EP1002143A1 - Alkalische bandpassivierung - Google Patents
Alkalische bandpassivierungInfo
- Publication number
- EP1002143A1 EP1002143A1 EP98942626A EP98942626A EP1002143A1 EP 1002143 A1 EP1002143 A1 EP 1002143A1 EP 98942626 A EP98942626 A EP 98942626A EP 98942626 A EP98942626 A EP 98942626A EP 1002143 A1 EP1002143 A1 EP 1002143A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- range
- passivation
- alkaline
- points
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C23C22/60—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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
- C23C22/66—Treatment of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the invention relates to a method for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum and its alloys in belt systems. This passivation creates a corrosion protection layer that can serve as the basis for subsequent painting.
- Alkaline passivation processes have long been known for the treatment of the metal surfaces mentioned.
- the treatment solutions usually contain toxic heavy metals such as nickel ions and / or cobalt ions. These ions are kept in solution under the alkaline conditions by means of suitable complexing agents. Examples of such passivation solutions are given in EP-A-405 340.
- the object of the invention is therefore to provide a process for the alkaline passivation of suitable metal surfaces which has a performance similar to that of processes containing nickel or cobalt, but does not use any toxic heavy metals.
- This object is achieved by a process for the alkaline passivation of galvanized and alloy-galvanized steel surfaces and of aluminum in strip plants, the metal surfaces being brought into contact with an alkaline, complexing agent and iron-containing aqueous solution, characterized in that the aqueous solution
- aluminum when used here, it means aluminum and aluminum alloys which contain more than 50% by weight of aluminum.
- Alkaline is understood to mean that the treatment solutions have a pH of above 9.5, preferably in the range from 10 to 13.
- the pH values are used less for the characterization of the treatment baths, but for the contents of free alkalinity and
- the free alkalinity is determined by titrating 2 ml bath solution, preferably diluted to 50 ml, with a 0.1 N acid such as hydrochloric acid or sulfuric acid up to a pH of 8.5 ml indicates the number of free alkalinity and the total alkalinity is determined accordingly by titrating 2 ml of treatment solution, diluted to 50 ml, with 0.1 N acid to a pH of 4.0, which inevitably means that the Total alkalinity is higher than the free alkalinity.
- the treatment solution can contain additional active substances that have a positive effect on the formation of layers and corrosion protection.
- additional active substances that have a positive effect on the formation of layers and corrosion protection.
- contents of about 0.001 to about 20 g / 1 of finely divided SiO 2 may be mentioned , for example fumed silica. Pyrogens are preferably used
- BET specific surface area
- Silicas are commercially available.
- Another optional component of the treatment solution are about 0.001 to about 10 g / 1 monomeric or oligomeric acrylate and / or methacrylate ions. These can be added to the treatment solution as soluble salts, for example sodium salts, or in the form of the free acid. In the subsequent drying step, at the latest when baking an applied lacquer, these ions polymerize and thereby improve the layer properties.
- the amino or hydroxy carboxylate ions serve to prevent the precipitation of iron and magnesium compounds at the alkaline pH of the treatment solution.
- all amino or hydroxy carboxylate ions which produce this effect are suitable. They can be introduced into the treatment solution in the form of soluble salts such as sodium salts or as free acids. Preference is given to monobasic hydroxy carboxylic acids with at least 4 carbon atoms and at least 2 alcoholic hydroxyl groups. Gluconate ions or the glucoheptanate ions which are one carbon atom longer are particularly preferred.
- the treatment solutions also contain the anions of the salts when the magnesium and iron (III) ions were introduced into the treatment solution.
- the nitrates are preferably used here, since nitrate ions have no negative influence on the corrosion protection.
- the process is designed for the treatment of running metal belts, so that the treatment time is in the range of a few seconds depending on the belt speed and the length of the treatment zone.
- the Treatment time is about 3 to about 30 seconds and is preferably in the range of 5 to 15 seconds.
- the metal surfaces are preferably brought into contact with an aqueous treatment solution which has a temperature in the range from about 40 to about 70 ° C. Spraying, dipping and rolling processes are suitable for contacting. Spray application is customary and suitable in the context of the inventive method. After the desired exposure time, the aqueous treatment solution is rinsed off.
- the corrosion protection effect can be further improved if the alkaline passivated metal surfaces are re-passivated.
- Processes containing chromium are widely used in the prior art for post-passivation after an alkaline passivation.
- a post-passivation containing chromium is also suitable as post-treatment after the alkaline passivation according to the invention.
- a particular advantage of the method according to the invention is that there is no need for an ecologically and toxicologically problematic chromium-containing aftertreatment and instead a chromium-free postpassivation can be carried out.
- a chromium-free post-passivation solutions are in particular aqueous solutions which contain titanium and / or zirconium compounds, in particular complex fluorides of these elements.
- such a post-passivation solution can contain a total of 0.4 to 10 g / l of complex fluorides of titanium and / or zirconium.
- the pH of this chromium-free post-passivation solution is preferably in the range from about 2 to about 4.
- the alkaline passivation step according to the invention thus represents a treatment stage of a multi-stage treatment chain in which the metal strips are usually first degreased and rinsed. This is followed by the alkaline passivation according to the invention, usually followed by the steps Rinsing, re-passivation, usually repeated rinsing, drying (at about 60 to about 100 ° C object temperature), painting.
- the alkaline passivation solution can be removed from Ott by
- Invention also an aqueous concentrate that when diluted with water by one
- Aluminum in conveyor systems results in a free alkalinity in the range of 5 to 20 points and a total alkalinity in the range of 7 to 30 points and
- the preparation of such concentrates is preferably carried out by first dissolving magnesium and iron salts, preferably nitrates, in water to the required concentration, then adding the complexing carboxylic acid and only then adding the alkaline pH by adding alkali, for example sodium hydroxide solution. Value.
- the following exemplary embodiments show that the alkaline passivation process according to the invention leads to corrosion protection results similar to those of comparison processes according to the prior art, which contain toxic nickel and / or cobalt ions.
- the galvanized and alloy-galvanized steel sheets listed in Table 2 were alkaline passivated according to Table 1, rinsed for 5 seconds with water, re-passivated with chrome-containing or chrome-free rinse solutions (treatment time: 5 seconds spraying), rinsed for 2 seconds with deionized water and in a circulating air Drying cabinet dried at a cabinet temperature of 70 ° C.
- 5 ⁇ m primer and 18 ⁇ m top coat, each based on polyester, were applied and baked at 216 and 249 ° C, respectively.
- test panels were then subjected to a 42-day salt spray test in accordance with the German standard DIN 50 021 SS.
- the results (paint infiltration in mm at the cut or at the edge) are shown in Table 2.
- the paint adhesion was examined after a T-Bend test. There were no significant differences between the method according to the invention and the nickel and / or cobalt-containing comparison methods.
- Chromium-containing post-passivation solution (1.5 g / 1 Cr (VI); pH 3.2)
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)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19733972 | 1997-08-06 | ||
DE19733972A DE19733972A1 (de) | 1997-08-06 | 1997-08-06 | Alkalische Bandpassivierung |
PCT/EP1998/004670 WO1999007917A1 (de) | 1997-08-06 | 1998-07-25 | Alkalische bandpassivierung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1002143A1 true EP1002143A1 (de) | 2000-05-24 |
EP1002143B1 EP1002143B1 (de) | 2002-04-03 |
Family
ID=7838122
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98942626A Expired - Fee Related EP1002143B1 (de) | 1997-08-06 | 1998-07-25 | Alkalische bandpassivierung |
Country Status (9)
Country | Link |
---|---|
US (1) | US6346295B1 (de) |
EP (1) | EP1002143B1 (de) |
AR (1) | AR015142A1 (de) |
AU (1) | AU730256B2 (de) |
CA (1) | CA2300275A1 (de) |
DE (2) | DE19733972A1 (de) |
ES (1) | ES2175763T3 (de) |
WO (1) | WO1999007917A1 (de) |
ZA (1) | ZA987032B (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102012000414A1 (de) | 2012-01-12 | 2013-07-18 | Thyssenkrupp Rasselstein Gmbh | Verfahren zur Passivierung von Weißblech |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005045034A1 (de) * | 2005-09-21 | 2007-03-29 | Rasselstein Gmbh | Verfahren zur Passivierung der Oberfläche von beschichteten Metallbändern und Vorrichtung für das Aufbringen der Passivschicht auf ein metallisch beschichtetes Stahlband |
DE102007006450A1 (de) | 2007-02-05 | 2008-08-07 | Henkel Ag & Co. Kgaa | Verfahren zur Gewinnung von entsalztem Wasser aus Zirkoniumhaltigem Spülwasser |
DE102007021364A1 (de) * | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallisierende Vorbehandlung von Zinkoberflächen |
DE102010001686A1 (de) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Zusammensetzung für die alkalische Passivierung von Zinkoberflächen |
CN103282547A (zh) | 2011-02-08 | 2013-09-04 | 汉高股份有限及两合公司 | 用于改善氧化锆预处理的锌表面的腐蚀性能的方法和组合物 |
EP2503025B1 (de) | 2011-03-22 | 2013-07-03 | Henkel AG & Co. KGaA | Mehrstufige korrosionsschützende Behandlung metallischer Bauteile, die zumindest teilweise Oberflächen von Zink oder Zinklegierungen aufweisen |
EP2532769A1 (de) * | 2011-06-10 | 2012-12-12 | Amcor Flexibles Kreuzlingen Ltd. | Verfahren zur Herstellung von Chrom-frei Konversionsschicht auf einer Oberfläche von Aluminium- oder Aluminiumlegierungsband |
MX353928B (es) | 2011-10-24 | 2018-02-06 | Chemetall Gmbh | Metodo para recubrir superficies metalicas con una composicion acuosa con multiples componentes. |
EP2631333A1 (de) | 2012-02-24 | 2013-08-28 | Henkel AG & Co. KGaA | Vorbehandlung von Zinkoberflächen vor einer Passivierung |
DE102012215679A1 (de) * | 2012-09-04 | 2014-05-15 | Henkel Ag & Co. Kgaa | Verfahren zur korrosionsschützenden Oberflächenbehandlung von metallischen Bauteilen in Serie |
EP3569734A1 (de) | 2018-05-18 | 2019-11-20 | Henkel AG & Co. KGaA | Passivierungszusammensetzung auf basis von dreiwertigem chrom |
EP3663435B1 (de) | 2018-12-05 | 2024-03-13 | Henkel AG & Co. KGaA | Passivierungszusammensetzung auf basis von mischungen von phosphor- und phosphonsäuren |
WO2021139955A1 (en) | 2020-01-06 | 2021-07-15 | Henkel Ag & Co. Kgaa | Passivation composition suitable for inner surfaces of zinc coated steel tanks storing hydrocarbons |
EP4274865A1 (de) | 2021-01-06 | 2023-11-15 | Henkel AG & Co. KGaA | Verbesserte cr(iii)-basierte passivierung für zink-aluminium-beschichteten stahl |
GB2603194A (en) | 2021-02-01 | 2022-08-03 | Henkel Ag & Co Kgaa | Improved cr(iii) based dry-in-place coating composition for zinc coated steel |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE316668B (de) * | 1963-09-23 | 1969-10-27 | Parker Ste Continentale | |
US3349043A (en) * | 1966-01-19 | 1967-10-24 | Manning Dev Corp | Methods and compositions for controlling oxidation of metal surfaces |
US3444007A (en) * | 1967-03-13 | 1969-05-13 | Hooker Chemical Corp | Process of forming paint-base coatings on zinc and zinc alloy surfaces |
US3895970A (en) * | 1973-06-11 | 1975-07-22 | Pennwalt Corp | Sealing rinse for phosphate coatings of metal |
GB8608508D0 (en) * | 1986-04-08 | 1986-05-14 | Pyrene Chemical Services Ltd | Coating metal surfaces |
JPH0331484A (ja) | 1989-06-27 | 1991-02-12 | Nippon Parkerizing Co Ltd | 亜鉛または亜鉛系メッキ材料の黒色化処理法 |
US5294266A (en) | 1989-07-28 | 1994-03-15 | Metallgesellschaft Aktiengesellschaft | Process for a passivating postrinsing of conversion layers |
DE4017186A1 (de) | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | Erzeugung von konversionsueberzuegen auf zink- oder zinklegierungsoberflaechen |
DE3938087A1 (de) | 1989-11-16 | 1991-05-23 | Madeker Heinz | Schuh-haft-sohle als zusatzsohle fuer strassenschuhe im innenbereich |
FR2654440B1 (fr) * | 1989-11-16 | 1993-07-30 | Produits Ind Cie Fse | Procede de conversion chimique de substrats metalliques, bain mis en óoeuvre dans ce procede et concentre pour la preparation du bain. |
DE4317217A1 (de) * | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chromfreie Konversionsbehandlung von Aluminium |
US5531820A (en) * | 1993-08-13 | 1996-07-02 | Brent America, Inc. | Composition and method for treatment of phosphated metal surfaces |
-
1997
- 1997-08-06 DE DE19733972A patent/DE19733972A1/de not_active Withdrawn
-
1998
- 1998-07-25 CA CA002300275A patent/CA2300275A1/en not_active Abandoned
- 1998-07-25 DE DE59803640T patent/DE59803640D1/de not_active Expired - Fee Related
- 1998-07-25 AU AU90693/98A patent/AU730256B2/en not_active Ceased
- 1998-07-25 WO PCT/EP1998/004670 patent/WO1999007917A1/de active IP Right Grant
- 1998-07-25 ES ES98942626T patent/ES2175763T3/es not_active Expired - Lifetime
- 1998-07-25 US US09/485,275 patent/US6346295B1/en not_active Expired - Fee Related
- 1998-07-25 EP EP98942626A patent/EP1002143B1/de not_active Expired - Fee Related
- 1998-08-05 AR ARP980103868A patent/AR015142A1/es unknown
- 1998-08-05 ZA ZA987032A patent/ZA987032B/xx unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9907917A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102012000414A1 (de) | 2012-01-12 | 2013-07-18 | Thyssenkrupp Rasselstein Gmbh | Verfahren zur Passivierung von Weißblech |
WO2013104530A2 (de) | 2012-01-12 | 2013-07-18 | Thyssenkrupp Rasselstein Gmbh | VERFAHREN ZUR PASSIVIERUNG VON WEIßBLECH |
Also Published As
Publication number | Publication date |
---|---|
ZA987032B (en) | 1999-02-08 |
EP1002143B1 (de) | 2002-04-03 |
AU730256B2 (en) | 2001-03-01 |
AR015142A1 (es) | 2001-04-18 |
DE19733972A1 (de) | 1999-02-11 |
WO1999007917A1 (de) | 1999-02-18 |
DE59803640D1 (de) | 2002-05-08 |
AU9069398A (en) | 1999-03-01 |
ES2175763T3 (es) | 2002-11-16 |
US6346295B1 (en) | 2002-02-12 |
CA2300275A1 (en) | 1999-02-18 |
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