EP2732063B1 - Procédé fournissant un revêtement multifonctionnel sur un substrat métallique - Google Patents

Procédé fournissant un revêtement multifonctionnel sur un substrat métallique Download PDF

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Publication number
EP2732063B1
EP2732063B1 EP12735468.6A EP12735468A EP2732063B1 EP 2732063 B1 EP2732063 B1 EP 2732063B1 EP 12735468 A EP12735468 A EP 12735468A EP 2732063 B1 EP2732063 B1 EP 2732063B1
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EP
European Patent Office
Prior art keywords
layer
lubricating
metal
metal substrate
passivating
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.)
Not-in-force
Application number
EP12735468.6A
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German (de)
English (en)
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EP2732063A1 (fr
Inventor
Helen BRADFORD
Peter Holliman
Vernon John
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.)
Tata Steel UK Ltd
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Tata Steel UK Ltd
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Publication date
Application filed by Tata Steel UK Ltd filed Critical Tata Steel UK Ltd
Priority to EP12735468.6A priority Critical patent/EP2732063B1/fr
Priority to PL12735468T priority patent/PL2732063T3/pl
Publication of EP2732063A1 publication Critical patent/EP2732063A1/fr
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Publication of EP2732063B1 publication Critical patent/EP2732063B1/fr
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    • 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

Definitions

  • the present invention relates to a method of providing a multifunctional coating on a metal substrate.
  • a surface treatment e.g. an oil or chemical surface passivation such as chromate or phosphate to a metal substrate, e.g. steel, zinc and zinc alloy coated steel, tinplate, hot dip galvanised steel to confer corrosion protection of the respective metal or alloy during storage and transport.
  • a surface treatment may affect further downstream processes such as shaping and painting.
  • the friction of the metal surface thus treated can assist or detract from any mechanical deformation process such as simple bending, roll-forming, stamping and deep drawing.
  • the surface may or may not be directly paintable.
  • Metal substrates that have been surface passivated generally require the use of lubricants, typically an oil-in-water emulsion comprising a hydrocarbon in water, in order to provide a low coefficient of friction to effect three dimensionally (3D) shaping operations, such as roll-forming or deep-drawing.
  • lubricants typically an oil-in-water emulsion comprising a hydrocarbon in water
  • the lubricant may need to be removed by degreasing in preparation for subsequent finishing step such as paint pre-treatment of the product and final painting thereof.
  • degreasing fluids results in wastes that have a serious impact on the environment.
  • TOCs Thin organic coatings having thicknesses typically ranging from 1-5 micrometer are known in the art for application to hot dip galvanized steel in order to offer corrosion protection and colour to the underlying metal.
  • a disadvantage of these TOCs is that they are often up to 10 times more expensive than commercially available traditional passivation systems. Furthermore, in forming operations oil-based lubricants may still be required.
  • EP 1 634 932 A1 describes a method of providing a coating to a metal substrate, comprising at least the subsequent steps of applying a first layer to the surface of the metal substrate, and then applying a second layer that can contain solid lubricants and pigments, wherein the first layer contains watersoluble phosphate.
  • a further object is to provide a method of modifying a metal substrate in order to offer improved corrosion resistance, colour, inherent lubricity and direct paintability properties.
  • Yet another object is to provide a method of producing a three-dimensional product from a flat metal substrate, e.g. by one or more 3D deformation steps, that does not need an additional lubricant.
  • the present invention which according to a first aspect defines a method of providing a coating to a passivated surface of a metal substrate, comprising at least the subsequent steps of applying a lubricating layer to the passivated surface of the metal substrate and applying a dyeing layer to the lubricating layer as described in claim 1.
  • a passivated surface of a metal substrate is subjected to a multistep coating process for achieving a multifunctional coated metal substrate having useful properties for further processing in addition to corrosion resistance derived from the passivated surface.
  • a lubricating compound is permanently, chemically, preferably covalently bonded to the passivated surface thereby providing an inherent lubricating property to the metal substrate obviating the need for any additional fluid lubricant, in particular an organic one, in a further forming operation. If needed, water may be used as a coolant for the equipment used.
  • the lubricating layer preferably having hydrophobic properties, repels the water molecules such that an aqueous buffer layer is formed between the two metal surfaces.
  • the inventors found that providing water on the lubricating layer further increases the lubricating properties of the lubricating layer.
  • the dyeing layer is applied to the lubricating layer. It has unexpectedly been discovered that adding dyes to the coating system can further improve lubricity and corrosion resistance, as well as providing surface colour, at least temporarily. In addition to the aesthetic benefit of a coloured metal substrate, the dye offers a tool for quality control by identifying where the lubricating surface treatment has taken place.
  • the dye preferably an ionic dye, is believed to covalently bond to sites of the passivated surface not occupied by the lubricating compound, as well as possibly to the lubricating compound itself.
  • the surface treatment according to the invention affords a multifunctional coating, the functions comprising at least two of corrosion protection, inherent lubricity, colour and direct paintability.
  • inherent lubricity means that additional oil-based lubricants are not needed. Water may be required as a coolant for cooling the tool(s) used, in particular in shaping operations., "Direct paintability” means that the product can be painted directly without the need for further surface preparation or pre-treatment.
  • the lubricating and/or dyeing layers are applied at monomolecular level.
  • the lubricating compound has a hydrophobic nature offering a good lubricating property between the metal substrate treated according to the invention and a shaping tool without needing an additional oil-based fluid lubricant.
  • the metal substrate to which the present method is applied has a passivated surface.
  • chromium free passivation systems are preferred, in particular for hot dip galvanised steel products.
  • the non-chromium (VI) passivation layer of the metal substrate can be obtained by applying a metal phosphate, metal silicate, metal titanate, metal zirconate or other metal oxide type layer, as well as Cr3+ based passivation layers. Surface oxidation of the metal substrate is also possible.
  • the coating weight of such a passivation layer typically ranges from tens of milligrams up to about 1 gram per square meter.
  • the passivation layer is rich in oxide/hydroxide at the surface for bonding of the lubricant and/or dye in the surface treatment according to the invention.
  • the lubricating compound generally comprises a linker group capable of forming a covalent bond to typically a metal oxide surface.
  • Suitable linker groups include silanes, carboxylic acids, sulphates, phosphates.
  • a hydrocarbon chain preferably a saturated one like alkyl, is directly attached to the linker group. Relatively long chained alkyl groups are more preferred.
  • the hydrocarbon chain may be substituted, in particular halogenated. Substituting one or more hydrogen atoms by fluorine atoms in order to obtain a mono- or polyfluorinated derivative is preferred.
  • Another suitable substituent may be selected from anionic substituents like carboxylic acids, sulphates, phosphates in order to control the surface tension of the resultant surface layer.
  • covalently bonding of a polyfluorinated lower carboxylic acid to an oxide/hydroxide rich passivation layer may involve a condensation reaction involving loss of water and the formation of an ester link.
  • Silanes may react via a sol-gel reaction to form a silyl ether linkage.
  • the saturated hydrocarbon chain contains 2 - 20 carbon atoms, preferably 3 - 18 carbon atoms.
  • the lubricant is preferably selected from the group comprising pentafluoropropionic acid, chloroethyldimethyl silane, ethyldimethylchlorosilane, octadecyidimethylchlorosilane, pentadecafluorooctanoic acid and stearic acid.
  • pentadecafluorooctanoic acid is particularly preferred in view of its hydrophobicity and solubility in water.
  • An indication of the inherent lubricating property is hydrophobicity, illustrated by the contact angle between a droplet of water and the surface treated. The higher the contact angle, the less water spreads out, the better the auto-lubricating property.
  • the dye is preferably an ionic dye suitable for covalent binding to unoccupied sites of the passivated surface and to the lubricating compound.
  • Preferred examples of useful anionic dyes comprise rhodamine and copper (II) phthalocyanine-tetrasulphonic acid tetra sodium salt.
  • the coating method is carried out in a continuous manner on a moving metal strip, such as hot dip galvanised steel strip.
  • a second aspect of the invention relates to a metal product having a multifunctional coating the product comprising a metal body, a lower passivation layer, a lubricating layer and an outer dye layer.
  • the metal product according to the invention has a lubricating layer that is permanently bonded to the passivation layer.
  • the lubricating layer is covered with the dye layer.
  • the invention also relates to a method of producing a three dimensional product starting from a flat metal substrate having a passivated surface, the method comprising at least the subsequent steps of applying a lubricating layer to the passivated surface of the metal substrate, applying a dyeing layer to the lubricating layer and 3D deforming of the dyed and lubricated metal substrate.
  • the metal product thus produced may be painted directly in a subsequent step. Again the preferences explained hereinbefore are similarly applicable to this third aspect of the present invention.
  • Samples of a hot dip galvanised steel strip were dipped into a solution of titanium isopropoxide in isopropanol, thereby obtaining a titanate passivation layer.
  • Three different concentrations of isopropoxide were used 0.001 M, 0.01 M and 0.1 M.
  • three lubricity compounds pentafluoropropionic acid, chlorethyldimethyl silane and ethyl dimethylchlorosilane were deposited on the substrates. To determine whether the samples had been successfully treated dye solutions (100 mg/L) were applied.
  • a first sample A received only this passivating treatment.
  • a second sample B was additionally coated with a cloroethyldimethyl silane lubricant.
  • Another sample C received the lubricant followed by rhodamine dye.
  • Experiment 1 was repeating, but using copper (II) phthalocyaninetetrasulphonic acid tetrasodium salt as blue dye. Similar results as in Experiments 1 and 2 were obtained.
  • LFT Linear friction tests
  • a first sample (A) was coated with a titanate passivation layer.
  • a second sample (B) additionally comprised a pentafluoropropionic acid lubricity compound and a third sample (C) comprised an octadecyldimethylchlorosilane lubricity compound.
  • Each sample was tested dry, with deionised water and in the presence of four commercial lubricants (DA Stuart Drawsol 1050E 12% (L1), Castrol Cooledge B1 8% (L2), Gulf Vanishing Oil CN 100% (L3) and Rocol 8% (L4).
  • the LFT results are shown in Table 1.
  • Table 1 shows that the coefficient of friction observed on the dry titania surface was 0.562 and that this value can be reduced by providing a commercial emulsion based lubricant on the titanate surface. The presence of water also reduces the coefficient of friction (0.275) compared to the dry sample.
  • the coefficient of friction observed for sample C was 0.101.
  • the observed CoF values were all higher than the value obtained for the dry sample (C).
  • the observed coefficient of friction for sample C was 0.089. This value is much lower than the values obtained for the dry sample and the samples tested in the presence of the commercial lubricants.

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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)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (16)

  1. Procédé fournissant un revêtement sur un substrat métallique, comprenant au moins les étapes consécutives consistant à appliquer une couche de passivation sur la surface du substrat métallique, à appliquer une couche de lubrification sur la couche de passivation sur le substrat métallique et à appliquer une couche de teinture sur la couche de lubrification, ladite étape de passivation comprenant l'application d'une couche d'oxyde métallique n'étant pas à base de chrome (VI), une couche de phosphate métallique, une couche de silicate métallique ou une couche de titanate métallique sur la surface du substrat métallique et ladite étape de lubrification comprenant la liaison chimique d'un composé lubrifiant à la couche de passivation, le composé lubrifiant étant de nature hydrophobe.
  2. Procédé selon la revendication 1, ledit substrat métallique étant une bande d'acier galvanisée à chaud.
  3. Procédé selon la revendication 1 ou 2, ladite étape de passivation comprenant l'application d'une couche de passivation sans chromate.
  4. Procédé selon l'une quelconque des revendications précédentes, ladite couche de passivation étant riche en oxyde/hydroxyde.
  5. Procédé selon l'une quelconque des revendications précédentes, ladite liaison chimique comprenant une liaison covalente.
  6. Procédé selon l'une quelconque des revendications précédentes, ledit composé lubrifiant étant appliqué à l'échelle moléculaire.
  7. Procédé selon l'une quelconque des revendications précédentes, ledit composé lubrifiant comprenant un groupe lieur, ledit groupe lieur comprenant un silane, un acide carboxylique, un sulfate ou un phosphate.
  8. Procédé selon l'une quelconque des revendications précédentes, ledit composé lubrifiant comprenant une chaîne hydrocarbonée ou une chaîne hydrocarbonée substituée.
  9. Procédé selon la revendication 8, ladite chaîne hydrocarbonée ou ladite chaîne hydrocarbonée substituée étant une chaîne hydrocarbonée saturée contenant 2 à 20 atomes de carbone.
  10. Procédé selon la revendication 8 ou 9, ladite chaîne hydrocarbonée substituée comprenant un halogène et/ou un substituant anionique.
  11. Procédé selon la revendication 10, ledit halogène étant choisi dans le groupe constitué par le fluor ou le chlore et/ou ledit substituant anionique comprenant un acide carboxylique, un sulfate ou un phosphate.
  12. Procédé selon l'une quelconque des revendications précédentes, ledit composé lubrifiant étant choisi dans le groupe comprenant l'acide pentafluoropropionique, le chloroéthyldiméthylsilane et l'éthyldiméthylchlorosilane, l'octadécyldiméthylchlorosilane, l'acide pentadécafluorooctanoïque et l'acide stéarique.
  13. Procédé selon l'une quelconque des revendications précédentes, ladite couche de teinture comprenant un composé colorant choisi parmi les colorants anioniques, en particulier la rhodamine et le sel de tétrasodium d'acide phtalcyanine tétrasulfonique de cuivre (II).
  14. Produit métallique enduit, ledit produit comprenant un corps métallique, une couche de passivation inférieure, une couche de lubrification et une couche de teinture externe, ladite couche de passivation étant une couche d'oxyde métallique n'étant pas à base de chrome (VI), une couche de phosphate métallique, une couche de silicate métallique ou une couche de titanate métallique et ladite couche de lubrification comprenant un composé lubrifiant lié chimiquement à la couche de passivation, ledit composé lubrifiant étant de nature hydrophobe.
  15. Produit métallique enduit selon la revendication 14, ladite couche de lubrification étant liée par covalence à la couche de passivation inférieure.
  16. Procédé de fabrication d'un produit tridimensionnel à partir d'un substrat métallique plat comportant une surface passivée, comprenant au moins les étapes consécutives consistant à appliquer une couche de lubrification sur la surface passivée du substrat métallique, appliquer une couche de teinture sur la couche de lubrification et déformer de façon tridimensionnelle le substrat métallique ainsi enduit, ladite surface passivée comprenant un oxyde métallique n'étant pas à base de chrome (VI), un phosphate métallique, un silicate métallique ou un titanate métallique et l'étape de lubrification comprenant la liaison chimique d'un composé lubrifiant à la surface de passivation, ledit composé lubrifiant étant de nature hydrophobe.
EP12735468.6A 2011-07-13 2012-07-13 Procédé fournissant un revêtement multifonctionnel sur un substrat métallique Not-in-force EP2732063B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP12735468.6A EP2732063B1 (fr) 2011-07-13 2012-07-13 Procédé fournissant un revêtement multifonctionnel sur un substrat métallique
PL12735468T PL2732063T3 (pl) 2011-07-13 2012-07-13 Sposób zapewnienia wielofunkcyjnej powłoki na podłożu metalowym

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11005710 2011-07-13
PCT/EP2012/002952 WO2013007390A1 (fr) 2011-07-13 2012-07-13 Procédé fournissant un revêtement multifonctionnel sur un substrat métallique
EP12735468.6A EP2732063B1 (fr) 2011-07-13 2012-07-13 Procédé fournissant un revêtement multifonctionnel sur un substrat métallique

Publications (2)

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EP2732063A1 EP2732063A1 (fr) 2014-05-21
EP2732063B1 true EP2732063B1 (fr) 2015-12-16

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EP (1) EP2732063B1 (fr)
ES (1) ES2559359T3 (fr)
PL (1) PL2732063T3 (fr)
WO (1) WO2013007390A1 (fr)

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CN109234657A (zh) * 2018-11-22 2019-01-18 江苏齐天铁塔制造有限公司 一种高压输电铁塔的表面处理方法

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JPS61177237A (ja) * 1985-02-02 1986-08-08 日新製鋼株式会社 マフラ−用塗装鋼板およびその製造方法
JP4500113B2 (ja) * 2003-06-16 2010-07-14 Ｊｆｅスチール株式会社 高耐食性表面処理鋼板及びその製造方法

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ES2559359T3 (es) 2016-02-11
PL2732063T3 (pl) 2016-04-29
WO2013007390A1 (fr) 2013-01-17
EP2732063A1 (fr) 2014-05-21

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