EP0796356B1 - Method of applying phosphate coatings to metal surfaces - Google Patents
Method of applying phosphate coatings to metal surfaces Download PDFInfo
- Publication number
- EP0796356B1 EP0796356B1 EP95941068A EP95941068A EP0796356B1 EP 0796356 B1 EP0796356 B1 EP 0796356B1 EP 95941068 A EP95941068 A EP 95941068A EP 95941068 A EP95941068 A EP 95941068A EP 0796356 B1 EP0796356 B1 EP 0796356B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- phosphate
- phosphating
- alloys
- phosphating solution
- 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.)
- Expired - Lifetime
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 58
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 57
- 239000010452 phosphate Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title abstract description 16
- 239000002184 metal Substances 0.000 title abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 49
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 238000009736 wetting Methods 0.000 claims abstract description 10
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 3
- 239000002253 acid Substances 0.000 abstract description 17
- 238000001035 drying Methods 0.000 abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052748 manganese Inorganic materials 0.000 abstract description 11
- 239000011572 manganese Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 48
- 230000008569 process Effects 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000009189 diving Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JCYPECIVGRXBMO-FOCLMDBBSA-N methyl yellow Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1 JCYPECIVGRXBMO-FOCLMDBBSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000008237 rinsing water Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-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
- 229910002651 NO3 Inorganic materials 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the invention relates to a method for applying Phosphate coatings on surfaces of zinc, iron, aluminum or their alloys by wetting with a divalent cation and Phosphate-containing phosphating solution and subsequent Drying up the liquid film.
- Such phosphating solutions usually have a pH between about 1.8 and 3.8 and contain zinc and phosphate ions as process-determining components. Besides the cation zinc can other cations, e.g. Ammonium, calcium, cobalt, iron, potassium, Copper, sodium, magnesium, manganese, be present.
- the phosphating solutions in general oxidizing agents, such as bromate, chlorate, nitrate, nitrite, organic nitro compounds, perborate, persulfate or Hydrogen peroxide added.
- additives such as Fluoride, silicon fluoride, boron fluoride, citrate and tartrate. Due to the large number of individual components and their possible combinations results in a variety of different compositions of the Phosphating solutions.
- a special design of the phosphating process is the so-called low-zinc processes.
- the used here Phosphating solutions contain zinc in concentrations of only about 0.4 to 1.7 g / l and produce phosphate layers especially on steel with a high proportion of phosphophyllite, which has better paint adhesion and a higher resistance to paint infiltration Corrosion stress offers than it does in the generation of Phosphate layers based on Hopeit from phosphating solutions with higher Zinc content is common.
- a comparatively new development are phosphating processes, which are referred to in the professional world as the trication method.
- low-zinc phosphating processes in which Use of nickel in e.g. Quantities of 0.3 - 2.0 g / l and manganese in Amounts of e.g. 0.5-1.5 g / l phosphate coatings are obtained which are characterized by increased alkali resistance and therefore for the cathodic electrocoating, in particular of Car bodies are important.
- Another trication method provides for the concentrations of nickel to a value between about 80 and 94 mol%, of manganese between about 0.5 and 10 mol% and zinc between about 5.5 and 19.5 mol% (based to the sum of the cations).
- the content of Total acidity 10 to 40 points, the free acidity 0.5 to 2 points and the ratio of total acid to free acid is 10 to 60 (US-A-4596607).
- the aforementioned phosphating process has in common that the Phosphating solution in dipping, flooding or spraying with the Phosphating solution in dipping, flooding or spraying with the treating workpiece surfaces is brought into contact.
- Critalline phosphate layer is required for the removal of on the Surface remaining phosphating chemicals of a rinsing treatment, which is usually carried out in several stages.
- rinsing solutions that are not disposed of in this form can, but must be sent to a wastewater treatment plant.
- a disadvantage of such a procedure is, however, that due to the requirement that the Components of the phosphating solution the freedom for adaptation the composition of the phosphating solution to the Practice needs are severely limited.
- Coating solutions can be applied while diving or Spray and then squeeze off the excess solution or by roller application, in which only the required Amount of liquid is applied to the metal surface, respectively.
- the treatment solution can be applied while diving or Spray and then squeeze off the excess solution or by roller application, in which only the required Amount of liquid is applied to the metal surface, respectively.
- which depends on the application of the treatment liquid subsequent drying can in principle be carried out at room temperature respectively. In general, however, it is common to have higher temperatures apply, preferably temperatures between 50 and 100 ° C. to get voted.
- the process consists of using a metal surface To wet phosphating liquid that has a pH of 1.5 to 3, is chromium-free and, in addition to metal phosphate, soluble molybdate, Contains tungstate, vanadate, niobate and / or tantalate ions (EP-B-15 020).
- the cationic component of the solution metal phosphate by calcium, magnesium, barium, Aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese be formed.
- a disadvantage of the latter method is that due to the required additives molydate, tungstate, vanadate, niobate and Tantalizations cost more than the process conventional phosphating process, another is that the obtained Phosphate coatings do not meet all requirements today, e.g. B. with regard to alkali resistance and thus resistance to a subsequent cathodic electrocoating and the desired corrosion resistance, especially in connection with a subsequent painting, are sufficient.
- the object of the invention is to provide a method for applying Phosphate coatings on surfaces of zinc, iron, aluminum or their To provide alloys that are known, in particular does not have the aforementioned disadvantages, yet inexpensive and is simple to implement and of high quality Phosphate coatings leads.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surfaces are coated with a phosphating solution which is free from elements of the 5th and 6th subgroups of the Periodic Table of the Elements, 0.5 to 8 g / l nickel 2 to 20 g / l manganese 18 to 170 g / l Phosphate (calculated as P 2 O 5 ) contains and has an S value of 0.4 to 0.8, wetted in such a way that a phosphate layer weight of 0.3 to 3.0 g / m 2 results after drying, the phosphating solution in the case of phosphating surfaces from iron, aluminum or their alloys necessarily contains 0.5 to 5 g / l zinc and can contain zinc ions in the case of phosphating surfaces made of zinc or zinc alloys.
- the S value is expediently set using nickel oxide, manganese oxide or possibly zinc oxide or with ammonia solution.
- An expedient embodiment of the invention provides, in the case of Treatment of zinc or zinc alloys with a surface To wet the phosphating solution, which is zinc-free. In this In a special case comes the necessary for the formation of the coating Amount of zinc from the surface of the treated material.
- the wetting of the respective metal surfaces can e.g. by Diving and then draining, by pouring over and Spin off, by brushing, by spraying with compressed air, air-les as well as electrostatically.
- Diving and then draining by pouring over and Spin off
- brushing by spraying with compressed air, air-les as well as electrostatically.
- a particularly elegant one The method of application of the phosphating solution is carried out by Rolling with structured or smooth rolls in synchronism or in the opposite direction.
- drying can take place at room temperature. However, it is advantageous to work at higher temperatures because thereby the time for the formation of the phosphate layer considerably is shortened. Drying is preferably carried out at temperatures between 50 and 200 ° C, but with an object temperature of 90 ° C should not be exceeded.
- a preferred development of the invention consists in wetting the surfaces with a phosphating solution 0.8 to 6 g / l Nickel, 3 to 16 g / l Manganese, 30 to 140 g / l Phosphate (calculated as P 2 O 5 ) and in the case of phosphating surfaces made of iron or aluminum or their alloys contains 0.8 to 4 g / l zinc.
- a phosphating solution 0.8 to 6 g / l Nickel, 3 to 16 g / l Manganese, 30 to 140 g / l Phosphate (calculated as P 2 O 5 ) and in the case of phosphating surfaces made of iron or aluminum or their alloys contains 0.8 to 4 g / l zinc.
- Further advantageous embodiments of the invention consist of wetting the surfaces with a phosphating solution which has an S value of 0.5 to 0.7 or wetting the surfaces with the phosphating solution in such a way that after drying a phosphate layer weight of 0, 5 to 2 g / m 2 results.
- the setting of the preferred S value of 0.5 to 0.7 is particularly important in the treatment of zinc surfaces with zinc-free phosphating solutions, since the pickling attack of the phosphating solution on the zinc surface, which is responsible for the zinc content of the phosphate coating, then proceeds particularly optimally.
- the embodiment of the invention with the setting of a phosphate coating weight of 0.5 to 2 g / m 2 enables the phosphate coating to be formed in a particularly short time and also of particularly high quality.
- phosphate layers are produced which contain 0.5 to 3% by weight of nickel 1.5 to 8% by weight manganese 1.0 to 35% by weight zinc 25 to 40% by weight Phosphate (calculated as P 2 O 5 ) contain.
- the metal surfaces must be sufficiently clean be. This is generally the case when e.g. B. tape material immediately after the galvanizing by the method according to the invention is treated. However, if the metal surface is oiled or is dirty, degreasing or cleaning with the help of itself to connect known methods and then to rinse.
- the phosphating solution to be used in the process according to the invention is expediently used at a temperature in the range from 20 to 80 ° C.
- the amount of the solution is usually between 2 and 10 ml per m 2 of metal surface. The drying takes place - if it happens under the influence of heat - practically immediately after wetting the surface, ie after an exposure time of about 0.5 to 5 seconds.
- the present invention provides a method that is able to produce phosphate coatings in a matter of seconds. Another advantage over known methods is that there is no need for an activating pre-treatment before phosphating can.
- the phosphate coatings produced are particularly high Quality with regard to the provision of detention afterwards applied paints, plastics or adhesives. They are the same their quality is that produced with the help of the so-called trication method Phosphate layers. This is surprising in that the one after Phosphate coatings obtained according to the process of the invention as a rule are amorphous, whereas those formed by the trication method Layers are always crystalline.
- Another significant advantage of the invention is that Phosphate layers are generated that change the forming behavior of the so treated metals significantly improved without the Weldability is significantly affected.
- the phosphate coatings produced by the process according to the invention are good in all areas where phosphate coatings are applied applicable.
- a particularly advantageous application is in Preparation of the metal surfaces for the subsequent painting, especially electrocoating.
- the invention is particularly important Process for its application to the phosphating of galvanized or galvanized steel strips.
- Galvanized or alloy galvanized steel strips become strips understood that an edition of Elektroytzink (ZE), Feuerzink (Z), Alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or Zinc / aluminum (ZA or AZ).
- ZE Elektroytzink
- ZNE zinc / nickel
- ZF zinc / iron
- ZA or AZ Zinc / aluminum
- the latter are usually also alloys with e.g. B. 55 wt .-% Al and 45 wt .-% Zn counted.
- the total score (GS) is determined by using 1 ml of the Phosphating solution after dilution with water to about 50 ml Use of phenolphthalein as an indicator until the color changes from titrated colorless to red. The number of used for this ml n / 10 sodium hydroxide solution give the total number of points.
- the so-called S value is obtained by dividing the free acid by the total P 2 O 5 .
- the total P 2 O 5 is determined by, after the determination of the free acid, the titration solution after adding 20 ml of 30% strength neutral potassium oxalate solution against phenolphthalein as an indicator until the color changes to red with n / 10 NaOH is titrated.
- the consumption of ml n / 10 NaOH between the envelope with dimethyl yellow and the envelope with phenolphthalein gives the total P 2 O 5 .
- the phosphating solution had a temperature of 25 ° C, one pH value of 1.7 and an S value of 0.6.
- the content was Free acid 5.9 ml, total acid 17.1 ml.
- the phosphating solution was applied with the help of a roll coating machine (roll coater), as is also used for coil coating.
- the wet film of 5 ml of phosphating solution per m 2 of metal surface applied was dried in a continuous oven at 200 ° C. after an exposure time of 2 seconds. When leaving the furnace, the belt had an object temperature of 60 ° C.
- the strip phosphated by the process according to the invention can also pass through the process usual in the automotive plant.
- the phosphating takes place here during a treatment time of 3.5 min and a temperature of the phosphating solution of 52 ° C.
- the composition of the phosphating solution is: 14 g / l Phosphate (calculated as P 2 O 5 ) 1.4 g / l zinc 1.0 g / l manganese 1.0 g / l nickel 70 mg / l Sodium nitrite 185 mg / l free fluoride.
- the free acid content was 1.5 and the total acid content 27.8 Points were measured using a 10 ml bath sample. Of the S value was set to 0.08.
- the phosphate coating produced in this way has a weight per unit area of 2.56 g / m 2 and contained 31% by weight of P 2 O 5 , 35% by weight of zinc, 6.4% by weight of manganese, 1.7% by weight. -% nickel.
- the bodies are first provided with a cathodic electrodeposition paint and then with the customary automotive paint structure.
- Test sheets with which the aforementioned process was simulated were subjected to the following tests: Stone chip test plus VDA alternating test, outdoor weathering, cross-cut plus 240 h condensation water constant climate test.
- phosphating solution with a temperature of 27 ° C, which had the following composition, was applied to an electrolytically galvanized strip surface: phosphate 134 g / l (calculated as P 2 O 5 ) manganese 14.8 g / l nickel 5.42 g / l.
- the solution had an S value of 0.62, a free acid content of 10.3 and a total acid content of 29.7 (based on a bath sample of 1 ml).
- the wet film of the solution on the belt surface was 3 ml / m 2 .
- the solution had an S value of 0.56, containing free acid of 9.4 and a total acid content of 29.2 (based on 1 ml Bath sample).
- the dry phosphate layer had a basis weight of 1.95 g / m 2 and a composition of 37% by weight of P 2 O 5 , 3.9% by weight of manganese, 1.5% by weight of nickel and 1.9% by weight .-% zinc.
- the properties of the phosphate layer with regard to adhesion and corrosion protection in connection with a subsequently applied coating were in line with expectations.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen von Zink, Eisen, Aluminium oder deren Legierungen durch Benetzen mit einer zweiwertige Kationen- und Phosphat enthaltenden Phosphatierungslösung und anschließendes Auftrocknen des Flüssigkeitfilms.The invention relates to a method for applying Phosphate coatings on surfaces of zinc, iron, aluminum or their alloys by wetting with a divalent cation and Phosphate-containing phosphating solution and subsequent Drying up the liquid film.
In der metallverarbeitenden Industrie wird in großem Umfang das Verfahren der Erzeugung von Phosphatüberzügen mittels wässriger Zinkphosphatlösungen angewendet. Die mit diesem Verfahren auf den behandelten Metalloberflächen erzeugten Phosphatschichten dienen insbesondere zur Erleichterung des Gleitens, zur Vorbereitung für die spanlose Kaltumformung sowie zum Korrosionsschutz und als Lackhaftgrund.In the metalworking industry, this becomes very large Process for the production of phosphate coatings by means of aqueous Zinc phosphate solutions applied. Those with this procedure on the Treated metal surfaces generated phosphate layers are used especially to facilitate sliding, to prepare for the chipless cold forming as well as for corrosion protection and as Varnish primer.
Derartige Phosphatierungslösungen weisen üblicherweise einen pH-Wert zwischen etwa 1,8 und 3,8 auf und enthalten Zink- und Phosphationen als verfahrensbestimmende Komponenten. Außer dem Kation Zink können noch weitere Kationen, z.B. Ammonium, Kalzium, Kobalt, Eisen, Kalium, Kupfer, Natrium, Magnesium, Mangan, anwesend sein. Zur Beschleunigung der Phosphatschichtbildung werden den Phosphatierungslösungen im allgemeinen Oxidationsmittel, wie Bromat, Chlorat, Nitrat, Nitrit, organische Nitroverbindungen, Perborat, Persulfat oder Wasserstoffperoxid, zugesetzt. Um die Schichtausbildung auf bestimmten Werkstoffen zu optimieren, dienen Zusätze von z.B. Fluorid, Silicofluorid, Borfluorid, Zitrat und Tartrat. Aufgrund der großen zahl von Einzelkomponenten und ihrer Kombinationsmöglichkeiten ergibt sich eine Vielzahl von unterschiedlichen Zusammensetzungen der Phosphatierungslösungen.Such phosphating solutions usually have a pH between about 1.8 and 3.8 and contain zinc and phosphate ions as process-determining components. Besides the cation zinc can other cations, e.g. Ammonium, calcium, cobalt, iron, potassium, Copper, sodium, magnesium, manganese, be present. For acceleration the phosphate layer formation are the phosphating solutions in general oxidizing agents, such as bromate, chlorate, nitrate, nitrite, organic nitro compounds, perborate, persulfate or Hydrogen peroxide added. Around the layer formation To optimize certain materials, additives such as Fluoride, silicon fluoride, boron fluoride, citrate and tartrate. Due to the large number of individual components and their possible combinations results in a variety of different compositions of the Phosphating solutions.
Eine spezielle Ausgestaltung der Phosphatierverfahren stellen die sogenannten Niedrigzink-Verfahren dar. Die hierbei verwendeten Phosphatierungslösungen enthalten Zink in Konzentrationen von nur etwa 0,4 bis 1,7 g/l und erzeugen insbesondere auf Stahl Phosphatschichten mit einem hohen Anteil an Phosphophyllit, der eine bessere Lackhaftung und eine höhere Beständigkeit gegen Lackunterwanderung bei Korrosionsbeanspruchung bietet als es bei der Erzeugung von Phosphatschichten auf Basis Hopeit aus Pnosphatierlösungen mit höherem Zinkgehalt üblich ist. (DE-A-22 32 067, EP-A-15 021, EP-A-39 093, EP-A-56 881, EP-A-64 790, K. Wittel: "Moderne Zinkphosphatierverfahren-Niedrig-Zink-Technik", Industrie-Lackierbetrieb, 5/83, Seite 169 und 6/83, Seite 210).A special design of the phosphating process is the so-called low-zinc processes. The used here Phosphating solutions contain zinc in concentrations of only about 0.4 to 1.7 g / l and produce phosphate layers especially on steel with a high proportion of phosphophyllite, which has better paint adhesion and a higher resistance to paint infiltration Corrosion stress offers than it does in the generation of Phosphate layers based on Hopeit from phosphating solutions with higher Zinc content is common. (DE-A-22 32 067, EP-A-15 021, EP-A-39 093, EP-A-56 881, EP-A-64 790, K. Wittel: "Modern Zinc Phosphating Process-Low-Zinc Technology", Industrial paint shop, 5/83, pages 169 and 6/83, page 210).
Eine vergleichsweise neue Entwicklung stellen Phosphatierverfahren dar, die in der Fachwelt als Trikation-Verfahren bezeichnet werden. Hierbei handelt es sich um Niedrigzink-Phosphatierverfahren, bei denen durch Mitverwendung von Nickel in z.B. Mengen von 0,3 - 2,0 g/l und Mangan in Mengen von z.B. 0,5 - 1,5 g/l Phosphatüberzüge erhalten werden, die sich durch eine erhöhte Alkalibeständigkeit auszeichnen und mithin für die kathodische Elektrotauchlackierung, insbesondere von Autokarosserien, von Bedeutung sind. (EP-A-135 622, Tab. 1 u 3).A comparatively new development are phosphating processes, which are referred to in the professional world as the trication method. Here are low-zinc phosphating processes in which Use of nickel in e.g. Quantities of 0.3 - 2.0 g / l and manganese in Amounts of e.g. 0.5-1.5 g / l phosphate coatings are obtained which are characterized by increased alkali resistance and therefore for the cathodic electrocoating, in particular of Car bodies are important. (EP-A-135 622, tab. 1 and 3).
Ein weiteres Trikation-Verfahren sieht vor, die Konzentrationen von Nickel auf einen Wert zwischen etwa 80 und 94 Mol-%, von Mangan zwischen etwa 0,5 und 10 Mol-% und von Zink zwischen etwa 5,5 und 19,5 Mol-% (bezogen auf die Summe der Kationen) einzustellen. Dabei sollen der Gehalt an Gesamt-Säure 10 bis 40 Punkte, der an Freier Säure 0,5 bis 2 Punkte und das Verhältnis Gesamt-Säure zu Freier Säure 10 bis 60 betragen (US-A-4596607).Another trication method provides for the concentrations of nickel to a value between about 80 and 94 mol%, of manganese between about 0.5 and 10 mol% and zinc between about 5.5 and 19.5 mol% (based to the sum of the cations). The content of Total acidity 10 to 40 points, the free acidity 0.5 to 2 points and the ratio of total acid to free acid is 10 to 60 (US-A-4596607).
Speziell für die Phosphatierung von elektrolytisch verzinktem oder schmelztauchverzinktem Stahlband sind Verfahren entwickelt worden, die die Ausbildung einer Phosphatschicht entsprechend dem Trikation-Verfahren innerhalb einer Kontaktzeit von 2 - 30 sec gestatten. (WO 91/02829)Especially for the phosphating of electrolytically galvanized or Hot-dip galvanized steel strip processes have been developed the formation of a phosphate layer corresponding to the Trication procedure within a contact time of 2 - 30 sec allow. (WO 91/02829)
Den vorgenannten Phosphatierverfahren ist gemeinsam, daß die Phosphatierungslösung im Tauchen, Fluten oder Spritzen mit den zu Phosphatierungslösung im Tauchen, Fluten oder Spritzen mit den zu behandelnden Werkstückoberflächen in Berührung gebracht wird. Nach erfolgter chemischer Reaktion und Ausbildung der festverwachsenen, kritallinen Phosphatschicht bedarf es zwecks Entfernung von auf der Oberfläche verbleibenden Phosphatierchemikalien einer Spülbehandlung, die üblicherweise in mehreren Stufen durchgeführt wird. Hierdurch fallen Spüllösungen an, die in dieser Form nicht entsorgt werden können, sondern einer Abwasseraufbereitung zugeführt werden müssen.The aforementioned phosphating process has in common that the Phosphating solution in dipping, flooding or spraying with the Phosphating solution in dipping, flooding or spraying with the treating workpiece surfaces is brought into contact. After chemical reaction and formation of the firmly integrated, Critalline phosphate layer is required for the removal of on the Surface remaining phosphating chemicals of a rinsing treatment, which is usually carried out in several stages. Hereby there are rinsing solutions that are not disposed of in this form can, but must be sent to a wastewater treatment plant.
Es hat zwar diverse Vorschläge gegeben, die Spülwassermengen zu reduzieren oder aber ganz zu eliminieren, so ist beispielsweise die Spülung in einer sogenannten Spülwasserkaskade mit einer erheblichen Reduktion des anfallenden Spülwassers verbunden. Eine Aufarbeitung der auch in verringerter Menge anfallenden Spülwässer ist jedoch unvermeidlich. Zwecks Vermeidung von Spülwässern ist vorgeschlagen worden, ein Zinkphosphatierverfahren anzuwenden, dessen Phosphatierungslösungen in der Weise zusammengesetzt sind, daß sich praktisch alle Komponenten mit Kalziumhydroxid ausfällen lassen. Auf diese Weise wird die Spülwasseraufbereitung wesentlich erleichtert, und gleichzeitig besitzt das Verfahren den Vorzug, daß Wasser mit ausreichend guter Qualität für den Prozeß wiedergewonnen werden kann. (DE-C-23 27 304). Nachteilig bei einer derartigen Verfahrensführung ist jedoch, daß durch die aufgestellte Forderung der Fällbarkeit der Bestandteile der Phosphatierungslösung die Freiheit für die Anpassung der Zusammensetzung der Phosphatierungslösung an die Praxisbedürfnisse stark eingeschränkt ist. Schließlich sind Verfahren zur Erzeugung eines Konversionsüberzuges bekannt, bei denen nach einer eventuell erforderlichen Reinigung und Wasserspülung Überzugslösungen aufgebracht und anschließend aufgetrocknet werden. Die Applikation der Behandlungslösung kann dabei im Tauchen oder Spritzen mit anschließendem Abquetschen der überschüssigen Lösung oder aber durch Walzenauftrag, bei dem nur die erforderliche Flüssigkeitsmenge auf die Metalloberfläche aufgebracht wird, erfolgen. Die sich an die Aufbringung der Behandlungsflüssigkeit anschließende Auftrocknung kann im Prinzip bereits bei Raumtemperatur erfolgen. Im allgemeinen ist es jedoch üblich, höhere Temperaturen anzuwenden, wobei vorzugsweise Temperaturen zwischen 50 und 100°C gewählt werden. Ein derartiges zur Vorbereitung von Metalloberflächen zur anschließenden Beschichtung mit organischen Überzügen bestimmtes Verfahren besteht darin, die Metalloberfläche mit einer Phosphatierungsflüssigkeit zu benetzen, die einen pH-Wert von 1,5 bis 3 aufweist, chromfrei ist und neben Metallphosphat lösliche Molybdat-, Wolframat-, Vanadat-, Niobat- und/oder Tantalat-Ionen enthält (EP-B-15 020). Dabei kann die kationische Komponente des in der Lösung befindlichen Metallphosphats durch Kalzium, Magnesium, Barium, Aluminium, Zink, Cadmium, Eisen, Nickel, Kobalt und/oder Mangan gebildet werden.There have been various suggestions to increase the amount of flushing water reduce or eliminate entirely, for example Rinsing in a so-called rinsing water cascade with a considerable Reduction of the resulting rinse water. A reappraisal of the rinse water also obtained in a reduced amount inevitable. It is proposed to avoid rinsing water been to apply a zinc phosphating process, the Phosphating solutions are composed in such a way that let practically all components precipitate with calcium hydroxide. On in this way the rinse water treatment is made considerably easier, and at the same time the method has the advantage that water with sufficiently good quality can be recovered for the process. (DE-C-23 27 304). A disadvantage of such a procedure is, however, that due to the requirement that the Components of the phosphating solution the freedom for adaptation the composition of the phosphating solution to the Practice needs are severely limited. After all, there are procedures known for generating a conversion coating, in which after any cleaning and water rinsing that may be required Coating solutions are applied and then dried. The treatment solution can be applied while diving or Spray and then squeeze off the excess solution or by roller application, in which only the required Amount of liquid is applied to the metal surface, respectively. Which depends on the application of the treatment liquid subsequent drying can in principle be carried out at room temperature respectively. In general, however, it is common to have higher temperatures apply, preferably temperatures between 50 and 100 ° C. to get voted. One for the preparation of metal surfaces certain for subsequent coating with organic coatings The process consists of using a metal surface To wet phosphating liquid that has a pH of 1.5 to 3, is chromium-free and, in addition to metal phosphate, soluble molybdate, Contains tungstate, vanadate, niobate and / or tantalate ions (EP-B-15 020). The cationic component of the solution metal phosphate by calcium, magnesium, barium, Aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese be formed.
Ein Nachteil des zuletzt genannten Verfahrens ist, daß infolge der erforderlichen Zusätze Molydat-, Wolframat-, Vanadat-, Niobat- und der Tantalationen das Verfahren kostenmäßig aufwendiger als die herkömmlichen Phosphatierverfahren ist, ein anderer, daß die erhaltenen Phosphatüberzüge nicht allen heute gestellten Anforderungen, z. B. hinsichtlich Alkalibeständigkeit und damit Resistenz bei einer anschließenden kathodischen Elektrotauchlackierung sowie der erwünschten Korrosionsbeständigkeit, insbesondere in Verbindung mit einer anschließenden Lackierung, genügen.A disadvantage of the latter method is that due to the required additives molydate, tungstate, vanadate, niobate and Tantalizations cost more than the process conventional phosphating process, another is that the obtained Phosphate coatings do not meet all requirements today, e.g. B. with regard to alkali resistance and thus resistance to a subsequent cathodic electrocoating and the desired corrosion resistance, especially in connection with a subsequent painting, are sufficient.
Aufgabe der Erfindung ist es, ein Verfahren zum Aufbringen von Phosphatüberzügen auf Oberflächen von Zink, Eisen, Aluminium oder deren Legierungen bereitzustellen, daß die bekannten, insbesondere vorgenannten Nachteile nicht aufweist, dennoch kostengünstig und einfach in der Durchführung ist und zu qualitativ hochwertigen Phosphatüberzügen führt.The object of the invention is to provide a method for applying Phosphate coatings on surfaces of zinc, iron, aluminum or their To provide alloys that are known, in particular does not have the aforementioned disadvantages, yet inexpensive and is simple to implement and of high quality Phosphate coatings leads.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art
entsprechend der Erfindung derart ausgestaltet wird, daß man die
Oberflächen mit einer Phosphatierungslösung, die frei von Elementen der
5. und 6. Nebengruppe des Periodischen Systems der Elemente ist,
Die vorgenannte Formulierung hinsichtlich des Zink-Gehaltes soll zum Ausdruck bringen, daß im Falle der Behandlung von Oberflächen aus Eisen, Aluminium oder deren Legierungen ein Zinkgehalt in den genannten Konzentrationen unerläßlich ist. Bei der Behandlung von Zink oder Zinklegierungsoberflächen kann die Phosphatierungslösung ebenfalls Zink enthalten, jedoch ist ein Zinkgehalt nicht erforderlich. Elemente der 5. und 6. Nebengruppe des Periodischen Systems der Elemente sind Vanadin, Niob, Tantal, Chrom, Molybdän und Wolfram.The aforementioned formulation with regard to the zinc content is said to Express that in the case of treating surfaces Iron, aluminum or their alloys have a zinc content in the mentioned concentrations is essential. In the treatment of Zinc or zinc alloy surfaces can be the phosphating solution also contain zinc, but there is no zinc content required. Elements of the 5th and 6th subgroup of the periodic Systems of elements are vanadium, niobium, tantalum, chrome, and molybdenum Tungsten.
Um zu vermeiden, daß der Phosphatüberzug nach dem Auftrocknen einen Gehalt an wasserlöslichen Verbindungen aufweist, erfolgt die Einstellung des S-Wertes zweckmäßigerweise mit Nickeloxid, Manganoxid oder ggf. Zinkoxid oder aber mit Ammoniaklösung.To prevent the phosphate coating from drying out after drying Has content of water-soluble compounds, the takes place The S value is expediently set using nickel oxide, manganese oxide or possibly zinc oxide or with ammonia solution.
Eine zweckmäßige Ausgestaltung der Erfindung sieht vor, im Falle der Behandlung von Zink oder Zinklegierungen die Oberflächen mit einer Phosphatierungslösung zu benetzen, die zinkfrei ist. In diesem speziellen Fall stammt die zur Überzugsbildung erforderliche Zinkmenge aus der Oberfläche des behandelten Materials.An expedient embodiment of the invention provides, in the case of Treatment of zinc or zinc alloys with a surface To wet the phosphating solution, which is zinc-free. In this In a special case comes the necessary for the formation of the coating Amount of zinc from the surface of the treated material.
Die Benetzung der jeweiligen Metalloberflächen kann z.B. durch Tauchen und anschließendes Abtropfenlassen, durch Übergießen und Abschleudern, durch Bürsten, durch Spritzen mit Preßluft, air-les sowie auf elektrostatischem Wege erfolgen. Eine besonders elegante Methode der Applikation der Phosphatierungslösung erfolgt durch Aufwalzen mit strukturierten oder glatten Walzen im Gleichlauf oder im Gegenlauf.The wetting of the respective metal surfaces can e.g. by Diving and then draining, by pouring over and Spin off, by brushing, by spraying with compressed air, air-les as well as electrostatically. A particularly elegant one The method of application of the phosphating solution is carried out by Rolling with structured or smooth rolls in synchronism or in the opposite direction.
Die sich an die Benetzung der Metalloberfläche anschließende Trocknung kann im Prinzip bereits bei Raumtemperatur erfolgen. Vorteilhaft ist es jedoch, bei höheren Temperaturen zu arbeiten, weil dadurch die Zeit zur Ausbildung der Phosphatschicht erheblich verkürzt wird. Vorzugsweise erfolgt die Auftrocknung bei Temperaturen zwischen 50 und 200°C, wobei jedoch eine Objekttemperatur von 90°C nicht überschritten werden sollte.The one that follows the wetting of the metal surface In principle, drying can take place at room temperature. However, it is advantageous to work at higher temperatures because thereby the time for the formation of the phosphate layer considerably is shortened. Drying is preferably carried out at temperatures between 50 and 200 ° C, but with an object temperature of 90 ° C should not be exceeded.
Eine bevorzugte Weiterbildung der Erfindung besteht darin, die
Oberflächen mit einer Phosphatierungslösung zu benetzen, die
Eine zusätzliche Verbesserung der Qualität der Phosphatüberzüge ist
erreichbar, wenn man gemäß einer vorteilhaften Ausgestaltung der
Erfindung die Oberflächen mit einer Phosphatierungslösung benetzt, die
zusätzlich
Weitere vorteilhafte Ausführungsformen der Erfindung bestehen darin, die Oberflächen mit einer Phosphatierungslösung zu benetzen, die einen S-Wert von 0,5 bis 0,7 aufweist bzw. die Oberflächen derart mit der Phosphatierungslösung zu benetzen, daß nach dem Auftrocknen ein Phosphatschichtgewicht von 0,5 bis 2 g/m2 resultiert.Further advantageous embodiments of the invention consist of wetting the surfaces with a phosphating solution which has an S value of 0.5 to 0.7 or wetting the surfaces with the phosphating solution in such a way that after drying a phosphate layer weight of 0, 5 to 2 g / m 2 results.
Die Einstellung des bevorzugten S-Wertes von 0,5 bis 0,7 ist insbesondere bei der Behandlung von Zinkoberflächen mit zinkfreien Phosphatierungslösungen von Bedeutung, da dann der für den Zinkgehalt des Phosphatüberzuges verantwortliche Beizangriff der Phosphatierungslösung auf die Zinkoberfläche besonders optimal verläuft. Die Ausgestaltung der Erfindung mit Einstellung eines Phosphatüberzugsgewichtes von 0,5 bis 2 g/m2 ermöglicht die Ausbildung des Phosphatüberzuges in besonders kurzer Zeit und zudem von besonders hoher Qualität.The setting of the preferred S value of 0.5 to 0.7 is particularly important in the treatment of zinc surfaces with zinc-free phosphating solutions, since the pickling attack of the phosphating solution on the zinc surface, which is responsible for the zinc content of the phosphate coating, then proceeds particularly optimally. The embodiment of the invention with the setting of a phosphate coating weight of 0.5 to 2 g / m 2 enables the phosphate coating to be formed in a particularly short time and also of particularly high quality.
Bei Anwendung des erfindungsgemäßen Verfahrens werden
Phosphatschichten erzeugt, die 0,5 bis 3 Gew.-% Nickel
Damit eine einwandfreie Benetzung mit der Phosphatierungslösung gewährleistet ist, müssen die Metalloberflächen hinreichend rein sein. Dies ist im allgemeinen der Fall, wenn z. B. Bandmaterial unmittelbar nach der Verzinkung nach dem erfindungsgemäßen Verfahren behandelt wird. Falls die Metalloberfläche jedoch beölt oder verschmutzt ist, ist eine Entfettung bzw. Reinigung mit Hilfe an sich bekannter Verfahren vorzuschalten und anschließend zu spülen.This ensures perfect wetting with the phosphating solution is guaranteed, the metal surfaces must be sufficiently clean be. This is generally the case when e.g. B. tape material immediately after the galvanizing by the method according to the invention is treated. However, if the metal surface is oiled or is dirty, degreasing or cleaning with the help of itself to connect known methods and then to rinse.
Die beim erfindungsgemäßen Verfahren anzuwendende Phosphatierungslösung wird zweckmäßigerweise mit einer Temperatur im Bereich von 20 bis 80°C eingesetzt. Die Menge der Lösung liegt in der Regel zwischen 2 und 10 ml pro m2 Metalloberfläche. Die Auftrocknung erfolgt - sofern sie unter Wärmeeinwirkung geschieht - praktisch unverzüglich nach dem Benetzen der Oberfläche, d. h. nach einer Einwirkzeit von etwa 0,5 bis 5 sec.The phosphating solution to be used in the process according to the invention is expediently used at a temperature in the range from 20 to 80 ° C. The amount of the solution is usually between 2 and 10 ml per m 2 of metal surface. The drying takes place - if it happens under the influence of heat - practically immediately after wetting the surface, ie after an exposure time of about 0.5 to 5 seconds.
Mit der vorliegenden Erfindung wird ein Verfahren bereitgestellt, das in der Lage ist, Phosphatüberzüge in Sekundenschnelle zu erzeugen. Ein weiterer Vorteil gegenüber bekannten Verfahren liegt darin, daß eine aktivierende Vorbehandlung vor der Phosphatierung entfallen kann. Die erzeugten Phosphatüberzüge sind insbesondere von hoher Qualität hinsichtlich der Haftvermittlung von nachträglich aufgebrachten Lacken, Kunststoffen oder Klebern. Sie gleichen in ihrer Qualität den mit Hilfe des sog. Trikation-Verfahrens erzeugten Phosphatschichten. Dies ist insofern überraschend als die nach dem erfindungsgemäßen Verfahren erhaltenen Phosphatüberzüge in der Regel amorph sind, wohingegen die nach dem Trikation-Verfahren gebildeten Schichten stets kristallin sind.The present invention provides a method that is able to produce phosphate coatings in a matter of seconds. Another advantage over known methods is that there is no need for an activating pre-treatment before phosphating can. The phosphate coatings produced are particularly high Quality with regard to the provision of detention afterwards applied paints, plastics or adhesives. They are the same their quality is that produced with the help of the so-called trication method Phosphate layers. This is surprising in that the one after Phosphate coatings obtained according to the process of the invention as a rule are amorphous, whereas those formed by the trication method Layers are always crystalline.
Ein weiterer wesentlicher Vorteil der Erfindung besteht darin, daß Phosphatschichten erzeugt werden, die das Umformverhalten der so behandelten Metalle deutlich verbessert, ohne daß dadurch die Schweißbarkeit wesentlich beeinträchtigt wird.Another significant advantage of the invention is that Phosphate layers are generated that change the forming behavior of the so treated metals significantly improved without the Weldability is significantly affected.
Die mit dem erfindungsgemäßen Verfahren erzeugten Phosphatüberzüge sind auf allen Gebieten, auf denen Phosphatüberzüge angewendet werden, gut einsetzbar. Ein besonders vorteilhafter Anwendungsfall liegt in der Vorbereitung der Metalloberflächen für die anschließende Lackierung, insbesondere die Elektrotauchlackierung.The phosphate coatings produced by the process according to the invention are good in all areas where phosphate coatings are applied applicable. A particularly advantageous application is in Preparation of the metal surfaces for the subsequent painting, especially electrocoating.
Von besonders herausragender Bedeutung ist das erfindungsgemäße Verfahren für seine Anwendung auf die Phosphatierung von verzinkten oder legierungsverzinkten Stahlbändern. Unter der Bezeichnung verzinktes oder legierungsverzinktes Stahlband werden Bänder verstanden, die eine Auflage von Elektroytzink (ZE), Feuerzink (Z), Legierungen auf Basis Zink/Nickel (ZNE), Zink/Eisen (ZF) oder Zink/Aluminium (ZA bzw. AZ) aufweisen. Zu letzeren werden üblicherweise auch Legierungen mit z. B. 55 Gew.-% Al und 45 Gew.-% Zn gezählt.The invention is particularly important Process for its application to the phosphating of galvanized or galvanized steel strips. Under the label Galvanized or alloy galvanized steel strips become strips understood that an edition of Elektroytzink (ZE), Feuerzink (Z), Alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or Zinc / aluminum (ZA or AZ). The latter are usually also alloys with e.g. B. 55 wt .-% Al and 45 wt .-% Zn counted.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the examples below and explained in more detail.
Die in den Beispielen genannten Werte für Freie Säure und Gesamtsäure wurden wie folgt bestimmt:The values for free acid and total acid given in the examples were determined as follows:
Zur Bestimmung der Freien Säure wird 1 ml Badlösung nach Verdünnung auf ca. 50 ml mit destilliertem Wasser, gegebenenfalls unter Zusatz von K3(Co(CN)6) oder K4(Fe(CN)6) zwecks Beseitigung störender Metallkationen, unter Verwendung von Dimethylgelb als Indikator mit n/10 NaOH bis zum Umschlag von rosa nach gelb titriert. Die verbrauchten ml n/10 NaOH ergeben die Freie Säure. Es entspricht 1 ml n/10 Natronlauge 7,098 mg freies P2O5. To determine the free acid, 1 ml bath solution after dilution to approx. 50 ml with distilled water, optionally with the addition of K 3 (Co (CN) 6 ) or K 4 (Fe (CN) 6 ) to remove interfering metal cations, is used titrated from dimethyl yellow as an indicator with n / 10 NaOH to a change from pink to yellow. The ml n / 10 NaOH consumed give the free acid. It corresponds to 1 ml of n / 10 caustic soda, 7.098 mg of free P 2 O 5 .
Die Gesamtpunktezahl (GS) wird ermittelt, indem 1 ml der Phosphatierungslösung nach Verdünnung mit Wasser auf etwa 50 ml unter Verwendung von Phenolphthalein als Indikator bis zum Farbumschlag von farblos nach rot titriert wird. Die Anzahl der hierfür verbrauchten ml n/10 Natronlauge ergeben die Gesamtpunktezahl.The total score (GS) is determined by using 1 ml of the Phosphating solution after dilution with water to about 50 ml Use of phenolphthalein as an indicator until the color changes from titrated colorless to red. The number of used for this ml n / 10 sodium hydroxide solution give the total number of points.
Der sogenannte S-Wert ergibt sich durch Division der Freien Säure durch das Gesamt-P2O5. Hierbei wird das Gesamt-P2O5 bestimmt, indem im Anschluß an die Ermittlung der Freien Säure die Titrationslösung nach Zugabe von 20 ml 30-%-iger neutraler Kaliumoxalatlösung gegen Phenolphthalein als Indikator bis zum Umschlag von farblos nach rot mit n/10 NaOH titriert wird. Der Verbrauch an ml n/10 NaOH zwischen dem Umschlag mit Dimethylgelb und dem Umschlag mit Phenolphthalein ergibt das Gesamt-P2O5. (Vgl. W. Rausch "Die Phosphatierung von Metallen "Eugen G. Leuze-Verlag 1988, S. 300ff)The so-called S value is obtained by dividing the free acid by the total P 2 O 5 . Here, the total P 2 O 5 is determined by, after the determination of the free acid, the titration solution after adding 20 ml of 30% strength neutral potassium oxalate solution against phenolphthalein as an indicator until the color changes to red with n / 10 NaOH is titrated. The consumption of ml n / 10 NaOH between the envelope with dimethyl yellow and the envelope with phenolphthalein gives the total P 2 O 5 . (See W. Rausch "The Phosphating of Metals" Eugen G. Leuze-Verlag 1988, p. 300ff)
Unmittelbar im Anschluß an die Schmelztauchverzinkung von Stahlband
wurde auf die noch 35°C warme Bandoberfläche eine
Phosphatierungslösung aufgebracht, die folgende Bestandteile - in
vollentsalztem Wasser aufgelöst - enthielt.
Die Phosphatierungslösung hatte eine Temperatur von 25°C, einen pH-Wert von 1,7 und einen S-Wert von 0,6. Es betrugen der Gehalt an Freier Säure 5,9 ml, an Gesamtsäure 17,1 ml.The phosphating solution had a temperature of 25 ° C, one pH value of 1.7 and an S value of 0.6. The content was Free acid 5.9 ml, total acid 17.1 ml.
Die Application der Phosphatierungslösung erfolgte mit Hilfe einer Walzenbeschichtungsmaschine (Rollcoater), wie sie auch zur Bandlackierung verwendet wird. Der hierbei aufgebrachte Naßfilm von 5 ml Phosphatierungslösung pro m2 Metalloberfläche wurde nach einer Einwirkzeit von 2 sec in einem Durchlaufofen bei 200°C aufgetrocknet. Beim Verlassen des Ofens hatte das Band eine Objekttemperatur von 60°C. The phosphating solution was applied with the help of a roll coating machine (roll coater), as is also used for coil coating. The wet film of 5 ml of phosphating solution per m 2 of metal surface applied was dried in a continuous oven at 200 ° C. after an exposure time of 2 seconds. When leaving the furnace, the belt had an object temperature of 60 ° C.
Der aufgebrachte Phosphatüberzug war gleichmäßig, geschlossen und hatte
ein Trockenschichtgewicht von
Das nach dem erfindungsgemäßen Verfahren phosphatierte Band kann auch
den im Automobilwerk üblichen Verfahrensgang durchlaufen. Das heißt, es
können zunächst in üblicher Weise die einzelnen Karosserieteile geformt
und durch Schweißen unter Ausbildung der Karosserie zusammengesetzt
werden und danach die Behandlungsanlage Reinigen-Spülen-Aktivieren-Phosphatieren-Spülen-Nachspülen
passieren. Hierbei erfolgt die
Phosphatierung während einer Behandlungszeit von 3,5 min und einer
Temperatur der Phosphatierungslösung von 52°C. Die Zusammensetzung der
Phosphatierungslösung ist:
Der Gehalt an Freier Säure lag bei 1,5, der an Gesamtsäure bei 27,8 Punkten jeweils unter Verwendung einer Badprobe von 10 ml gemessen. Der S-Wert war auf 0,08 eingestellt.The free acid content was 1.5 and the total acid content 27.8 Points were measured using a 10 ml bath sample. Of the S value was set to 0.08.
Der auf diese Weise erzeugte Phosphatüberzug hat ein Flächengewicht von
2,56 g/m2 und enthielt 31 Gew.-% P2O5, 35 Gew.-% Zink, 6,4 Gew.-% Mangan,
1,7 Gew.-% Nickel.
Im Anschluß an die Phosphatierbehandlung werden die Karosserien
zunächst mit einem kathodischen Elektrotauchlack und anschließend mit
dem üblichen Automobil-Lackaufbau versehen. The phosphate coating produced in this way has a weight per unit area of 2.56 g / m 2 and contained 31% by weight of P 2 O 5 , 35% by weight of zinc, 6.4% by weight of manganese, 1.7% by weight. -% nickel.
Following the phosphating treatment, the bodies are first provided with a cathodic electrodeposition paint and then with the customary automotive paint structure.
Probebleche, mit denen der vorgenannte Verfahrensgang simuliert
wurde, wurden folgenden Prüfungen unterworfen:
Steinschlag-Test plus VDA-Wechseltest, Freibewitterung, Gitterschnitt
plus 240 h Schwitzwasser-Konstantklima-Test.Test sheets with which the aforementioned process was simulated were subjected to the following tests:
Stone chip test plus VDA alternating test, outdoor weathering, cross-cut plus 240 h condensation water constant climate test.
Die Tests ergaben, daß die Ergebnisse in jedem Punkt den gestellten Erwartungen entsprachen. Insbesondere zeigte sich, daß die Phosphatierung in der 1. Stufe zu gleich guten Ergebnissen führte wie die Phosphatierung nach den herkömmlichen Trikation-Verfahren.The tests showed that the results were the same in every point Met expectations. In particular, it was found that the Phosphating in the 1st stage led to equally good results as phosphating according to conventional trication processes.
Auf eine elektrolytisch verzinkte Bandoberfläche wurde mit Hilfe
eines Rollcoaters eine Phosphatierungslösung mit einer Temperatur von
27°C aufgebracht, die folgende Zusammensetzung hatte:
Die Lösung hatte einen S-Wert von 0,62, einen Gehalt an Freier Säure
von 10,3 und einen solchen von Gesamtsäure von 29,7 (bezogen auf eine
Badprobe von 1 ml). Der Naßfilm der Lösung auf der Bandoberfläche
betrug
3 ml/m2.The solution had an S value of 0.62, a free acid content of 10.3 and a total acid content of 29.7 (based on a bath sample of 1 ml). The wet film of the solution on the belt surface was
3 ml / m 2 .
Nach dem Trocknen des Naßfilms bei einer Ofentemperatur von 200°C wurde ein gleichmäßiger geschlossener Phosphatüberzug mit einem Schichtgewicht von 1,6 g/m2 erhalten.After drying the wet film at an oven temperature of 200 ° C., a uniform, closed phosphate coating with a layer weight of 1.6 g / m 2 was obtained.
Eine Überprüfung des Phosphatüberzuges bezüglich Zusammensetzung, Verformbarkeit, Schweißbarkeit, Haftung und Korrosionsschutz nachträglich aufgebrachter organischer Lacküberzüge zeigte Ergebnisse, die sonst mit Hilfe der herkömmlichen Phosphatierverfahren entsprechend dem Trikation-Verfahren erzeugt werden können. A check of the phosphate coating with regard to composition, Deformability, weldability, adhesion and corrosion protection subsequently applied organic varnish coatings showed Results otherwise using conventional Phosphating process generated according to the trication process can be.
Auf eine gereinigte und gespülte Bandoberfläche aus Stahl wurde mit
Hilfe eines Walzenstuhls bei Raumtemperatur ein Naßfilm von 5 ml/m2
einer Phosphatierungslösung aufgebracht, die folgende Zusammensetzung
hatte:
Die Lösung hatte einen S-Wert von 0,56, einen Gehalt an Freier Säure von 9,4 und einen Gehalt an Gesamtsäure von 29,2 (bezogen auf 1 ml Badprobe).The solution had an S value of 0.56, containing free acid of 9.4 and a total acid content of 29.2 (based on 1 ml Bath sample).
Nach dem Trocknen des Naßfilms bei einer Temperatur von 150°C wurde ein
gleichmäßiger und geschlossener Phosphatüberzug mit einem
Schichtgewicht von 1,0 g/m2 erhalten, der folgende Zusammensetzung
hatte:
37 Gew.-% P2O5, 4,2 Gew.-% Mangan, 1,6 Gew.-% Nickel,
2,1 Gew.-% Zink.After drying the wet film at a temperature of 150 ° C., a uniform and closed phosphate coating with a layer weight of 1.0 g / m 2 was obtained, which had the following composition:
37 wt% P 2 O 5 , 4.2 wt% manganese, 1.6 wt% nickel, 2.1 wt% zinc.
Eine Überprüfung des Phosphatüberzuges bezüglich Haftung und Korrosionsschutz nachträglich aufgebrachter organischer Lacküberzüge zeigte, daß die gestellten Anforderungen voll erfüllt werden.A review of the phosphate coating for liability and Corrosion protection of subsequently applied organic lacquer coatings showed that the requirements are fully met.
Auf die Oberfläche gereinigter und gespülter Aluminiumbleche der Legierung AlMgSi wurden bei Raumtemperatur 6 ml/m2 der Phosphatierungslösung aus Beispiel 3 mit Hilfe einer Walze aufgebracht und der Naßfilm bei 150°C während einer Dauer von 15 sec in einem Umluftofen aufgetrocknet. Die trockene Phosphatschicht hatte ein Flächengewicht von 1,95 g/m2 und eine Zusammensetzung von 37 Gew.-% P2O5, 3,9 Gew.-% Mangan, 1,5 Gew.-% Nickel und 1,9 Gew.-% Zink. Auch hier waren die Eiaenschaften der Phosphatschicht hinsichtlich Haftung und Korrosionsschutz in Verbindung mit einem anschließend aufgebrachten Überzug den Erwartungen entsprechend.6 ml / m 2 of the phosphating solution from Example 3 were applied to the surface of cleaned and rinsed aluminum sheets of the alloy AlMgSi at room temperature with the aid of a roller, and the wet film was dried at 150 ° C. for 15 seconds in a forced air oven. The dry phosphate layer had a basis weight of 1.95 g / m 2 and a composition of 37% by weight of P 2 O 5 , 3.9% by weight of manganese, 1.5% by weight of nickel and 1.9% by weight .-% zinc. Here, too, the properties of the phosphate layer with regard to adhesion and corrosion protection in connection with a subsequently applied coating were in line with expectations.
Claims (7)
- A method for applying phosphate coatings to surfaces of zinc, iron, aluminium or alloys thereof by wetting with a phosphating solution containing divalent cations and phosphate and subsequent drying-on of the liquid film, characterised in that the surfaces are wetted with a phosphating solution which is free of elements of the 5th and 6th subgroup of the periodic table of the elements, contains
0.5 to 8 g/l nickel, 2 to 20 g/l manganese, 18 to 170 g/l phosphate (calculated as P2O5) - A method according to Claim 1, characterised in that in the case of phosphating surfaces of zinc or zinc alloys a phosphating solution is used which is zinc-free.
- A method according to Claim 1, characterised in that the surfaces are wetted with a phosphating solution which contains
0.8 to 6 g/l nickel, 3 to 16 g/l manganese, 30 to 140 g/l phosphate (calculated as P2O5) - A method according to Claim 1, 2 or 3, characterised in that the surfaces are wetted with a phosphating solution which additionally contains2 to 10 g/l SiO2 and0.05 to 0.5 g/l fluoride (calculated as F).
- A method according to one or more of Claims 1 to 4, characterised in that the surfaces are wetted with a phosphating solution which has an S value of 0.5 to 0.7.
- A method according to one or more of Claims 1 to 5, characterised in that the surfaces are wetted with the phosphating solution such that after drying-on a phosphate layer weight of 0.5 to 2 g/m2 results.
- A method according to one or more of Claims 1 to 6, characterised in that the surfaces to be phosphated consist of zinc-plated or zinc alloy-plated steel strip.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4443882A DE4443882A1 (en) | 1994-12-09 | 1994-12-09 | Process for applying phosphate coatings on metal surfaces |
| DE4443882 | 1994-12-09 | ||
| PCT/EP1995/004774 WO1996017977A1 (en) | 1994-12-09 | 1995-12-05 | Method of applying phosphate coatings to metal surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0796356A1 EP0796356A1 (en) | 1997-09-24 |
| EP0796356B1 true EP0796356B1 (en) | 1998-11-04 |
Family
ID=6535385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95941068A Expired - Lifetime EP0796356B1 (en) | 1994-12-09 | 1995-12-05 | Method of applying phosphate coatings to metal surfaces |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5904786A (en) |
| EP (1) | EP0796356B1 (en) |
| JP (1) | JPH10510322A (en) |
| KR (1) | KR970707322A (en) |
| CN (1) | CN1066207C (en) |
| AT (1) | ATE173034T1 (en) |
| AU (1) | AU700492B2 (en) |
| CA (1) | CA2207932C (en) |
| DE (2) | DE4443882A1 (en) |
| ES (1) | ES2124032T3 (en) |
| MX (1) | MX9704126A (en) |
| WO (1) | WO1996017977A1 (en) |
| ZA (1) | ZA9510440B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19749508A1 (en) * | 1997-11-08 | 1999-05-12 | Henkel Kgaa | Corrosion protection of galvanized and alloy galvanized steel strips |
| CN1111569C (en) * | 1998-04-13 | 2003-06-18 | 赵全玺 | Inorganic phosphate paint |
| US6235111B1 (en) * | 1998-11-25 | 2001-05-22 | Ez Environmental Solutions, Corporation | Closed-loop phosphatizing system and method |
| DE10010355A1 (en) | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution |
| US6530999B2 (en) | 2000-10-10 | 2003-03-11 | Henkel Corporation | Phosphate conversion coating |
| US20040188323A1 (en) * | 2003-03-24 | 2004-09-30 | Tzatzov Konstantin K. | Active coating system for reducing or eliminating coke build-up during petrochemical processes |
| CN100338260C (en) * | 2004-05-14 | 2007-09-19 | 深圳市成功科技有限公司 | Composite nickel plating method for aluminum alloy heating piece |
| US20060002832A1 (en) * | 2004-05-19 | 2006-01-05 | Ez Environmental Solutions Corporation, A California Corporation | Selectable closed-loop phosphatizing wash & rinse system and method |
| US7514153B1 (en) | 2005-03-03 | 2009-04-07 | The United States Of America As Represented By The Secretary Of The Navy | Method for deposition of steel protective coating |
| CN100366796C (en) * | 2005-04-22 | 2008-02-06 | 吉林大学 | Method for preparing film of inorganic phosphate in aqueous solution |
| US8137805B2 (en) * | 2007-06-21 | 2012-03-20 | Caterpillar Inc. | Manganese based coating for wear and corrosion resistance |
| US8137761B2 (en) * | 2008-06-13 | 2012-03-20 | Caterpillar Inc. | Method of coating and induction heating a component |
| CN101660164B (en) * | 2008-08-26 | 2011-12-28 | 宝山钢铁股份有限公司 | Lubricating electro-galvanized steel plate and production method thereof |
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| DE2907094A1 (en) * | 1979-02-23 | 1980-09-04 | Metallgesellschaft Ag | PHOSPHATION SOLUTIONS |
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-
1994
- 1994-12-09 DE DE4443882A patent/DE4443882A1/en not_active Withdrawn
-
1995
- 1995-12-05 MX MX9704126A patent/MX9704126A/en unknown
- 1995-12-05 AT AT95941068T patent/ATE173034T1/en active
- 1995-12-05 JP JP8517316A patent/JPH10510322A/en active Pending
- 1995-12-05 EP EP95941068A patent/EP0796356B1/en not_active Expired - Lifetime
- 1995-12-05 US US08/860,350 patent/US5904786A/en not_active Expired - Lifetime
- 1995-12-05 KR KR1019970702491A patent/KR970707322A/en not_active Application Discontinuation
- 1995-12-05 DE DE59504172T patent/DE59504172D1/en not_active Expired - Lifetime
- 1995-12-05 CN CN95196688A patent/CN1066207C/en not_active Expired - Lifetime
- 1995-12-05 AU AU42599/96A patent/AU700492B2/en not_active Ceased
- 1995-12-05 CA CA002207932A patent/CA2207932C/en not_active Expired - Fee Related
- 1995-12-05 ES ES95941068T patent/ES2124032T3/en not_active Expired - Lifetime
- 1995-12-05 WO PCT/EP1995/004774 patent/WO1996017977A1/en not_active Application Discontinuation
- 1995-12-08 ZA ZA9510440A patent/ZA9510440B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE173034T1 (en) | 1998-11-15 |
| JPH10510322A (en) | 1998-10-06 |
| ZA9510440B (en) | 1997-06-09 |
| EP0796356A1 (en) | 1997-09-24 |
| CN1169165A (en) | 1997-12-31 |
| AU700492B2 (en) | 1999-01-07 |
| CN1066207C (en) | 2001-05-23 |
| CA2207932C (en) | 2007-05-08 |
| US5904786A (en) | 1999-05-18 |
| DE59504172D1 (en) | 1998-12-10 |
| MX9704126A (en) | 1998-02-28 |
| WO1996017977A1 (en) | 1996-06-13 |
| CA2207932A1 (en) | 1996-06-13 |
| AU4259996A (en) | 1996-06-26 |
| ES2124032T3 (en) | 1999-01-16 |
| KR970707322A (en) | 1997-12-01 |
| DE4443882A1 (en) | 1996-06-13 |
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