EP3006600B1 - Supplément et procédé de production d'un matériau métallique traité en surface - Google Patents
Supplément et procédé de production d'un matériau métallique traité en surface Download PDFInfo
- Publication number
- EP3006600B1 EP3006600B1 EP13886009.3A EP13886009A EP3006600B1 EP 3006600 B1 EP3006600 B1 EP 3006600B1 EP 13886009 A EP13886009 A EP 13886009A EP 3006600 B1 EP3006600 B1 EP 3006600B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zirconium
- fluorine
- metallic material
- ion
- replenisher
- 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.)
- Active
Links
- 239000007769 metal material Substances 0.000 title claims description 149
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000013589 supplement Substances 0.000 title 1
- 239000000126 substance Substances 0.000 claims description 48
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 46
- 239000011737 fluorine Substances 0.000 claims description 45
- 229910052731 fluorine Inorganic materials 0.000 claims description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 43
- 150000003755 zirconium compounds Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000007739 conversion coating Methods 0.000 claims description 26
- 229910052726 zirconium Inorganic materials 0.000 claims description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 15
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 124
- 238000000576 coating method Methods 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 39
- 238000012360 testing method Methods 0.000 description 35
- 150000002500 ions Chemical class 0.000 description 32
- 238000003860 storage Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000007774 longterm Effects 0.000 description 11
- 238000004381 surface treatment Methods 0.000 description 11
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- -1 fluoride ions Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910020148 K2ZrF6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007740 Zr—F Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- HPMLGNIUXVXALD-UHFFFAOYSA-N benzoyl fluoride Chemical compound FC(=O)C1=CC=CC=C1 HPMLGNIUXVXALD-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- AOMUALOCHQKUCD-UHFFFAOYSA-N dodecyl 4-chloro-3-[[3-(4-methoxyphenyl)-3-oxopropanoyl]amino]benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(Cl)C(NC(=O)CC(=O)C=2C=CC(OC)=CC=2)=C1 AOMUALOCHQKUCD-UHFFFAOYSA-N 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/86—Regeneration of coating baths
Definitions
- the present invention relates to a replenisher and a method for producing a surface-treated metallic material.
- a surface thereof is normally subjected to a chemical conversion treatment including phosphate treatment and chromate treatment depending on its application.
- Patent Literature 1 and Patent Literature 2 a chemical conversion coating using a zirconium compound and the like is proposed as a new coating treatment to replace the phosphate treatment or the chromate treatment.
- a zirconium-based chemical conversion coating (hereinafter, also referred to simply as coating) can be formed on/over the surface of the metallic material, thereby imparting excellent performance to the surface of the metallic material.
- zirconium ion in the metallic material surface treating solution is consumed while being converted into oxides and deposited as the coatings, whereby the zirconium ion concentration in the metallic material surface treating solution gradually decreases.
- an amount of fluorine ion that is taken into the coatings is smaller than that of zirconium ion so that a decrease in the fluorine ion concentration in the metallic material surface treating solution per unit area is smaller than that of the zirconium ion concentration.
- H 2 ZrF 6 is often used in the metallic material surface treating solution containing zirconium ion, and the reaction formula thereof is as shown below.
- H 2 ZrF 6 + 2H 2 O -> ZrO 2 ⁇ + 6HF ⁇ Formula (1)
- a zirconium-based coating includes zirconium oxide or the like is formed on/over the surface of the metallic material.
- H 2 ZrF 6 is normally supplied, but because of this ratio between zirconium ion and fluorine ion, accumulation of HF cannot be inhibited. Accordingly, in order to inhibit accumulation of HF, the method in which part of the metallic material surface treating solution is automatically drained (auto-drained) during continuous operation to keep the HF concentration constant has been conventionally adopted in many cases. However, in the environmental and economical point of view, it is not preferable to auto-drain the solution containing a large amount of zirconium ion or HF into drainage water in spite of the fact that the coatings with reduced environmental loads have been proposed, and thus improvements are desired.
- Patent Literature 3 proposes that the above-described problem can be solved by replenishing the metallic material surface treating solution with zirconium ion in such an amount that the balance with the amount of supplied fluorine ion is taken into consideration using a replenisher containing a fluorine-containing zirconium compound and a fluorine-free zirconium compound.
- US 2011/083580 A1 describes replenisher compositions and methods of replenishing pretreatment compositions.
- the methods include adding a replenisher composition to a pretreatment composition wherein the replenisher composition includes: (a) a dissolved complex metal fluoride ion wherein the metal ion comprises a Group IIIA metal, Group IVA metal, Group IVB metal, or combinations thereof; (b) a component comprising an oxide, hydroxide, or carbonate of Group IIIA, Group IVA, Group IVB metals, or combinations thereof; and optionally (c) a dissolved metal ion comprising a Group IB metal, Group IIB metal, Group VIIB metal, Group VIII metal, Lanthanide Series metal, or combinations thereof.
- JP 2009 084623 A relates to the problem to provide a method for manufacturing a steel sheet covered with a conversion treatment film, which is a steel strip covered with a conversion treatment film obtained by continuously and cathodically electrolyzing the steel strip in a treatment solution that contains Zr fluoride ions, while stably supplying Zr ions to the treatment solution.
- the treatment solution contains the Zr ions in an amount of 0.05 to 30 g/L, and fluorine ions in an amount of 0.5 to 10 times that of Zr ions.
- the manufacturing method includes supplying the Zr ions to the treatment solution with the use of two or more types of Zr compounds selected from the group consisting of a Zr halide, Zr hydroxide, Zr carbonate, a Zr ammoniate, Zr nitrate, Zr sulfate and Zr acetate, in cathodic electrolysis treatment.
- the treatment solution contains the ions originating in the selected two or more types of the Zr compounds in an amount of 10 times of Zr ions or less, respectively.
- a replenisher used to replenish the metallic material surface treating solution with zirconium ion is usually stored for a long time in a storehouse or the like after purchase.
- the replenisher has to be in a usable condition after a long-term storage.
- it is required that, when the replenisher is stored in the high-temperature environment for a long period of time, precipitation or the like not occur in the replenisher.
- the inventors of the present invention studied storage stability of the replenisher specifically described in Patent Literature 3 and found that the storage stability thereof was not at the recent satisfactory level, and further improvements were necessary.
- the accumulated treatment load refers to a value (S/V(m 2 /L)) obtained by dividing the accumulated treatment area (Sm 2 ) of a metallic material by the volume (VL) of the metallic material surface treating solution as the result of continuous operation of the coating treatment.
- the present inventors performed continuous operation of coating treatment using the replenisher specifically described in Patent Literature 3, studied the coating treatment performance when the accumulated treatment load is larger, and discovered that the coating weight on/over the metallic material would have decreased.
- an object of the present invention is to provide a replenisher that can replenish the metallic material surface treating solution with zirconium ion at the higher concentration while inhibiting an increase of the HF concentration in the metallic material surface treating solution such that chemical conversion treatment and/or electrolysis treatment can be continuously performed on/over metallic materials, and that exhibits excellent long-term storage stability.
- an object of the present invention also is to provide a method for producing a surface-treated metallic material using the replenisher.
- the present inventors discovered that the above-described problem can be solved by using a replenisher with high zirconium ion concentration that is obtained by using the predetermined compound.
- the present invention can provide a replenisher having more excellent long-term storage stability and capable of replenishing the metallic material surface treating solution with zirconium ion at high concentration while the HF concentration in the metallic material surface treating solution is inhibited from increasing such that chemical conversion treatment and/or electrolysis treatment can be continuously performed on/over metallic materials.
- the method for producing a surface-treated metallic material using the replenisher can be provided.
- the replenisher of the present invention contains a predetermined fluorine-free zirconium compound (A), a predetermined fluorine-containing compound (B) and a predetermined acid component (C), and contains zirconium ion (Zr ion) at a high concentration.
- a ratio (M AC /M F ) between the total molar quantity (M AC ) of anions derived from the acid component (C) and the total molar quantity (M F ) of fluorine ion (F ion), and a ratio (M F /M Zr ) between the total molar quantity (M Zr ) of zirconium ion and the total molar quantity (M F ) of fluorine ion fall within predetermined ranges.
- the metallic material surface treating solution is continuously replenished with the replenisher in continuous production of chemical conversion coatings
- increase of HF can be inhibited and a large amount of zirconium ion can be continuously supplied.
- the chemical conversion treatment and/or electrolysis treatment can be continuously performed on/over metallic materials while the amount of auto-drained solution is suppressed.
- the ratio (M AC /M F ) to fall within the predetermined range, the replenisher that has more excellent long-term storage stability and that enables the chemical conversion treatment and/or electrolysis treatment to be continuously performed on/over metallic materials can be provided.
- the replenisher of the present invention is used to mainly supply zirconium ion to a metallic material surface treating solution that contains zirconium ion and fluorine ion and that is used to form on/over a metallic material surface a chemical conversion coating containing zirconium as the main component through chemical conversion treatment and/or electrolysis treatment. Meanwhile, it should be noted that implementation of auto-drainage in the continuous production of chemical conversion coatings is not denied.
- the fluorine-free zirconium compound (A) contained in the replenisher of the present invention is a compound that does not contain fluorine atoms but contains Zr atoms.
- the fluorine-containing compound (B) contained in the replenisher of the present invention is a compound that contains fluorine atoms and that supplies the replenisher with F ion.
- hexafluorozirconic acid or a salt thereof is used as the fluorine-containing compound (B)
- Zr ion is also supplied into the replenisher.
- the fluorine-containing compound (B) includes at least one compound selected from the group consisting of hydrofluoric acid, a salt of hydrofluoric acid, hexafluorozirconic acid and a salt of hexafluorozirconic acid.
- hydrofluoric acid or hexafluorozirconic acid is more preferable from the standpoint of improving the excellent effect of the present invention.
- Examples of the salt of hydrofluoric acid includes a salt of hydrofluoric acid with a base (such as an amine compound) and preferably a salt of hydrofluoric acid with a base that contains no metal, such as an ammonium salt.
- examples of the salt of hexafluorozirconic acid include metal acid salts (for example, sodium salt, potassium salt, lithium salt, ammonium salt and the like) such as K 2 ZrF 6 .
- the acid component (C) contained in the replenisher of the present invention performs roles as adjusting a pH of the replenisher and promoting solubility of other components (fluorine-free zirconium compound (A) and/or fluorine-containing compound (B)).
- Two or more acid components described above may be used as the acid component (C).
- the ratio (M AC /M F ) of the total molar quantity (M AC ) of anions derived from the acid component (C) with respect to the total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) is 0.35 or more and less than 2.00.
- the replenisher has excellent storage stability and enables continuous and stable production of chemical conversion coatings without accumulation of HF in the metallic material surface treating solution.
- the ratio (M AC /M F ) is preferably more than 0.40 and less than 2.00, more preferably more than 0.50 and less than 2.00, further more preferably more than 0.50 and 1.60 or less, and yet further more preferably 1.00 or more and 1.60 or less.
- the ratio (M AC /M F ) is less than 0.35, the long-term storage stability of the replenisher is inferior. If the ratio (M AC /M F ) is 2.00 or more, when the replenisher is continuously used, the coating weight would decrease, and the desired coating cannot be formed.
- Anions derived from the acid component (C) are NO 3 - , Cl - , SO 4 2- , and CH 3 COO - .
- the total concentration (g/L) of zirconium ion derived from the fluorine-free zirconium compound (A) and from the fluorine-containing compound (B) is 25 or higher.
- the concentration is within the range, chemical conversion coatings can be more economically produced.
- the total concentration (g/L) of zirconium ion is preferably 30 or higher, and more preferably 35 or higher, since the amount of replenisher used can be reduced, and the operation economy can be better.
- the upper limit of the concentration is often 70 or lower, in view of solubility of the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) .
- the ratio (M F /M Zr ) of the total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) with respect to the total molar quantity (M Zr ) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 2.00 or more and less than 6.00.
- the ratio (M F /M Zr ) is preferably 2.50 to 5.50, and more preferably 3.00 to 5.00.
- the ratio (M F /M Zr ) is less than 2.00, it is difficult to have zirconium compounds dissolved in the replenisher.
- the ratio (M F /M Zr ) is 6.00 or more, when the replenisher is continuously used, accumulation of HF in the metallic material surface treating solution cannot be inhibited. Therefore, for stable production of chemical conversion coatings, the amount of auto-drained solution needs to be increased, which is not preferable from the environmental and economical standpoint.
- the respective ions described above can be measured using a known measurement device, atomic absorption, ICP, ion chromatography, or a fluorine ion meter.
- the fluorine-free zirconium compound (A) content is not particularly limited as long as the above-described relationships (I) to (III) are satisfied, but is preferably 0.1 to 500 parts by mass, and more preferably 10 to 300 parts by mass, with respect to 100 parts by mass of the fluorine-containing compound (B), since the deposition efficiency of the chemical conversion coating is excellent.
- the pH of the replenisher of the present invention is not particularly limited, but is preferably less than 4.0, and more preferably more than 0 and 1.5 or less, since the replenisher has excellent stability.
- an alkaline component can be also used.
- the alkaline component include alkali metal oxides such as sodium hydroxide, potassium hydroxide and the like; hydroxides of alkali earth metals such as calcium hydroxide, magnesium hydroxide and the like; and organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and the like. Among these, ammonia is preferably used since it has no metallic contamination and contains no organic solvent.
- the replenisher of the present invention may contain a solvent as necessary.
- the type of solvent used is not particularly limited, and water and/or an organic solvent is normally used.
- organic solvent examples include an alcohol-based solvent and the like. While the organic solvent content may be within the range in which stability of the replenisher and of the metallic material surface treating solution to be replenished with the replenisher is not impaired, no organic solvent is preferably contained from the standpoint of the working environment.
- the total mass of the above-described fluorine-free zirconium compound (A), fluorine-containing compound (B) and acid component (C) when the replenisher contains a solvent is preferably 2 mass% to 90 mass%, and more preferably 4 mass% to 80 mass%, with respect to the whole quantity of replenisher, since the deposition efficiency of the chemical conversion coating is more excellent.
- the method for producing the replenisher of the present invention is not particularly limited, and any known method is adopted. Examples thereof include the method in which the fluorine-free zirconium compound (A), the fluorine-containing compound (B) and the acid component (C) are added in the solvent(s) and mixed.
- the method for producing the surface-treated metallic materials of the present invention is a method in which chemical conversion treatment and/or electrolysis treatment is continuously performed on/over a metallic material in a metallic material surface treating solution containing zirconium ion and fluorine ion to form a chemical conversion coating containing zirconium on/over the metallic material.
- the zirconium ion concentration in the metallic material surface treating solution decreases accordingly, making it harder to form a coating containing a zirconium compound.
- the metallic material surface treating solution is replenished with the replenisher described above.
- the replenisher is preferably added to the metallic material surface treating solution in such a manner that the zirconium ion concentration does not decrease by 20% or more.
- the total amount of fluorine ion supplied together with zirconium is preferably an amount obtained by subtracting the amount of fluorine ion in HF generated in the metallic material surface treating solution as a by-product during producing the coating containing the zirconium compound from the sum of all fluorine ion that is taken into the chemical conversion coating and all fluorine ion in the metallic material surface treating solution that adheres to the metallic material having the chemical conversion coating formed on/over the surface when the metallic material is taken out from the bath.
- the method for adding the replenisher of the present invention into the metallic material surface treating solution is not particularly limited, and examples thereof include the method in which the replenisher is divided into small portions and added in several times (method A) and the method in which the replenisher in a predetermined amount is added at once (method B).
- method A the method in which the replenisher is divided into small portions and added in several times
- method B the method in which the replenisher in a predetermined amount is added at once
- the method A is preferable, since component variation in the metallic material surface treating solution is small and the surface-treated metallic materials can be continuously and stably produced.
- the metallic material surface creating solution used in the method for producing the surface-treated metallic materials of the present invention described above contains Zr ion and fluorine ion.
- Examples of the supply source of zirconium ion in the metallic material surface treating solution include the above-described fluorine-free zirconium compound (A), hexafluorozirconic acid or a salt thereof.
- Zr ion in the metallic material surface treating solution refers to both (1) zirconium fluoride complex ion in which 1 to 6 moles of fluorine are coordinated to 1 mole of zirconium as expressed by ZrF n ( 4-n ) and (2) zirconium ion or zirconyl ion generated from inorganic acid zirconium such as zirconium nitrate and zirconium sulfate or inorganic acid zirconyl, or alternatively, an organic acid zirconium or organic acid zirconyl such as zirconium acetate and zirconyl acetate.
- Any known compound containing fluorine (fluorine-containing compound) can be used as the supply source of fluorine ion in the metallic material surface treating solution.
- a fluorine compound having at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al and B is preferably used as the fluorine-containing compound.
- Specific examples thereof include complexes in which 1 to 3 hydrogen atoms are coordinated to anions such as (Ti 7 F 6 ) 2- , (ZrF 6 ) 2- , (HfF 6 ) 2- , (SiF 6 ) 2- , (AlF 6 ) 3- and (BF 4 OH) - , and ammonium salts and metal salts of these anions.
- fluorine-containing compound examples include hydrofluoric acid and its ammonium salt and alkali metal salts; metal fluorides (such as aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, manganese fluoride, ferrous fluoride and ferric fluoride or the like); and acid fluorides (such as fluorine oxide, acetyl fluoride and benzoyl fluoride or the like).
- metal fluorides such as aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, manganese fluoride, ferrous fluoride and ferric fluoride or the like
- acid fluorides such as fluorine oxide, acetyl fluoride and benzoyl fluoride or the like.
- Fluorine ion in the metallic material surface treating solution refers to both fluorine ion (F - ) derived from HF present in the metallic material surface treating solution and fluorine ion in fluorine-containing complex ion such as the above-described zirconium: fluoride complex ion, and the total fluorine ion concentration described above and later refers to the concentration of the sum of both fluorine ion.
- Free fluorine concentration refers to the concentration of HF-derived fluorine ion (F - ).
- the total amount of fluorine ion contained in the metallic material surface treating solution is not particularly limited but is preferably 0.050 g/L to 10.000 g/L, and more preferably 0.100 g/L to 3.000 g/L as the total fluorine ion concentration, since the metallic material surface treating solution has more excellent stability, and the deposition efficiency of the chemical conversion coating is also excellent.
- the free fluorine ion concentration is preferably 5 mg/L to 400 mg/L, and more preferably 10 mg/L to 250 mg/L.
- the amounts (concentrations) of Zr ion, total fluorine ion, and free fluorine ion in the metallic material surface treating solution can be measured by using atomic absorption, ICP, ion chromatography or a fluorine ion meter.
- the pH of the metallic material surface treating solution is appropriately adjusted according to the metallic material to be treated or the condition of the chemical conversion treatment or electrolysis treatment, but is preferably about 2.5 to 5.0, and more preferably 3.0 to 5.0, since the metallic material surface treating solution has more excellent stability and the deposition efficiency of the chemical conversion coating is also more excellent.
- the pH of the metallic material surface treating solution can be measured by using a pH meter.
- the type of metallic material used is not particularly limited, and any known metallic material can be used. Examples thereof include iron material, plating material, zinc material, aluminum material, magnesium material and the like.
- the shape of the metallic material is not particularly limited and can be a plate shape or any other shape.
- Examples of the other shapes include a vehicle body of a transporting device such as an automobile and its constituent component, a farm equipment and its constituent component, steel furniture, building material and the like.
- the chemical conversion treatment using the metallic material surface treating solution described above can be performed using known treatment facilities under a known condition.
- the chemical conversion treatment is a treatment in which a metallic material is brought into contact (immersion, coating or spraying) with a predetermined metallic material surface treating solution that is at normal temperature or heated, whereby a coating is formed on/over the surface of the metallic material.
- the duration of contact between the metallic material and the metallic material surface treating solution is appropriately adjusted depending on the quality or shape of the metallic material to be treated, treatment method, application thereof and the targeted coating weight, and is normally about 0.1 second to 600 seconds in many cases, since the chemical conversion coating has more excellent properties.
- the electrolysis treatment (anodic electrolysis treatment, cathodic electrolysis treatment) using the metallic material surface treating solution can be performed using known electrolysis treatment facilities under a known condition.
- the current density is preferably 0.1 A/dm 2 to 20.0 A/dm 2 , and more preferably 0.5 A/dm 2 to 10.0 A/dm 2 since the deposition efficiency of the chemical conversion coating is excellent.
- the coating weight of zirconium in the formed chemical conversion coating is appropriately adjusted depending on the quality or application of the metallic material to be treated, and is normally about 1 mg/m 2 to 70 mg/m 2 in many cases in both the chemical conversion treatment and the electrolysis treatment, since the chemical conversion coating has more excellent properties.
- test sheets (1) to (3) were used in Examples and Comparative Examples.
- the fluorine-free zirconium compound (A), the fluorine-containing compound (B) and the acid component (C) were mixed in water so as to have compositions shown in Table 1, whereby the various replenishers were prepared.
- the above degreasing process was performed using an alkaline degreasing agent, Finecleaner L4460 (2.0%; 45°C, 120 seconds, spraying) manufactured by Nihon Parkerizing Co., Ltd.
- any one of the following continuous treating methods 1 to 3 was performed.
- the treating solution was adjusted to have a pH of 4.0 and heated to 40°C to prepare a metallic material surface treating solution.
- the metallic material surface treating solution was stirred and a test sheet (1) was immersed in the metallic material surface treating solution for 180 seconds, whereby the surface treatment was performed to achieve a target Zr coating weight of 13 mg/m 2 .
- This process was regarded as one cycle and repeated using new test sheets (1) so as to perform surface treatment (continuous treating test).
- the test was conducted until the processing load reached 13.3 m 2 /L, and the Zr coating weight at the beginning of the continuous treating test and the Zr coating weight at the time when the processing load became 13.3 m 2 /L were measured.
- the Zr coating weight on the surface of the treated material was quantitatively determined using X-ray fluorescence (XRF) analysis.
- a bath was made up of 10L of a treating solution having the components of concentrations described below, the treating solution was adjusted to have a pH of 4.0 and heated to 40°C to prepare a metallic material surface treating solution.
- the metallic material surface treating solution was stirred and a test sheet (2) was immersed in the metallic material surface treating solution for 120 seconds, whereby the surface treatment was performed to achieve a target Zr coating weight of 20 mg/m 2 .
- This process was regarded as one cycle and repeated using new test sheets (2) so as to perform surface treatment (continuous treating test).
- the test was conducted until the processing load reached 16.7 m 2 /L, and the Zr coating weight at the beginning of the continuous treating test and the Zr coating weight at the time when the processing load became 16.7 m 2 /L were measured.
- the Zr coating weight on the surface of the treated material was quantitatively determined using X-ray fluorescence (XRF) analysis.
- the treating solution was adjusted to have a pH of 3.7 and heated to 40°C to prepare a metallic material surface treating solution.
- the metallic material surface treating solution was stirred and a test sheet (3) was immersed in the metallic material surface treating solution for 30 seconds, thereby the surface treatment was performed to achieve a target Zr coating weight of 10 mg/m 2 .
- This process was regarded as one cycle and repeated using new test sheets (3) so as to perform surface treatment (continuous treating test).
- the test was conducted until the processing load reached 45.5 m 2 /L, and the Zr coating weight at the beginning of the continuous treating test and the Zr coating weight at the time when the processing load became 45.5 m 2 /L were measured.
- the Zr coating weight on the surface of the treated material was quantitatively determined using X-ray fluorescence (XRF) analysis.
- the replenisher shown in Table 1 was put in a plastic container, which was sealed.
- the replenisher was stored for a maximum of 6 months at 35°C immediately after sealed, and appearance of the solution was then evaluated.
- the evaluation standards are described below. Practically, "Good” or “Excellent” is preferable. Excellent: Appearance does not change on or later than 6 months from the start of storage. Good: Appearance changes in a period starting on or later than 3 months and ending earlier than 6 months from the start of storage. Fair: Appearance changes in a period starting on or later than 2 weeks and ending earlier than 3 months from the start of storage. Poor: Precipitation, or turbidness or gelation of the solution is observed earlier than 2 weeks from the start of storage.
- Continuous treating test was conducted according to the treating methods shown in Table 1, the Zr coating weight on the test piece (test sheet) was determined at the beginning of the test (first cycle) and at the time when the treating solution was 100% replaced, and the thus determined values were compared.
- the evaluation standards are described below. Practically, “Good” or “Excellent” is preferable. Excellent: The Zr coating weight after 100% replacement is 95% or more and less than 105% with respect to the Zr coating weight at the beginning of the continuous treating rest. Good: The Zr coating weight after 100% replacement is 85% or more and less than 95% with respect to the Zr coating weight at the beginning of the continuous treating test.
- the Zr coating weight after 100% replacement is 50% or more and less than 85% with respect to the Zr coating weight at the beginning of the continuous treating test.
- Poor The Zr coating weight after 100% replacement is less than 50% with respect to the Zr coating weight at the beginning of the continuous treating test.
- Zr Carb refers to zirconium carbonate
- Zr Basic Carb refers to zirconium basic carbonate
- Zr Concentration refers to zirconium ion concentration (g/L).
- the replenisher made from the mixture solution of hexafluorozirconic acid and zirconium nitrate described in paragraph [0033] of Patent Literature 3 has the ratio M AC /M F of 0.33 and could not achieve the desired effect, as being apparent from Comparative Examples 1 to 3 in Table 1.
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Claims (4)
- Régénérateur utilisé pour régénérer une solution de traitement de surface de matériau métallique avec des ions zirconium, la solution de traitement de surface de matériau métallique contenant des ions zirconium et des ions fluor et étant utilisée pour former un revêtement de conversion chimique contenant du zirconium sur/par-dessus un matériau métallique par le biais d'un traitement de conversion chimique et/ou d'un traitement d'électrolyse, le régénérateur comprenant :un composé de zirconium exempt de fluor (A) contenant au moins un élément choisi dans un groupe consistant en le carbonate basique de zirconium, le carbonate de zirconium, l'hydroxyde de zirconium et le carbonate d'ammonium zirconium ; un composé contenant du fluor (B) contenant au moins un élément choisi dans le groupe consistant en l'acide fluorhydrique, un sel d'acide fluorhydrique, l'acide hexafluorozirconique et un sel d'acide hexafluorozirconique ; et un composant d'acide (C) contenant au moins un élément choisi dans le groupe consistant en l'acide nitrique, l'acide chlorhydrique, l'acide sulfurique et l'acide acétique,dans lequel les relations (I) à (III) suivantes sont satisfaites :(I) un rapport (MAC/MF) entre une quantité molaire totale (MAC) d'anions dérivés du composant d'acide (C) et une quantité molaire totale (MF) d'ions fluor dérivés du composé contenant du fluor (B) est de 0,35 ou plus et inférieur à 2,00 ;(II) une concentration totale (g/L) d'ions zirconium dérivés du composé de zirconium exempt de fluor (A) et du composé contenant du fluor (B) est de 25 ou plus ; et(III) un rapport (MF/MZr) entre une quantité molaire totale (MF) d'ions fluor dérivés du composé contenant du fluor (B) et une quantité molaire totale (MZr) d'ions zirconium dérivés du composé de zirconium exempt de fluor (A) et du composé contenant du fluor (B) est de 2,00 ou plus et inférieur à 6,00.
- Régénérateur selon la revendication 1, dans lequel le rapport (MAC/MF) dépasse 0,50 et est inférieur à 2,00.
- Régénérateur selon la revendication 1 ou 2, dans lequel le rapport (MAC/MF) dépasse 0,50 et est de 1,60 ou moins.
- Procédé de production d'un matériau métallique traité en surface comprenant :la réalisation en continu d'un traitement de conversion chimique et/ou d'un traitement d'électrolyse sur/par-dessus un matériau métallique dans une solution de traitement de surface de matériau métallique contenant des ions zirconium et des ions fluor pour former un revêtement de conversion chimique contenant du zirconium sur/par-dessus le matériau métallique ; etla régénération de la solution de traitement de surface de matériau métallique avec des ions zirconium en ajoutant le régénérateur selon l'une quelconque des revendications 1 à 3 à la solution de traitement de surface de matériau métallique.
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WO1995014539A1 (fr) * | 1993-11-29 | 1995-06-01 | Henkel Corporation | Composition et procede de traitement de metaux |
US6916414B2 (en) * | 2001-10-02 | 2005-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Light metal anodization |
TW567242B (en) * | 2002-03-05 | 2003-12-21 | Nihon Parkerizing | Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment |
US6881279B2 (en) * | 2002-12-11 | 2005-04-19 | Henkel Corporation | High performance non-chrome pretreatment for can-end stock aluminum |
JP2008240045A (ja) | 2007-03-27 | 2008-10-09 | Nippon Paint Co Ltd | 鋼製ドラム缶の製造方法 |
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JP2010090407A (ja) | 2008-10-03 | 2010-04-22 | Nippon Parkerizing Co Ltd | 金属表面処理液、および金属表面処理方法 |
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EP2581471B1 (fr) * | 2010-06-09 | 2019-12-04 | Chemetall GmbH | Agent de traitement de surface métallique dépourvue de chrome inorganique |
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2013
- 2013-05-28 US US14/894,488 patent/US20160186351A1/en not_active Abandoned
- 2013-05-28 WO PCT/JP2013/064801 patent/WO2014192082A1/fr active Application Filing
- 2013-05-28 CN CN201380076902.7A patent/CN105378144B/zh active Active
- 2013-05-28 JP JP2015519528A patent/JP6055915B2/ja active Active
- 2013-05-28 KR KR1020157033718A patent/KR101726536B1/ko active IP Right Grant
- 2013-05-28 EP EP13886009.3A patent/EP3006600B1/fr active Active
-
2015
- 2015-11-27 PH PH12015502678A patent/PH12015502678A1/en unknown
Non-Patent Citations (1)
Title |
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JPWO2014192082A1 (ja) | 2017-02-23 |
PH12015502678A1 (en) | 2016-03-07 |
US20160186351A1 (en) | 2016-06-30 |
KR101726536B1 (ko) | 2017-04-12 |
EP3006600A4 (fr) | 2017-01-18 |
CN105378144A (zh) | 2016-03-02 |
KR20160003134A (ko) | 2016-01-08 |
CN105378144B (zh) | 2017-05-31 |
JP6055915B2 (ja) | 2016-12-27 |
WO2014192082A1 (fr) | 2014-12-04 |
EP3006600A1 (fr) | 2016-04-13 |
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