EP2510061A2 - Revêtements protecteurs pour substrats - Google Patents
Revêtements protecteurs pour substratsInfo
- Publication number
- EP2510061A2 EP2510061A2 EP10795940A EP10795940A EP2510061A2 EP 2510061 A2 EP2510061 A2 EP 2510061A2 EP 10795940 A EP10795940 A EP 10795940A EP 10795940 A EP10795940 A EP 10795940A EP 2510061 A2 EP2510061 A2 EP 2510061A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- metal
- coated steel
- coated
- weight
- 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.)
- Withdrawn
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 69
- 239000011253 protective coating Substances 0.000 title description 9
- 238000000576 coating method Methods 0.000 claims abstract description 144
- 239000011248 coating agent Substances 0.000 claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000008199 coating composition Substances 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- 239000004411 aluminium Substances 0.000 claims abstract description 35
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000077 silane Inorganic materials 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000002923 metal particle Substances 0.000 claims abstract description 11
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 10
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 117
- 239000010959 steel Substances 0.000 claims description 117
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 31
- 229910000712 Boron steel Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 23
- 238000002156 mixing Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000005507 spraying Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- -1 aluminum metals Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical compound CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
-
- 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
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
Definitions
- the present invention relates to a coated cold-rolled steel substrate comprising a water reducible coating composition and a process for the manufacture of a cure coated steel article, which steel article is produced by hot-forming or cold-forming.
- water reducible coating composition and a coated metal substrate wherein use is made of the said water reducible coating composition.
- the invention further relates to processes for the manufacture of hot-formed and cold-formed metal articles, wherein use is made of the coated metal substrate, hot-formed and cold-formed articles produced by said processes and a cured coated substrate intermediate.
- the permanent deformation of a metal may be accomplished by applying a thermo-mechanical treatment to the metal surface.
- the primary objective of applying such a treatment is to produce a metal article having a certain shape or size or to improve certain physical properties such as strength.
- the heating must be performed in a non- oxidising atmosphere to suppress the formation of oxide scales and decarburisation of its surface layers.
- the steel substrate is typically heated up to austenisation temperatures ⁇ 950'C for approximately 5-10 minutes.
- the requirement to heat steel to temperatures of approximately 950 ° C in an inert atmosphere further increases the costs of the hot-forming process.
- the steel surface is exposed to atmospheric oxygen prior to hot-forming, which inevitably leads to scale formation.
- the scale layer is rough, brittle, flakes off and does not constitute a basis for subsequent processing such as spot welding or painting.
- Scale removal can be achieved through shot blasting, pickling or the like, but this results in a considerable cost increase. Further, if shot blasting is employed, the shape of the formed article may deteriorate.
- Anti-scale coatings can be used to reduce oxide scale formation during hot-forming. Such coatings are based on compositions containing binders, metallic pigments and high concentrations of organic and/or inorganic solvents. However, the use of such solvents in high concentrations can be problematic both in terms of handling and the environment. As a consequence it is often necessary to incorporate incinerators into coating lines.
- Another problem of current anti-scale coatings is that after the hot-forming process many of the coatings show reduced welding performance and in certain cases are not spot weldable, meaning a further process step is required to remove the coating. This effect is typically observed when after hot-forming, the electrical resistance of the coating is too high (> 5 mOhms), which prevents sufficient flow of welding current and leads to an inconsistent welding range.
- a coated cold-rolled steel substrate comprising a water-reducible coating composition, which coating composition comprises water, an organic solvent, a silane as binder, a coating additive and a metal, wherein the metal is a metal particle or a metal alloy particle having an aluminium content greater than 50 weight % and a balance of less than 50 weight % of a non-aluminium metal, and wherein the coating has a wet film thickness in the range of 6 m to 90 ⁇ .
- a water reducible coating is more environmentally friendly and very suitable for coating bare steel substrates that are to be hot-formed.
- cold-rolled steel substrates which are first coated with the water reducible coating and then hot- formed exhibit a reduction in oxide scale formation at the steel surface, improved corrosion resistance, improved paintability and a conductivity that permits hot-formed coated steel substrates to be spot welded.
- the coating should contain a metal particle and/or a metal alloy particle having an aluminium content greater than 50 weight% otherwise the coatings have reduced corrosion resistance, exhibit reduced spot weldability and are less effective at preventing oxidation of the steel substrate.
- the coating comprises a metal particle and/or a metal alloy particle comprising zinc and/or magnesium as the non-aluminium metal.
- a non-aluminium metal particle or a metal alloy particle such as zinc and/or magnesium further improves the corrosion resistance of the coating since zinc and magnesium prevent oxidation of iron in steel by forming a protective barrier and by acting as a sacrificial anode if this protective barrier is damaged.
- the metal particle or metal alloy particle which comprises greater than 50 weight % aluminium and a balance of less than 50 weight % of a non-aluminium metal such as zinc and/or magnesium may be provided in the form of a flake, an alloyed flake, a pigment, a powder or mixtures 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 pm 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 30pm.
- the inventors also found that by increasing the non- aluminium metal content to 20 and 30 weight %, further improvements in sacrificial corrosion protection could be obtained and that the overall corrosion protection of the coatings also improved without having a detrimental effect on either the anti-scale properties or the conductivity of the coating.
- Another advantage of the water reducible coating is that the aluminum and non aluminum metals such as zinc and magnesium act to increase the conductivity of the coating to an extent where it is possible to spot weld hot-formed steel substrates.
- the inventors also found that bare cold-rolled steel substrates which were coated with the water reducible coating and which were heat treated under inert or reducing conditions and subsequently hot-formed, exhibited a further reduction in oxide scale formation at the steel surface, improved corrosion resistance properties and improved welding range.
- the observed reduction in oxide scale formation at the steel surface may also be attributed, in part, to the presence of the silane binder, which during a heat treatment that precedes hot- forming and/or during hot-forming, converts the coating composition into a dense protective coating (coating consolidation).
- the thermal energy from the heat treatment also sinters the metal particle and/or the metal alloy particle to further reduce the occurrence of oxides at the steel surface.
- the heat treatment is carried out under non-oxidising conditions to minimise oxidation of the coating.
- the water reducible coating has a wet film thickness in the range of 6 ⁇ to 90 ⁇
- the wet film thickness should be 90 ⁇ at most since thicker coatings are not compatible with high speed coil coating lines.
- the wet coating thickness should be no lower than 6 ⁇ otherwise the coating may not be robust enough to survive the heat treatment and/or hot-forming.
- the cold-rolled steel substrate is a hot-formable steel or a boron steel.
- the steel may be a steel strip, sheet or blank.
- hot- formable steels and boron steels which have been coated with the water reducible coating are able to withstand high temperature hot-forming conditions and also exhibit a reduction in the extent of oxidation at the steel surface.
- the non-aluminium metal comprises zinc, magnesium, nickel, copper, tin, molybdenum or mixtures thereof.
- the presence of zinc and/or magnesium improves the sacrificial corrosion protection properties of the water reducible coating when it is applied on steel.
- the addition of nickel, copper, tin or molybdenum can further increase the conductivity of the coating to an extent whereby it is possible to spot weld the formed steel substrate.
- the aluminium and/or non-aluminium metal particle or alloy particle is encapsulated with silica, titania, acrylates or derivatives thereof.
- the non-aluminium is magnesium and/or zinc. The encapsulation of aluminium, magnesium or zinc may be necessary to prevent said metals reacting with water, which is present in the water reducible coating composition of the invention.
- the water reducible coating composition contains in weight %: 15 to 80 %, preferably 25 to 70 % water; 0 to 35 %, preferably 0 to 25 % , more preferably 0 to 10 % and even more preferably 0 to 2 % organic solvent; 10 to 35 %, preferably 15 to 30 % silane binder; 0.5 to 3 %, preferably 1 to 2 % of a coating additive and 10 to 35 %, preferably 15 to 30 % metal, wherein the water reducible coating composition amounts to 100 weight %.
- coatings having a water content between 15 and 80 weight % were particularly suitable for coil coating and that the viscosity and the solids content could be controlled by varying the amount of water in the coating or by adding a coating additive such as a viscosity modifier. It is preferable to keep the organic solvent content as low as possible and preferably the organic solvent content is 0%. Increasing the silane binder content to above 30 weight % may reduce the conductivity of the coating whereas coatings having a binder content below 10% may not provide sufficient mechanical and barrier properties during the heat treatment and/or hot forming.
- the water reducible coating composition comprises a coating additive content of 0.5 to 3% to improve the processability of the coating. Coatings comprising a coating additive content below 0.5 weight % do not provide enough functional benefits, for example, the dispersability and/or wettability of the coating is reduced, whereas coatings comprising a coating additive content above 3% will be detrimental to the processability of the coating.
- the organic solvent of the coating composition is a water-compatible high boiling point solvent which has a boiling point at atmospheric pressure above 100 ° C.
- High boiling point solvents in accordance with the invention comprise tri-ethyleneglycol, tetra-ethyleneglycol, di- propyleneglycol, tri-propyleneglycol and the monomethyl, dimethyl and ethyl ethers of these glycols.
- the organic solvent of the coating composition is a by-product of the hydrolysis reaction between the silane binder and water and may be present only in small amounts. The presence and use of such solvents leads to improvements in coating processability and can reduce coating defects such as blistering during curing.
- the coating additive is provided to enhance coating processability and/or coating performance.
- Coating additives such as 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.
- Other 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. Moreover, 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 water reducible coating composition may be applied on steel using a coil coating process.
- the use of a coil coating process requires the coating to have a certain solids content and to be of a certain viscosity.
- the coating has a viscosity of 150 to 1000 mPas and a solids content in the range of 20-50%; the viscosity of the coating depends on the application method.
- the silane binder is an epoxy functional silane, an amino functional silane or a mixture thereof.
- the silane binders are fully miscible with water.
- the inventors found that silanes have good compactability with organic compounds that may also be present in the water reducible coating composition. Moreover, silanes provide robustness to the water reducible coating composition at ambient conditions before the coated steel substrate is subjected to the heat treatment and hot-forming.
- Suitable epoxy functional silane binders include glycidyloxypropylalkoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane and 3- glycidyloxypropylmethyldiethoxysilane or a mixture thereof.
- Suitable amino functional silane binders include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane or a mixture thereof.
- Other functional silanes such as alkyl, acrylate and vinyl functional silanes can also be added to improve coating performance. The use of such binders permits the manufacture of water reducible coatings that possess improved anti-scale and anti-corrosion properties.
- the weight ratio of the silane binder and the metal is between 4: 1 and 1 :4 and preferably between 2: 1 and 1 :2. If the binder: metal ratio is above 4: 1 then the spot weldability of the coated steel substrate decreases. Moreover, if the metal: binder ratio is above 4:1 then the mechanical and barrier properties of the coating are diminished.
- a process for the manufacture of a cure coated steel article which comprises the steps of:
- Curing the water reducible coating of the coated steel substrate at least partially removes water and the organic solvent from the coating. Preferably water and the organic solvent are fully removed.
- the curing step also partially sinters the particulate metal which should increase coating adherence, robustness and the conductivity of the water reducible coating prior to the heat treatment and hot-forming.
- the curing may be performed using electromagnetic radiation such as infrared and preferably near infrared radiation.
- the use of infrared radiation means that fully cured coatings can be obtained within a period of 90 seconds or less, preferably 60 seconds or less.
- Curing the coating also improves coating integrity and coating stability during handling and blanking operations.
- a process for the manufacture of a cured coated steel substrate according to the second aspect of the invention which after being subjected to a heat treatment of at least 700°C has an electrical resistance of 5 mOhms or less. Electrical resistances of 5 mOhms or less are obtainable when heat treatments are carried out up to 1000°C and preferably between 700 and 900°C. Cure coated steel substrates were deemed to have bad spot weldability if the measured electrical resistance was greater than 5 mOhms.
- the cured coating of the cure coated metal article contains in weight % 25 to 75%, preferably 40 to 60% silane binder, 1 to 6% , preferably 2 to 4% of a coating additive and 25 to 75%, preferably 40 to 60% metal.
- Cured coatings having a silane binder content above 75 weight % exhibited a significant reduction in electrical conductivity whereas cured coatings having a silane content below 25 weight % have reduced physical properties.
- Cured coatings which comprise a metal content above 75 weight % exhibit a significant reduction in the physical properties of the coating.
- the coating additives are used to improve the dispersability, wetting and processability of the coating before it is cured. These additives will remain in the coating until the coating is heated prior to hot-forming the coated substrate.
- a process for the manufacture of a cured coated steel substrate wherein the coating has a dry film thickness in the range of 2 ⁇ to 30 ⁇
- the inventors found that coatings having a dry film thickness below 2 yim were not robust enough to withstand subsequent processing steps and coatings having a dry film thickness above 30 ⁇ were not suitable for coil coating and had a tendency to crack due to a reduction in coating flexibility.
- a process for the manufacture of a cure coated steel article according to the second aspect of the invention which further comprises the steps of:
- the metal is a hot-formable steel or a boron steel since such steels are able to withstand the high temperature conditions of the heat treatment and hot-forming.
- the cured water reducible coating is consolidated to form a protective coating to reduce oxidation at the steel surface.
- the consolidated coating may also provide anti-corrosion properties if non-aluminium metals are provided that are corroded in preference to iron.
- the coating of the invention is robust and flexible enough to withstand hot- forming.
- a hot-formed coated steel article wherein the coating of the hot-formed coated steel article contains in weight %: greater than 50% aluminium; 0 to 35%, preferably 0 to 25% zinc; less than 50%, magnesium, and 0 to 10%, preferably 0 to 1 % of nickel, copper, tin or molybdenum. Coating corrosion performance is reduced if the coating of the hot-formed coated steel article comprises aluminium and non-aluminium metals in a weight % that is outside the ranges specified above.
- hot-formed coated steel articles which comprise a coating having an aluminium content greater than 50 weight % are characterised by improved barrier properties whereas coatings having a nickel, copper, tin or molybdenum content above 10% reduce the interfacial bonding between the steel substrate and the coating.
- Coatings which comprise 0 weight % of magnesium and/or zinc will exhibit anti-scale and barrier protection properties only, i.e. the coatings will not have any sacrificial corrosion protection.
- Magnesium improves the corrosion performance by acting as a sacrificial anode to zinc, thereby extending the lifetime of zinc and consequently the lifetime of the coated hot-formed steel article.
- Magnesium also limits the amount of zinc that is evaporated during the heat treatment and/or hot-forming at temperatures above 850 ° C. If zinc and/or magnesium are provided to afford sacrificial corrosion protection to the coating then the zinc content should be no greater than 35 weight % otherwise after hot-forming the barrier properties of the coating will be compromised. The magnesium content should not exceed 50 weight % otherwise unfavourable surface oxides will accumulate at the coated surface; which oxides will be detrimental to the adhesion of subsequent surface coatings, i.e. when phosphonating or painting the coated hot-formed steel article.
- zinc and magnesium are provided to afford sacrificial corrosion protection, the lower limits of which are 10 % and 20 % respectively.
- a process for the manufacture of a cure coated cold-rolled steel substrate which further comprises the steps of cold-forming the cure coated cold-rolled steel substrate to produce a cold-formed steel article having a temperature resistance of 550°C or less.
- temperature resistance it is meant that the coating does not thermally degrade.
- the coating of the invention is robust and flexible enough to withstand cold forming. Moreover the coating is resistant to temperatures of 550 ° C or less and is suitable for protecting cold-formed coated steel articles which may experience temperatures of 550 ° C or less during high temperature service conditions.
- the coating of the cold-formed coated steel article contains in weight %: greater than 50%, preferably greater than 75% aluminium; less than 50%, preferably less than 20% magnesium and 0 to 10%, preferably 0 to 1 % of nickel, copper, tin or molybdenum.
- Coating performance is reduced if the coating of the cold-formed coated steel article comprises aluminium and non-aluminium metals in a weight % that is outside the ranges specified above. For example, coatings which contain less than 50% aluminium exhibited a reduction in corrosion durability and coatings having a nickel, copper, tin or molybdenum content above 1% reduced the interracial bonding between the coating and the cold-formed steel article.
- Figure 1 shows the results of a spot weldability test (BS1140) for a hot-formed coated boron steel article comprising the coating of Example 9.
- the spot welding test was carried out to determine the welding range. Splash occurs between the sheets in region C whereas a minimum spot weld diameter(dp) of min ⁇ 4Vt (t is the steel substrate thickness) has not been approached in region A.
- Region B shows the useful spot welding range for example 9.
- the dotted lines (i), (ii) and (iii) correspond to a weld size of 3.5, 4 and 5 Vt respectively.
- the water reducible coating was formed under the same conditions as in Example 1. To 100g of this solution a further 7g of tetraisopropyltitinate (20%) in isopropanol was subsequently added to the mixing vessel and mixed. The water reducible coating composition thus obtained was then applied on a boron steel strip by spraying to provide a uniform coating thereon. The coated steel strip was then cured using infrared heating to provide a cure coated steel strip.
- aluminium flake paste (Eckart Stapa ® Hydroxal w1515nl) containing 35 weight% of water and aluminium particles having a particle thickness of less than one micron and a particle size of 13 micron was added to a mixing vessel.
- 100g of water was also added under moderate agitation (500-800rpm) to form a mixture.
- 100g of water and 100g of gamma-glycidyloxypropyltrimethoxysilane were added and the mixture was mixed for 10 minutes using an ultrasonic mixer.
- 0.4g of BYK348 and 1.6g of BYK024 were added.
- the water reducible coating composition thus obtained was then applied on a boron steel strip by spraying to provide a uniform coating thereon.
- the coated steel strip was then cured using infrared heating to provide a cure coated steel strip.
- Table 1 shows in weight % the contribution of each component to the water reducible coating composition of Examples 1-9.
- 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 steel strip sample.
- the cure coated steel strips 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 1 Contribution in weight % of each component to the water reducible coating composition of Examples 1 -9. * Trace organic solvent.
- Table 2 Curing cycles for coated boron steel substrates coated with the coating compositions of Example 1 and Example 5.
- Table 3 Assessment of anti-scale properties, electrical resistance and corrosion resistance for boron steel substrates coated with the coating compositions of Examples 1 to 6 following a heat treatment and hot-forming.
- Examples 1 , 2, 3 and 5 have an organic solvent content higher than 10% weight, but the other examples represent the preferred compositional range for the organic solvent form 0 to a maximum of 10% weight.
- organic solvent will be present as a by-product of the hydrolysis reaction between water and the silane binder, but only in trace amounts.
- the coated steel strips were assessed to determine the presence and thickness of oxide scales after hot-forming. 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 5 ⁇ or less were formed at the steel surface. Coated steel strips were deemed to have good anti-scale properties if oxide scales having a thickness between 6 and 30 ⁇ were formed at the steel surface.
- Example C1 relates to a bare boron steel substrate which was subjected to the heat treatment and hot-forming under oxidising conditions.
- the uncoated boron steel strip showed severe oxide scale formation with oxide scales possessing an average thickness of 80 ⁇ .
- boron steels coated with the coating composition of Example 1 had excellent anti- scale properties following the heat treatment and hot-forming, which were carried out under the same conditions. Oxide scales having a thickness of 5 ⁇ were observed but the coating was free of cracks and free of flakes.
- 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 5 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.
- the bare boron steel substrate after heat treatment 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 1 had excellent corrosion resistance after 96 hours and excellent corrosion resistance after 120 hours, with little to no red rust being observed.
- the spot weldability of the coated steel strip was examined by measuring electrical resistance (BS1 140). A lower electrical resistance generally results in better spot weldability.
- coated boron steel strips were deemed to have excellent spot weldability if the measured electrical resistance was equal to 2 mOhm or less.
- Coated steel strips were deemed to have good spot weldability if the measured electrical resistance was between 2 and 5 mOhm.
- Coated steel strips were deemed to have bad spot weldability if the measured electrical resistance was greater than 5 mOhm.
- Example E relates to a cold rolled substrate (DP600CR), which has been coated with the coating composition of Example 9 and cured.
- Table 4 Electrical resistance of coated boron steel strips.
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Abstract
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10795940A EP2510061A2 (fr) | 2009-12-11 | 2010-12-10 | Revêtements protecteurs pour substrats |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09015364 | 2009-12-11 | ||
| PCT/EP2010/007521 WO2011069663A2 (fr) | 2009-12-11 | 2010-12-10 | Revêtements protecteurs qui respectent l'environnement et destinés à des substrats |
| EP10795940A EP2510061A2 (fr) | 2009-12-11 | 2010-12-10 | Revêtements protecteurs pour substrats |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2510061A2 true EP2510061A2 (fr) | 2012-10-17 |
Family
ID=41668427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10795940A Withdrawn EP2510061A2 (fr) | 2009-12-11 | 2010-12-10 | Revêtements protecteurs pour substrats |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2510061A2 (fr) |
| CN (1) | CN102652157A (fr) |
| WO (1) | WO2011069663A2 (fr) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013056848A1 (fr) * | 2011-10-19 | 2013-04-25 | Tata Steel Uk Limited | Revêtements anti-incrustation et anticorrosion pour des substrats en acier |
| WO2013056847A1 (fr) * | 2011-10-19 | 2013-04-25 | Tata Steel Uk Limited | Revêtements hybrides anti-tartre et anti-corrosion pour substrats en acier |
| DE102012022731A1 (de) | 2012-11-21 | 2014-05-22 | Epg (Engineered Nanoproducts Germany) Ag | Hochabriebfeste Antikalkschichten mit hoher chemischer Beständigkeit |
| JP6165529B2 (ja) * | 2013-07-12 | 2017-07-19 | 日新製鋼株式会社 | 化成処理鋼板の製造方法および製造装置 |
| DE112015001450T5 (de) * | 2014-03-25 | 2017-01-19 | Magna Powertrain Inc. | Verfahren zur Herstellung von Kraftübertragungskomponenten unter Verwendung eines wärmeunterstützten Kalibrierungsprozesses und unter Verwendung des Verfahrens hergestellte Kraftübertragungskomponenten |
| CN107876358B (zh) * | 2017-09-28 | 2021-02-02 | 中国科学院金属研究所 | 一种用于镍基金属非渗镀表面的防护涂层及防护方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7078076B2 (en) * | 2001-02-14 | 2006-07-18 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
| CA2501349C (fr) * | 2002-10-07 | 2012-08-21 | Coatings For Industry, Inc. | Formation de revetement resistant a la corrosion |
| FR2866029B1 (fr) * | 2004-02-11 | 2006-05-26 | Dacral | Composition de revetement anti-corrosion en dispersion aqueuse comprenant un titanate et/ou un zirconate organique |
| MXPA06010676A (es) * | 2004-03-19 | 2007-02-21 | Doerken Ewald Ag | Microrevestimiento comprendiendo siloxanos. |
-
2010
- 2010-12-10 WO PCT/EP2010/007521 patent/WO2011069663A2/fr not_active Ceased
- 2010-12-10 EP EP10795940A patent/EP2510061A2/fr not_active Withdrawn
- 2010-12-10 CN CN2010800559824A patent/CN102652157A/zh active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2011069663A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102652157A (zh) | 2012-08-29 |
| WO2011069663A3 (fr) | 2011-08-25 |
| WO2011069663A2 (fr) | 2011-06-16 |
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