DE8916143U1 - Acidic chromium (III) -containing and fluoride-containing passivation bath concentrate for surfaces made of zinc, zinc alloys and cadmium - Google Patents
Acidic chromium (III) -containing and fluoride-containing passivation bath concentrate for surfaces made of zinc, zinc alloys and cadmiumInfo
- Publication number
- DE8916143U1 DE8916143U1 DE8916143U DE8916143U DE8916143U1 DE 8916143 U1 DE8916143 U1 DE 8916143U1 DE 8916143 U DE8916143 U DE 8916143U DE 8916143 U DE8916143 U DE 8916143U DE 8916143 U1 DE8916143 U1 DE 8916143U1
- Authority
- DE
- Germany
- Prior art keywords
- passivation bath
- passivation
- bath according
- zinc
- 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
- 238000002161 passivation Methods 0.000 title claims description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052725 zinc Inorganic materials 0.000 title claims description 15
- 239000011701 zinc Substances 0.000 title claims description 15
- 239000012141 concentrate Substances 0.000 title claims description 14
- 230000002378 acidificating effect Effects 0.000 title claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims description 11
- 229910052793 cadmium Inorganic materials 0.000 title claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 7
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 5
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 title description 6
- 239000011651 chromium Substances 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000004532 chromating Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 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
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 150000001413 amino acids Chemical class 0.000 claims 1
- 229940125810 compound 20 Drugs 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
- 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 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
- 150000003141 primary amines Chemical class 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 10
- -1 alkali metal chromate Chemical class 0.000 description 5
- 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
- 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
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 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
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 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
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 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
- 201000004624 Dermatitis Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001784 detoxification Methods 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
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 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
- 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
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Chemically Coating (AREA)
Description
Saures chrom-(III)-haitiges und fluoridhaUiges Passiviei-ungSbacf-KonzgeflratJfUr Oberflächen ausAcidic chromium (III)-containing and fluoride-containing passivation concentrate for surfaces made of
Zink, Zinklegierungen und CadmiumZinc, zinc alloys and cadmium
Die Erfindung betrifft ein saures chromhaltiges und fluoridhaltiges Passivierungsbad-Konzentrat
für Zink- oder Cadmiumoberflachen sowie eine Anwendungslösung aus diesem Passivierungsbad-Konzentrat.
The invention relates to an acidic chromium-containing and fluoride-containing passivation bath concentrate
for zinc or cadmium surfaces as well as an application solution made from this passivation bath concentrate.
Es ist z.B. aus der US-PS 4 263 059 bzw. der DE-OS 30 38 699 ein saures chromhaltiges Passivierungsbad für Zink- oder Cadmiumoberflächen bekannt, das neben einer "blauen Lösung" aus dreiwertigem Chrom und einer Säure, wie Ameisen-, Essig- oder Propionsäure oder Salpeter-, Schwefel-, Salz- und Fluorwasserstoffsäure ein Fluorid enthält mit einer "grünen Lösung" aus sechswertigem Chrom, z.B. Chromtrioxid, Alkalimetallchromat und -dichromat und einem Reduktionsmittel, wie ein Aldehyd oder Alkohol oder einem Alkalimetallsulfit, -bisulfit. -metabisulfit. -iodid. Wasserstoffperoxid. Schwefeldioxid oder einem Eisen-Il-Salz gebildet wird.For example, an acidic chromium-containing passivation bath for zinc or cadmium surfaces is known from US-PS 4 263 059 or DE-OS 30 38 699, which contains a fluoride 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 with a "green solution" of hexavalent chromium, e.g. 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.
&iacgr;&ogr; Hierdurch werden Oberflächen aus Zink. Zinklegierungen, galvanisch oder durch Feuerverzinkung auf &iacgr;&ogr; This produces surfaces made of zinc. Zinc alloys, galvanized or hot-dip galvanized on
Eisen oder Stahl aufgebrachte Zinkschichten oder Cadmiumoberflächen korrosionsfester gemacht, was durch eine Färbung angezeigt wird, die von blau über schwarz und gelb bis zu oliv reicht und auch für Dekorationszwecke Anwendung findet. Insbesondere wird durch eine solche Passivierung z.B. die sogenannte Blaupassivierung. d.h. die Erzeugung einer leicht blauen, sehr dünnen Passivierungsschicht mit gutem dekorativen Aussehen, eine Bildung der Zinkkorrosionsprodukte auch "Weißrost" genannt, stark ) verzögert.Zinc layers or cadmium surfaces applied to iron or steel are made more corrosion-resistant, which is indicated by a color that ranges from blue to black and yellow to olive and is also used for decorative purposes. In particular, such passivation (eg the so-called blue passivation, ie the creation of a slightly blue, very thin passivation layer with a good decorative appearance) greatly delays the formation of zinc corrosion products, also known as "white rust " .
Ein Maß für den Korrosionsschutz dieser Chromatierungen liefert der Salzsprühtest nach OIN 50021. Dabei wird ein zinkbeschichtetes und passiviertes Teil bei 40* C und 100 % Luftfeuchtigkeit einem 5%igen Natriumchloridnebel ausgesetzt. Angegeben wird dann die Zeit, die benötigt wird, 5-10% der Fläche zuA measure of the corrosion protection of these chromates is provided by the salt spray test according to OIN 50021. In this test, a zinc-coated and passivated part is exposed to a 5% sodium chloride mist at 40* C and 100% humidity. The time required to dry 5-10% of the surface is then specified.
so Weißrost zu oxidieren. to oxidize white rust.
Bei der Blaupassivierung sollte der Korrosionsschutz nach OIN 50021 bei 20 bis 24 h liegen.
Durch das Vorhandensein von giftigen Chrom-(lV)-Verbindungen in den Passivierungslösungen des
Standes der Technik ist es jedoch möglich, dass Chrom-(VI) in die Passivierungsschicht eingebaut wird,
was insbesondere bei Verwendung solcher Schichten zu Dermatitiserkrankungen führen kann und auch aus
diesem Grunde in Geräten der Nahrungsmittelindustrie bedenklich ist. Die Abwasserbehandlung zur
Entgiftung von Passtvierungslösungsresten bzw. bei Spülwässern bietet Probleme und die Lösungen
verbrauchen sich schnell und können nur begrenzt nachgeschärft (regeneriert) werden, müssen vielmehr
bald entsorgt werden. Vielmehr läßt der Korrosionsschutz nach kurzer Zeit, oft schon nach einem Tag,
nach. Andere saure Lösungen, die Chrom-(lll)-lonen enthalten und neben diesen auch Oxidationsmittel (US-PS
4 171 231) und weitere Zusätze wie Silikate und/oder andere Metallionen (Us-PS 4 384 902, 4 359 347,With blue passivation, the corrosion protection according to OIN 50021 should be 20 to 24 hours.
However, due to the presence of toxic chromium (IV) compounds in the passivation solutions of the state of the art, it is possible that chromium (VI) is incorporated into the passivation layer, which can lead to dermatitis, particularly when such layers are used, and is therefore also of concern in equipment in the food industry. The waste water treatment for detoxifying passivation solution residues or rinsing water presents problems and the solutions are used up quickly and can only be re-sharpened (regenerated) to a limited extent; in fact, they must be disposed of quickly. In fact, the corrosion protection wears off after a short time, often after just one day. Other acidic solutions that contain chromium (III) ions and, in addition to these, oxidizing agents (US-PS 4,171,231) and other additives such as silicates and/or other metal ions (US-PS 4,384,902, 4,359,347,
4 367 099) oder Organophosphorverbindungen (US-PS 4 539 348) bzw. Carbonsäuren (US-PS 4 349 392) enthalten, haben zwar die Eigenschaft, dekorative Blau· bzw. Gelbpassivierungen zu bilden, die aber nicht nachträglich einfärbbar sind und deren Korrosionsverhalten in der Größenordnung von maximal 6 h auf 10% Weißrost nach DIN 50021 lag. Wegen des Vorhandenseins von Oxidationsmitteln sind die Schichten 35 nicht frei von Chrom-(V!)-Verbindungen, die insbesondere auch bei der pH-Wert-Erhöhung im Sedimentationsbecken der Abwasserbehandlung entstehen und die Entgiftung erschweren.4 367 099) or organophosphorus compounds (US-PS 4 539 348) or carboxylic acids (US-PS 4 349 392) have the property of forming decorative blue or yellow passivations, but these cannot be subsequently colored and their corrosion behavior was in the order of a maximum of 6 hours for 10% white rust according to DIN 50021. Due to the presence of oxidizing agents, the layers 35 are not free of chromium (V!) compounds, which are formed in particular when the pH value is increased in the sedimentation basin of wastewater treatment and make detoxification more difficult.
Zwar sind aus J. Am. Chem. Soc. 74(1952) Seiten 3509 - 3512 Chrom-illO-Fluor-Komplexe von Chromtill) bekannt, deren Bildung durch Zink beschleunigt wird, jedoch findet sich bei dieser Untersuchung von Gleichgewichtskonstanten kein Hinweis auf die Blaupassivierung von Zink bzw. verzinkten Eisenoberflächen, -to auf denen keine Chrommetallabscheidung erfolgt, sondern eine polymere Verbindung mit zweiwertigem Chrom abgeschieden wird.Although chromium-III-fluorine complexes of chromium (III) are known from J. Am. Chem. Soc. 74(1952) pages 3509 - 3512, the formation of which is accelerated by zinc, this investigation of equilibrium constants does not reveal any indication of the blue passivation of zinc or galvanized iron surfaces, on which no chromium metal deposition takes place, but rather a polymeric compound with divalent chromium is deposited.
Ferner wird durch saure Chromatierungslösungen bei verzinkten Eisengegenständen eine gewisse Menge Eisen der Lösung gelöst, wodurch nach einer gewissen Zeit derartige Lösungen , insbesondere wenn sie Cr3 enthalten, unbrauchbar werden. Insbesondere ist dies der Fall bei Gegenständen, die aus geometrischen Gründen keine ganz geschlossene Zinkschicht aufweisen. Xere,'-h-U,Uu*.t Furthermore, acidic chromating solutions dissolve a certain amount of iron in the solution of galvanized iron objects, which after a certain time renders such solutions unusable, especially if they contain Cr 3. This is particularly the case with objects which, for geometric reasons, do not have a completely closed zinc layer. Xere,'-hU,Uu*.t
Aufgabe der Erfindung ist die Vermeidung der genannten Nachteile durch S eines sauren.The object of the invention is to avoid the above-mentioned disadvantages by using an acidic solvent.
chromhaltigen Passivierungsbades, das nur Chrom-(lll)-verbindungen. aber keine Oxidationsmittel und keine starken Komplexbilder enthält, das eine lange Standzeit hat. einfärbbare Passivierungen erzeugt und erlaubt, organische Polymere auf die erzeugte Passivierungsschicht besser adsorbieren zu lassen sowiechromium-containing passivation bath, which only contains chromium (III) compounds, but no oxidizing agents and no strong complexing agents, which has a long service life, produces colorable passivations and allows organic polymers to be better adsorbed onto the passivation layer produced, and
so nicht durch eventuell im 8ad gelöstes Eisen unbrauchbar wird.so that it is not rendered unusable by any iron dissolved in the 8ad.
Diese Aufgabe wird erfindungsgemäB durch ein saures, chrom-(III)-haltiges und fluoridhaltiges
Passivierungsbad-Konzentrat für Oberflächen aus Zink, Zinklegierungen und Cadmium aus
20 bis 200 g/l einer löslichen Chrom-(III)-Verbindung,
20 bis 600 g/l eines löslichen Nitrats (Gesamtnitrat),This object is achieved according to the invention by an acidic, chromium (III)-containing and fluoride-containing
Passivation bath concentrate for surfaces made of zinc, zinc alloys and cadmium from
20 to 200 g/l of a soluble chromium (III) compound,
20 to 600 g/l of soluble nitrate (total nitrate),
5 bis 100 g/l eines Fluorids5 to 100 g/l of fluoride
und einer Säure gemäß Anspruch 1 sowie einer Anwendungslösung gemäß Anspruch 11 gelöst, das
dadurch gekennzeichnet ist, daß als Säure SaJj* o'der SalpelersäuVejbis W:and an acid according to claim 1 and an application solution according to claim 11, the
characterized in that the acid used is SaJj* or salpel acid W:
einem pH-Wert 1,8 bis 2.2 zugesetzt wird, daß ein Anion aus der Gruppe, ausgewählt aus Nitrat. Sulfat. „ Phosphat. Chlorid. Bromid. Fluorid, und Jodid zugesetzt wird, daß das lösliche Nitrat in einer Konzentration in g/l zugesetzt wird, die größer als die Chrom-(lll)-Konzentration^st. dass das Gemisch entweder auf 60 * C erwärmt oder mit einem Katalysator oberhalb 15* C behandelt wird und daß das erhaltene Konzentrat gegebenenfall auf eine Anwendungskonzentration von 2 bis 20 Gew.-% in Wasser gebracht wird.a pH value of 1.8 to 2.2 is added, that an anion from the group selected from nitrate, sulfate, phosphate, chloride, bromide, fluoride, and iodide is added, that the soluble nitrate is added in a concentration in g/l which is greater than the chromium (III) concentration, that the mixture is either heated to 60 * C or treated with a catalyst above 15 * C and that the resulting concentrate is optionally brought to an application concentration of 2 to 20% by weight in water.
Ferner ist das Bad im Falle des Vorhandenseins von Eisen dadurch gekennzeichnet, dass es zusätzlich w einen sauren, mit Cr3 beladenen Jonenaustauscher und/oder ein Mittel zum Uniöslichmachen von Fe3*- Jonen in einer Menge von 0.1 bis 100 g/l enthält.Furthermore, in the case of the presence of iron, the bath is characterized in that it additionally contains an acidic ion exchanger loaded with Cr 3 and/or an agent for insolubilizing Fe 3 * ions in an amount of 0.1 to 100 g/l.
Es wurde nun gefunden, dass das Bad besonders schnell wirksam ist, wenn es vonder Anwendung auf mindestens 60* C erwärmt oder mit einem Karalysator oberhalb 15* C behandelt worden ist. Diese Behandlung wird vorteilhaft mit dem Badkonzentrat vor der Verdünnung auf Anwendungskonzentration durchgeführt.It has now been found that the bath is particularly effective when it has been heated to at least 60* C before use or has been treated with a catalyst above 15* C. This treatment is advantageously carried out with the bath concentrate before dilution to application concentration.
80* C. scheint die Bildung der stabileren Chrom-(l!l)-komplexe zu fördern, was Ober raschend ist, dass bei80* C. seems to promote the formation of the more stable chromium-(l!l) complexes, which is surprising that at
unbrauchbar sind.are unusable.
[CriH20)6-xFxV3~X)+ A(3-~x)[ CriH 2 0) 6-x F xV 3 ~ X)+ A (3-~x)
vor. worin &khgr; = 1 - 3 (Anzahl der Ruoridionen) &eegr; s Wertigkeit des Anions A und A = Nitrat Sulfat Phosphat Chlorid, Bromid, Fluorid und Jodid, was durch Leitfähigkeitsmessungen an der Ruorid-Elektrode bestimmt werden kann.where &khgr; = 1 - 3 (number of ruoride ions) &eegr; s valence of the anion A and A = nitrate, sulfate, phosphate, chloride, bromide, fluoride and iodide, which can be determined by conductivity measurements on the ruoride electrode.
Erfindungsgemäß bevorzugte Passivierungsbäder enthalten folgenden Mengen in einem Konzentrat das üblicherweise in einer Konzentration von 2 bis 20 Gew.-% in Wasser angewendet wird: 20 - 200 g/1 Chrom-(!ll)-verbindung. z.B. als Chromchlorid oder Chromnitrat 20 - 600 g/l lösliches Nitrat wie Natrium. Kalium- oder Ammoniumnitrat 5 - 100 g/l Ruorid. z.B. Natrium. Kalium-, Ammoniumfluorid Salz- oder Salpetersäure bis zu einem pH-Wert 1.8 bis 2.2.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 (II) 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 value of 1.8 to 2.2.
Aus diesem Konzentrat hergestellte Passivierungsbäder zeigen Korrosionsschutzwerte einer Blaupassivierung nach DIN 50021 von 44 bis 50 h. eine Einfärbbarkeit der Schichten und ein gutes Aufziehen organischer Polymere auf die Schichten.Passivation baths made from this concentrate show corrosion protection values of a blue passivation according to DIN 50021 of 44 to 50 hours, the layers can be colored and organic polymers can be easily absorbed onto the layers.
Es wurde ein Konzentrat folgender Zusammensetzung hergestellt: 50 g/l Chrom-(l!l)-chlorid 125 g/l Natriumnitrat 50 g/l NatrtumfluoridA concentrate with the following composition was produced: 50 g/l chromium (l!l) chloride 125 g/l sodium nitrate 50 g/l sodium fluoride
&Ngr;03·(3-&khgr;) 0 3·(3-χ)
Das Bad wurde mit Wasser im Gew.-Verhältnis 1:10 gemischt und mit Salpetersäure auf den pH-Wert 2.0 eingestellt. Mit diesem Bad wurden feuerverzinkte Eisenstangen von 2 cm Durchmesser und 20 cm Länge blaupassiviert. Nach 3 see wurden die Stangen aus dem Bad genommen und auf Korrosionsverhalten nach DlN 50021 geprüft. Der Korrosionsschutzwert betrug 48 h.The bath was mixed with water in a weight ratio of 1:10 and adjusted to a pH value of 2.0 with nitric acid. Hot-dip galvanized iron rods with a diameter of 2 cm and a length of 20 cm were blue passivated using this bath. After 3 hours, the rods were removed from the bath and tested for corrosion behavior according to DIN 50021. The corrosion protection value was 48 hours.
EP ff 337:4&Pgr;EP ff 337:4&Pgr;
Durch Zugabe von 50 g/l Acetylaceton wurde die Haltbarkeit des Bades um den Faktor 10 verlängert.By adding 50 g/l acetylacetone, the shelf life of the bath was extended by a factor of 10.
Ein Bad wurde aus 60 g/l Cr(NOj)3 .9H2O 100 g/l NaNO3 40 g/l NaF NHO3 ad pH 2.1A bath was prepared from 60 g/l Cr(NOj) 3 .9H 2 O 100 g/l NaNO 3 40 g/l NaF NHO 3 ad pH 2.1
und ohne Erhitzen, aber durch Behandeln 10 min mit gekörnter Aktivkohle in einem porösen Säckchen hergestellt und nach Mischen mit Wasser im Gew.-Verhältnis 1 : 12 für den gleichen Versuch verwendet. Es enthielt Komplexe der Formeland without heating, but by treating it for 10 minutes with granulated activated carbon in a porous bag and used for the same experiment after mixing with water in a weight ratio of 1:12. It contained complexes of the formula
[Cr(H.[Cr(H.
NONO
n-n-
3·(3-&khgr;)3·(3-&khgr;)
Es wurde der gleiche Korrosionsschutzwert erhalten. Im Vergleichsversuch auf einer normalen Blauchroma·
tierung (handelsüblich) wurden folgende Ergebnisse erhalten: mit
Cr Vl (handelsüblich): 15 mg Cr/m2 Zink: 24h Korrosionsschutz
Cr III (erfindungsgemäß : 30 mg Cr/m2 Zink: 48" Korrosionsschutz.The same corrosion protection value was obtained. In a comparison test on a normal blue chromate coating (commercially available), the following results were obtained: with
Cr Vl (commercially available): 15 mg Cr/m 2 Zinc: 24 h corrosion protection
Cr III (according to the invention: 30 mg Cr/m 2 Zinc: 48" corrosion protection.
Die Haltbarkeit des Bades wurde um den Faktor 5 durch Zugabe von 20 g/I Salicylsäure verlängert.The shelf life of the bath was extended by a factor of 5 by adding 20 g/l salicylic acid.
Es wurde ein Bad gemäß Beispiel 1 mit einem stark sauren Ionenaustauscher, der mit einer 3 M Chrom-(lll)-Nitrat!ösung beladen worden war. in einem Bad mit 1.0 g/I Fe3'-Gehalt eingesetzt Zum Vergleich wurde das gleiche Bad ohne Ionenaustauscher verwendetA bath according to Example 1 with a strongly acidic ion exchanger which had been loaded with a 3 M chromium (III) nitrate solution was used in a bath with 1.0 g/l Fe 3 ' content. For comparison, the same bath was used without ion exchanger.
Das Bad mit dem Jonenaustauscher ergab eine einwandfreie Blaupassivierung.während 'das Vergleichsbad nach kurzer Zeit unbrauchbar war. Eine Zugabe von 10 g/I Fumarsäure erhöht die Lebensdauer des Bades um Faktor S.The bath with the ion exchanger produced a perfect blue passivation, while the comparison bath was unusable after a short time. Addition of 10 g/l fumaric acid increases the service life of the bath by a factor of 5.
Es wurden vier Lösungen aus je 100 ml einer i0%igen Passivterungslösung nach Beispiel 1 angesetzt (pH 1,6) und mit den in der Tabelle angegebenen Mengen eines Gemisches aus Alkylaminen und Amiden mit S - 12 C-Atomen versetzt. Es wurde 1mm dickes Eisenblech mit einer Fläche von 1 dm2 eingelegt. Nach 12 Stunden wurden die Eisengehalte der Lösungen analytisch durch Atomadsorptionspektrometrie bestimmt. Es wurden folgende Ergebnisse erhalten, die die Abhängigkeit des Eisengehalts der Passivierungslösung von der Menge zugesetzten Inhibitor, d.h. Mittel zum Unlöslichmachen der gelösten Fe3"-Jonen zeigen. Der Zusatz von Ig/l Inhibitor ergab praktisch einen nur geringen Unterschied hinsichtlich Farbe und Korrosionsschutz gegenüber der Passivierungslösung ohne Inhibitor.Four solutions were prepared, each containing 100 ml of a 10% passivation solution according to Example 1 (pH 1.6) and mixed with the amounts of a mixture of alkylamines and amides with S - 12 C atoms specified in the table. 1 mm thick iron sheet with an area of 1 dm 2 was inserted. After 12 hours, the iron content of the solutions was determined analytically by atomic adsorption spectrometry. The following results were obtained, which show the dependence of the iron content of the passivation solution on the amount of inhibitor added, i.e. agent for insolubilizing the dissolved Fe 3 " ions. The addition of 1 g/l inhibitor resulted in practically only a slight difference in terms of color and corrosion protection compared to the passivation solution without inhibitor.
Feppm / 1
Fe
+ 1 g/L"
+ 5 g/l "
+ 10 g/l "without inhibitor
+ 1 g/L"
+ 5 g/l "
+ 10 g/l "
250
60
301000
250
60
30
Claims (11)
20 bis 600 g/l eines löslichen Nitrats (Gesamtnitrat) 5 bis 100 g/l eines Fluorids und einer Säure,20 to 200 g/l of a soluble chromium III compound
20 to 600 g/l of a soluble nitrate (total nitrate) 5 to 100 g/l of a fluoride and an acid,
Blauchromatierung (Abzweigung) · ···!..! \ ·..*..!!.<[File-ANM\SU9908A1.doc] Claims, 2112.1993 .· ··*· # ·· 4 j
Blue chromating (branch) · ···!..! \ ·..*..!!.<
125 g/l Natriumnitrat;50 g/l chromium III chloride;
125 g/l sodium nitrate;
Salpetersäure;
wobei der PH-Wert bis zu 2,0 beträgt.50 g/l sodium fluoride; and
Nitric acid;
where the pH value is up to 2.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE8916143U DE8916143U1 (en) | 1988-04-12 | 1989-04-11 | Acidic chromium (III) -containing and fluoride-containing passivation bath concentrate for surfaces made of zinc, zinc alloys and cadmium |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3812076A DE3812076A1 (en) | 1988-04-12 | 1988-04-12 | ACID CHROMIUM (III) AND FLUORIDE-BASED PASSIVATION BATH FOR SURFACES OF ZINC, ZINC ALLOYS AND CADMIUM |
| DE8916143U DE8916143U1 (en) | 1988-04-12 | 1989-04-11 | Acidic chromium (III) -containing and fluoride-containing passivation bath concentrate for surfaces made of zinc, zinc alloys and cadmium |
| EP89106447A EP0337411B1 (en) | 1988-04-12 | 1989-04-11 | Process for preparing an acidic passivating bath for zinc, zinc alloys an cadmium surfaces, containing chromium III and fluoride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE8916143U1 true DE8916143U1 (en) | 1994-05-11 |
Family
ID=27197465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE8916143U Expired - Lifetime DE8916143U1 (en) | 1988-04-12 | 1989-04-11 | Acidic chromium (III) -containing and fluoride-containing passivation bath concentrate for surfaces made of zinc, zinc alloys and cadmium |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE8916143U1 (en) |
-
1989
- 1989-04-11 DE DE8916143U patent/DE8916143U1/en not_active Expired - Lifetime
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