EP1988189A1 - Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc - Google Patents
Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc Download PDFInfo
- Publication number
- EP1988189A1 EP1988189A1 EP07713636A EP07713636A EP1988189A1 EP 1988189 A1 EP1988189 A1 EP 1988189A1 EP 07713636 A EP07713636 A EP 07713636A EP 07713636 A EP07713636 A EP 07713636A EP 1988189 A1 EP1988189 A1 EP 1988189A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel sheet
- zinc phosphate
- galvanized steel
- surface conditioning
- conditioning agent
- 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
- 238000000034 method Methods 0.000 title claims abstract description 225
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 193
- 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 title claims abstract description 189
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 136
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 136
- 230000008569 process Effects 0.000 title claims abstract description 125
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 301
- 238000000576 coating method Methods 0.000 claims abstract description 171
- 239000011248 coating agent Substances 0.000 claims abstract description 166
- 230000003750 conditioning effect Effects 0.000 claims abstract description 138
- 238000001035 drying Methods 0.000 claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 claims abstract description 72
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 52
- 239000010452 phosphate Substances 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 34
- 238000002835 absorbance Methods 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- 238000000862 absorption spectrum Methods 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 8
- 239000007785 strong electrolyte Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 13
- 229910000831 Steel Inorganic materials 0.000 description 99
- 239000010959 steel Substances 0.000 description 99
- 230000000052 comparative effect Effects 0.000 description 53
- 238000011156 evaluation Methods 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 238000005507 spraying Methods 0.000 description 39
- 239000000243 solution Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002585 base Substances 0.000 description 21
- 229910052783 alkali metal Inorganic materials 0.000 description 20
- 150000001340 alkali metals Chemical class 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 18
- 238000005246 galvanizing Methods 0.000 description 17
- 239000007853 buffer solution Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 12
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000007921 spray Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000007747 plating Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 230000001050 lubricating effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 239000003484 crystal nucleating agent Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910018137 Al-Zn Inorganic materials 0.000 description 3
- 229910018573 Al—Zn Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000004931 aggregating effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229960004838 phosphoric acid Drugs 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910003110 Mg K Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- -1 metasilicate Chemical compound 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 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 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
Definitions
- the present invention relates to a method for manufacturing a hot-dip galvanized steel sheet which is used in a field of automotive manufacturing and so on to enhance press formability and exhibits excellent in lubricity and/or adhesiveness. More specifically, the invention relates to a method for manufacturing a hot-dip galvanized steel sheet having zinc phosphate coating which is capable to enhance productivity such as operatability of manufacturing for hot-dip galvanized steel sheet having the above properties in a continuous hot-dip galvanized steel sheet manufacturing-line.
- a hot-dip galvanized steel sheet has been used. In most automotive applications, press forming is given to the galvanized steel sheet. However, compared with a cold-rolled steel sheet, the galvanized steel sheet is known to be inferior in press formability. About an electrogalvanized (EG) steel sheet or a hot-dip galvanized (GI) steel sheet, since zinc in the plating surface is soft, the zinc may cause seizing with dies at a time of scraping; or about a hot-dip galvanized steel sheet, soft eta-phase may remain, these factors lower the slidability. Also, about galvannealed (GA) steel sheet, as soft alloy layer like zeta-phase is formed on the plating surface at a time of alloying, which same as above lower the slidability.
- EG electrogalvanized
- GI hot-dip galvanized
- GAC galvannealed
- Patent Document 1 discloses a technique to enhance the lubricity by providing iron-zinc alloy electroplated coating over the galvanized coating; this technique is widely and practically used. Nevertheless, by this technique, electroplating equipment is needed, which results in a large increase of manufacturing cost.
- Patent Document 2 discloses a technique to produce hot-dip galvanized steel sheet which exhibits excellent lubricity by making zinc phosphate coating as an upper layer, instead of using plated coating described in Patent Document 1.
- This means that the invention having the zinc phosphate coating configures, for example, a zinc-containing metal-plated steel sheet complex excellent in high-speed press formability at a time of coach-building.
- Patent Documents 4 and 5 disclose methods, wherein, before a contact with zinc phosphate aqueous solution, a base material is rinsed and then dipped in the surface conditioning agent such as titanium-colloid aqueous solution for surface treatment.
- the surface conditioning agent such as titanium-colloid aqueous solution for surface treatment.
- a technique which imparts organic solid lubricant coating like wax and fat to a galvanized surface is conventionally disclosed (Japanese Patent No. 3006455 , etc.); chaff produced by press adheres to the dies at a time of press forming, occurrence of defect of press products attributed to the chaff, and odor problem at a time of welding connection (organic substance is decomposed by heat of welding that exert a harmful influence in the working environment.).
- the inorganic lubricant coating is characterizing in that it does not cause problems like unusual odor at a time of welding connection and it is capable to impart stable formability to the material to be formed.
- phosphoric-acid series coating is conventionally used, and this has proposed various techniques.
- Patent Document 6 discloses that Mg-containing zinc phosphate coating is provided on the galvanized surface and this coated material is suitably used for automotive body.
- Patent Document 7 and Patent Document 8 disclose that forming ZnO oxide on the surface of plated layer and forming Mn-Zn-OH-P series crystalline oxide over the surface make it possible to obtain a galvanized steel sheet which exhibits excellent lubricity, chemical conversion treatability, and adhesive compatibility.
- Patent Document 9 discloses a steel sheet having an inorganic lubricant coating which has sufficient adhesiveness with various adhesives including Mastic-type adhesive.
- the technique forming these phosphoric-acid series coating is called "reactive surface chemical-conversion treatment”. It is a technique such that a treatment agent containing a primary phosphoric acid, Zn, Ni, Mn, Mg, nitric acid, nitrous acid, fluorine compound, and so on is contacted with a surface of galvanized steel sheet and reacts thereon to form a coating. More specifically, the treatment agent is supplied by spray and the like to the galvanized surface, meanwhile coating reaction is proceeded together with etching of galvanizing.
- an object of the present invention is to provide a method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating which is possible to keep the composition balance of the treatment agent constant, to reduce the manufacturing cost, and to minimize the burden to the environment.
- Another object of the invention is to provide a galvanized steel sheet having zinc phosphate coating which exhibits excellent lubricity and adhesiveness by the above method.
- the present inventors have been conducted serious studies in order to solve the above problems. As a result, the present inventors have acquired following ideas and developed a method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating of the present invention.
- the present invention has been completed based on the above ideas. It is described in detail as follows.
- the first aspect of the present invention is a method for continuously manufacturing hot-dip galvanized steel sheet having zinc phosphate coating comprising the steps of: a surface conditioning agent supply process for supplying a surface conditioning agent to a surface of hot-dip galvanized steel sheet; a pre-drying process for drying the surface conditioning agent in a post-process of the surface conditioning agent supply process; and a treatment agent supply process for supplying a treatment agent containing zinc phosphate solution to the surface of the hot-dip galvanized steel sheet in a post-process of the pre-drying process, so as to solve the problems.
- hot-dip galvanized steel sheet is a concept including not only “hot-dip galvanized steel sheet” itself but also “galvannealed steel sheet”. Also, the wording "galvanized steel sheet” is a generic name including “electrogalvanized steel sheet”, “hot-dip galvanized steel sheet” and “galvannealed steel sheet”.
- zinc phosphate of "zinc phosphate coating” means a crystalline zinc phosphate (Zn 3 (PO 4 ) 2 ⁇ 4H 2 O) which shows Hopeite diffraction in a normal X-ray diffraction analysis.
- the second aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to the first aspect of the invention, wherein the surface conditioning agent used in the surface conditioning agent supply process is an aqueous liquid containing zinc phosphate particles.
- the third aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to the second aspect of the invention, wherein average diameter of the zinc phosphate particles contained in the surface conditioning agent of the surface conditioning agent supply process is 10 ⁇ m or less.
- the fourth aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to the second aspect of the invention, wherein average diameter of the zinc phosphate particles contained in the surface conditioning agent of the surface conditioning agent supply process is 10 ⁇ m or less, and pH of the surface conditioning agent is 5 or more.
- the fifth aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the first to fourth aspects of the invention, wherein the surface conditioning agent used in the surface conditioning agent supply process contains more than 0 mol/L and 0.5 mol/L or less of zinc phosphate particles, and contains a total of 0.3 mol/L or less of one element selected from a group consisting of Li, Na, K, Be, Mg, and Ca.
- the sixth aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the first to fifth aspects of the invention, wherein the treatment agent used in the treatment agent supply process contains 0.001 to 0.7 mol/L of phosphate root and contains 0.7 or less of.Zn ion in mole ratio to the phosphate root.
- the seventh aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the first to sixth aspects of the invention, wherein zinc phosphate solution of the treatment agent used in the treatment agent supply process contains Zn ion and phosphate root, has a pH of 4 or less, and contains one element, other than the Zn ion and the phosphate root, selected from a group of strong electrolyte anion consisting of 0.2 or less of nitrate root, 0.2 or less of nitrous root, 0.1 or less of hydrofluoric root, and 0.05 or less of sulfuric root in mole ratio to 1 mole of the phosphate root.
- the eighth aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the first to seventh aspects of the invention, wherein phosphorus adhered to a hot-dip galvanized surface by the surface conditioning agent supply process and the treatment agent supply process is prepared to be 30 to 500 mg/m 2 in phosphorus equivalent.
- Phosphorus adhesion quantity with regard to "phosphorus equivalent” can be calculated by measurement associated with chemical dissolution or fluorescent X-ray.
- the method by chemical dissolution is the one to dissolve a galvanized layer of galvanized steel sheet having a predetermined area with predetermined amount of strong acid (e.g., hydrochloric acid) and to measure the phosphorus concentration in the above solution by ICP (inductively-coupled plasma emission spectrometry) to calculate phosphorus equivalent.
- strong acid e.g., hydrochloric acid
- the method associated with fluorescent X-ray is the one to obtain fluorescent X-ray strength by making various phosphorus adhesion quantity, measuring fluorescent X-ray strength attributing to PK ⁇ in the fluorescent X-ray method, calculating the phosphorus adhesion quantity by the method of the above chemical dissolution, and producing an analytical curves.
- the fluorescent X-ray method it is capable to obtain the phosphorus adhesion quantity without breaking the galvanized layer of galvanized steel sheet, in a same method for the following samples.
- the ninth aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to the second aspect of the invention, wherein pH of the surface conditioning agent used in the surface conditioning agent supply process is 5 or more, and average diameter of the zinc phosphate particles is 0.1 to 3 ⁇ m.
- the 10th aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to the second or ninth aspect of the invention, wherein 0.01 to 5 mg/m 2 of the zinc phosphate particles in phosphorus equivalent is adhered to a surface of galvanized steel sheet which has come through the surface conditioning agent supply process and the pre-drying process.
- the 11th aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the second, ninth, and 10th aspects of the invention, wherein the treatment agent used in the treatment agent supply process contains Zn and phosphate root, has a pH of 4 or less, and contains one element, other than the zinc and phosphate root, selected from a group of strong electrolyte anion consisting of 0.2 or less of nitrate root, 0.2 or less of nitrous root, 0.1 or less of hydrofluoric root, 0.05 or less of sulfuric root in mole ratio to 1 mole of phosphate root.
- the 12th aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the second, ninth to 11th aspects of the invention, wherein the method further comprising a post-drying process for drying the treatment agent after the treatment agent supply process, and the zinc phosphate coating is adhered at an amount of 30 to 250 mg/m 2 in phosphorus equivalent after the post-drying process.
- the 13th aspect of the invention is the method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating according to any one of the first to 12th aspects of the invention, wherein either one of or both of supplying methods for the surface conditioning agent in the surface conditioning agent supply process and for the treatment agent in the treatment agent supply process is roll coating method.
- the 14th aspect of the invention is a hot-dip galvanized steel sheet having crystalline zinc phosphate coating formed on the surface thereof manufactured in accordance with the methods described in any one of the ninth to 13th aspects of the invention, the hot-dip galvanized steel sheet is characterizing in that: an absorption spectrum obtained by a reflected light of infrared light incoming from a direction at an angle of 60° to a normal line of the zinc phosphate coating surface has a plurality of absorption bands within a wavelength range of 8 to 12 ⁇ m; further, ratio of integrated absorption strength of a s-polarized light to a p-polarized light within the wavelength range is 1.2 or more.
- p-polarized light means a vertical component of polarized light to the surface; while “s-polarized light” means a horizontal component of polarized light to the surface.
- ratio of integrated absorption strength means ratio of integrated absorption strength of the absorption spectrum of p-polarized light and s-polarized light.
- the 15th aspect of the invention is a hot-dip galvanized steel sheet having crystalline zinc phosphate coating formed on the surface thereof manufactured in accordance with the methods described in any one of the ninth to 13th aspects of the invention, the hot-dip galvanized steel sheet is characterizing in that: an absorption spectrum obtained from the reflected light of infrared light incoming from a direction at an angle of 60° to a normal line of the phosphate coating has a plurality of absorption bands within a wavelength range of 8 to 12 ⁇ m; a p-polarized light absorbance within a wavelength of 8.4 to 9.2 ⁇ m of the absorption spectrum is twice as much as a s-polarized light absorbance; and the p-polarized light absorbance within wavelength range of 10.2 to 11.0 ⁇ m is twice as much as the s-polarized light absorbance.
- the surface conditioning agent in liquid condition is not brought into the treatment agent supply process, the surface conditioning agent does not contaminate the treatment agent; thereby composition balance of the treatment agent can be maintained for a long time.
- this invention makes it possible to manufacture the hot-dip galvanized steel sheet having zinc phosphate coating in consideration of the environment. Hence, decreased treatment agent is a portion which adhered to the sheet, the manufacturing process is simply established by supplying the decreased treatment agent. Therefore, zinc phosphate coating can be formed in a continuous hot-dip galvanized steel sheet line in the closed-system.
- crystal nucleating agent contained in the surface conditioning agent is not dried and aggregated, it is capable to furthermore steadily form a zinc phosphate coating to be coated.
- the third aspect of the invention is capable to enhance operatability and stability of the surface conditioning agent.
- the fourth aspect of the invention is capable to enhance operatability and stability of the surface conditioning agent more.
- the fifth aspect of the invention it is possible to enhance stability of the surface conditioning agent and to homogenize the reaction in the sheet surface in the pre-drying process.
- the sixth aspect of the invention is capable to enhance operatability and stability of the treatment agent.
- the seventh aspect of the invention is capable to enhance stability of the treatment agent more and to enhance homogeneity of the coating.
- the preparation is easy; therefore it is capable to accurately prepare a suitable amount of phosphorus.
- the ninth aspect of the invention it is possible to enhance stability of the surface conditioning agent furthermore; in view of cost and environment, a furthermore advantageous method for manufacturing the hot-dip galvanized steel sheet having zinc phosphate coating can be provided.
- the provided zinc phosphate particles can be more evenly supplied to the galvanized surface.
- the 10th aspect of the invention is capable to enhance stability of the surface conditioning agent and also capable to easily prepare a total amount of phosphorus adhesion quantity at a time of treatment agent supply, further, lubricity thereof can be enhanced.
- stability of the treatment agent can be enhanced; in view of cost and environment, a furthermore advantageous method for manufacturing the hot-dip galvanized steel sheet having zinc phosphate coating can be provided.
- lubricity thereof can be enhanced.
- the 14th aspect of the invention is capable to provide a hot-dip galvanized steel sheet having zinc phosphate coating, which exhibits excellent adhesiveness and lubricity.
- the 15th aspect of the invention is capable to provide a hot-dip galvanized steel sheet having zinc phosphate coating, which can maintain the slidability and further exhibits excellent adhesiveness.
- FIG. 1 shows a flow of an embodiment of the manufacturing method for galvanized steel sheet having zinc phosphate coating of the invention.
- the manufacturing method includes: a surface conditioning agent supply process (S1) for supplying a surface conditioning agent to a base material; a pre-drying process (S2) for drying the surface conditioning agent; a treatment agent supply process (S3) for supplying a treatment agent; and a pre-drying process (S4) for drying the treatment agent after the treatment agent supply process (S3).
- S1 surface conditioning agent supply process
- S2 pre-drying process
- S3 treatment agent supply process
- S4 pre-drying process
- the surface conditioning agent supply process (S1) is a process to supply surface conditioning agent containing a crystal nucleating agent to the galvanized steel sheet.
- the method for supplying the surface conditioning agent of the surface conditioning agent supply process (S1) is not particularly limited.
- the examples include: roll coater, spray coating, in addition, post-spray air knife, post-spray wringer roll, and post-spray squeezing roll.
- roll coater and post-spray squeezing roll are preferable. Further, among these, roll coater is preferable as it requires shorter contact time between galvanizing and the surface conditioning agent than other methods does.
- This method needs no troublesome component preparation and pH control for the surface conditioning agent, but it just needs addition of a surface conditioning agent having exactly the same component to refill the decreased portion of the surface conditioning agent. Control of component of surface conditioning agent, concentration thereof, and pH thereof of one component is only necessary. Further, as change of component of the surface conditioning agent is controlled, discharge of the surface conditioning agent becomes unnecessary; in view of reduction of cost and environmental burden, it is preferable.
- a crystal nucleating agent contained in the surface conditioning agent is not particularly limited to; an agent normally used for the base-coating treatment process of automotive body can be used.
- the examples include: an aqueous liquid wherein Ti-colloid is dispersed in a sodium pyrophosphate aqueous solution and an aqueous liquid in which zinc phosphate particles are dispersed.
- the aqueous liquid in which zinc phosphate particles are dispersed is particularly preferable. Because, even if this aqueous liquid is supplied and dried in the below-mentioned pre-drying process (S2), without aggregating, zinc phosphate particles can be absorbed to the galvanized surface while maintaining the particle size.
- the crystal nucleating agent may possibly be dried and aggregated in the pre-drying process (S2).
- Adhesion quantity of the surface conditioning agent is preferably less than 30 mg/m 2 . This is because, in the range of 30 mg/m 2 or more, spots in the base treatment occur and the appearance is sometimes damaged. It is preferably 15 mg/m 2 or less, and more preferably 10 mg/m 2 or less. Meanwhile, even if more than 30 mg/m 2 of the surface conditioning agent is applied, effect as the base treatment is saturated, it may rather affect the treatment agent in the post-process; thus the above upper limit is preferable.
- supply of the aqueous liquid in which zinc phosphate particles are dispersed is preferably 0.01 to 5 mg/m 2 in phosphorus equivalent in the zinc phosphate at a time of drying. If it is less than 0.01 mg/m 2 , sufficient adhesiveness cannot be obtained; meanwhile if it is over 5 mg/m 2 , the effect becomes saturated. It is preferably 0.1 to 2 mg/m 2 . Further, concentration of zinc phosphate may be 0.05 to 5 mol/L. This is because, in the range less than 0.05 mol/L, wet-film layer thickness becomes too thick to obtain predetermined adhesion quantity; thereby coating unevenness tends to occur. On the other hand, in the range over 5 mol/L, viscosity of the surface conditioning agent becomes excessively high; thereby, in the same way, coating unevenness tends to occur.
- zinc phosphate particles used for crystalline nucleation may be crystalline, amorphous, or mixture thereof. Whether or not it is crystalline can be determined by a general X-ray diffraction analysis.
- pH of the surface conditioning agent is preferably 5 or more. If pH is less than 5, when the surface conditioning agent is supplied to a galvanized sheet surface, zinc liquates out from the sheet surface. Further, aqueous liquid in which zinc phosphate particles are dispersed itself may slightly cause dissolution reaction of zinc phosphate particles, stability of the particles may possibly be deteriorated.
- the pH of the agent is further preferably in the range of 7 to 10. If pH is more than 10, dissolution reaction of zinc phosphate itself is set off.
- buffer solution for controlling pH may be added to the surface conditioning agent. Examples of the buffer solution include a buffer solution consisting of K 2 HPO 4 and NaOH. Concentration of the buffer solution in the surface conditioning agent is preferably 0.1 to 2 g/L. If the concentration is less than 0.1 g/L, the desired provision is hard to be obtained; if it is over 2 g/L, it might affects to the homogenous supply.
- Particle diameter of the dispersed zinc phosphate particles is preferably 10 ⁇ m or less. Because, if the diameter becomes over 10 ⁇ m, dispersing element becomes unstable, this may deteriorates life of the aqueous liquid. It is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less. Lower limit of the particle diameter is not particularly limited to; in view of viscosity of the aqueous liquid, it is preferably 0.1 ⁇ m or more. With regard to the below-mentioned galvanized steel sheet also showing excellent adhesiveness, the particle diameter is preferably 3 ⁇ m or less. It is further more preferably 1 ⁇ m or less. The particle diameter can be measured in a state of dispersed aqueous liquid by a laser diffractometer.
- Content of the zinc phosphate particles is 0.5 mol/L or less. This is because, when concentration of the zinc phosphate particles becomes over 0.5 mol/L, content of the dispersing element becomes too high, which may deteriorates life of the aqueous liquid. In view of stability of the aqueous liquid, it is preferably 0.3 mol/L or less.
- the content of the zinc phosphate particles can be converted from atomic weight as Zn 3 (PO 4 ) 2 by measuring zinc concentration.
- At least one or more kinds selected from: alkali metal of Li, Na, and K; and alkali earth metal of Be, Mg, and Ca may be added. Because, if these metals are added, below-mentioned reaction in the surface of the base material under the pre-drying process becomes more even, therefore, this makes it possible to stably manufacture the hot-dip galvanized steel sheet. Concentration of these alkali metal and alkali earth metal is 0.3 mol/L or less as a total of the above alkali metal and alkali earth metal.
- alkali metal and alkali earth metal may be added in forms of orthophosphate, metaphosphate, pyrophosphate, orthosilicate, metasilicate, carbonate, bicarbonate, borate, and etc.
- ammonium salt or ammonium aqueous solution, and so on may be used.
- the concentration is a total of approximately 0.05 mol/L or less
- metal or metal salt particles of such as Fe, Co, Ni, Cu, Mn, and Cr may be included.
- the buffer solution include one consisting of K 2 HPO 4 and NaOH.
- these buffer solutions inhibit pH change, stable manufacturing is sometimes carried out.
- commercially available surface conditioning agent which is used for base treatment and the like for coating, may be used as long as it satisfies the above composition.
- the pre-drying process (S2) is a process for drying a surface conditioning agent supplied to the surface of a base material without water rinsing. Drying temperature is not specifically limited to, in view of manufacturing cost and so on, the steel-sheet highest achieving temperature is preferably less than 200°C. More preferably, the temperature is less than 150°C, furthermore preferably 50 to 120°C. Drying duration is not specifically limited to as well; from the viewpoint of surface appearance and productivity, it is preferably less than 30 seconds, more preferably less than 10 seconds.
- the drying method is not particularly limited to; it is suitably selected. Examples thereof include air knife, drier, and oven.
- the treatment agent supply process (S3) is a process to supply a treatment agent for forming a zinc phosphate coating over a base material treated by the above pre-drying process (S2).
- Supplying method of the treatment agent to the base material is not particularly limited to; for example, there may be spray-wringer method and roll-coating method.
- the equipment can be effectively simplified. So, in view of manufacturing the hot-dip galvanized steel sheet with lower cost, it is possible to suitably adopt a treatment by roll-coating method. In view of operatability of the treatment agent, treatment by roll-coating method is most preferable.
- temperature of the fed steel sheet which has come through the pre-drying process (S2), at a time of feeding into the treatment agent supply process (S3) is preferably less than 80°C. Because, if temperature of the steel sheet is higher, activation of the steel sheet becomes more than a protective-coating-like effect of the surface conditioning agent, which may cause elution of galvanized coating into the treatment agent.
- the temperature is preferably less than 60°C.
- the lower limit is preferably 30°C or more. If the temperature is less than 30°C, reaction by heating in the dry-process after the treatment process does not sufficiently occur; thereby coating may be uneven. Control of the above temperature of the fed steel sheet can be achieved by providing a cooling zone of the steel sheet, but also it can be achieved by using roll-cooling such as water-cooling roll.
- the treatment agent supplied in the treatment agent supply process (S3) is a zinc phosphate solution.
- the zinc phosphate solution is an aqueous solution containing phosphate root and Zn ion.
- the wording "phosphate root" is a generic name of H 2 PO 4 - , HPO 4 2- , PO 4 3- ; it is represented by [PO 4 3- ].
- the zinc phosphate solution contains 0.001 to 0.7 mol/L of phosphate root [PO 4 3- ], and contains 0.7 or less of Zn ion in mole ratio to this phosphate root.
- the reason for specifying the concentration of phosphate root in the range of 0.001 to 0.7 mol/L is because, if the zinc phosphate solution contains more than 0.7 mol/L of phosphate root, stability of the treatment agent might be deteriorated. Meanwhile, if the concentration is in the range less than 0.001 mol/L, pH of the treatment agent becomes higher; reaction becomes inhibited thereby there is a possibility that the desired performance cannot be obtained.
- the reason for containing 0.7 or less of Zn ion in mole ratio to this phosphate root is because, by making zinc phosphate solution contain the concentration of Zn ion, it is possible to form an even crystalline coating. This is also because there is a fear of occurrence of sludge that may deteriorate the surface quality.
- the content is preferably 0.5 or less.
- sludge means the one wherein Zn 3 (PO 4 ) 2 is solidified in the aqueous solution.
- forming reaction of the crystalline zinc phosphate is a reaction shown by the following formula (A) or (B) ; 1.5 times of zinc atoms are required to the phosphate root in the treatment agent.
- S3 treatment agent supply process
- the excessive amount of zinc raises pH and solidifies the treatment agent.
- pH of the treatment agent is preferably 4 or less. Because, if it becomes more than 4, stability of the treatment agent becomes lowered and sludge occurs, thereby these raise a possibility for damaging the surface quality; also, there is a fear that zinc phosphate coating cannot be formed since the reaction does not proceed smoothly.
- the pH is furthermore preferably 3 or less.
- adding one or more kinds of strong electrolyte anion selected from a group of strong electrolyte anion consisting of: 0.2 or less of nitrate root (NO 3- ), 0.2 or less of nitrous root (NO 2- ), 0.1 or less of hydrofluoric root (F - ), and 0.05 or less of sulfuric root (SO 4 2- ) in mole ratio to the phosphate root is to have a stable reaction with the treatment agent for the purpose of improving the evenness of the coating. Specifically, by this reaction, it is capable to obtain etching effect and oxidation effect. If the strong electrolyte anion is added in an amount over the above upper limit, stability of the treatment agent is lowered and life of the treatment agent may be shortened.
- ammonium salt, or ammonium aqueous solution, and so on may be added to the zinc phosphate solution.
- Concentration of ammonium ion is preferably 0.02 or less in mole ratio to phosphate root.
- other metal ions apart from zinc may be mixed.
- a total mole ratio of the metal ion to the phosphate root is preferably 0.2 or less.
- Adhesion quantity of the zinc phosphate solution in terms of adhesion quantity of coating eventually formed is calculated in phosphorus equivalent by a sum of supply in the above surface conditioning agent supply process (S1) and the treatment agent supply process (S3), it is preferably 30 to 500 mg/m 2 . Because, if it is less than 30 mg/m 2 , lubricity of the coating is not reflected to the formability of the steel sheet; meanwhile if it is over 500 mg/m 2 , the effect becomes saturated. It is further preferably 30 to 400 mg/m 2 .
- the pre-drying process (S2) is provided as a pre-process of the treatment agent supply process (S3), the surface conditioning agent is not brought into the treatment agent supply process (S3); thereby it is possible to adequately keep balance of the treatment agent for a long time. Accordingly, treatment agent control and drain facility can be simplified.
- the post-drying process (S4) is a process to dry a treatment agent supplied to the surface of a base material without water rinsing. Drying temperature is not particularly limited to; in view of manufacturing cost, the steel-sheet highest achieving temperature is preferably less than 250°C, more preferably less than 180°C. Drying duration is not specifically limited to as well; from the viewpoint of surface appearance and productivity, it is preferably less than 100 seconds after the application, and more preferably less than 50 seconds.
- the drying method is not particularly limited to; it is suitably selected. Examples thereof include air knife, drier, and oven.
- the galvanized steel sheet having a zinc phosphate coating comprises a base material, a galvanizing coating over a surface of the base material, and a zinc phosphate coating formed on outside of the galvanizing coating. These are respectively described as below.
- Kind of steel sheet to be the base material is not particularly limited to; any kind of cold-rolled steel sheet and hot-rolled steel sheet are applicable.
- Chemical composition of the base material is not specifically limited to, either; the applicable examples include dead soft steel and low-carbon steel both containing Ti, Nb, and so on depending on the necessity, or high-strength steel or high-tensile steel both adequately containing Si, Mn, P, Cr, Ni, Cu, V, and so on.
- the galvanizing of the galvanized steel sheet having a zinc phosphate coating of the invention hot-dip galvanizing or electrogalvanizing may be adopted. By galvanizing the above base material, the galvanized steel sheet can be produced.
- GI steel sheet As a hot-dip galvanized steel sheet, for example, there may be GI steel sheet which does not have thermal alloying treatment and thermal alloyed GA steel sheet.
- GI steel sheet means a steel sheet where alloying treatment is not given after hot-dip galvanizing and that contains 2 mass % or less of Fe. If Fe content becomes more than 2 mass %, Fe-Zn alloy layer appears at a part of the surface, which is not preferable with regard to the appearance.
- GA steel sheet means a steel sheet where alloying treatment is given after hot-dip galvanizing and that contains 7 to 15 mass % of Fe to that of the galvanized layer.
- Fe content is less than 7 mass %, eta-phase remains in the vicinity of surface of the alloyed hot-dip galvanized layer, which is not preferable with regard to the appearance. It is preferably 8 mass % or more. If Fe content becomes over 15 mass %, powder tends to be generated at a time of press forming. It is preferably 13 mass % or less.
- the hot-dip galvanized layer of the above GI steel sheet and GA steel sheet may contain 0.05 to 0.5 mass % of Al. As a result, it is capable to enhance the adhesiveness between the hot-dip galvanized coating and the base material.
- metals of Cu, Ni, Cr, Si, Mn, Pb, Sb, Sn, misch metal, and so on may be slightly contained or added to the hot-dip galvanized layer.
- alloy phase is not specifically limited to; eta-phase, zeta-phase, delta-phase may be mixed in the GI steel sheet; meanwhile zeta-phase, delta 1-phase, gamma 1-phase, gamma-phase may be mixed in the GA steel sheet.
- adhesion quantity of the hot-dip galvanized coating is not particularly limited to. However, from the viewpoint of workability, weldability, and productivity, the adhesion quantity of the hot-dip galvanized coating is preferably 150 g/m 2 or less.
- GI steel sheet and GA steel sheet have been described; other than these, 5 mass % Al-Zn plated steel sheet (GF steel sheet), 55 mass % Al-Zn plated steel sheet (GL), and 3 mass % Mg-Al-Zn plated steel sheet (MZ steel sheet) may be available.
- GF steel sheet 5 mass % Al-Zn plated steel sheet
- GL 55 mass % Al-Zn plated steel sheet
- MZ steel sheet 3 mass % Mg-Al-Zn plated steel sheet
- Examples of the electrogalvanized steel sheet include EG steel sheet consisting of eta-phase, 10 mass % Fe-Zn electrogalvanized steel sheet (FZ steel sheet), and 13 mass % Ni-Zn (ZnNi steel sheet). Among these, applying the zinc phosphate coating of the invention to the EG steel sheet is preferable.
- Manufacturing of the galvanized steel sheet to be used for the present invention can apply any kinds of galvanizing methods. For instance, GI steel sheet is dipped into the plating bath and also cooled in the bath. On the other hand, GA steel sheet is dipped into the plating bath, later alloying treatment is given. If necessary, temper rolling (skin-pass rolling), planarization (leveler), and so on may be imparted. By temper rolling, surface condition and surface roughness of the GI steel sheet and GA steel sheet are varied, these changes may be permitted. These changes do not affect adhesiveness and the like.
- the zinc phosphate coating is a coating of a crystalline zinc phosphate formed on the outer layer of the above galvanized steel sheet.
- the zinc phosphate coating of the galvanized steel sheet having zinc phosphate coating of the present invention has any one of configurations as follows:
- the zinc phosphate coating of the galvanized steel sheet having zinc phosphate coating of the invention has a plurality of absorption bands within a wavelength range of 8 to 12 ⁇ m in a spectrum obtained by absorption spectrum measurement method measuring a surface reflected light of infrared light incoming from a direction at an angle of 60° to a normal line of the galvanized steel sheet having zinc phosphate coating. This is attributed to P-O bonds of zinc phosphate forming the zinc phosphate coating, the coating usually has about five absorption bands.
- the reason for making the infrared light income from a direction at an angle of 60° to a normal line of the galvanized steel sheet having zinc phosphate coating is to inhibit the influence of reflected light coming from the galvanized steel sheet to the absorption spectrum. As a result, it is capable to obtain a desirable SN ratio.
- the reflected light is detected from a direction at an angle of 60° corresponding to the incident light. Reflected light may be diffused depending on the roughness of the steel sheet surface, which sometimes decreases intensity of reflected light coming into the detector. In such a case, a light-concentrating device may be provided in front of the detector.
- the zinc phosphate coating described in the above (i) has a configuration such that a ratio of integrated strength (P/S) obtained by an absorption spectrum of the p-polarized light (P) to an absorption spectrum of the s-polarized light (S) is 1.2 or more.
- P/S integrated strength
- the zinc phosphate coating of the galvanized steel sheet having zinc phosphate coating of the invention has a configuration such that almost vertical orientation to the steel sheet is stronger.
- P/S is further preferably 2 or more.
- orientation of P-O band is a zinc phosphate coating having a configuration in the range described in (ii).
- the orientation described in (ii) shows a configuration of absorbance of the zinc phosphate coating used for the galvanized steel sheet having zinc phosphate coating of the invention by paying attention to two wavelength ranges of 8.4 to 9.2 ⁇ m and 10.2 to 11.0 ⁇ m within the wavelength range of 8 to 12 ⁇ m of the above P-O bond. The reason for specifying these two wavelength ranges is because these two generate characteristic absorption of spectrums.
- ratio (Pa/Sa) of (absorption A): absorbance (Pa) of p-polarized light to absorbance (Sa) of s-polarized light is 2 or more in an absorption spectrum within the wavelength range of 8.4 to 9.2 ⁇ m
- ratio (Pb/Sb) of (absorption B): absorbance (Pb) of p-polarized light to absorbance (Sb) s-polarized light is 2 or more in an absorption spectrum within the wavelength range of 10.2 to 11.0 ⁇ m. Both ratios are further preferably 3 or more.
- Adhesion quantity of the zinc phosphate coating may be 30 mg/m 2 or more. It is more preferably 50 mg/m 2 or more. This is because adhesion quantity thereof affects lubricity; so if it is less than 30 mg/m 2 , preferable lubricity may not be obtained.
- adhesion quantity of the zinc phosphate coating is preferably 250 mg/m 2 or less, furthermore preferably 200 mg/m 2 or less, and most preferably 150 mg/m 2 or less. If adhesion quantity of the zinc phosphate coating is larger, the adhesiveness may be deteriorated.
- Example 1 operatability and lubricity evaluations were carried out about two hot-dip galvanized steel sheets: one was a dead soft GI steel sheet (plating adhesion quantity: 90 g/m 2 , Al concentration of the coating: 0.4 mass %, Fe concentration: 1.5 mass %) having a size of 0.8 mm in thickness and 200 mm x 250 mm; and another one was a same size of GA steel sheet (plating adhesion quantity: 60 g/m 2 , Al concentration of the coating: 0.30 mass %, Fe concentration: 9.5 mass %).
- the evaluation is based on whether or not the above pre-drying process is included in the manufacturing process in case of changing the components of surface conditioning agent and treatment agent.
- the component of surface conditioning agent is shown in Table 1 and the content of treatment agent is also shown in Table 2.
- Evaluation criteria of the operatability are as follows. "No need to adjust concentration" in the following evaluation criteria means that there were no need for water-rinsing equipment and supplement, waste-liquid facilities.
- Rust preventive oil was applied onto the obtained hot-dip galvanized steel sheet having zinc phosphate coating, and friction coefficient measurement was carried out under the following condition using Pin-On-Disk type friction and wear tester. The lubricity was evaluated based on the friction coefficient. Evaluation criteria of the friction coefficient are shown as below.
- Stability of each surface conditioning agent and treatment agent was measured by "40°C by 7 days Test". This is a test wherein each conditioning agent and treatment agent is kept at 40°C for 7 days. Evaluation criteria of stability of surface conditioning agent and treatment agent are as follows.
- Example 4 (Table 4) Stability of the surface conditioning agent No. Stability Notes 1 ⁇ Example 2 ⁇ Example 3 ⁇ Example 4 ⁇ Example 5 ⁇ Example 6 ⁇ Example 7 ⁇ Reference example 8 ⁇ Example 9 ⁇ Example 10 ⁇ Reference example 11 ⁇ Reference example 12 ⁇ Reference example 13 - Conventional example 14 - Conventional example 15 ⁇ Example note: "Example” means an example of the present invention.
- the surface conditioning agent in terms of Nos. 7, 10, and 12 shown in Table 4 did not show excellent stability. In terms of No. 7, according to Table 1, this is thought that a total of alkali metal and alkali earth metal reaches 0. 401 mol/L. Also, in terms of Nos. 10 and 12, it is thought that particle diameter and content of zinc phosphate are respectively large in both cases. These elements do not necessarily affect the operatability of treatment agent; nevertheless, higher stability is preferable.
- Example 2 in a manufacturing line of continuous hot-dip galvanized steel sheet, a 0.8 mm thick GA steel sheet (dead soft steel sheet, plating adhesion quantity: 45 g/m 2 , Al concentration of the coating: 0.25 mass %, Fe concentration: 9.0 mass %) was treated with skin-pass mill (rolling reduction ratio: 1.0 %); in the surface conditioning agent supply process, surface conditioning agents of Nos. 1, 4, and 6 shown in Table 1 were supplied; in the treatment agent supply process, zinc phosphate coating treatment was carried out using treatment agent of a, d, e, and i shown in Table 2. Conditions of each process are as follows.
- Evaluation criteria of the operatability are as follows. "No need to adjust concentration" in the following evaluation criteria means that there were no need for water-rinsing equipment and supplement, waste-liquid facilities.
- Rust preventive oil was applied onto the obtained hot-dip galvanized steel sheet having zinc phosphate coating and friction coefficient measurement was carried out under the following condition by using Pin-On-Disk type friction and wear tester. The lubricity was evaluated based on the friction coefficient. Evaluation criteria of the friction coefficient are shown as below.
- Spot welding was carried out to the obtained hot-dip galvanized steel sheet having zinc phosphate coating by using spot welding machine in accordance with the following conditions; and number of points of welding in which nugget diameter (mm) is up to 4t and 1/2 (t: steel sheet thickness (mm)) or less was evaluated.
- Anticorrosion evaluation was carried out by a method generally used as a performance evaluation of steel sheet for automotive manufacturing and so on. Specifically, a steel sheet was coated by electrodeposition after chemical conversion treatment and then it was provided with a single cut; finally evaluated with maximum swelling width after 500 hours of 5 mass % salt-spray test. Conditions of the chemical conversion treatment and electrodeposition coating are shown as follows.
- a surface conditioning agent shown in Table 8 was supplied to a galvanized steel sheet.
- Supplying method was any one of spray (S in Table 10), post-spraying squeezing roll (SR in Table 10), post-spraying air knife (AK in Table 10), and roll coating (RC in Table 10).
- the adhesion quantity was obtained by fluorescent X-ray.
- Drying in pre-drying process was done by hot-air drier.
- the drying temperature was set with reference to the steel-sheet temperature; it was carried out within the range of no drying to drying at 150°C. Drying duration for all examples having pre-drying process was standardized to 10 seconds.
- a treatment agent shown in Table 9 was supplied to a galvanized steel sheet. Supply process was done by either of post-spray squeezing roll or roll coating.
- Drying in post-drying process was carried out by hot-air oven.
- the drying temperature was set with reference to the steel-sheet temperature; it was standardized at 80°C when carrying out the post-drying. Drying duration for all examples having post-drying process was standardized to 10 seconds.
- the obtained galvanized steel sheet having a coating was cut into a size of 25mm x 100 mm, and measured in accordance with the following method.
- "S-300" manufactured by Bio-Rad Laboratories was used.
- Measurement was carried out by making the infrared light income from a direction at an angle of 60° to a normal line of the galvanized steel sheet as the object to be measured to detect infrared lights reflected to a direction corresponding to the angle of 60°.
- incoming infrared light was polarized into a vertical direction (p-polarized light) and a horizontal direction (s-polarized light) against the surface by KRS-5 polarized photon; the reflected infrared light were all detected. Specifically, this was done in accordance with the following procedure.
- infrared reflectance spectrum of respective p-polarized light and s-polarized light were measured. Then, about p-polarized light, p-polarized light relative reflectance spectrum of steel sheet surface to p-polarized light reflectance of evaporated film was measured; meanwhile about s-polarized light, relative reflectance spectrum of steel sheet surface to s-polarized light reflectance of Au evaporated film was also measured.
- FIGs. 2 (a) and 2 (b) show an example of relation between the obtained wavelength and absorbance in a form of graph.
- FIG. 2 (a) is a graph about p-polarized light
- FIG. 2 (b) is a graph about s-polarized light.
- Pa and Sa respectively means absorbance of p-polarized light and s-polarized light within the wavelength range of 8.4 to 9.2 ⁇ m
- Pb and Sb respectively means absorbance of p-polarized light and s-polarized light within the wavelength range of 10.2 to 11.0 ⁇ m.
- integral intensities P and S were calculated by carrying out background correction by deducting absorbance at a wavelength of 12 ⁇ m from each absorbance of each wavelength within the range of 8 ⁇ m to 12 ⁇ m about infrared absorption spectrum of the obtained p-polarized light and s-polarized light, and adding absorbance of each wavelength. Specifically, these are represented by the following formulas (E) and (F).
- P P ⁇ 8 ⁇ m - P ⁇ 12 ⁇ m + ... + ( P ⁇ 12 ⁇ m - P ⁇ 12 ⁇ m )
- S S ⁇ 8 ⁇ m - S ⁇ 12 ⁇ m + ... + ( S ⁇ 12 ⁇ m - S ⁇ 12 ⁇ m )
- Adhesion quantity of zinc phosphate coating could be obtained by phosphorus adhesion quantity using fluorescent X-ray measurement method about the obtained steel sheet. Crystallization characteristics of zinc phosphate were evaluated using "RINT2500" measuring device manufactured by Rigaku Industrial Corp. in accordance with the following method. X-ray diffraction measurement with 2 ⁇ (CoK ⁇ ) in a direction at an angle of 5 to 60° was carried out, identifying two kinds of diffraction lines A, B attributed to zinc phosphate ⁇ 4 hydrate; then, coating having both of diffraction lines A and B were determined as a crystalline material. The A and B are respectively:
- FIG. 3 shows a schematic view of method of T-Peeling test. As shown in FIG.
- the test was carried out by clutching respective ends, where adhesive 2 was not adhered, of steel sheets 1, 1 a part of which were adhered to each other, and pulling the respective ends in directions shown by arrows T, T which were vertical to the adhered face and opposite each other.
- the evaluation was done based on a baking duration as a standard such that cohesive-failure area ratio became 90% or more; the specific criteria were as follows. ⁇ (very good): 20 minutes or less; ⁇ (good): over 20 minutes and 30 minutes or less; ⁇ (not bad): 30 minutes and 40 minutes or less; ⁇ (bad): over 40 minutes.
- the obtained steel sheet was cut into a size of 25 mm x 100 mm; rust preventive oil was applied thereto at an amount of 2 g/m 2 per side; then adhesive "OROTEX 580" manufactured by Iida Industry Co., Ltd. was applied to the surface at an area of 25 mm x 25 mm and thickness of 0.1 mm; later, the sheet was baked. Baking was done at 170°C for 20 minutes, 30 minutes, and 40 minutes; after baking, Shear-tensile test was carried out. The method for shear-tensile test is schimatically shown in FIG. 4 . As shown in FIG.
- the test was carried out by clutching respective ends, where adhesive 4 was not adhered, of steel sheets 3, 3 a part of which were adhered to each other, and pulling the respective ends in directions shown by arrows S, S which were parallel to the adhered face and opposite each other.
- the evaluation was done based on a baking duration as a standard such that cohesive-failure area ratio became 90% or more; the specific criteria were as follows. ⁇ (very good): 20 minutes or less; ⁇ (good): over 20 minutes and 30 minutes or less; ⁇ (not bad): over 30 minutes and 40 minutes or less; ⁇ (bad): over 40 minutes.
- Measurement of lubricity with regard to a galvanized steel sheet having the obtained coating was carried out by measuring the friction coefficient. Specifically, by using Pin-On-Disk type friction and wear tester, rust preventive oil "NOX-RUST 550S” manufactured by Parker Industries, Inc. was applied to the steel sheet at an amount of 2 g/m 2 per side; then friction coefficient was measured.
- the test duration and evaluation criteria are shown as follows.
- Table 10 shows conditions of each Example, Comparative example, and Reference example.
- distinction of process is expressed by S1 process, S2 process, S3 process, and S4 process.
- S1 process means a surface conditioning agent supply process
- S2 process means a pre-drying process
- S3 process means a treatment agent supply process
- S4 process means a post-drying process.
- kinds of plating are identified by abbreviated names described in Table 7
- kinds of surface conditioning agent are identified by codes shown in Table 8
- kinds of treatment agent are identified by Nos. shown in Table 9.
- Test Nos. 1 to 4 are the results of examples in cases that any one of processes S1 to S4 for manufacturing the galvanized steel sheet having zinc phosphate coating are skipped. According to these, if any one of processes are skipped, adequate value of P/S cannot be obtained, adhesiveness is also unfavorable. Consequently, by having manufacturing process from the above S1 process to S4 process, it is capable to manufacture the galvanized steel sheet having zinc phosphate coating which exhibits high repeatability, as well as excellent adhesiveness and lubricity. Meanwhile, test No. 12 in which no process was skipped has only 0.1 of P/S. As pH of the surface conditioning agent is 5 or less, so as to obtain more favorable P/S, it is preferable not to skip process and preferable to control pH of the surface conditioning agent.
- Table 12 shows a result of operatability. According to the table, the operatability was varied depending on surface conditioning agent applied to each process, kinds of treatment agent, and pre-and-post drying condition. So, by having manufacturing process under adequate conditions, a galvanized steel sheet having zinc phosphate coating which exhibits excellent performance in view of cost and environment can be manufactured.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2006043105A JP4654346B2 (ja) | 2006-02-20 | 2006-02-20 | リン酸亜鉛皮膜を有する溶融亜鉛系めっき鋼板の製造方法 |
| JP2006043099A JP4645470B2 (ja) | 2006-02-20 | 2006-02-20 | 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 |
| PCT/JP2007/050650 WO2007097139A1 (fr) | 2006-02-20 | 2007-01-18 | Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc |
Publications (3)
| Publication Number | Publication Date |
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| EP1988189A1 true EP1988189A1 (fr) | 2008-11-05 |
| EP1988189A4 EP1988189A4 (fr) | 2012-01-25 |
| EP1988189B1 EP1988189B1 (fr) | 2014-03-12 |
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| EP07713636.4A Not-in-force EP1988189B1 (fr) | 2006-02-20 | 2007-01-18 | Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1988189B1 (fr) |
| KR (1) | KR101068708B1 (fr) |
| TW (1) | TWI348500B (fr) |
| WO (1) | WO2007097139A1 (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115485A1 (fr) * | 2008-03-20 | 2009-09-24 | Henkel Ag & Co. Kgaa | Peinture électrophorétique par immersion optimisée d'éléments assemblés et partiellement préphosphatés |
| WO2016102265A1 (fr) * | 2014-12-22 | 2016-06-30 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Procédé de production de particules anisotropes de phosphate de zinc et de phosphate mixte zinc/métal et leur utilisation |
| WO2018178108A1 (fr) | 2017-03-30 | 2018-10-04 | Tata Steel Ijmuiden B.V. | Composition acide aqueuse pour le traitement des surfaces métalliques, procédé de traitement l'utilisant et utilisation de la surface métallique traitée |
| EP3392376A1 (fr) * | 2017-04-21 | 2018-10-24 | Henkel AG & Co. KGaA | Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série |
| EP3392375A1 (fr) * | 2017-04-21 | 2018-10-24 | Henkel AG & Co. KGaA | Procédé de phosphatation au zinc formant des couches de composants métalliques en série |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101523546B1 (ko) | 2015-02-16 | 2015-05-28 | 한영선재(주) | 냉간압조용 소성가공 금속 재료의 비인피막 처리방법 |
| KR20190043155A (ko) | 2016-08-24 | 2019-04-25 | 피피지 인더스트리즈 오하이오 인코포레이티드 | 금속 기판을 처리하기 위한 알칼리성 조성물 |
| JP6733839B2 (ja) * | 2018-04-03 | 2020-08-05 | 日本製鉄株式会社 | 亜鉛系電気めっき鋼板 |
| TWI812437B (zh) * | 2022-08-30 | 2023-08-11 | 中國鋼鐵股份有限公司 | 快速辨識熱浸鍍鋅鋼材缺陷黑化的方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6196084A (ja) * | 1984-10-17 | 1986-05-14 | Kawasaki Steel Corp | 鋼板の化成処理前処理方法 |
| WO1995008007A1 (fr) * | 1993-09-17 | 1995-03-23 | Brent International Plc | Rincage preliminaire destine au depot de phosphate sur des surfaces metalliques |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3199980B2 (ja) | 1995-04-28 | 2001-08-20 | 新日本製鐵株式会社 | 潤滑性、化成処理性、接着剤適合性に優れた亜鉛系めっき鋼板 |
| JP3153097B2 (ja) | 1995-04-28 | 2001-04-03 | 新日本製鐵株式会社 | 潤滑性、化成処理性、接着剤適合性、溶接性に優れた亜鉛系めっき鋼板 |
| 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 |
| JP3934784B2 (ja) | 1998-05-07 | 2007-06-20 | 新日本製鐵株式会社 | 耐食性、加工性に優れた表面処理鋼板の製造方法 |
| 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 |
| JP2001064781A (ja) | 1999-08-30 | 2001-03-13 | Kansai Paint Co Ltd | 亜鉛系めっき鋼板の表面処理方法 |
| JP2001098383A (ja) | 1999-09-27 | 2001-04-10 | Sumitomo Metal Ind Ltd | プレス成形性に優れた無機被覆亜鉛系めっき鋼板の製造法 |
| JP3903743B2 (ja) | 2000-06-02 | 2007-04-11 | 住友金属工業株式会社 | 接着性、加工性、溶接性に優れた亜鉛系めっき鋼板とその製造方法 |
| JP3810677B2 (ja) | 2001-12-10 | 2006-08-16 | 日新製鋼株式会社 | 塗装原板および塗装原板の表面調整方法ならびに加工部耐食性に優れた塗装鋼板の製造方法 |
| JP3864148B2 (ja) * | 2002-06-13 | 2006-12-27 | 日本ペイント株式会社 | リン酸亜鉛含有表面調整剤、リン酸塩化成処理鋼板及び塗装鋼板並びにリン酸亜鉛分散液 |
| ATE353987T1 (de) * | 2002-06-13 | 2007-03-15 | Nippon Paint Co Ltd | Zinkphosphatkonditioniermittel für phosphatkonversionsbeschichtung von stahlplatte und entsprechendes produkt |
| JP3966244B2 (ja) | 2003-08-05 | 2007-08-29 | 住友金属工業株式会社 | プレフォスフェイト鋼板およびその製造方法 |
| JP3807388B2 (ja) | 2003-08-05 | 2006-08-09 | 住友金属工業株式会社 | プレフォスフェイト鋼板の製造方法および装置 |
-
2007
- 2007-01-18 WO PCT/JP2007/050650 patent/WO2007097139A1/fr active Application Filing
- 2007-01-18 EP EP07713636.4A patent/EP1988189B1/fr not_active Not-in-force
- 2007-01-18 KR KR1020087019659A patent/KR101068708B1/ko active IP Right Grant
- 2007-01-25 TW TW096102898A patent/TWI348500B/zh not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6196084A (ja) * | 1984-10-17 | 1986-05-14 | Kawasaki Steel Corp | 鋼板の化成処理前処理方法 |
| WO1995008007A1 (fr) * | 1993-09-17 | 1995-03-23 | Brent International Plc | Rincage preliminaire destine au depot de phosphate sur des surfaces metalliques |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO2007097139A1 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115485A1 (fr) * | 2008-03-20 | 2009-09-24 | Henkel Ag & Co. Kgaa | Peinture électrophorétique par immersion optimisée d'éléments assemblés et partiellement préphosphatés |
| US8329013B2 (en) | 2008-03-20 | 2012-12-11 | Henkel Ag & Co. Kgaa | Optimized electrocoating of assembled and partly prephosphated components |
| US10774223B2 (en) | 2014-12-22 | 2020-09-15 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Method for producing anisotropic zinc phosphate particles |
| KR20170106342A (ko) * | 2014-12-22 | 2017-09-20 | 라이브니츠-인스티투트 퓌어 노이에 마테리알리엔 게마인누찌게 게엠베하 | 이방성 아연 포스페이트 입자 및 아연 금속 혼합된 포스페이트 입자의 생성 방법 및 그의 용도 |
| WO2016102265A1 (fr) * | 2014-12-22 | 2016-06-30 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Procédé de production de particules anisotropes de phosphate de zinc et de phosphate mixte zinc/métal et leur utilisation |
| WO2018178108A1 (fr) | 2017-03-30 | 2018-10-04 | Tata Steel Ijmuiden B.V. | Composition acide aqueuse pour le traitement des surfaces métalliques, procédé de traitement l'utilisant et utilisation de la surface métallique traitée |
| US11453947B2 (en) | 2017-03-30 | 2022-09-27 | Tata Steel Ijmuiden B.V. | Aqueous acidic composition for treating metal surfaces, treating method using this composition and use of treated metal surface |
| EP3392376A1 (fr) * | 2017-04-21 | 2018-10-24 | Henkel AG & Co. KGaA | Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série |
| EP3392375A1 (fr) * | 2017-04-21 | 2018-10-24 | Henkel AG & Co. KGaA | Procédé de phosphatation au zinc formant des couches de composants métalliques en série |
| WO2018192709A1 (fr) * | 2017-04-21 | 2018-10-25 | Henkel Ag & Co. Kgaa | Procédé de phosphatation au zinc filmogène d'éléments métalliques en série |
| WO2018192707A1 (fr) * | 2017-04-21 | 2018-10-25 | Henkel Ag & Co. Kgaa | Procédé de phosphatation au zinc, filmogène et exempte de boue, d'éléments métalliques en série |
| US11479865B2 (en) | 2017-04-21 | 2022-10-25 | Henkel Ag & Co. Kgaa | Method for zinc phosphating metal components in series in a sludge-free manner so as to form layers |
| US11486044B2 (en) | 2017-04-21 | 2022-11-01 | Henkel Ag & Co. Kgaa | Method for zinc phosphating metal components in series so as to form layers |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1988189B1 (fr) | 2014-03-12 |
| EP1988189A4 (fr) | 2012-01-25 |
| TW200732510A (en) | 2007-09-01 |
| KR101068708B1 (ko) | 2011-09-28 |
| TWI348500B (en) | 2011-09-11 |
| KR20080094039A (ko) | 2008-10-22 |
| WO2007097139A1 (fr) | 2007-08-30 |
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