WO2013056848A1 - Revêtements anti-incrustation et anticorrosion pour des substrats en acier - Google Patents

Revêtements anti-incrustation et anticorrosion pour des substrats en acier Download PDF

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Publication number
WO2013056848A1
WO2013056848A1 PCT/EP2012/004385 EP2012004385W WO2013056848A1 WO 2013056848 A1 WO2013056848 A1 WO 2013056848A1 EP 2012004385 W EP2012004385 W EP 2012004385W WO 2013056848 A1 WO2013056848 A1 WO 2013056848A1
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WIPO (PCT)
Prior art keywords
steel substrate
hot
metal
coated steel
coating
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PCT/EP2012/004385
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English (en)
Inventor
Douglas Jesus Figueroa Gordon
Tim Harding
Sivasambu BÖHM
Wu Li
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Tata Steel Uk Limited
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Publication of WO2013056848A1 publication Critical patent/WO2013056848A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62—Quenching devices
    • C21D1/673—Quenching devices for die quenching

Definitions

  • the present invention relates to a coated steel substrate and to a method for producing the same.
  • the invention also relates to a method of hot-forming or cold-forming the coated steel substrate to produce hot-formed and cold-formed articles.
  • the invention further relates to the use of the hot-formed and cold-formed articles in the manufacture of automotive vehicles.
  • Hot-forming is usually performed by providing a steel sheet blank, heating the blank in a heating furnace to a temperature between 800 and 1200°C, placing the heated blank in a hot forming press, forming the blank into a part in the hot forming press and hardening the hot formed part.
  • protective metallic coatings are based on zinc or zinc alloys.
  • Zinc or zinc alloy coatings rely on the formation of a diffusion layer to prevent against high temperature oxidation, which diffusion layer comprises at least oxides of zinc.
  • the diffusion layer provides protection against high temperature oxidation of the substrate and ensures good adhesion between the metal coating and the substrate, the thin oxide layer has a negative impact on spot weldability, and therefore an additional process step to remove the oxide layer is required.
  • Another object of the invention is to provide a coated steel substrate having improved weldability properties, particularly with respect to zinc or zinc alloy coated steel substrates, after hot-forming or other high temperature processes.
  • a further object of the invention is to provide a coated steel substrate, which after hot-forming or other high temperature processes, is resistant to corrosion. DESCRIPTION OF THE INVENTION
  • the first aspect of the invention relates to a method of producing a coated steel substrate suitable for hot-forming or other high temperature applications, which comprises the steps of:
  • the above method avoids the problems associated with hot-dip galvanising since the coating mixture can be applied by low temperature application methods such as roller coating, spraying and dipping.
  • the coated steel substrate produced according to the above method exhibits improved oxidation protection relative to bare steel substrates and comparable oxidation protection relative to conventional aluminised and hot-dip galvanised coatings having greater coating layer thicknesses.
  • the coated steel substrate was substantially free from oxide scales after a heat treatment of at least 700"C, and up to 950 ° C in the case of hot-forming.
  • a further advantage is that no red rust or limited amounts of red rust are obtained after the heat treatment and/or hot-forming which is indicative of excellent corrosion protection.
  • the coated substrate After the heat treatment and/or hot-forming the coated substrate also exhibits an electrical resistance as low as 1 mOhm or less. Such a low electrical resistance generally results in excellent spot-weldability and avoids the subsequent step of having to remove a deleterious oxide layer from the coated steel substrate, which is the case for hot-dip galvanised steel substrates.
  • the inventors found that coating mixtures comprising a metal particle and/or a metal alloy particle having an aluminium content greater than 50 weight% were particularly effective in reducing the formation of oxide scales at the steel substrate surface during/after the heat treatment and/or hot-forming or during high temperature service conditions up to 550'C.
  • the non-aluminium metal comprises zinc, magnesium, nickel, copper, tin or mixtures thereof.
  • the presence of these non-aluminium metals reduces the formation of oxide scales at the steel substrate surface by forming a diffusion layer with iron at elevated temperatures above 700 ° C and by forming an intermetallic barrier layer at approximately 900°C.
  • Zinc and magnesium also contribute to improving the corrosion resistance of the intermetallic barrier layer by acting as a sacrificial anode if the barrier layer is damaged. If nickel, copper or tin are used as the non-aluminium metal then the coating mixture should comprise less than 1 wt% of these metals to avoid reduced interfacial bonding between the coating and the substrate.
  • the metal or metal alloy particle is not aluminium.
  • the inventors have found that when the coating mixture comprises particles comprising aluminium and at least 1 wt% of a non-aluminium metal, the corrosion protection afforded to the steel substrate is improved. Increasing the non-aluminium metal content up to 30 wt% further improves the corrosion resistance afforded to the substrate without having a detrimental effect on either the anti-scale properties or the conductivity of the coating.
  • a preferred non-aluminium metal content is between 1 and 20 wt%, more preferably between 10 and 20 wt%.
  • the metal or metal alloy particle is in the form of a powder, flake or a mixture thereof.
  • Aluminium and zinc flakes may be produced by milling and preferably by ball milling. Flakes having a width of 80pm or less and a thickness of 1 ⁇ can be manufactured in this way. Extremely thin flakes may be provided if a physical vapour deposition method is used.
  • the preferred particle size is between 5 and 30 ⁇
  • Particularly preferred metal particle mixtures or metal alloy particles are Al/Zn and Al/Mg/Zn. Commercially available products of such metal alloys include ZnAI 6 Mg 6 and ZnAI 3 Mg 3 .
  • the curable organic binder comprises polyamic acid, preferably an aromatic polyamic acid.
  • the corresponding polyimide When cured, the corresponding polyimide binds together the other constituents of the coating and provides barrier protection to the underlying steel substrate before the coated steel substrate is subjected to the heat treatment and/or hot-forming or used in other high temperature applications such as high temperature service conditions.
  • Other suitable curable organic binders comprise polyesters and polyurethanes.
  • the steel substrate comprises in weight %: ⁇ 0.5 C, ⁇ 3.0 Mn, ⁇ 2.5 Si. More preferably the steel contains in weight %: 0.08 - 0.5 C, 0.5 - 3.0 n, 0.1 - 2.5 Si, ⁇ 0.1 Al, ⁇ 1 .0 Cr, ⁇ 0.2 Ti, ⁇ 0.1 P, ⁇ 0.05 S, ⁇ 0.08 B, ⁇ 0,1 V, ⁇ 0.5 Mo, ⁇ 0.003 ppm Ca, optionally ⁇ 0.1 Nb, unavoidable impurities, the remainder being iron.
  • Steel substrates having the above composition are particularly suitable for hot-forming, cold-forming and for use in high temperature service conditions.
  • the ratio of the organic curable binder and the particulate metal or metal alloy is between 4:1 and 1 :4, preferably between 2:1 and 1 :2. If the organic curable binder: metal ratio is above 4:1 then the spot weldability of the coated steel substrate decreases because the organic binder is insulating. Moreover, if the metal: organic curable binder ratio is above 4:1 then the mechanical and barrier properties of the coating are reduced .
  • the use of an organic curable binder: metal pigment ratio range between 2:1 and 1 :2 provides a coating having good spot weldability, mechanical and barrier properties.
  • the aluminium and/or non-aluminium particle or alloy particle is encapsulated with an encapsulating component prior to the step of preparing the coating mixture.
  • the encapsulation of aluminium and/or the non-aluminium particle such as zinc and magnesium may be necessary to prevent said metals from reacting with water during paint production or storage.
  • the encapsulating component comprises silica, titania, acrylates or derivatives thereof. These encapsulating components have proven particularly effective in preventing aluminium and non-aluminium metals from reacting with water during paint production and storage.
  • the coating mixture additionally comprises a non-metallic conductive component.
  • the non-metallic conductive component comprises ferrophos (Fe 2 P) pigments, micaceous iron oxide, carbon nanotubes, titanium nitride, titanium carbide, tantalum carbide and boron nitride.
  • Fe 2 P ferrophos
  • micaceous iron oxide carbon nanotubes
  • titanium nitride titanium carbide
  • tantalum carbide titanium carbide
  • boron nitride Preferably ⁇ 5 wt% of the non-metallic conductive component is added to the coating mixture. An addition of 1 -4 wt% is most preferred.
  • Ferrophos pigments consist essentially of Fe 2 P although trace amounts of silicon dioxide are also present. These pigments are electrically and thermally conductive and chemically inert under standard atmospheric conditions. Ferrophos has a melting point of 1320°C making it particularly suitable as a conductive component for use in high temperature applications.
  • Micaceous iron oxide (MIO) consists essentially of Fe 2 0 3 and differs from other well known iron oxide pigments.
  • micaceous iron oxide is insoluble in water, organic solvents and alkalis and is only soluble in strong acids which are heated to elevated temperatures.
  • MIO has a melting point in excess of 1500'C and is particularly suitable for use in high temperature applications such as hot-forming.
  • MIO thin flakes having a thickness between 1-7 ⁇ align substantially parallel to the substrate surface to produce a protective barrier of overlapping flakes.
  • the addition of 1 -4 wt% of MIO to the coating mixture is particularly effective in improving the barrier properties of the coating.
  • the coating mixture comprises 30-85 wt% organic solvent, 5-15 wt% organic curable binder, 10-25 wt% particulate metal or metal alloy and 0-5 wt% non-metallic conductive component.
  • the coating mixture comprises 65-80 wt% organic solvent, 5- 10 wt% organic curable binder, 10-20 wt% particulate metal or metal alloy and 1 -4 wt% non- metallic conductive component.
  • the organic solvent is a high boiling point solvent having a boiling point at atmospheric pressure above 100'C. The use of such high boiling solvents improves coating processability and can reduce the occurrence of blisters when the coating mixture is cured.
  • NMP N- methyl-2-pyrrolidone
  • the organic curable binder is a polyamic acid.
  • Polyamic acid is a high molecular weight polyimide precursor in NMP, which when cured is thermally converted into an intractable polyimide film.
  • the coating mixture may also comprise coating additives to improve the dispersability, wetting and processability of the coating mixture before it is cured. These additives will remain in the coating until the coating is heated prior to hot-forming the coated substrate. Additives such DisperpBYK 192 or other copolymers having pigment affinic groups are able deflocculate pigments through steric stabilisation. Coatings comprising such additives show improved wetting and reduced viscosity, which enables higher pigment loads to be used.
  • coating additives include polysiloxanes and/or hydrophobic solids in glycol, which are suitable defoamers for water based systems.
  • An example of a particularly suitable defoamer is BYK019 and BYK024 ®.
  • coatings comprising such additives are easier to apply on substrates through rolling, brushing and spraying applications.
  • Polyether modified siloxanes may also be used to further improve substrate wetting.
  • Alternative additives such as an ion exchange bentonite clay and more preferably a cerium doped bentonite clay can also be used.
  • the coating mixture is dried and cured between 80 and 400°C to remove the organic solvent and to convert the organic curable binder into a dense network coating.
  • the coating exhibits improved coating adhesion relative to the coating mixture and is robust enough to withstand the processing steps prior to hot-forming, for instance during handling and blanking operations.
  • Curing may be performed using electromagnetic radiation such as infrared and preferably near infrared radiation.
  • the second aspect of the invention relates to a coated steel substrate produced according to the method of the first aspect of the invention.
  • the coating of the coated steel substrate has a dry film thickness of 3-30 pm.
  • the inventors have found that coatings having dry film thicknesses below 3 ⁇ did not offer sufficient oxidation protection, whereas a dry film thickness above 30 pm meant that the coatings were prone to delamination.
  • a dry film thickness of 6-20 pm is preferred so that a good balance between coating integrity, flexibility and oxidation protection properties is obtained.
  • the third aspect of the invention relates to a method of producing a hot-formed article comprising the steps of:
  • a hot-forming apparatus comprising a die; iv. quenching the formed coated steel substrate in the die to form the hot-formed article.
  • the substrate When the coated steel substrate is used in hot-forming, the substrate is heated in a heating furnace to a temperature above Ac1 to austenise the steel substrate. The austenised substrate is then transferred to a press where the substrate is press quenched to obtain a hot-formed article having a high tensile strength. Before the Ac1 temperature is reached, the organic film having the dense network structure is 'burnt off (removed) at approximately 600 ° C. The metal or metal alloy particles that are left behind subsequently form a diffusion layer with iron at the steel substrate surface, which provides protection against high temperature oxidation. At approximately 900°C the diffusion layer is converted into an intermetallic barrier layer which is flexible enough to withstand hot-forming.
  • the barrier layer contains metals that corrode in preference to iron as the non-aluminum metal, then the barrier layer additionally provides sacrificial corrosion protection after hot-forming.
  • the intermetallic barrier layer comprises iron alloys of aluminum and the non-aluminum metal, for instance Al-Fe, Zn-Fe, Mg- Fe or a mixture thereof.
  • the fourth aspect of the invention relates to the hot-formed article produced according to the third aspect of the invention wherein the electrical resistance of the hot-formed article is less than 5 mOhm, preferably between 0.1 and 2 mOhm. This has the advantage that the hot- formed article is very suitable for spot welding because no further process is required to increase the conductivity of the hot-formed article.
  • the hot-formed article produced after hot-forming the coated steel substrate of the first aspect of the invention comprises oxide scales having a thickness of 30 pm or less, preferably 6 pm or less. Relative to bare steel substrates, the inventors have found that a significant reduction in oxide scale formation occurs when the coated steel substrate of the invention is used in hot- forming. In most cases oxide scales present at the steel substrate surface had a thickness of 6 pm or less. These coatings were free from cracks and flaking thereby increasing the paintability of such coatings.
  • the fifth aspect of the invention relates to a method for producing a cold-formed article which comprises the steps of:
  • the cured coating of the coated steel substrate is flexible and robust enough to withstand cold- forming. Since the coating is thermally stable up to 600 ° C it can provide protection against high temperature oxidation and corrosion when the cold-formed article is used in high temperature service conditions up to 550"C, for instance in exhausts for automotive vehicles.
  • the sixth aspect of the invention relates to the cold-formed article produced according to the method of the fifth aspect of the invention.
  • the coating of the cold-formed article acts as a protective barrier whereas the metal or metal alloy particles contribute to reducing the formation of oxide scales at the steel substrate surface.
  • the oxidation protection performance of the coated steel substrate is comparable to that of aluminised coatings that are typically used in high temperature service conditions.
  • Advantageously the comparable properties are obtained at reduced coating thicknesses relative to the aluminised coatings. Sacrificial corrosion protection may also be afforded to the substrate when metals that are corroded in preference to iron are used as the non-aluminum metal.
  • the seventh aspect of the invention relates to the use of the hot-formed article according to the fourth aspect of the invention and/or the cold-formed article of the sixth aspect of the invention in the manufacture of automotive vehicles.
  • Example 1 Preparation of a coating mixture
  • Table 1 shows the contribution in weight % of each component of coating mixtures 1-4.
  • a mixing vessel was charged with 80g of aluminium flake paste (Eckart - Stapa ® Hydrolan 1515nl) containing 35 weight% of isoproanol and aluminium particles having a particle size of 13 microns and a particle thickness of less than 1 micron.
  • Eckart - Zn GTT flake particles (20g) were then added which was followed by the addition of 200g of NMP [N-methyl-2-pyrrolidone] and 4g of BYK192 under moderate agitation (500-800rpm).
  • NMP N-methyl-2-pyrrolidone
  • BYK192 moderate agitation
  • a mixing vessel was charged with 80g of aluminium flake paste (Eckart - Stapa ® Hydrolan 1515nl) containing 35 weight% of isopropanol and aluminium particles having a particle size of 13 microns and a particle thickness of less than 1 micron.
  • Eckart - STAPA4 ZnAI6Mg6 flake particles (20g), having a particle size of 15-20 microns, and Ferrophos pigments (10g) were then added to the mixing vessel.
  • Under moderate agitation (500-800rpm) 200g of NMP and 4g of BYK192 were subsequently provided.
  • 200g of Polyamic acid (15.0 wt % ⁇ 0.5 wt%) in NMP (Aldrich chemicals) was then added to this solution, which was then mixed for 10 minutes using a high speed Dispermat with 2000 rpm.
  • a mixing vessel was charged with 40g of aluminium flake paste (Eckart - Stapa ® Hydrolan 1515nl) containing 35 weight% of isoproanol and aluminium particles having a particle thickness of less than one micron and particle size of around 13 micron.
  • Eckardt - Atomised Aluminium Powder 5 WA 58 G 40g having a particle size of 4 micron
  • Eckart - STAPA4 ZnAI6Mg6 flake particles (20g) having a particle size of 15-20 microns
  • Ferrophos pigments (10g) were subsequently added to the mixing vessel.
  • Under moderate agitation (500- 800 rpm) 200g of NMP, 4g of BYK192 and 0.2% BYK024 were subsequently provided.
  • 200g of Polyamic acid (15.0 wt % ⁇ 0.5 wt%) in NMP (Aldrich chemicals) was then added to this solution, which was then mixed for 10 minutes using a high speed Dispermat with 2000 rpm.
  • a mixing vessel was charged with 60g of aluminium flake paste (Eckart - Stapa ® Hydrolan 1515nl) containing 35 weight% of isoproanol and aluminium particles having a particle thickness of less than one micron and a particle size of around 13 micron.
  • Eckardt - STAPA Zn GTT flake particles 40g having a particle size of 15-20 microns were then added which was followed by the addition of 200g of NMP and 4g of BYK192 under moderate agitation (500- 800rpm). to form a mixture.
  • 200g of polyamic acid (15.0 wt % ⁇ 0.5 wt%) in NMP (Aldrich chemicals) was provided and this mixture was mixed for 10 minutes using a high speed Dispermat with 2000 rpm..
  • Coating mixtures 1-4 were applied on a boron steel strip substrate by bar coating or by spray coating to provide a uniform coating thereon. Steel strips provided with the above coating mixtures were subsequently cured using a Mathis oven, having a temperature of 280°C for a period up to 120s, to partially cure the applied coating. Examples of the curing cycles used are shown in Table 2. The peak metal temperature was measured by attaching a K-type thermocouple to the back of the boron steel strip substrate.
  • Table 2 Curing cycles for coated boron steel strip substrates coated with coating mixtures 1 and 2.
  • the partially cured coated boron steel strip substrates were then subjected to a heat treatment (700-900"C) and assessed in terms of their anti-scale properties, corrosion resistance and electrical resistance.
  • the conditions employed during the heat treatment and the results of the assessment are summarised in Table 3.
  • Table 3 Assessment of anti-scale properties, electrical resistance and corrosion resistance for boron steel strip substrates coated with coating mixtures 1 -3 following a heat treatment up to 900'C.
  • the coated steel strips were assessed to determine the presence and thickness of oxide scales after the heat treatment of 900 " C.
  • Coated steel strips were deemed to have excellent anti-scale properties if no oxide scales were observed or if oxide scales having a thickness of 6 pm or less were formed at the boron steel surface.
  • Coated steel strips were deemed to have good anti-scale properties if oxide scales having a thickness between 7 and 30 ⁇ were formed at the boron steel surface.
  • Coated steel strips were deemed to have bad anti-scale properties if oxide scales having a thickness greater than 30 ⁇ were formed at the boron steel surface and/or if the coating cracked or delaminated from the steel surface.
  • Example C1 relates to a bare boron steel substrate which was subjected to the heat treatment under oxidising conditions.
  • the uncoated boron steel strip showed severe oxide scale formation with oxide scales possessing an average thickness of 80 ⁇ .
  • boron steel substrates coated with any one of coating mixtures 1-3 exhibited excellent anti-scale properties.
  • Corrosion resistance was assessed by visual inspection after subjecting the coated steel strip to a cyclic humidity test (relative humidity (100%). Coated steel strips were deemed to have excellent corrosion resistance if there was no formation of red rust. Coated steel substrates were deemed to have good corrosion resistance if 6 or less red rust spots were observed at the steel surface. Coated steel substrates were deemed to have bad corrosion resistance if severe red rust formation was observed. After the heat treatment the bare boron steel substrate (C1 ) was subjected to a cyclic humidity test (relative humidity 100%) for 96 hours, after which severe red rust formation was observed. In contrast boron steel strips coated with the coating composition of Example 2 had excellent corrosion resistance after 250 hours and excellent corrosion resistance after 500 hours, with little to no red rust being observed.
  • a cyclic humidity test relative humidity (100%). Coated steel strips were deemed to have excellent corrosion resistance if there was no formation of red rust. Coated steel substrates were deemed to have good corrosion resistance if 6 or less
  • a lower electrical resistance generally results in better spot weldability.
  • the coated boron steel strips were deemed to have excellent spot weldability if the measured electrical resistance was ⁇ 2 mOhm or less.
  • Coated steel strips were deemed to have good spot weldability if the measured electrical resistance was > 2 ⁇ 5 mOhm.
  • Coated steel strips were deemed to have bad spot weldability if the measured electrical resistance was > 5 mOhm.
  • Table 3 shows that when the coated steel substrates are heated up to 900°C under N 2 , excellent spot weldability properties are obtained. However, the electrical resistance increases to > 2 ⁇ 5 mOhm when the coated substrates are heated under oxidising conditions. The bare steel substrate exhibited bad spot weldability properties.

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Abstract

La présente invention porte sur un procédé de production d'un substrat en acier revêtu approprié pour le formage à chaud ou d'autres applications à haute température, qui comprend les étapes consistant à : (i) utiliser un substrat en acier ; (ii) préparer un mélange pour revêtement comprenant un solvant organique, un liant organique durcissable et des particules métalliques ou d'alliage métallique, les particules métalliques ou d'alliage métallique ayant une teneur en aluminium d'au moins 50 % en poids et le complément inférieur ou égal à 50 % en poids d'un métal qui n'est pas de l'aluminium ; (iii) appliquer le mélange sur le substrat en acier ; et (iv) faire durcir le mélange afin de produire une structure de réseau dense du revêtement sur le substrat en acier.
PCT/EP2012/004385 2011-10-19 2012-10-19 Revêtements anti-incrustation et anticorrosion pour des substrats en acier WO2013056848A1 (fr)

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EP11008420 2011-10-19
EP11008420.9 2011-10-19

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CN103433482A (zh) * 2013-07-31 2013-12-11 江苏麟龙新材料股份有限公司 含有La和Ce的鳞片状多元铝锌硅合金粉末及其制备方法
CN103433480A (zh) * 2013-07-31 2013-12-11 江苏麟龙新材料股份有限公司 含有La，Pr和Nd的鳞片状多元铝锌硅合金粉末及其制备方法
CN104354366A (zh) * 2014-11-13 2015-02-18 常熟市星源金属涂层厂 一种耐磨金属涂层
DE102014004652A1 (de) 2014-03-29 2015-10-01 Daimler Ag Bauteil, insbesondere Strukturbauteil für einen Kraftwagen, sowie Verfahren zum Herstellen eines solchen Bauteils
WO2015149918A1 (fr) 2014-03-29 2015-10-08 Daimler Ag Composant, en particulier composant structural conçu pour un véhicule à moteur et procédé de production d'un tel composant
WO2015160582A1 (fr) * 2014-04-15 2015-10-22 Valspar Sourcing, Inc. Composition de revêtement résistant à la corrosion
DE102014018650A1 (de) 2014-12-13 2016-06-16 Daimler Ag Bauteil, insbesondere Strukturbauteil für einen Kraftwagen, sowie Verfahren zum Herstellen eines solchen Bauteils
EP3184228A1 (fr) 2015-12-22 2017-06-28 Ewald Dörken Ag Utilisation de revetements faisant barriere a oxygene sur des substrats metalliques

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US20100098956A1 (en) * 2005-12-12 2010-04-22 Stefan Sepeur Coating Material for Protecting Metals, Especially Steel, From Corrosion and/or Scaling, Method for Coating Metals and Metal Element
WO2010069588A1 (fr) * 2008-12-19 2010-06-24 Corus Staal Bv Procédé pour la fabrication d'une pièce revêtue à l'aide de techniques de formage à chaud
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CN103433482A (zh) * 2013-07-31 2013-12-11 江苏麟龙新材料股份有限公司 含有La和Ce的鳞片状多元铝锌硅合金粉末及其制备方法
CN103433480A (zh) * 2013-07-31 2013-12-11 江苏麟龙新材料股份有限公司 含有La，Pr和Nd的鳞片状多元铝锌硅合金粉末及其制备方法
CN103433480B (zh) * 2013-07-31 2015-10-21 江苏麟龙新材料股份有限公司 含有La,Pr和Nd的鳞片状多元铝锌硅合金粉末及其制备方法
CN103433482B (zh) * 2013-07-31 2015-10-21 江苏麟龙新材料股份有限公司 含有La和Ce的鳞片状多元铝锌硅合金粉末及其制备方法
DE102014004652A1 (de) 2014-03-29 2015-10-01 Daimler Ag Bauteil, insbesondere Strukturbauteil für einen Kraftwagen, sowie Verfahren zum Herstellen eines solchen Bauteils
WO2015149918A1 (fr) 2014-03-29 2015-10-08 Daimler Ag Composant, en particulier composant structural conçu pour un véhicule à moteur et procédé de production d'un tel composant
WO2015160582A1 (fr) * 2014-04-15 2015-10-22 Valspar Sourcing, Inc. Composition de revêtement résistant à la corrosion
CN106232737A (zh) * 2014-04-15 2016-12-14 威士伯采购公司 耐腐蚀性涂料组合物
CN106232737B (zh) * 2014-04-15 2020-04-21 宣伟投资管理有限公司 耐腐蚀性涂料组合物
CN104354366A (zh) * 2014-11-13 2015-02-18 常熟市星源金属涂层厂 一种耐磨金属涂层
DE102014018650A1 (de) 2014-12-13 2016-06-16 Daimler Ag Bauteil, insbesondere Strukturbauteil für einen Kraftwagen, sowie Verfahren zum Herstellen eines solchen Bauteils
EP3184228A1 (fr) 2015-12-22 2017-06-28 Ewald Dörken Ag Utilisation de revetements faisant barriere a oxygene sur des substrats metalliques

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