EP1208247A1 - Procede de traitement contre la corrosion ou de traitement posterieur de surfaces metalliques - Google Patents
Procede de traitement contre la corrosion ou de traitement posterieur de surfaces metalliquesInfo
- Publication number
- EP1208247A1 EP1208247A1 EP00953020A EP00953020A EP1208247A1 EP 1208247 A1 EP1208247 A1 EP 1208247A1 EP 00953020 A EP00953020 A EP 00953020A EP 00953020 A EP00953020 A EP 00953020A EP 1208247 A1 EP1208247 A1 EP 1208247A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- treatment
- solution
- free
- range
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- -1 m-nitrobenzene sulfonate ions Chemical class 0.000 claims abstract description 26
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 239000010959 steel Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- 238000005260 corrosion Methods 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001204 N-oxides Chemical class 0.000 claims description 6
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000010960 cold rolled steel Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- ZCZPJZYQBNOPLT-UHFFFAOYSA-N 2,3,5,6-tetramethylaniline Chemical compound CC1=CC(C)=C(C)C(N)=C1C ZCZPJZYQBNOPLT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- LIBWRRJGKWQFSD-UHFFFAOYSA-M sodium;2-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC=C1S([O-])(=O)=O LIBWRRJGKWQFSD-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the invention is in the field of anti-corrosion treatment of surfaces of steel, galvanized or alloy galvanized steel or of aluminum or its alloys.
- the process can serve as an independent anti-corrosion treatment before painting and can be used, for example, instead of iron phosphating.
- the method is also suitable for post-treating non-layer-forming or layer-forming phosphated metal surfaces.
- it is suitable for a corrosion-protective aftertreatment of components such as, for example, automobile bodies, which were produced from pre-phosphated material.
- the phosphate layer on cut edges or on grinding points is removed or damaged.
- Such areas have weakened corrosion protection.
- the aftertreatment of such components according to the invention on the one hand enhances the corrosion protection effect of the existing phosphate layer and on the other hand causes spots with removed or damaged phosphate layer to be coated with a corrosion protection layer.
- the components can then be painted.
- EP-B-713 540 teaches an aqueous treatment solution for metal surfaces which contain as essential components: a) fluorometallate anions of the elements titanium, zirconium, hafnium, silicon, aluminum and boron, b) cations of selected metals, for example copper, c) phosphorus containing inorganic oxo anions and / or phosphonate ions and d) water-soluble or water-dispersible polymer.
- WO 97/02369 discloses aqueous solutions for the treatment of aluminum surfaces which contain a) phosphate ions, b) titanium ions or titanium compounds, c) fluoride ions or fluorine-containing compounds and d) an accelerator. It can be assumed that fluorine complexes of titanium form from components b) and c). Oxidizers are selected as accelerators, selected from nitrite, nitrate, tungstate, molybdate, permanganate and water-soluble organoperoxides.
- the invention relates to a method for the corrosion-protective treatment or aftertreatment of bare or phosphated surfaces of steel, galvanized or alloy-galvanized steel or of aluminum or its alloys, the metal surfaces being brought into contact with an aqueous solution which a) 0.05 to 10 g / l complex fluorides of boron, silicon, titanium and / or zirconium and b) one or more phosphating accelerators selected from 0.05 to 2 g / l m-nitrobenzenesulfonate ions,
- the method according to the invention can be used as a corrosion protection method for a bare metal surface, which is then coated immediately or, if appropriate, after a longer period of transport and / or storage.
- This provides an alternative for conventional non-layer-forming iron phosphating, which is similarly simple in terms of process technology and which offers advantages in terms of corrosion protection compared to iron phosphating.
- the process for Post-treatment suitable for non-layer-forming and in particular layer-forming phosphated metal surfaces. It thus represents an alternative to the still widespread aftertreatment processes with chromium (VI) -containing solutions.
- the aftertreatment according to the invention leads to improved corrosion protection.
- the method is particularly suitable for the aftertreatment of components such as, for example, automobile bodies, which have been produced from pre-phosphated material.
- areas that have no or a damaged phosphate layer are adequately protected against corrosion so that they can then be painted.
- Aftertreatment of a zinc phosphate layer with the process according to the invention makes it possible to use solutions for zinc phosphating which contain little or no nickel.
- Such phosphating systems have disadvantages with regard to paint adhesion and corrosion protection on certain materials compared to nickel-containing phosphating systems. These disadvantages are compensated for by an aftertreatment with the method according to the invention. It is therefore possible to use a nickel-free or low-nickel phosphating process in connection with the aftertreatment process according to the invention. In this way, the advantages of the nickel-free zinc phosphating process with regard to wastewater treatment and sludge disposal can be exploited without having to accept the disadvantages of a nickel-free process.
- Solutions are preferably used that contain complex fluorides of titanium and / or zircon. If the process for a belt treatment is used as a "no-rinse process", contents of complex fluorides in the range from 1000 to 10000 mg / l are preferred. If components are treated for a longer period of time, which are subsequently rinsed, contents of complex Fluorides in the range from 100 to 1000, in particular 150 to 500 mg / l are preferred.
- Phosphating accelerators of group b) are known as components of a layer-forming phosphating, in particular a zinc phosphating. They have the property of supporting the formation of a desired fine-crystalline, closed phosphate layer.
- component b) 50 to 1000 mg / l m-nitrobenzenesulfonate ions, 1 to 10 g / l organic N-oxides, preferably N-methylmorpholine-N-oxide or 0.5 to 10 g / l, preferably 0.8 to 5 g / l hydroxylamine in free or bound form.
- hydroxylamine as such, as a salt, in particular as a sulfate or phosphate, or in the form of a hydroxylamine-releasing compound can be used.
- Hydroxylamine is preferably used as such or as sulfate.
- the acid-base balance between free hydroxylamine and hydroxylammonium ions is established.
- an additional use of 50 to 2000 mg / l, preferably 100 to 1000 mg / l, of fluoride ions can offer advantages due to their complexing action for the metals mentioned.
- the treatment solution can contain further metal ions, in particular those which are known as components of zinc phosphating or of rinse solutions after zinc phosphating.
- Preferred metal ions are: Zn (ll), Mn (ll), Ce (III), Ca (II), Ni (II), Ag (III) and Pd (II). Their concentrations are preferably 0.3 to 3 g / l each.
- the pH of the treatment solution for the process according to the invention is preferably set to a range from 2 to 5.5, in particular from 3.5 to 5. If necessary, the pH can be lowered to the desired range by using the free acids of components a), and in the case of excessively acidic solutions to the desired range by adding alkali metal hydroxide, alkali metal carbonate or ammonia.
- This embodiment takes into account the development that more and more pre-phosphated material is used, for example, for the construction of vehicles and household appliances. This is supplied in tape form to the component manufacturer. This cuts the strip into pieces, which are formed and assembled into the desired components, for example by welding or flanging. While car bodies made of pre-phosphated material are phosphated again in the automotive industry, household appliances made of pre-phosphated material are cleaned after assembly if necessary, but no longer phosphated.
- a complex phosphating system could also be dispensed with in the automotive industry if the bodies made of pre-phosphated material require cleaning and a one-step aftertreatment before painting in order to achieve the required corrosion protection. Until now, this was not possible because there is no or a damaged phosphate layer at the cut edges or at grinding points. At these points, the corrosion protection effect is at least insufficient if the body is not made of galvanized steel.
- the method according to the invention has the advantage that the corrosion protection effect of the phosphate layer present is increased and that a sufficient corrosion protection layer is produced at those points where the phosphate layer is missing or damaged.
- M Ti or Zr, content of the treatment solution of Ti or Zr in ppm
- HAS hydroxylammonium sulfate
- Ludigol m-nitrobenzenesulfonate
- MOON N-methylmorpholine-N-oxide
- the phosphating was carried out in dipping for a period of 4 minutes with a phosphating solution at a temperature of 40 ° C. and the following composition:
- the rinsing was carried out with treatment solutions of different temperatures by immersion for a period of 4 minutes. Further tests showed that values of 1 to 3 minutes were even better than those of 4 minutes.
- the aftertreatment was carried out with solutions containing such an amount
- Hexafluorozirconate contained that the Zr concentration was 100 ppm.
Landscapes
- Chemical & Material Sciences (AREA)
- General 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)
Abstract
Procédé de traitement contre la corrosion ou de traitement postérieur de surface nues ou phosphatées en acier, en acier zingué ou recouvert d'un alliage de zinc ou en aluminium ou ses alliages. Ledit procédé consiste à mettre en contact les surfaces métalliques avec une solution aqueuse qui contient 0,05 à 10 g/l de fluorures complexes de bore, silicium, titane et/ou zirconium ainsi qu'un ou plusieurs accélérateurs de phosphatation, de préférence choisis parmi des ions de m-nitrobenzènesulfonate, du N-méthylmorpholine-N-oxyde et de l'hydroxylamine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19933189A DE19933189A1 (de) | 1999-07-15 | 1999-07-15 | Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen |
| DE19933189 | 1999-07-15 | ||
| PCT/EP2000/006397 WO2001006035A1 (fr) | 1999-07-15 | 2000-07-06 | Procede de traitement contre la corrosion ou de traitement posterieur de surfaces metalliques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1208247A1 true EP1208247A1 (fr) | 2002-05-29 |
Family
ID=7914902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00953020A Withdrawn EP1208247A1 (fr) | 1999-07-15 | 2000-07-06 | Procede de traitement contre la corrosion ou de traitement posterieur de surfaces metalliques |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1208247A1 (fr) |
| JP (1) | JP2003505590A (fr) |
| KR (1) | KR20020019460A (fr) |
| AU (1) | AU6562100A (fr) |
| DE (1) | DE19933189A1 (fr) |
| WO (1) | WO2001006035A1 (fr) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI280988B (en) | 2001-12-04 | 2007-05-11 | Nippon Steel Corp | Metal oxide and/or metal hydroxide coated metal materials and method for their production |
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| US20040187967A1 (en) | 2002-12-24 | 2004-09-30 | Nippon Paint Co., Ltd. | Chemical conversion coating agent and surface-treated metal |
| DE60324379D1 (de) * | 2002-12-24 | 2008-12-11 | Chemetall Gmbh | Chemisches Konversionsbeschichtungsmittel und beschichtete Metalloberflächen |
| US8075708B2 (en) | 2002-12-24 | 2011-12-13 | Nippon Paint Co., Ltd. | Pretreatment method for coating |
| CA2454199C (fr) * | 2002-12-24 | 2011-07-05 | Nippon Paint Co., Ltd. | Agent de revetement par conversion chimique et metal a surface traitee |
| DE10352075A1 (de) * | 2003-11-07 | 2005-06-16 | Henkel Kgaa | Chromfreie, farbige Konversionsschichten auf Metalloberflächen |
| JP4966480B2 (ja) * | 2004-01-23 | 2012-07-04 | 日本パーカライジング株式会社 | 耐食性および上塗り塗装性に優れるリン酸亜鉛系処理材用後処理方法ならびに後処理されたリン酸亜鉛系処理材 |
| DE102005059314B4 (de) | 2005-12-09 | 2018-11-22 | Henkel Ag & Co. Kgaa | Saure, chromfreie wässrige Lösung, deren Konzentrat, und ein Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen |
| DE102007043479A1 (de) * | 2007-09-12 | 2009-03-19 | Valeo Schalter Und Sensoren Gmbh | Verfahren zur Oberflächenbehandlung von Aluminium und ein Schichtaufbau eines Bauteils aus Aluminium mit einer elektrischen Kontaktierung |
| DE102007057185A1 (de) | 2007-11-26 | 2009-05-28 | Henkel Ag & Co. Kgaa | Zirconiumphosphatierung von metallischen Bauteilen, insbesondere Eisen |
| DE102008038653A1 (de) * | 2008-08-12 | 2010-03-25 | Henkel Ag & Co. Kgaa | Sukzessive korrosionsschützende Vorbehandlung von Metalloberflächen in einem Mehrstufenprozess |
| US20150315718A1 (en) * | 2014-05-05 | 2015-11-05 | Ppg Industries Ohio, Inc. | Metal pretreatment modification for improved throwpower |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
| CN121110030B (zh) * | 2025-11-14 | 2026-02-13 | 湖南善德储能新材料研究院有限公司 | 一种无电子逸出干扰的复合金属涂层及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1933013C3 (de) * | 1969-06-28 | 1978-09-21 | Gerhard Collardin Gmbh, 5000 Koeln | Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels komplexe Fluoride enthaltender Lösungen |
| DE2031358C3 (de) * | 1970-06-25 | 1981-10-15 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels saurer, komplexe Fluoride enthaltender, Lösungen |
| JPS5424232A (en) * | 1977-07-26 | 1979-02-23 | Nippon Packaging Kk | Surface treating method of aluminum |
| JPS5983775A (ja) * | 1982-11-02 | 1984-05-15 | Nippon Paint Co Ltd | 金属表面の化成処理方法 |
| JPH04341574A (ja) * | 1991-05-18 | 1992-11-27 | Nippon Paint Co Ltd | 金属表面のリン酸亜鉛処理方法 |
| JP2828409B2 (ja) * | 1994-03-24 | 1998-11-25 | 日本パーカライジング株式会社 | アルミニウム含有金属材料用表面処理組成物および表面処理方法 |
| JP3349851B2 (ja) * | 1994-12-22 | 2002-11-25 | 日本パーカライジング株式会社 | スラッジ抑制性に優れたアルミニウム含有金属材料用表面処理組成物および表面処理方法 |
| DE4441710A1 (de) * | 1994-11-23 | 1996-05-30 | Henkel Kgaa | Korrosionsschutz und Reibungsverminderung von Metalloberflächen |
| DE19511573A1 (de) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Verfahren zur Phosphatierung mit metallhaltiger Nachspülung |
| JP3623015B2 (ja) * | 1995-06-30 | 2005-02-23 | 日本パーカライジング株式会社 | アルミニウム含有金属材料用表面処理液および表面処理方法 |
| WO1998020186A1 (fr) * | 1996-11-06 | 1998-05-14 | Henkel Corporation | Composition et procede de revetement par conversion a phosphate |
| WO1999007916A1 (fr) * | 1997-08-06 | 1999-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatation accelere par n-oxydes |
-
1999
- 1999-07-15 DE DE19933189A patent/DE19933189A1/de not_active Withdrawn
-
2000
- 2000-07-06 AU AU65621/00A patent/AU6562100A/en not_active Abandoned
- 2000-07-06 JP JP2001511240A patent/JP2003505590A/ja active Pending
- 2000-07-06 EP EP00953020A patent/EP1208247A1/fr not_active Withdrawn
- 2000-07-06 WO PCT/EP2000/006397 patent/WO2001006035A1/fr not_active Ceased
- 2000-07-06 KR KR1020017015940A patent/KR20020019460A/ko not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0106035A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020019460A (ko) | 2002-03-12 |
| WO2001006035A1 (fr) | 2001-01-25 |
| DE19933189A1 (de) | 2001-01-18 |
| JP2003505590A (ja) | 2003-02-12 |
| AU6562100A (en) | 2001-02-05 |
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