EP1310578A1 - Procédé de phosphatation accéléré par l'hydroxylamine et des composés organiques nitrogénés - Google Patents
Procédé de phosphatation accéléré par l'hydroxylamine et des composés organiques nitrogénés Download PDFInfo
- Publication number
- EP1310578A1 EP1310578A1 EP02024329A EP02024329A EP1310578A1 EP 1310578 A1 EP1310578 A1 EP 1310578A1 EP 02024329 A EP02024329 A EP 02024329A EP 02024329 A EP02024329 A EP 02024329A EP 1310578 A1 EP1310578 A1 EP 1310578A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- phosphating solution
- phosphating
- hydroxylamine
- free
- 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- Withdrawn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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000002897 organic nitrogen compounds Chemical class 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 16
- -1 zinc (II) ions Chemical class 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- 150000001204 N-oxides Chemical class 0.000 claims abstract description 6
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000680 Aluminized steel Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- OURXRFYZEOUCRM-UHFFFAOYSA-N 4-hydroxymorpholine Chemical compound ON1CCOCC1 OURXRFYZEOUCRM-UHFFFAOYSA-N 0.000 claims description 2
- MRAUNPAHJZDYCK-BYPYZUCNSA-N L-nitroarginine Chemical compound OC(=O)[C@@H](N)CCCNC(=N)N[N+]([O-])=O MRAUNPAHJZDYCK-BYPYZUCNSA-N 0.000 claims description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- IWYYIZOHWPCALJ-UHFFFAOYSA-N 4-methyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=[N+]([O-])C=C1 IWYYIZOHWPCALJ-UHFFFAOYSA-N 0.000 claims 1
- CFZKDDTWZYUZKS-UHFFFAOYSA-N picoline N-oxide Chemical compound CC1=CC=CC=[N+]1[O-] CFZKDDTWZYUZKS-UHFFFAOYSA-N 0.000 claims 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 229910001453 nickel ion Inorganic materials 0.000 description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- MRAUNPAHJZDYCK-UHFFFAOYSA-N 5-[[amino(nitramido)methylidene]amino]-2-azaniumylpentanoate Chemical compound OC(=O)C(N)CCCN=C(N)N[N+]([O-])=O MRAUNPAHJZDYCK-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910001465 mixed metal phosphate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing 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
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C23C22/364—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 containing also manganese cations
- C23C22/365—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 containing also manganese cations containing also zinc and nickel cations
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
-
- 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
- C23C22/364—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 containing also manganese cations
Definitions
- the invention relates to a phosphating solution and a phosphating process for phosphating metal surfaces.
- This is a layer-forming phosphating, due to the on the metal surface firmly grown crystalline metal phosphate layers are generated. This improve corrosion resistance especially related to a subsequent painting and increase the adhesion of the paint on the Metal surface.
- the present invention further develops the phosphating process described in WO 95/07370.
- This document discloses a process for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc, manganese and phosphate ions and as accelerators hydroxylamine or a hydroxylamine compound and / or m-nitrobenzenesulfonic acid or its water-soluble salts, characterized in that the metal surfaces are mixed with in contact with a phosphating solution which is free of nickel, cobalt, copper, nitrite and oxo anions from halogens and which 0.3 to 2 g / l Zn (II) 0.3 to 4 g / l Mn (II) 5 to 40 g / l phosphate ions 0.1 to 5 g / l hydroxylamine in free or bound form and / or 0.2 to 2 g / l M-nitrobenzenesulfonate and at most 0.5 g / l nitrate
- a phosphating process is sought in which the phosphating solution contains the lowest possible levels of accelerator and with which the in materials occurring in practice are equally reliable even with a aged phosphating solution can be phosphated.
- the concentration increases Active components.
- the accelerator levels therefore decrease during the phosphating process. Even when you leave the bath accelerator levels may decrease due to spontaneous decomposition.
- the accelerator contents can also, if no dosing is made in time fall below the actually desired minimum limits. It can even be tolerated as long as no metal surfaces with the phosphating solution get in touch.
- the phosphate ions are only too low Partly as tertiary phosphate ions, but mainly as primary and secondary Phosphate ions in connection with free phosphoric acid.
- the determination of the content is phosphoric acid and all phosphate ions treated as if they were present as tertiary phosphate ions.
- hydroxylamine lies in accordance with its acid-base balance partly as free amine, partly in protonated form. It is therefore irrelevant whether you use hydroxylamine as a free base or in the form of a Salt. If hydroxylamine is used in salt form, this is particularly so Sulfate and the primary phosphate are suitable. Hydroxylamine can also be in the form of Compounds are present at the pH values mentioned hydroxylamine secede. Examples include acetaldehyde oxime and acetoxime (WO 96/16204).
- organic N-oxide is used as the organic nitrogen compound used, this is preferably selected from the group of the following compounds from: pyrridine-N-oxide, 2-methylpyrridine-N-oxide, 4-methylpyrridine-N-oxide, morpholine-N-oxide and N-methylmorpholine-N-oxide.
- One embodiment of the phosphating solution according to the invention is characterized in that it additionally contains 0.7 to 5 g / l nitrate ions. Nitrate ions act as co-accelerators and thereby improve the layer formation. It is part of the phosphating of galvanized steel It is recommended that the chloride content of the phosphating solution is not 100 mg / l exceeds. Otherwise there is a risk of white defects (specks) forming on certain galvanized steels.
- the nitrate concentration of the Keep phosphating solution below 0.5 g / l, which also helps Chloride contents above 50 mg / l white specks can be avoided.
- the phosphating solution additionally 0.001 to 3 g / l contains free and / or complex fluoride ions, but up to a maximum of 0.8 g / l free fluoride ions.
- This improves the phosphatability of hot-dip galvanized steel and in particular aluminum and its Alloys. Higher levels of free and / or complex fluoride ions can however lead to defects.
- Free fluoride ions are those that are hydrated Form in the aqueous solution. They can be in the form of hydrofluoric acid or in the form of soluble fluorides such as sodium, potassium or Ammonium fluoride can be used.
- complex fluoride ions Anions understood where 2 or more fluorine atoms are attached to a central atom are bound. As central atoms come in particular boron, silicon, titanium and Zircon in question. Hexafluorosilicate ions are particularly preferred.
- the complex Fluoride ions can be in the form of the free acid or in the form of water-soluble salts be introduced into the phosphating solution.
- the phosphating solution additionally one or both of the contains the following cations: 0.2 to 4 g / l of manganese ions and / or 0.05 to 2.5 g / l Nickel ions. From the wastewater point of view, the presence of nickel ions undesirable. Therefore, it may be preferable that the phosphating solution is none Contains nickel ions.
- nickel ions from phosphating waste water as far to remove and even regain that legal waste water limits for Germany are far below. If such a system is available, it is preferred that the phosphating solution both Contains manganese ions as well as nickel ions.
- the phosphating solution Hydroxylamine in free, ionic or bound form in the concentration range contained from 0.05 to 0.75 g / l. This cheapens the phosphating process and facilitates waste water treatment in particular. Phosphating problems that especially by a higher concentration of the breakdown products of the Accelerators can be avoided are avoided.
- the concentrations to couple the individual accelerators to each other the higher the Concentration of an accelerator, the lower the concentration of the other accelerator can be selected.
- the organic Nitrogen compound is present in maximum concentration.
- the individual components of the phosphating solution are preferably in following concentration ranges: zinc ions 0.5 to 2 g / l, manganese ions 0.5 up to 1.5 g / l, nickel ions 0.1 to 1.5 g / l, phosphate ions 10 to 20 g / l, nitrate ions 0.7 up to 2 g / l.
- the pH is preferably set in a range from 3 to 3.4 on. Except through the concentration information of the individual components Phosphating solutions often by the parameters "free acid” and "total acid” characterized. These terms are known to the person skilled in the art.
- the free Acidity can be determined, for example, by taking a bath sample diluted from 10 ml with water to 50 ml and with 0.1N sodium hydroxide solution up to a pH value of 3.8 titrated. The consumption in ml of sodium hydroxide solution indicates the content free acid in points. The content of is determined accordingly Total acidity in points by taking the bath sample up to a pH of 8.5 titrated.
- the free acid is preferably in the range between 0.3 and 1.5 Total acidity in the range between 15 and 30 points.
- an aqueous concentrate for Prepare or supplement a phosphating solution that is diluted with Water in the weight ratio concentrate: water in the range from 1: 5 to 1:30 gives a phosphating solution as described above.
- the present invention relates to a method for Phosphating of metal surfaces selected from surfaces of steel, galvanized or alloy galvanized steel, aluminized or alloy-aluminized steel or of aluminum or aluminum alloys
- a method for Phosphating of metal surfaces selected from surfaces of steel, galvanized or alloy galvanized steel, aluminized or alloy-aluminized steel or of aluminum or aluminum alloys
- the treatment time is preferably in the range from 2 to 4 Minutes.
- the phosphating solution preferably has a temperature in the Range from 40 to 55 ° C.
- the phosphating process according to the invention is in particular for this suitable, metal surfaces selected from surfaces of aluminized or alloy-aluminized steel or of aluminum or aluminum alloys consist of at least 50 atomic percent aluminum, alone or together with surfaces of steel, galvanized or alloy galvanized steel phosphatize. Even an aged bath does not lead to phosphating problems on aluminum surfaces, as is otherwise the case at higher concentrations of organic nitro compounds caused by their degradation products can be.
- the phosphating process is therefore particularly suitable for Phosphating of vehicle bodies suitable, the components made of aluminum or aluminum alloys alone or together with steel components and / or galvanized steel.
- the phosphating time was 3 minutes.
- the sheets were then rinsed with water and dried.
- the phosphating result was assessed optically.
- the mass per unit area of the phosphate layer (“layer weight") was determined by detaching the phosphate layer and by weighing the sheets before and after detaching the layer.
- the optical evaluation gave a good and closed one for Examples 1 to 4 Layer image.
- the layer weights are in the technically desirable range.
- the Phosphating solutions according to the invention thus deliver despite a small amount Accelerator content good phosphating results.
- Example 5 Comparative Example 1 : Mixing an aged phosphating solution A with fresh phosphating solution B.
- a used solution A was used for this, in an automobile phosphating plant was in operation and because of the enriched Decomposition products of the m-nitrobenzenesulfonate was colored black.
- the visual assessment showed only a partial and therefore insufficient Phosphating of the test sheet.
- the visual assessment showed a uniform, closed Phosphate layer.
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- 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)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2001155666 DE10155666A1 (de) | 2001-11-13 | 2001-11-13 | Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren |
| DE10155666 | 2001-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1310578A1 true EP1310578A1 (fr) | 2003-05-14 |
Family
ID=7705562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02024329A Withdrawn EP1310578A1 (fr) | 2001-11-13 | 2002-11-02 | Procédé de phosphatation accéléré par l'hydroxylamine et des composés organiques nitrogénés |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1310578A1 (fr) |
| JP (1) | JP2003183846A (fr) |
| DE (1) | DE10155666A1 (fr) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007370A1 (fr) * | 1993-09-06 | 1995-03-16 | Henkel Kommanditgesellschaft Auf Aktien | Procedes de phosphatage sans nickel |
| WO1996016204A1 (fr) * | 1994-11-23 | 1996-05-30 | Ppg Industries, Inc. | Compositions a base de phosphate de zinc, utilisees pour des revetements et contenant des accelerateurs oximes |
| WO1999007916A1 (fr) * | 1997-08-06 | 1999-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatation accelere par n-oxydes |
| DE19808440A1 (de) * | 1998-02-27 | 1999-09-09 | Metallgesellschaft Ag | Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen |
| DE19939519A1 (de) * | 1999-08-20 | 2001-02-22 | Henkel Kgaa | Beschleuniger für die Phosphatierung von Metalloberflächen |
-
2001
- 2001-11-13 DE DE2001155666 patent/DE10155666A1/de not_active Withdrawn
-
2002
- 2002-10-30 JP JP2002316207A patent/JP2003183846A/ja active Pending
- 2002-11-02 EP EP02024329A patent/EP1310578A1/fr not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007370A1 (fr) * | 1993-09-06 | 1995-03-16 | Henkel Kommanditgesellschaft Auf Aktien | Procedes de phosphatage sans nickel |
| WO1996016204A1 (fr) * | 1994-11-23 | 1996-05-30 | Ppg Industries, Inc. | Compositions a base de phosphate de zinc, utilisees pour des revetements et contenant des accelerateurs oximes |
| WO1999007916A1 (fr) * | 1997-08-06 | 1999-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Procede de phosphatation accelere par n-oxydes |
| DE19808440A1 (de) * | 1998-02-27 | 1999-09-09 | Metallgesellschaft Ag | Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen |
| DE19939519A1 (de) * | 1999-08-20 | 2001-02-22 | Henkel Kgaa | Beschleuniger für die Phosphatierung von Metalloberflächen |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003183846A (ja) | 2003-07-03 |
| DE10155666A1 (de) | 2003-05-22 |
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