EP3612663A1 - Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie - Google Patents
Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serieInfo
- Publication number
- EP3612663A1 EP3612663A1 EP18716514.7A EP18716514A EP3612663A1 EP 3612663 A1 EP3612663 A1 EP 3612663A1 EP 18716514 A EP18716514 A EP 18716514A EP 3612663 A1 EP3612663 A1 EP 3612663A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- activation
- mmol
- alkaline aqueous
- aqueous dispersion
- 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.)
- Granted
Links
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 82
- 239000011701 zinc Substances 0.000 title claims abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title description 12
- 239000002184 metal Substances 0.000 title description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 51
- 235000021317 phosphate Nutrition 0.000 claims abstract description 46
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000000470 constituent Substances 0.000 claims abstract description 12
- 229910052827 phosphophyllite Inorganic materials 0.000 claims abstract description 10
- SPDJAIKMJHJYAV-UHFFFAOYSA-H trizinc;diphosphate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SPDJAIKMJHJYAV-UHFFFAOYSA-H 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 33
- 230000002378 acidificating effect Effects 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000003618 dip coating Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 150000002222 fluorine compounds Chemical class 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001994 activation Methods 0.000 abstract description 49
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 6
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000010452 phosphate Substances 0.000 description 13
- 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 12
- 229910000165 zinc phosphate Inorganic materials 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- 238000001636 atomic emission spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000012465 retentate Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000000184 acid digestion Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [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
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical class [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
- C23F11/188—Mixtures of inorganic inhibitors containing 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C22/362—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 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
- C23C22/34—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
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Definitions
- the present invention relates to a process for zinc phosphating of components comprising surfaces of zinc for suppressing the formation of insoluble components of phosphating loosely adhering to the surfaces of zinc, and thus further
- Method is based on an activation of the zinc surfaces by means of dispersions containing particulate hopeite, phosphophyllite, scholzite and / or hureaulite, wherein the proportion of particulate phosphates in the activation of the amount of free fluoride and dissolved silicon in the zinc phosphating must be adjusted.
- the zinc phosphating is initiated with an activation of the metal surfaces of the component to be phosphated.
- the wet-chemical activation takes place by contact with colloidal dispersions of phosphates, which in this respect on the
- Suitable dispersions are colloidal, mostly alkaline aqueous compositions based on phosphate crystallites, which have only small crystallographic deviations in their crystal structure from the type of zinc phosphate layer to be deposited.
- Jernstedt salt a colloidal composition based on phosphate crystallites, which have only small crystallographic deviations in their crystal structure from the type of zinc phosphate layer to be deposited.
- WO 98/39498 A1 teaches in this connection in particular bi- and trivalent phosphates of the metals Zn, Fe, Mn, Ni, Co, Ca and Al, wherein technically preferred phosphates of the metal zinc are used for activation for a subsequent zinc phosphating.
- Each type of activation has its peculiarity with respect to the phosphating to be carried out in the subsequent step, which becomes particularly significant in the treatment of components composed of a mix of different metallic materials. Closed crystalline zinc phosphate coatings can no longer be formed on steel surfaces of components activated with Jernstedt salts if, in the zinc phosphating bath, the proportion of dissolved aluminum reaches a certain threshold value, for example in the case of components with high contents
- Phosphate coatings can be achieved on the aluminum surfaces. Activation with bi- and trivalent phosphates, however, in zinc phosphating baths, where also layer-forming surfaces of aluminum are to be treated, often gives rise to defective coatings on the zinc surfaces, characterized by loose adhesions of components of the zinc phosphate coating observable in the following Dipcoating significantly reduce the paint adhesion on the zinc surfaces.
- the loose adhesions consisting of phosphates are partly passed through into a dip coating following the zinc phosphatization, where they are in turn partly dissolved in the aqueous binder dispersion.
- the carryover of phosphates can be the cause of increased stoving temperatures, in particular for immersion lacquers which contain, in addition to the dispersed resin, water-soluble salts of yttrium and / or bismuth.
- This object is surprisingly achieved in that the proportion of contributing to the activation of particulate phosphates is adjusted to the amount of free fluoride and silicon in the zinc phosphating.
- the present invention thus relates to a method for corrosion-protective treatment of a series of metallic components which comprises metallic components which at least partially have surfaces of zinc, in which the metallic components of the series successively undergo the following wet-chemical treatment steps: (I) activation by contacting with an alkaline aqueous dispersion having a D50 value of less than 3 ⁇ and whose inorganic particulate component comprises phosphates, wherein the totality of these phosphates at least partially from hopeite, phosphophyllite, scholzite and / or Hureaulith is composed;
- Component of the alkaline aqueous dispersion of the activation in mmol / kg based on PÜ4 to the sum of the concentration of free fluoride and the concentration of silicon in each case in the acidic aqueous composition of the zinc phosphating and in each case in mmol / kg is greater than 0.5.
- the components treated in accordance with the present invention can be any arbitrarily shaped and designed spatial structures which originate from a fabrication process, in particular also semi-finished products such as strips, sheets, rods, tubes, etc. and composite constructions
- a component is metallic if its geometric surface is formed by at least 10% of metallic surfaces.
- galvanized steel grades according to the invention form surfaces of zinc, whereas according to the invention surfaces of iron can be exposed at the cut edges and cut-through parts, for example, an automobile body, which is made solely of galvanized steel.
- the components of the series which at least partially have surfaces of zinc, preferably at least 5%, based on the component surface surfaces of zinc.
- Steel grades such as hot-formed steel may also be provided with a metallic coating of aluminum and silicon several microns thick to prevent scaling and forming.
- Such a coated steel material although the base material is steel, has an aluminum surface in the context of the present invention.
- Corrosion-preventing treatment of the components in series occurs when a plurality of components are brought into contact with the treatment solution provided in the respective treatment steps and usually stored in system tanks, wherein the in-contact Bring the individual components one after the other and thus separated from each other in time.
- the system tank is the container in which the pre-treatment solution is in series for the purpose of anti-corrosive treatment.
- the treatment steps of activation and zinc phosphating are carried out for a component of the anticorrosive treatment in series then "successively", unless they are interrupted by any other than the respectively provided subsequent wet chemical treatment.
- a rinsing step is used exclusively for the complete or partial removal of soluble residues, particles and active components, which are abducted adhering to the component from a previous wet-chemical treatment step, of the component to be treated, without active components based on metallic or semi-metallic elements being contained in the rinsing liquid itself. which are already consumed by the mere contact bringing the metallic surfaces of the component with the rinsing liquid. So the flushing liquid can only be city water.
- pH value corresponds to the negative decadic logarithm of the hydronium ion activity at 20 ° C. and can be determined by means of pH-sensitive glass electrodes and accordingly a composition is acidic if its pH value is Value is below 7, and alkaline if its pH is above 7.
- a coordination of the individual treatment steps of activation and zinc phosphating is implemented in such a way that closed coatings are formed on the zinc surfaces of the metallic components in the course of zinc phosphating, on which no finely divided constituents of the zinc phosphate coating are deposited. Accordingly, coatings are available in the subsequent dip coating, which adhere well to the zinc surfaces treated according to the invention.
- concentration of silicon in the acidic aqueous composition of the zinc phosphating is to be determined in the filtrate of a membrane filtration of the acidic aqueous composition, which is carried out using a membrane with a nominal pore size of 0.2 ⁇ , by means of atomic emission spectrometry (ICP-OES).
- the particulate constituent of the alkaline aqueous dispersion is that solid fraction which, after drying the retentate, remains an ultrafiltration of a defined partial volume of the alkaline aqueous dispersion with a nominal cutoff limit of 10 kD (NMWC, Nominal Molecular Weight Cut Off).
- the ultrafiltration is carried out with the addition of deionized water ( ⁇ ⁇ 1 ⁇ 8 ⁇ 1 ) until a conductivity below 10 ⁇ 8 ⁇ is measured in the filtrate.
- the inorganic particulate component of the alkaline aqueous dispersion is, in turn, that which remains when the particulate component obtained from the drying of the ultrafiltration retentate pyrolyzes in a reaction furnace while feeding a CO 2 -free oxygen stream at 900 ° C. without admixing catalysts or other additives until an infrared sensor in the outlet of the reaction furnace delivers a signal identical to the CO2-free carrier gas (blank value).
- Component contained phosphates are after acid digestion of the same with aqueous 10 wt .-% HNO3 solution at 25 ° C for 15 min as phosphorus content means
- ICP-OES Atomic emission spectrometry
- the alkaline aqueous dispersion has a D50 value of less than 3 ⁇ , otherwise only a very high and thus non-economic proportions of particulate components sufficient occupancy of the
- the D50 value of the alkaline aqueous dispersion of the activation is therefore less than 2 ⁇ , particularly preferably less than 1 ⁇ , wherein the D90 value, preferably less than 5 ⁇ , so that at least 90 vol. -% of particulate contained in the alkaline aqueous composition
- the D50 value in this context refers to the volume-average particle diameter which does not exceed 50% by volume of the particulate constituents contained in the alkaline aqueous composition.
- Promote phosphating and activate the metal surfaces in this sense are composed primarily of phosphates, which in turn at least partially include hopeite, phosphophyllite, scholzite and / or hureau.
- such activation is preferred in which the phosphate fraction of the inorganic particulate constituents of the alkaline aqueous dispersion of the activation is calculated at at least 30% by weight, more preferably at least 35% by weight, particularly preferably at least 40% by weight PC and based on the inorganic particulate component of the dispersion.
- Activation in the context of the present invention is thus essentially based on the phosphates according to the invention in particulate form, wherein the phosphates are preferably at least partially composed of hopeite, phosphophyllite and / or scholzite, particularly preferably hopeite and / or phosphophyllite and particularly preferably hopite are.
- the phosphites hopeite, phosphophyllite, scholzite and / or hureaulite may be dispersed into an aqueous solution to provide the alkaline aqueous dispersion as finely ground powders or as a powder paste triturated with a stabilizer.
- Hopeite without consideration of water of crystallization, comprise stoichiometrically Zn3 (P04) 2 and the nickel and manganese variants Zn2Mn (PÜ4) 3, Zn2Ni (P04) 3, whereas phosphophyllite consists of Zn2Fe (PÜ4) 3, Scholzite of Zn2Ca (P04) 3 and Hureaulith Mn3 (PÜ4) 2 exists.
- the existence of the crystalline phases hopeite, phosphophyllite, scholzite and / or hureaulite in the alkaline aqueous dispersion may, after separation of the particulate component by ultrafiltration with a nominal cutoff limit of 10 kD (NMWC) as described above and drying of the retentate to constant mass at 105 ° C using X-ray diffractometric methods (XRD).
- NMWC nominal cutoff limit of 10 kD
- Zinc phosphate coatings according to the invention preferably in which the alkaline aqueous dispersion of the activation of at least 20 wt .-%, preferably at least 30 wt .-%, particularly preferably at least 40 wt .-% of zinc in the inorganic particulate component of the alkaline aqueous dispersion based on the phosphate content of inorganic particulate matter calculated as PÜ4.
- activation in the sense of the present invention should not be achieved by means of colloidal solutions of titanium phosphates, as otherwise the layer-forming zinc phosphating Surfaces of iron, especially steel, not reliable succeeds and the advantage of thin effectively effective against corrosion protective phosphate coatings on aluminum is not realized.
- the proportion of titanium in the inorganic particulate component of the alkaline aqueous dispersion of the activation is preferably less than 5 wt .-%, more preferably less than 1 wt .-% based on the inorganic particulate component of the dispersion ,
- the alkaline aqueous dispersion of the activation contains a total of less than 10 mg / kg, more preferably less than 1 mg / kg of titanium.
- the proportion of the inorganic particulate components comprising phosphates should be adjusted accordingly.
- the proportion of phosphates in the inorganic particulate constituent based on the alkaline aqueous dispersion of the activation, of at least 40 mg / kg,
- the activation should be carried out with as dilute as possible colloidal solutions. It is therefore preferred that the proportion of the phosphates in the inorganic particulate constituent based on the alkaline aqueous dispersion of the activation is less than 0.8 g / kg, more preferably less than 0.6 g / kg, particularly preferably less than 0.4 g / kg calculated as PO4.
- the metal surfaces are only slightly stained during activation.
- the inorganic particulate constituents in particular the insoluble phosphates, should undergo only a slight degree of corrosion. Accordingly, it is preferred in the process according to the invention if the pH of the alkaline aqueous dispersion in the activation is greater than 8, more preferably greater than 9, but preferably less than 12, more preferably less than 1.
- the second zinc phosphating treatment step is followed by activation with or without intermediate rinsing step, immediately, so that each component of the series successively undergoes activation followed by zinc phosphating without intervening wet chemical treatment step.
- neither a rinsing nor a drying step takes place between the activation and the zinc phosphating for the components of the series.
- a drying step in the context of the present invention refers to a process in which the surfaces of the metallic component having a wet film are to be dried with the aid of technical measures, for example by supplying thermal energy or passing an air stream.
- the zinc phosphating succeeds insofar as the tuning according to the invention has been carried out with the activation, as a rule with conventional phosphating baths
- the amount of phosphate ions comprises the orthophosphoric acid and the anions of the salts of orthophosphoric acid dissolved in water, calculated as PO4.
- the preferred pH of the acidic aqueous composition of zinc phosphating in the process according to the invention is above 2.5, more preferably above 2.7, but preferably below 3.5, most preferably below 3.3.
- the proportion of the free acid in points in the acidic aqueous composition of the zinc phosphating is preferably at least 0.4, but preferably not more than 3, more preferably not more than 2.
- the proportion of free acid in points is determined by adding 10 ml sample volume of the diluted acidic aqueous composition to 50 ml and titrated with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of ml of sodium hydroxide gives the score of free acid.
- the acidic aqueous composition of the zinc phosphating additionally contains cations of the metals manganese, calcium and / or iron.
- the customary addition of zinc phosphating can also be carried out in an analogous manner according to the invention so that the acidic aqueous composition can contain the conventional accelerators such as hydrogen peroxide, nitrite, hydroxylamine, nitroguanidine and / or N-methylmorpholine-N-oxide.
- the conventional accelerators such as hydrogen peroxide, nitrite, hydroxylamine, nitroguanidine and / or N-methylmorpholine-N-oxide.
- a source of free fluoride ions is essential for the process of layer-forming
- Zinc phosphating on all metallic surfaces of the component selected from surfaces of zinc, iron and / or aluminum If all surfaces of the metallic materials of the components to be treated in the series are to be provided with a phosphate coating, the amount of the particulate constituents in the activation must be adapted to the amount of free fluoride required for layer formation in the zinc phosphating. Should in addition to the zinc surfaces as well as the surfaces of iron, especially steel, with a closed and defect-free phosphate coating, it is preferred in the process according to the invention if the amount of free fluoride in the acidic aqueous composition is at least 0.5 mmol / kg.
- the amount of free fluoride in the acidic aqueous composition is at least 2 mmol / kg.
- concentration of free fluoride should not exceed values above which the phosphate coatings predominantly have adhesions that are easily wipeable, since these can not be avoided by a disproportionately increased amount of particulate phosphates in the alkaline aqueous dispersion of the activation. Therefore, it is also advantageous for economic reasons, if in the process according to the invention the concentration of free fluoride in the acidic aqueous composition of the zinc phosphating is below 8 mmol / kg.
- Suitable sources of free fluoride are hydrofluoric acid and its water-soluble salts, such as ammonium bifluoride and sodium fluoride, as well as complex fluorides of the elements Zr, Ti and / or Si, in particular complex fluorides of the element Si.
- the source of free fluoride is therefore selected from hydrofluoric acid and its water-soluble salts and / or complex fluorides of the elements Zr, Ti and / or Si.
- Salts of hydrofluoric acid are water-soluble for the purposes of the present invention, if their solubility in deionized water ( ⁇ ⁇ Scnr 1 ) at 60 ° C is at least 1 g / L calculated as F.
- the source of free fluoride is at least partially selected from complex fluorides of the element Si, in particular from hexafluorosilicic acid and its salts.
- speckling one skilled in the phosphating art understands the phenomenon of local deposition of amorphous white zinc phosphate in an otherwise crystalline phosphate layer on the treated zinc surfaces or on the treated galvanized or alloy galvanized steel surfaces. The speckling is caused by a locally increased pickling rate of the substrate.
- Such point defects in the phosphating can be the starting point for the corrosive softening of subsequently applied organic coating systems, so that the occurrence of specks in practice is largely to be avoided.
- concentration of silicon in the acidic aqueous composition dissolved in water is to be determined in the filtrate of a membrane filtration of the acidic aqueous composition, which is carried out using a membrane with a nominal pore size of 0.2 ⁇ , by means of atomic emission spectrometry (ICP-OES).
- Another advantage of the method according to the invention is that in the course of which closed zinc phosphate coatings are also formed on surfaces of aluminum.
- the series of components to be treated in the method according to the invention preferably also includes the treatment of components which have at least one surface of aluminum. It is irrelevant whether the surfaces of zinc and aluminum are realized in a component composed of corresponding materials or in different components of the series.
- a dip coating particularly preferably an electrocoating, particularly preferably a cathodic electrodeposition coating on.
- Galvanized steel sheets were treated in zinc phosphating baths with different levels of free fluoride after previous activation with dispersions of particulate zinc phosphate and the appearance of the coatings evaluated immediately after zinc phosphating.
- Table 1 gives an overview of the activation and zinc phosphating compositions and the results of the evaluation of the quality of the coatings. The sheets went through the following steps in the order given:
- 0.5-3 g / kg contains 8.4 wt .-% of zinc in the form of ⁇ 3 ( ⁇ 4) 2 * 4 ⁇ 2 0
- the D50 value of the dispersion for activation was 0.25 ⁇ determined at 20 ° C on
- the free acid is determined from 10 ml sample volume diluted to 50 ml with VE
- the total acid is determined from 10 ml sample volume diluted to 50 ml with deionized water and subsequent titration with 0.1 N NaOH to pH 8.5, the consumption of sodium hydroxide solution in milliliters corresponding to the amount of total acid in points.
- Sodium nitrite
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Abstract
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EP17167478.1A EP3392376A1 (de) | 2017-04-21 | 2017-04-21 | Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie |
PCT/EP2018/055871 WO2018192709A1 (de) | 2017-04-21 | 2018-03-09 | Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie |
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EP3612663A1 true EP3612663A1 (de) | 2020-02-26 |
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EP17167478.1A Withdrawn EP3392376A1 (de) | 2017-04-21 | 2017-04-21 | Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie |
EP18716514.7A Active EP3612663B1 (de) | 2017-04-21 | 2018-03-09 | Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie |
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US (1) | US11486044B2 (de) |
EP (2) | EP3392376A1 (de) |
JP (1) | JP7287901B2 (de) |
CN (1) | CN110582592B (de) |
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WO (1) | WO2018192709A1 (de) |
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EP3828307A1 (de) * | 2019-11-26 | 2021-06-02 | Henkel AG & Co. KGaA | Ressourcenschonendes verfahren zur aktivierung einer metalloberfläche vor einer phosphatierung |
EP3964606A1 (de) * | 2020-09-04 | 2022-03-09 | Henkel AG & Co. KGaA | Einstufiges verfahren zur zinkphosphatierung |
CN113233598A (zh) * | 2021-05-21 | 2021-08-10 | 光大水务科技发展(南京)有限公司 | 一种连续循环水处理生化池及水处理方法 |
CZ309976B6 (cs) * | 2022-10-31 | 2024-03-27 | České vysoké učení technické v Praze | Způsob předúpravy povrchu ocelových komponent |
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JP3451334B2 (ja) | 1997-03-07 | 2003-09-29 | 日本パーカライジング株式会社 | 金属のりん酸塩皮膜化成処理前の表面調整用前処理液及び表面調整方法 |
JP3545974B2 (ja) * | 1999-08-16 | 2004-07-21 | 日本パーカライジング株式会社 | 金属材料のりん酸塩化成処理方法 |
US6723178B1 (en) * | 1999-08-16 | 2004-04-20 | Henkel Corporation | Process for forming a phosphate conversion coating on metal |
US20050205166A1 (en) | 2002-07-10 | 2005-09-22 | Jurgen Specht | Method for coating metallic surfaces |
DE10323305B4 (de) | 2003-05-23 | 2006-03-30 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung, Phosphatierlösung und Verwendung der behandelten Gegenstände |
JP4065289B2 (ja) | 2004-11-30 | 2008-03-19 | 本田技研工業株式会社 | アルミニウム合金の表面処理方法 |
JP4645470B2 (ja) | 2006-02-20 | 2011-03-09 | 住友金属工業株式会社 | 潤滑性、接着性に優れた亜鉛系めっき鋼板及びその製造方法 |
KR101068708B1 (ko) * | 2006-02-20 | 2011-09-28 | 수미도모 메탈 인더스트리즈, 리미티드 | 인산 아연 피막을 가지는 용융 아연 도금 강판의 제조 방법 |
DE102008000600B4 (de) | 2008-03-11 | 2010-05-12 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel, die hiermit erzeugte Beschichtung und ihre Verwendung |
JP5462467B2 (ja) * | 2008-10-31 | 2014-04-02 | 日本パーカライジング株式会社 | 金属材料用化成処理液および処理方法 |
DE102010030697A1 (de) * | 2010-06-30 | 2012-01-05 | Henkel Ag & Co. Kgaa | Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion |
US20120183806A1 (en) | 2011-01-17 | 2012-07-19 | Ppg Industries, Inc. | Pretreatment Compositions and Methods For Coating A Metal Substrate |
JP2012253317A (ja) | 2011-05-09 | 2012-12-20 | Kobe Steel Ltd | 圧粉磁心の製造方法、および該製造方法によって得られた圧粉磁心 |
EP3280830B1 (de) * | 2015-04-07 | 2021-03-31 | Chemetall GmbH | Verfahren zur gezielten einstellung der elektrischen leitfähigkeit von konversionsbeschichtungen |
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- 2018-03-09 WO PCT/EP2018/055871 patent/WO2018192709A1/de active Application Filing
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EP3392376A1 (de) | 2018-10-24 |
WO2018192709A1 (de) | 2018-10-25 |
EP3612663B1 (de) | 2024-03-06 |
JP7287901B2 (ja) | 2023-06-06 |
US11486044B2 (en) | 2022-11-01 |
CN110582592B (zh) | 2023-01-24 |
US20200032403A1 (en) | 2020-01-30 |
JP2020517823A (ja) | 2020-06-18 |
PL3612663T3 (pl) | 2024-06-24 |
CN110582592A (zh) | 2019-12-17 |
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