EP0240943A2 - Procédé pour appliquer des couches de conversion sur des surfaces de zinc ou de ses alliages - Google Patents

Procédé pour appliquer des couches de conversion sur des surfaces de zinc ou de ses alliages Download PDF

Info

Publication number: EP0240943A2
Authority: EP; European Patent Office
Prior art keywords: ions; solution; contact; brought; polyvalent metals
Prior art date: 1986-04-08
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP87104930A

Other languages

German (de)

English (en)

Other versions

EP0240943A3 (en

EP0240943B1 (fr

Inventor

George Higgins

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

GEA Group AG

Chemetall Ltd

Original Assignee

Metallgesellschaft AG

Brent Chemicals International PLC

Priority date (The priority date 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 date listed.)

1986-04-08

Filing date

1987-04-02

Publication date

1987-10-14

1987-04-02 Application filed by Metallgesellschaft AG, Brent Chemicals International PLC filed Critical Metallgesellschaft AG

1987-10-14 Publication of EP0240943A2 publication Critical patent/EP0240943A2/fr

1988-10-26 Publication of EP0240943A3 publication Critical patent/EP0240943A3/de

1990-10-10 Application granted granted Critical

1990-10-10 Publication of EP0240943B1 publication Critical patent/EP0240943B1/fr

2007-04-02 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims abstract description 21
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 8
229910052725 zinc Inorganic materials 0.000 title claims abstract description 8
239000011701 zinc Substances 0.000 title claims abstract description 8
238000007739 conversion coating Methods 0.000 title claims abstract description 7
229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 5
239000000243 solution Substances 0.000 claims abstract description 37
150000002500 ions Chemical class 0.000 claims abstract description 34
229910052751 metal Inorganic materials 0.000 claims abstract description 25
239000002184 metal Substances 0.000 claims abstract description 25
150000002739 metals Chemical class 0.000 claims abstract description 20
239000008139 complexing agent Substances 0.000 claims abstract description 17
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
150000003839 salts Chemical class 0.000 claims abstract description 11
239000010941 cobalt Substances 0.000 claims abstract description 9
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
229910052804 chromium Inorganic materials 0.000 claims abstract description 8
239000011651 chromium Substances 0.000 claims abstract description 8
229910052742 iron Inorganic materials 0.000 claims abstract description 7
RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 6
239000007864 aqueous solution Substances 0.000 claims abstract description 6
239000002253 acid Substances 0.000 claims abstract description 5
229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 5
229910001453 nickel ion Inorganic materials 0.000 claims abstract description 5
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 abstract description 4
VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 4
239000000174 gluconic acid Substances 0.000 claims abstract description 4
235000012208 gluconic acid Nutrition 0.000 claims abstract description 4
-1 iron (III) ions Chemical class 0.000 claims description 6
159000000000 sodium salts Chemical class 0.000 claims description 3
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
229910052783 alkali metal Inorganic materials 0.000 description 5
229910021645 metal ion Inorganic materials 0.000 description 5
150000007524 organic acids Chemical class 0.000 description 5
229910017052 cobalt Inorganic materials 0.000 description 4
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
150000001340 alkali metals Chemical class 0.000 description 3
150000001768 cations Chemical class 0.000 description 3
ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
150000002823 nitrates Chemical class 0.000 description 3
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
OFXXQEVJFJUPBD-UHFFFAOYSA-N 2,2,3,3,4,4-hexahydroxyheptanoic acid Chemical compound CCCC(O)(O)C(O)(O)C(O)(O)C(O)=O OFXXQEVJFJUPBD-UHFFFAOYSA-N 0.000 description 2
241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
150000008044 alkali metal hydroxides Chemical class 0.000 description 2
150000001450 anions Chemical class 0.000 description 2
239000011248 coating agent Substances 0.000 description 2
238000000576 coating method Methods 0.000 description 2
JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
239000003973 paint Substances 0.000 description 2
XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
229920002620 polyvinyl fluoride Polymers 0.000 description 2
YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
239000007921 spray Substances 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
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
229910052684 Cerium Inorganic materials 0.000 description 1
FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
239000004593 Epoxy Substances 0.000 description 1
LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
229910001335 Galvanized steel Inorganic materials 0.000 description 1
239000004471 Glycine Substances 0.000 description 1
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
229910019142 PO4 Inorganic materials 0.000 description 1
229920000388 Polyphosphate Polymers 0.000 description 1
229910000831 Steel Inorganic materials 0.000 description 1
ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
150000001242 acetic acid derivatives Chemical class 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
239000004480 active ingredient Substances 0.000 description 1
125000001931 aliphatic group Chemical group 0.000 description 1
239000003513 alkali Substances 0.000 description 1
229910001854 alkali hydroxide Inorganic materials 0.000 description 1
229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
150000008041 alkali metal carbonates Chemical class 0.000 description 1
229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
229910052910 alkali metal silicate Inorganic materials 0.000 description 1
229910052782 aluminium Inorganic materials 0.000 description 1
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
150000001413 amino acids Chemical class 0.000 description 1
229910052787 antimony Inorganic materials 0.000 description 1
WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
229910052793 cadmium Inorganic materials 0.000 description 1
BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
239000001913 cellulose Substances 0.000 description 1
229920002678 cellulose Polymers 0.000 description 1
ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
239000002738 chelating agent Substances 0.000 description 1
229910001430 chromium ion Inorganic materials 0.000 description 1
WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
235000015165 citric acid Nutrition 0.000 description 1
230000000052 comparative effect Effects 0.000 description 1
230000009918 complex formation Effects 0.000 description 1
150000001875 compounds Chemical class 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
230000007797 corrosion Effects 0.000 description 1
150000001991 dicarboxylic acids Chemical class 0.000 description 1
235000011180 diphosphates Nutrition 0.000 description 1
230000009189 diving Effects 0.000 description 1
238000001035 drying Methods 0.000 description 1
238000005516 engineering process Methods 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
235000019253 formic acid Nutrition 0.000 description 1
239000001530 fumaric acid Substances 0.000 description 1
239000008397 galvanized steel Substances 0.000 description 1
239000004310 lactic acid Substances 0.000 description 1
235000014655 lactic acid Nutrition 0.000 description 1
229910052749 magnesium Inorganic materials 0.000 description 1
239000011777 magnesium Substances 0.000 description 1
WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
150000007522 mineralic acids Chemical class 0.000 description 1
239000000203 mixture Substances 0.000 description 1
229910052750 molybdenum Inorganic materials 0.000 description 1
239000011733 molybdenum Substances 0.000 description 1
230000007935 neutral effect Effects 0.000 description 1
229910052759 nickel Inorganic materials 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
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
239000010452 phosphate Substances 0.000 description 1
235000021317 phosphate Nutrition 0.000 description 1
239000001205 polyphosphate Substances 0.000 description 1
235000011176 polyphosphates Nutrition 0.000 description 1
229960004889 salicylic acid Drugs 0.000 description 1
239000000600 sorbitol Substances 0.000 description 1
238000005507 spraying Methods 0.000 description 1
239000010959 steel Substances 0.000 description 1
150000005846 sugar alcohols Polymers 0.000 description 1
229910052718 tin Inorganic materials 0.000 description 1
239000010936 titanium Substances 0.000 description 1
229910052719 titanium Inorganic materials 0.000 description 1
VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
229910052721 tungsten Inorganic materials 0.000 description 1
239000010937 tungsten Substances 0.000 description 1
239000002966 varnish Substances 0.000 description 1
LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
229910000165 zinc phosphate Inorganic materials 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- 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 process for producing conversion coatings on zinc or zinc alloy surfaces by means of aqueous solutions which contain ions of polyvalent metals and complexing agents in sufficient amounts to keep the ions of polyvalent metals in solution and their pH is greater than ll is.
the object of the invention is to improve these properties of the conversion coatings produced and at the same time to reduce the concentration of the treatment solution and / or its application temperature.
the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface is brought into contact with a solution, the chromium III ions and ions contains at least two other polyvalent metals.
the cations of polyvalent metals that are also used in the aqueous solution in addition to chromium III ions can be of the aforementioned type.
a particularly advantageous embodiment of the invention provides for the surfaces to be brought into contact with a solution which contains iron III ions and cobalt and / or nickel ions as further ions of polyvalent metals.
Complexing agents suitable for the process according to the invention are organic chelating agents from a wide variety of groups, such as, for example, dicarboxylic acids (malonic acid, fumaric acid, etc.); Amino acids (eg glycine); Hydroxy carboxylic acids (citric acid, gluconic acid, lactic acid, etc.); Hydroxy aldehydes (e.g.
acetylacetone aliphatic polyalcohols (eg sorbitol, 1,2-ethanediol); aromatic carboxylic acids (eg salicylic acid, phthalic acid); Aminocarboxylic acids (eg ethylenediaminetetraacetic acid); other compounds, such as, for example, methanephosphonic acid diethanolamide or salts of low molecular weight lignosulphonic acids which are obtained in the production of cellulose, can also be used.
the amount of complexing agent that must be present is the amount that is at least sufficient to fully complex bind the existing ions of polyvalent metals. Thus, if the polyvalent metal ion content in the solution increases, the complexing agent content must also be increased.
complexing agents which are acidic in nature, can reduce the effective alkalinity of the solution
complexing agents in the form of the neutral salts, in particular the alkali metal salts are preferably used. It was found that excess complexing agents beyond the amounts required for complex formation have no advantage.
gluconic acid but especially hexahydroxy heptanoic acid or its salts, are used as complexing agents.
the most advantageous embodiment of the invention consists in adding chromium as chromium acetate and the ions of the other polyvalent metals as nitrates or other inorganic salts.
the aqueous solution must have a pH above II. Best results are achieved in the pH range from l2.2 to l3.3.
the adjustment of the pH value can e.g. by triethanolamine, alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal polyphosphates, alkali metal pyrophosphates or mixtures thereof.
alkali hydroxides especially sodium hydroxide.
the amount required to adjust the pH is usually between 5 and 35 g / l.
the metal surfaces are brought into contact with a solution which contains ions of the polyvalent metals in a total amount of 0.3 to 3 g / l, preferably 0.4 to 1 g / l.
the amount of the complexing agent (s) depends on the solution content of ions of the polyvalent metals. It must be sufficient to keep the ions mentioned in solution.
the surfaces are brought into contact with a solution which contains complexing agents in an amount of from 0.05 to 10 g / l, preferably from 1 to 5 g / l (based on the sodium salt of hexahydroxy heptanoic acid) . If other complexing agents are used, equivalent amounts are advantageous.
the metal surface is brought into contact with a solution which contains chromium III ions in an amount of 0.04 to 0.4 g / l, preferably 0.1 to 0.3 g / l if ferri ions are used, with a solution which contains these ions in an amount of 0.1 to 0.3 g / l, and if they have a cobalt and / or nickel ion content, with a solution containing these ions in an amount of 0.15 to 0.4 g / l.
the amount should be such that 15 to 60%, preferably 20 to 40%, of the total metal ions is assigned a corresponding anion.
the treatment of the zinc or zinc alloy surfaces takes place according to conventional technology, e.g. by diving, but especially by spraying.
the treatment temperature can in principle reach up to 90 ° C., it is preferably carried out at a temperature below 60 ° C., in particular below 50 ° C. but above 20 ° C.
a particular advantage of the invention is that it is possible to achieve very good results at a treatment temperature of 20 to 35 ° C, especially at about 25 ° C.
the treatment time is generally 2 to 60 seconds, preferably 5 to 30 seconds.
solutions with a lower metal ion concentration require higher temperatures and longer treatment times than those with higher metal ion concentrations.
the solution used in the method according to the invention is usually free of chromate ions. Although satisfactory results can also be achieved in other ways, it can be advantageous to use a solution containing chromate ions, advantageously after Treat water rinse.
drying can be carried out and, if necessary, a varnish or other coating can be applied.
the metal surface to be treated also has exposed iron or steel areas, it can be advantageous to connect a phosphating treatment with solutions based on zinc phosphate or alkali phosphate to the process according to the invention.
the cobalt and iron III ions were each introduced via their nitrates, and the chromium III ions were each introduced as acetates.
Hot-dip galvanized steel sheets with a zinc coating of 275 g / m2 and usual surface structure were cleaned and sprayed with solution l for 20 seconds at 45 ° C., rinsed with water, treated with a solution containing chromate ions, dried and with an epoxy basecoat and a top coat made of fluorinated polyvinyl fluoride (PVF2).
PVF2 fluorinated polyvinyl fluoride
the sheets were then scratched diagonally down to the metal surface and exposed to the salt spray test in accordance with ASTM B ll7 for 1000 h.
the bubble size and density were then assessed in accordance with BS 3900 Part H 1. Neither blistering nor paint peeling was found. Only a small amount of white rust had formed at the scratch points.

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Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Materials Engineering (AREA)
Mechanical Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
General Chemical & Material Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Chemical Treatment Of Metals (AREA)
Application Of Or Painting With Fluid Materials (AREA)

EP87104930A 1986-04-08 1987-04-02 Procédé pour appliquer des couches de conversion sur des surfaces de zinc ou de ses alliages Expired - Lifetime EP0240943B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
GB868608508A GB8608508D0 (en)	1986-04-08	1986-04-08	Coating metal surfaces
GB8608508		1986-04-08

Publications (3)

Publication Number	Publication Date
EP0240943A2 true EP0240943A2 (fr)	1987-10-14
EP0240943A3 EP0240943A3 (en)	1988-10-26
EP0240943B1 EP0240943B1 (fr)	1990-10-10

Family

ID=10595841

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP87104930A Expired - Lifetime EP0240943B1 (fr)	1986-04-08	1987-04-02	Procédé pour appliquer des couches de conversion sur des surfaces de zinc ou de ses alliages

Country Status (8)

Country	Link
US (1)	US4801337A (fr)
EP (1)	EP0240943B1 (fr)
KR (1)	KR870010219A (fr)
CN (1)	CN87103418A (fr)
CA (1)	CA1284762C (fr)
DE (2)	DE3765445D1 (fr)
ES (1)	ES2018188B3 (fr)
GB (2)	GB8608508D0 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
ITMI20102198A1 (it) *	2010-11-26	2012-05-27	Np Coil Dexter Ind Srl	Processo di pretrattamento su coil in acciaio zincato preverniciato esente da metalli pesanti
EP2503025A1 (fr) *	2011-03-22	2012-09-26	Henkel AG & Co. KGaA	Traitement en plusieurs étapes de protection contre la corrosion des pièces métalliques ayant au moins partiellement une surface en zinc ou en alliages de zinc
US9228088B2 (en)	2010-02-09	2016-01-05	Henkel Ag & Co. Kgaa	Composition for the alkaline passivation of zinc surfaces
IT201800009491A1 (it)	2018-10-17	2020-04-17	Condoroil Chemical Srl	Trattamento di conversione per coil zincati a caldo esente da cobalto.

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US7029541B2 (en) *	2002-01-24	2006-04-18	Pavco, Inc.	Trivalent chromate conversion coating
DE10223022A1 (de) *	2002-05-22	2003-12-11	Christoph Schulz	Konversionsschicht für aus Zink oder aus zinkhaltigen Legierungen bestehende Untergründe
JP4492434B2 (ja) *	2005-05-16	2010-06-30	日立電線株式会社	プリント配線板用銅箔とその製造方法およびその製造に用いる３価クロム化成処理液
JP5198727B2 (ja) *	2005-10-07	2013-05-15	ディップソール株式会社	亜鉛又は亜鉛合金上に黒色の６価クロムフリー化成皮膜を形成するための処理溶液
EP1984536B1 (fr) *	2006-02-14	2012-03-28	Henkel AG & Co. KGaA	Composition et procedes d'un revetement resistant a la corrosion a base de chrome trivalent par voie seche destine a une utilisation sur des surfaces metalliques
WO2007134152A1 (fr) *	2006-05-10	2007-11-22	Henkel Ag & Co. Kgaa.	Composition améliorée comprenant du chrome trivalent s'utilisant pour former des couches anti-corrosion sur des surfaces métalliques
US20110070429A1 (en) *	2009-09-18	2011-03-24	Thomas H. Rochester	Corrosion-resistant coating for active metals
MX361013B (es) *	2011-02-08	2018-11-26	Henkel Ag & Co Kgaa	Procesos y composiciones para mejorar el desempeño anti-corrosión de superficies de zinc pretratadas con óxido de zirconio.
US9573162B2 (en) *	2011-02-08	2017-02-21	Henkel Ag & Co., Kgaa	Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
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1986
- 1986-04-08 GB GB868608508A patent/GB8608508D0/en active Pending
1987
- 1987-04-01 GB GB8707748A patent/GB2188946B/en not_active Expired - Fee Related
- 1987-04-02 US US07/043,288 patent/US4801337A/en not_active Expired - Fee Related
- 1987-04-02 DE DE8787104930T patent/DE3765445D1/de not_active Expired - Lifetime
- 1987-04-02 ES ES87104930T patent/ES2018188B3/es not_active Expired - Lifetime
- 1987-04-02 DE DE19873711095 patent/DE3711095A1/de not_active Withdrawn
- 1987-04-02 EP EP87104930A patent/EP0240943B1/fr not_active Expired - Lifetime
- 1987-04-07 CN CN87103418A patent/CN87103418A/zh active Pending
- 1987-04-08 KR KR870003347A patent/KR870010219A/ko not_active Withdrawn
- 1987-04-08 CA CA000534152A patent/CA1284762C/fr not_active Expired - Lifetime

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US9228088B2 (en)	2010-02-09	2016-01-05	Henkel Ag & Co. Kgaa	Composition for the alkaline passivation of zinc surfaces
ITMI20102198A1 (it) *	2010-11-26	2012-05-27	Np Coil Dexter Ind Srl	Processo di pretrattamento su coil in acciaio zincato preverniciato esente da metalli pesanti
EP2458032A1 (fr) *	2010-11-26	2012-05-30	NP Coil Dexter Industries S.r.l.	Procédé de prétraitement dépourvu des métaux lourds des bobines en acier galvanisées et prépeintes
EP2503025A1 (fr) *	2011-03-22	2012-09-26	Henkel AG & Co. KGaA	Traitement en plusieurs étapes de protection contre la corrosion des pièces métalliques ayant au moins partiellement une surface en zinc ou en alliages de zinc
WO2012126734A1 (fr) *	2011-03-22	2012-09-27	Henkel Ag & Co. Kgaa	Traitement anticorrosion multiétape de pièces métalliques à surfaces de zinc
US9534301B2 (en)	2011-03-22	2017-01-03	Henkel Ag & Co. Kgaa	Multi-stage anti-corrosion treatment of metal components having zinc surfaces
IT201800009491A1 (it)	2018-10-17	2020-04-17	Condoroil Chemical Srl	Trattamento di conversione per coil zincati a caldo esente da cobalto.

Also Published As

Publication number	Publication date
GB8707748D0 (en)	1987-05-07
GB2188946A (en)	1987-10-14
EP0240943A3 (en)	1988-10-26
DE3711095A1 (de)	1987-10-15
GB2188946B (en)	1990-08-01
EP0240943B1 (fr)	1990-10-10
GB8608508D0 (en)	1986-05-14
US4801337A (en)	1989-01-31
CA1284762C (fr)	1991-06-11
CN87103418A (zh)	1987-11-11
KR870010219A (ko)	1987-11-30
DE3765445D1 (de)	1990-11-15
ES2018188B3 (es)	1991-04-01

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Publication	Publication Date	Title
EP0240943B1 (fr)	1990-10-10	Procédé pour appliquer des couches de conversion sur des surfaces de zinc ou de ses alliages
DE1219765B (de)	1966-06-23	Verfahren zum Passivieren von Metalloberflaechen
EP0328908B1 (fr)	1992-03-04	Procédé pour appliquer des couches de conversion
DE1521854B1 (de)	1970-11-05	Verfahren zum Aufbringen eines UEberzuges auf Oberflaechen,die Zink oder Zinklegierungen enthalten
DE1295961B (de)	1969-05-22	Verfahren zur Behandlung von chemisch aufgebrachten UEberzuegen auf Metallen
DE718157C (de)	1942-03-04	Verfahren zur Erzeugung korrosionsbestaendiger UEberzuege auf Metallen, insbesondere Eisen und Stahl
DE853694C (de)	1952-10-27	Verfahren zur Erhoehung der Korrosionsbestaendigkeit von Metallen
DE2715291C3 (de)	1981-10-22	Verfahren zur Herstellung einses amorphen, leichten, fest haftenden Phosphatüberzugs auf Eisenmetalloberflächen
DE1297952B (de)	1969-06-19	Verfahren zur Chromatierung von Zink- oder Aluminiumoberflaechen
EP2492371A1 (fr)	2012-08-29	Solution de passivation sans cobalt et procédé de séparation de couches de passivation sans cobalt sur des surfaces de zinc et d'alliage de zinc
DE2239581C3 (de)	1981-10-15	Lösung und Verfahren zum Aufbringen von Überzügen auf Zink oder Zinklegierungen
DE1257532B (de)	1967-12-28	Verfahren zum mehrstufigen Nachspuelen von Metalloberflaechen
EP0209143A2 (fr)	1987-01-21	Procédé de traitement de surface d'une tôle de fer revêtue d'un alliage zinc-aluminium
DE1248427B (de)	1967-08-24	Verfahren und Loesung zum Aufbringen von UEberzuegen auf Aluminium und dessen Legierungen
DE1521657A1 (de)	1969-10-02	Loesungen zum Chromatieren von Zink und seinen Legierungen
DE1521870A1 (de)	1969-10-23	Waessrige saure Loesungen und Verfahren zur Erzeugung von chemischen UEberzuegen auf zinkhaltigen Oberflaechen
DE1152591B (de)	1963-08-08	Verfahren zur Herstellung von UEberzuegen auf Zink und Zinklegierungen und Konzentrat zur Durchfuehrung des Verfahrens
EP0459549B1 (fr)	1994-08-17	Obtention de couches de conversion sur des surfaces en zinc ou en alliage de zinc
EP0154384B1 (fr)	1989-06-21	Procédé de prétraitement de surfaces en zinc pour le laquage
EP0171043B1 (fr)	1991-05-15	Procédé de passivation de surfaces en plomb ou contenant du plomb
DE69325035T2 (de)	2000-01-27	Zusammensetzung und verfahren zum behandeln von verzinnten stahlplatten
DE584411C (de)	1933-09-20	Verfahren zur Herstellung von korrosionsfesten UEberzuegen auf Eisen und Stahl
DE2419526A1 (de)	1974-11-14	Versiegelnde spuelung fuer phosphatueberzuege auf metallen
DE2134412B2 (de)	1980-12-11	Chromatbehandeltes Metallblech und Verfahren zu dessen Herstellung
DE1287891B (de)	1969-01-23	Verfahren zum Aufbringen eines PhosphatÜberzuges auf Oberflächen aus Eisen oder Zink