride-containing solution is applied and thereby at least in some areas a corrosion protection layer comprising hydrozincite, simoncollect and hydrotalcite is formed.
  • a corrosion protection layer comprising hydrozincite, simoncolleite and hydrotalcite.
  • Their corrosion-prone and superficial intermetallic phases can be supplemented with Simonkolleit and become more corrosion-resistant. This also resulted in a comparatively compact surface coating, which in turn can lead to increased mechanical strength of the protective coating.
  • the improved connectivity achieved in this way can be used for further layers, for example lacquers or the like, on this protective coating.
  • the production of the protective coating which is improved in corrosion resistance, is accelerated and the process can therefore be carried out comparatively quickly.
  • a solution which has 5 to 30% by weight NaCl has proven to be particularly advantageous. This is not only inexpensive and easy to manufacture, it also has a positive procedural influence. 5 to 10% by weight of NaCl can be particularly suitable in order to ensure a sufficiently high proportion of chloride in the solution for the process.
  • the solution applied to the protective coating consists of water, NaCl and HCl.
  • this solution can also have inevitable impurities due to the manufacturing process.
  • This solution which was easy to manufacture, was found to be particularly advantageous in the reaction with a Zn-Al-Mg protective coating, in which a proportion of Simonkolleit of over 80% was formed in the treated areas of the protective coating.
  • a comparatively high proportion of Simonkolleit can be ensured by the solution reacting with the coating for a maximum of 20 minutes. Even with this relatively short reaction time, the method according to the invention can ensure a particularly fast process and can subsequently also be used for industrial purposes.
  • reaction time of the solution with the protective coating can be reduced even further if the metallic substrate is anodically charged during the reaction with the solution.
  • the formation of Simonkolleit can be favored and the process can be further accelerated.
  • the invention can be particularly distinguished in the case of protective coatings based on Zn, which are applied to the sheet by means of a hot-dip process, that is to say produced on the sheet.
  • Known parameter fluctuations in the hot-dip process which can influence the corrosion resistance of the protective coating formed with it, can thus be compensated for.
  • the method according to the invention can therefore ensure the highest level of corrosion protection on metal sheets in a particularly reproducible manner.
  • reaction of the solution with the protective coating forms a corrosion protection layer with a layer thickness in the range from 150 nm to 1.5 ⁇ m, a result in a sufficiently compact reaction layer with Simonkolleit in order to reproducibly increase the corrosion resistance of the protective-coated substrate.
  • the chemical resistance of the protective coating based on Zn can be increased further if the reaction of the solution with the protective coating forms a corrosion protection layer with a proportion of at least 80%, in particular at least 90%, of Simonkolleit.
  • the method according to the invention can be distinguished in particular in the case of a Zn-Al-Mg protective coating in which the quotient of Al / (Al + Mg) is in the range from 0.5 to 1.0, in particular if the quotient of Al / (Al + Mg) is 0.5.
  • Table 1 Overview of the investigated protective coated steel sheets 1, 2, 3 Composition of the solution Simonkolleit Hydrozincite Hydrotalcite 1 no treatment undefined / variable 2nd 5% NaCl with a pH of 4-5 90% 5% 5% 3rd 10% NaCl with a pH of 5 90% 5% 5%
  • the protective-coated sheets treated with the solution according to the invention each showed compact corrosion-protective layers with layer thicknesses in the range from 150 nm to 1.5 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Claims (10)

  1. Procédé de traitement de surface pour l'amélioration de la résistance à la corrosion d'un substrat métallique, en particulier d'une tôle d'acier, muni d'un revêtement de protection à base de zinc, dans lequel une solution contenant un chlorure est appliquée sur ce revêtement protecteur et une couche de protection contre la corrosion contenant de l'hydrozincite et de la simonkolléite est ainsi formée, caractérisé en ce que le substrat muni du revêtement de protection réagit avec la solution, ajustée à un pH compris entre 4 et 6 à l'aide d'un acide et contenant entre 1,8 et 18,5 % en poids de chlorure, pour former une proportion de simonkolléite plus élevée que la proportion d'hydrozincite dans la couche de protection contre la corrosion, la solution réagissant pendant 20 minutes au maximum avec le revêtement et la réaction de la solution avec le revêtement protecteur formant une couche de protection contre la corrosion d'une épaisseur comprise entre 150 nm et 1,5 µm.
  2. Procédé selon la revendication 1, caractérisé en ce que le revêtement protecteur comporte une base de Zn-Al-Mg sur laquelle la solution contenant un chlorure est appliquée et une couche de protection contre la corrosion, contenant de l'hydrozincite, de la simonkolléite et de l'hydrotalcite, est ainsi formée au moins par zones.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la solution contient 5 et 30 % en poids, en particulier entre 5 et 10 % en poids, de NaCl.
  4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce que le pH des solutions est ajusté à l'aide de HCl.
  5. Procédé selon la revendication 4, caractérisé en ce que la solution appliquée sur le revêtement protecteur se compose d'eau, de NaCl et de HCl.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que le substrat métallique reçoit une charge anodique lors de la réaction avec la solution.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la température de la solution est ajustée dans une plage de 30 à 60° Celsius.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le revêtement protecteur à base de zinc est appliqué sur la tôle à l'aide d'un procédé d'immersion en bain de fusion.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que la réaction de la solution avec le revêtement protecteur forme une couche de protection contre la corrosion contenant une proportion de simonkolléite d'au moins 80 %, en particulier d'au moins 90 %.
  10. Procédé selon l'une des revendications 2 à 9, caractérisé en ce que le quotient d'Al/(Al+Mg) dans le revêtement protecteur Zn-Al-Mg est compris entre 0,5 et 1,0, de préférence est de 0,5.
EP14728808.8A 2013-04-29 2014-04-29 Procédé de traitement de surface d'un substrat métallique Active EP2992127B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14728808T PL2992127T3 (pl) 2013-04-29 2014-04-29 Sposób obróbki powierzchni metalowego podłoża

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50294/2013A AT514229B1 (de) 2013-04-29 2013-04-29 Verfahren zur Oberflächenbehandlung eines metallischen Substrats
PCT/AT2014/050110 WO2014176621A1 (fr) 2013-04-29 2014-04-29 Procédé de traitement de surface d'un substrat métallique

Publications (2)

Publication Number Publication Date
EP2992127A1 EP2992127A1 (fr) 2016-03-09
EP2992127B1 true EP2992127B1 (fr) 2020-07-08

Family

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Application Number Title Priority Date Filing Date
EP14728808.8A Active EP2992127B1 (fr) 2013-04-29 2014-04-29 Procédé de traitement de surface d'un substrat métallique

Country Status (8)

Country Link
US (1) US10011896B2 (fr)
EP (1) EP2992127B1 (fr)
JP (1) JP6865580B2 (fr)
CN (1) CN105378153B (fr)
AT (1) AT514229B1 (fr)
ES (1) ES2822378T3 (fr)
PL (1) PL2992127T3 (fr)
WO (1) WO2014176621A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6686653B2 (ja) * 2016-04-13 2020-04-22 日本製鉄株式会社 めっき鋼材
DE102018216317A1 (de) * 2018-09-25 2020-03-26 Thyssenkrupp Ag Verfahren zur Modifikation von feuerverzinkten Oberflächen
CN109750280A (zh) * 2019-03-18 2019-05-14 北京科技大学 一种提高碳钢耐蚀性的表面处理方法
CN110735098A (zh) * 2019-10-22 2020-01-31 首钢集团有限公司 一种耐黑变锌铝镁镀层钢板及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01127683A (ja) 1987-11-12 1989-05-19 Kobe Steel Ltd 耐食性に優れたＺｎ−Ｍｇ合金蒸着めっき材料
JP2654861B2 (ja) * 1990-10-27 1997-09-17 新日本製鐵株式会社 鉄心の加工性および耐熱性の優れた方向性電磁鋼板の絶縁皮膜形成方法
KR100268150B1 (ko) * 1997-05-29 2000-10-16 윤종용 복합 영상신호의 동기 신호 재생 회로
EP2186928A1 (fr) * 2008-11-14 2010-05-19 Enthone, Inc. Procédé pour le post-traitement des couches métalliques
JP2011168855A (ja) * 2010-02-19 2011-09-01 Nisshin Steel Co Ltd 端面耐食性に優れた塩ビ塗装鋼板
KR20120075235A (ko) * 2010-12-28 2012-07-06 주식회사 포스코 고내식 용융아연합금 도금강판과 그 제조방법

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Title
None *

Also Published As

Publication number Publication date
JP2016519220A (ja) 2016-06-30
US20160083828A1 (en) 2016-03-24
ES2822378T3 (es) 2021-04-30
CN105378153A (zh) 2016-03-02
WO2014176621A1 (fr) 2014-11-06
AT514229B1 (de) 2015-02-15
AT514229A1 (de) 2014-11-15
PL2992127T3 (pl) 2021-02-08
JP6865580B2 (ja) 2021-04-28
US10011896B2 (en) 2018-07-03
EP2992127A1 (fr) 2016-03-09
CN105378153B (zh) 2018-10-12

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