EP0337411B1 - Verfahren zur Herstellung eines sauren chrom-(III)-haltigen und fluoridhaltigen Passivierungsbades für Oberflächen aus Zink, Zinklegierungen und Cadmium - Google Patents
Verfahren zur Herstellung eines sauren chrom-(III)-haltigen und fluoridhaltigen Passivierungsbades für Oberflächen aus Zink, Zinklegierungen und Cadmium Download PDFInfo
- Publication number
- EP0337411B1 EP0337411B1 EP89106447A EP89106447A EP0337411B1 EP 0337411 B1 EP0337411 B1 EP 0337411B1 EP 89106447 A EP89106447 A EP 89106447A EP 89106447 A EP89106447 A EP 89106447A EP 0337411 B1 EP0337411 B1 EP 0337411B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluoride
- zinc
- chromium
- iii
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 15
- 239000011701 zinc Substances 0.000 title claims abstract description 15
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 230000002378 acidificating effect Effects 0.000 title abstract description 9
- 239000011651 chromium Substances 0.000 title description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 11
- 229910052804 chromium Inorganic materials 0.000 title description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 chromium(III) compound Chemical class 0.000 claims abstract description 12
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract 3
- 238000002161 passivation Methods 0.000 claims description 27
- 239000012141 concentrate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 150000001413 amino acids Chemical class 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 235000011087 fumaric acid Nutrition 0.000 claims 1
- 239000000174 gluconic acid Substances 0.000 claims 1
- 235000012208 gluconic acid Nutrition 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 abstract 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004532 chromating Methods 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GLTMCOADWUPWSC-UHFFFAOYSA-N [F].[Cr+3] Chemical class [F].[Cr+3] GLTMCOADWUPWSC-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- UUMMHAPECIIHJR-UHFFFAOYSA-N chromium(4+) Chemical class [Cr+4] UUMMHAPECIIHJR-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the invention relates to a method for producing an acidic chromium-containing and fluoride-containing passivation bath for zinc or cadmium surfaces.
- an acidic chromium-containing passivation bath for zinc or cadmium surfaces is known from US Pat. No. 4,263,059 and DE-OS 30 38 699, which, in addition to a "blue solution" of trivalent chromium and an acid, such as formic, acetic or propionic acid or nitric, sulfuric, hydrochloric and hydrofluoric acid contains a fluoride with a "green solution" of hexavalent chromium, for example Chromium trioxide, alkali metal chromate and dichromate and a reducing agent such as an aldehyde or alcohol or an alkali metal sulfite, bisulfite, metabisulfite, iodide, hydrogen peroxide, sulfur dioxide or an iron (II) salt is formed.
- a fluoride with a "green solution” of hexavalent chromium for example Chromium trioxide, alkali metal chromate and dichromate and a reducing
- surfaces made of zinc, zinc alloys, galvanically or by hot-dip galvanizing on iron or steel or zinc layers or cadmium surfaces are made more corrosion-resistant, which is indicated by a coloration that ranges from blue to black and yellow to olive and is also used for decorative purposes.
- a passivation for example, the so-called blue passivation, ie Generation of a light blue, very thin passivation layer with a good decorative appearance, formation of zinc corrosion products also called "white rust", greatly delayed.
- the salt spray test according to DIN 50021 provides a measure of the corrosion protection of these chromates.
- a zinc-coated and passivated part is exposed to a 5% sodium chloride mist at 40 ° C and 100% humidity. The time required to oxidize 5 - 10% of the surface to white rust is then given.
- the corrosion protection according to DIN 50021 should be 20 to 24 hours.
- Chromium (III) fluorine complexes of chromium (III) are known, the formation of which is accelerated by zinc, but there is no evidence of the blue passivation of zinc or galvanized in this investigation of equilibrium constants Iron surfaces, on where there is no chrome metal deposition, but a polymeric compound with divalent chromium is deposited.
- This object is achieved according to the invention by a process for producing an acidic, chromium (III) -containing and fluoride-containing passivation bath for surfaces made of zinc, zinc alloys and cadmium by mixing 20 to 200 g / l of a soluble chromium (111) compound 20 to 600 g / l of a soluble nitrate (total nitrate) 5 to 100 g / l of a fluoride and hydrochloric or nitric acid to a pH of 1.8 to 2.2 and an anion selected from the group consisting of sulfate, phosphate, chloride, bromide, fluoride and iodide, the soluble nitrate in greater concentration than the chromium (III ) Concentration (in g / l) is present, and the mixture is either heated to 60 ° C.
- the concentrate obtained is optionally brought to an application concentration of 2 to 20% by weight in water , dissolved, which is characterized in that it additionally contains an acidic ion exchanger loaded with Cr3+ and / or an agent for the insolubilization of Fe3+ ions in an amount of 0.1 to 100 g / l.
- a catalyst in particular with activated carbon at 15 ° C. or above, for example at room temperature (20-25 ° C.) or brief heating, for example 30 seconds to 15 minutes. to at least 60 to 80 ° C, seems to promote the formation of the more stable chromium (III) complexes, which is surprising is because only the hexahydrate complexes of chromium are stable at room temperature, but they are unusable for passivation.
- Passivation baths preferred according to the invention contain the following amounts in a concentrate which is usually used in a concentration of 2 to 20% by weight in water: 20-200 g / l chromium (III) compound, e.g. as chromium chloride or chromium nitrate, 20 - 600 g / l soluble nitrate, such as sodium, potassium or ammonium nitrate, 5 - 100 g / l fluoride, e.g. sodium, potassium, ammonium fluoride Hydrochloric or nitric acid up to a pH of 1.8 to 2.2.
- a concentrate which is usually used in a concentration of 2 to 20% by weight in water: 20-200 g / l chromium (III) compound, e.g. as chromium chloride or chromium nitrate, 20 - 600 g / l soluble nitrate, such as sodium, potassium or ammonium nitrate, 5 - 100
- Passivation baths made from this concentrate show corrosion protection values of a blue passivation according to DIN 50021 from 44 to 50 h, the layers can be colored and good organic polymers are applied to the layers.
- a concentrate of the following composition was produced: 50 g / l chromium (III) chloride 125 g / l sodium nitrate 50 g / l sodium fluoride
- the concentrate was heated to 65 ° C. It contained complexes of the formula
- the bath was mixed with water in a weight ratio of 1:10 and adjusted to pH 2.0 with nitric acid. With this bath, hot-dip galvanized iron bars of 2 cm in diameter and 20 cm in length were blue passivated. After 3 seconds, the rods were removed from the bath and checked for corrosion behavior in accordance with DIN 50021. The corrosion protection value was 48 hours.
- the durability of the bath was extended by a factor of 10 by adding 50 g / l of acetylacetone.
- a bath was out 60 g / l Cr (NO3) 3.9H2O 100 g / l NaNO3 40 g / l NaF HNO3 ad pH 2.1 and without heating, but prepared by treating with granular activated carbon in a porous bag for 10 minutes and, after mixing with water in a weight ratio of 1:12, used for the same experiment. It contained complexes of the formula The same corrosion protection value was obtained.
- the following results were obtained in a comparison test on normal blue chromating (commercially available): with Cr VI (commercially available): 15 mg Cr / m2 zinc; 24 h corrosion protection Cr III (according to the invention: 30 mg Cr / m2 zinc; 48 h corrosion protection.
- the durability of the bath was extended by a factor of 5 by adding 20 g / l salicylic acid.
- the bath with the ion exchanger showed a perfect blue passivation, while the comparison bath was unusable after a short time.
- the addition of 10 g / l fumaric acid increases the life of the bath by a factor of 5.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Chemically Coating (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Glass Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE8916143U DE8916143U1 (de) | 1988-04-12 | 1989-04-11 | Saures chrom-(III)-haltiges und fluoridhaltiges Passivierungsbad-Konzentrat für Oberflächen aus Zink, Zinklegierungen und Cadmium |
| AT89106447T ATE97700T1 (de) | 1988-04-12 | 1989-04-11 | Verfahren zur herstellung eines sauren chrom(iii)-haltigen und fluoridhaltigen passivierungsbades fuer oberflaechen aus zink, zinklegierungen und cadmium. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3812076 | 1988-04-12 | ||
| DE3812076A DE3812076A1 (de) | 1988-04-12 | 1988-04-12 | Saures chrom-(iii)-haltiges und fluoridhaltiges passivierungsbad fuer oberflaechen aus zink, zinklegierungen und cadmium |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0337411A2 EP0337411A2 (de) | 1989-10-18 |
| EP0337411A3 EP0337411A3 (en) | 1990-05-09 |
| EP0337411B1 true EP0337411B1 (de) | 1993-11-24 |
Family
ID=6351774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89106447A Expired - Lifetime EP0337411B1 (de) | 1988-04-12 | 1989-04-11 | Verfahren zur Herstellung eines sauren chrom-(III)-haltigen und fluoridhaltigen Passivierungsbades für Oberflächen aus Zink, Zinklegierungen und Cadmium |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0337411B1 (enrdf_load_stackoverflow) |
| AT (1) | ATE97700T1 (enrdf_load_stackoverflow) |
| DD (1) | DD280557A5 (enrdf_load_stackoverflow) |
| DE (2) | DE3812076A1 (enrdf_load_stackoverflow) |
| YU (1) | YU71689A (enrdf_load_stackoverflow) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6946201B2 (en) | 1996-04-19 | 2005-09-20 | Surtec International Gmbh | Chromium (VI)-free conversion layer and method for producing it |
| CN102912337A (zh) * | 2012-10-30 | 2013-02-06 | 四川华丰企业集团有限公司 | 一种镀镉工件的绿色钝化膜生产工艺 |
| US10400338B2 (en) | 2017-05-12 | 2019-09-03 | Chemeon Surface Technology, Llc | pH stable trivalent chromium coating solutions |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4135524C2 (de) * | 1991-10-28 | 1995-01-26 | Gc Galvano Consult Gmbh | Verfahren und Mittel zum Chromatieren von Oberflächen aus Zink oder Cadmium oder Legierungen davon |
| US7314671B1 (en) | 1996-04-19 | 2008-01-01 | Surtec International Gmbh | Chromium(VI)-free conversion layer and method for producing it |
| JP4145016B2 (ja) * | 2001-01-31 | 2008-09-03 | 日本パーカライジング株式会社 | 亜鉛系メッキ鋼板用防錆処理剤および亜鉛系メッキ鋼板 |
| US6761774B2 (en) * | 2001-05-24 | 2004-07-13 | Basf Corporation | Composition and method for the in situ removal scale from a substrate |
| US7101469B2 (en) * | 2004-11-10 | 2006-09-05 | Atotech Deutschland Gmbh | Metal pieces and articles having improved corrosion resistance |
| DE102009042861B4 (de) | 2009-09-24 | 2020-08-20 | AnJo Oberflächentechnik GmbH | Zusammensetzung, Anwendungslösung und Verfahren zur Passivierung von Zink und seinen Legierungen |
| WO2011127473A1 (en) * | 2010-04-09 | 2011-10-13 | Enthone Inc. | Passivation treatment of zinc-based coatings |
| DE102011013319B4 (de) | 2011-03-07 | 2018-06-14 | AnJo Oberflächentechnik GmbH | Zusammensetzung und Anwendungslösung zum Passivieren von Zink und seinen Legierungen |
| EP2708620A1 (de) | 2012-09-12 | 2014-03-19 | Anjo Oberflächentechnik GmbH | Zusammensetzung und Anwendungslösung zum Passivieren von Zink und seinen Legierungen |
| CN103215581B (zh) * | 2013-03-25 | 2015-06-03 | 沈阳帕卡濑精有限总公司 | 快速处理钢板表面钝化封闭一体的三价铬钝化剂 |
| CN103215580B (zh) * | 2013-03-25 | 2016-01-27 | 沈阳帕卡濑精有限总公司 | 用于钢板表面快速成膜具有高耐蚀性的三价铬钝化剂 |
| EP2907894B2 (de) * | 2014-02-13 | 2025-03-19 | Ewald Dörken Ag | Verfahren zum Herstellen eines mit einer Chrom-VI-freien und kobaltfreien Passivierung versehenen Substrats |
| NL2017398B1 (en) * | 2016-08-31 | 2018-03-08 | Ad Productions B V | Method of treating metal surfaces with an aqueous composition and aqueous composition |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2166737A1 (de) * | 1970-04-02 | 1975-06-05 | Du Pont | Verfahren zum herstellen von chromhaltigen, waessrigen loesungen |
| US4171231A (en) * | 1978-04-27 | 1979-10-16 | R. O. Hull & Company, Inc. | Coating solutions of trivalent chromium for coating zinc surfaces |
| US4298404A (en) * | 1979-09-06 | 1981-11-03 | Richardson Chemical Company | Chromium-free or low-chromium metal surface passivation |
| US4263059A (en) * | 1979-12-21 | 1981-04-21 | Rohco, Inc. | Coating solutions of trivalent chromium for coating zinc and cadmium surfaces |
| CA1228000A (en) * | 1981-04-16 | 1987-10-13 | David E. Crotty | Chromium appearance passivate solution and process |
| US4384902A (en) * | 1981-06-15 | 1983-05-24 | Occidental Chemical Corporation | Trivalent chromium passivate composition and process |
| US4367099A (en) * | 1981-06-15 | 1983-01-04 | Occidental Chemical Corporation | Trivalent chromium passivate process |
| US4359347A (en) * | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Chromium-free passivate solution and process |
| US4349392A (en) * | 1981-05-20 | 1982-09-14 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
| US4539348A (en) * | 1982-12-16 | 1985-09-03 | Celanese Corporation | Water-swellable crosslinked polymeric microgel particles and aqueous dispersions of organic film-forming resins containing the same |
| US4578122A (en) * | 1984-11-14 | 1986-03-25 | Omi International Corporation | Non-peroxide trivalent chromium passivate composition and process |
| NO168953C (no) * | 1986-08-27 | 1992-04-22 | Elektro Brite Gmbh | Surt kromholdig passiveringsbad for sink- eller kadmiumoverflater |
-
1988
- 1988-04-12 DE DE3812076A patent/DE3812076A1/de active Granted
-
1989
- 1989-04-10 DD DD89327449A patent/DD280557A5/de not_active IP Right Cessation
- 1989-04-10 YU YU00716/89A patent/YU71689A/xx unknown
- 1989-04-11 AT AT89106447T patent/ATE97700T1/de not_active IP Right Cessation
- 1989-04-11 EP EP89106447A patent/EP0337411B1/de not_active Expired - Lifetime
- 1989-04-11 DE DE89106447T patent/DE58906227D1/de not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6946201B2 (en) | 1996-04-19 | 2005-09-20 | Surtec International Gmbh | Chromium (VI)-free conversion layer and method for producing it |
| CN102912337A (zh) * | 2012-10-30 | 2013-02-06 | 四川华丰企业集团有限公司 | 一种镀镉工件的绿色钝化膜生产工艺 |
| CN102912337B (zh) * | 2012-10-30 | 2015-01-21 | 四川华丰企业集团有限公司 | 一种镀镉工件的绿色钝化膜生产工艺 |
| US10400338B2 (en) | 2017-05-12 | 2019-09-03 | Chemeon Surface Technology, Llc | pH stable trivalent chromium coating solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0337411A3 (en) | 1990-05-09 |
| ATE97700T1 (de) | 1993-12-15 |
| DE3812076C2 (enrdf_load_stackoverflow) | 1990-09-13 |
| EP0337411A2 (de) | 1989-10-18 |
| DE58906227D1 (de) | 1994-01-05 |
| YU71689A (en) | 1990-12-31 |
| DD280557A5 (de) | 1990-07-11 |
| DE3812076A1 (de) | 1989-10-26 |
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