EP1290242B1 - Method for treating or pre-treating components comprising aluminium surfaces - Google Patents
Method for treating or pre-treating components comprising aluminium surfaces Download PDFInfo
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- EP1290242B1 EP1290242B1 EP01953946A EP01953946A EP1290242B1 EP 1290242 B1 EP1290242 B1 EP 1290242B1 EP 01953946 A EP01953946 A EP 01953946A EP 01953946 A EP01953946 A EP 01953946A EP 1290242 B1 EP1290242 B1 EP 1290242B1
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- fluoride
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- phosphatizing
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- 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
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- 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
- C23C22/36—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 containing also phosphates
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- 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
- C23C22/36—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 containing also phosphates
- C23C22/364—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 containing also phosphates containing also manganese cations
- C23C22/365—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 containing also phosphates containing also manganese cations containing also zinc and nickel cations
Definitions
- the invention relates to a method for treating or pretreating parts with aluminum surfaces.
- Phosphating processes for aluminum and aluminum alloys are fundamental known.
- fluoride has been modified Phosphating process with at least 150 mg / l free fluoride especially proven. These processes are particularly important in the automotive industry are mainly used when a mix of substrates from different Metals or alloys are given by the plants.
- DE-A1-197 35 314 describes a method for pretreating components with Aluminum surfaces - possibly in the presence of magnesium, steel and / or zinc surfaces -
- a phosphating plant in which the components with a Degreasing solution degreased by treatment with a fluoride-containing Phosphating solution phosphated and then by treatment with a Passivation solution to be passivated.
- the proportion of aluminum or / and Magnesium surface on the entire surface of the components to be treated is at least 10%.
- the fluoride of the phosphating solution The content should only be added as complex-bound fluoride the free fluoride ions formed therefrom in the phosphating solution Phosphating of the steel and / or zinc surfaces without phosphating the Aluminum and / or magnesium surfaces kept at less than 100 mg / l become.
- the passivation solution should be composed so that it the phosphated steel and / or zinc surfaces passivated and on the Aluminum or / and magnesium surfaces forms a conversion layer.
- this method has the disadvantage that it is only comparatively small Area shares on aluminum surfaces, mostly only up to about 20% by area of all surfaces to be treated on the mix of substrates can. It also has the disadvantages that cryolite or / and related ones Precipitation products continue to be formed in the pretreatment bath and that the Layering reactions, especially on iron and steel surfaces in one increased aluminum content of the phosphating solution are affected, so that no longer the entire mix of substrates made of different metal and Alloy surfaces can be coated equally well in the bathroom.
- EP-A2-0 454 361 describes a zinc phosphating process in which the body is involved metallic surfaces are immersed in a zinc phosphating bath, which is next to a fluoride complex has a content of simple fluoride in the range from 200 to 300 mg / L contains and in which the molar ratio of the contents of complex fluoride to simple fluoride ⁇ 0.01, and then the body with a second zinc phosphating solution are sprayed, which contains simple Fluoride ⁇ 500 mg / L, but a higher content than the first Zinc phosphating solution.
- An external precipitation container can be used here be used.
- EP-A2-0 434 358 teaches a similar zinc phosphating process in which such bodies are brought into contact with a zinc phosphate solution only once with a solution of simple fluoride in the range of 200. up to 500 mg / L and at which the molar ratio of the contents Complex fluoride to simple fluoride is kept in the range of 0.01 to 0.5.
- the object of the invention is to overcome the disadvantages of the prior art and in particular a process for phosphating aluminum and aluminum-containing To propose alloys, even with increased proportions of aluminum-containing Surfaces of the components to be treated or pre-treated a good conversion layer that can be applied on an industrial scale or / and one appropriate passivation layer on the surfaces of aluminum or Alloys containing aluminum - possibly in a mix of substrates different metals or alloys - allowed to apply.
- the method according to the invention can be used for this be ensured that increasing levels of aluminum in the phosphating solution in a separate zone of the phosphating bath to contents less than or be reduced to 100 mg / l Al ions.
- the pickling attack dissolves aluminum on the metallic surface, and an aluminum content is taken up in the phosphating solution.
- someone specific Aluminum content can also be from other sources in the phosphating solution come like from registered chemicals of the rinse solution.
- the Aluminum content can be predominantly or entirely by precipitation, but also partially be lowered by complexation.
- the free fluoride content in the Phosphating solution is preferably in a range from 6 to 120 mg / l, particularly preferably in a range from 10 to 80 mg / l, very particularly preferably kept in a range of 20 to 50 mg / l.
- the aluminum content in the Phosphating solution is preferred especially at values ⁇ 80 mg / l preferably ⁇ 60 mg / l, very particularly preferably ⁇ 30 mg / l.
- the process according to the invention is also characterized in that aluminum is precipitated in the phosphating solution in the precipitation tank or in the separate zone of the bath by adding alkali metal ions, fluoride complexes and / or fluoride ions, in particular with Na or K Ion or with at least one easily dissociating fluoride such as NaF, NH 4 F, NaHF 2 or KF.
- alkali metal ions, fluoride complexes and / or fluoride ions in particular with Na or K Ion or with at least one easily dissociating fluoride such as NaF, NH 4 F, NaHF 2 or KF.
- the AlF x complex can already be pre-complexed. It is advantageous to control the process according to the invention in such a way that, despite the F addition, there is no increase in the free fluoride content in the bath.
- the contents of alkali ions in the phosphating bath are preferably 1 to 20 g / l and are preferably also kept in this range, in particular 3 to 10 g / l.
- the alkali ion content can also be far above the concentration of 20 g / l, for example 30 g / l. With such a high alkali concentration, instability of the bath can occur in many cases. In the case of a mixture of different alkali ions next to one another, a dominant content of sodium and / or potassium ions is preferred.
- the concentration of free fluoride is advantageously Phosphating solution in the phosphating bath 8 to 80 mg / l and in particular 10 up to 50 mg / l or in the precipitation tank or in the separate zone of the bath tank 5 to 500 mg / l free fluoride, in particular 20 to 200 mg / l, particularly preferably 30 up to 120 mg / l. It is therefore also preferred to have these levels in these concentrations to keep. Since usually below 5 mg / l there is no pickling attack on aluminum by free Fluoride occurs and because this pickling attack is needed as the subsequent one Passivation e.g.
- the inventive method will be used so that the Residence time of the phosphating solution in the precipitation tank or in the separate one Precipitation zone is up to 1 h, often up to 0.5 h.
- the volume flow from the bathroom to the Precipitation container and back is according to the selected volumes or Partial volumes and the desired aluminum content in the phosphating bath set.
- part in the sense of this application encompasses all types and forms of Sheets, strip and profile sections, shaped bodies, semi-finished products, components, Assemblies etc.
- the parts, profiles, to be treated or pretreated are usually Tapes and / or wires in the method according to the invention before pickling / phosphating cleaned, rinsed and, if necessary, separated from the rinsing and Cleaning stages with an activation solution, e.g. based on colloidal distribution Titanium phosphate contacted.
- Wires can rinsed and / or passivated after pickling / phosphating, in particular with a passivation solution based on a chromate-containing compound, Titanium fluoride, zirconium fluoride, soluble rare earth compound - especially cerium-containing Connection, self-organizing molecules e.g. based on phosphonate, based Silane, solvent-soluble and / or dispersible polymer.
- a passivation solution based on a chromate-containing compound, Titanium fluoride, zirconium fluoride, soluble rare earth compound - especially cerium-containing Connection, self-organizing molecules e.g. based on phosphonate, based Silane, solvent-soluble and / or dispersible polymer.
- the treated or pretreated and / or passivated parts, profiles, strips or / and wires can be after pickling / phosphating or after Passivation can be dried. In some cases such as at the immediate subsequent electrodeposition, however, drying is not necessary.
- the precipitation of the aluminum can be carried out under normal pressure and at a temperature in the Range from room temperature to 70 ° C, especially at one temperature in the range of 40 to 60 ° C.
- the pH is usually in the range of 2 to 4.
- the pH of Phosphating baths are always in the range around pH 3. at Values of pH ⁇ 4.0 are usually unstable, while values of pH ⁇ 4.0 2.0 the bath is so stable that usually no good layer formation occurs because the The pH value shift on the freshly pickled metallic surface does not increase a separation of the conversion layer is sufficient.
- the products thus produced according to the invention can be found in the Automotive industry, in the aviation industry, in apparatus and mechanical engineering, in the Furniture industry, construction, for household appliances, electrical appliances, measuring devices, Control devices, test devices, construction elements, housings, Cladding, shelves, frames, frames, room dividers, partitions, facings, Lighting fixtures, crash barriers, radiator or fence elements as well as small parts, especially for body parts or bodies.
- FIG. 1 shows a flow diagram which shows one possible of several principles of separate aluminum deposition schematically.
- the phosphating process according to the invention has been described in comparison with previously and practiced methods the advantage that the cryolite or / and related Sludge containing precipitation products largely in a separate Precipitation zone or in a separate precipitation container and from there can be disposed of. It is also with the method according to the invention possible to treat different metallic substrates in one mix or pretreatment without affecting the layer formation e.g. on Steel is coming. Due to the reduced levels of free fluoride in the Phosphating solution also occurs less pickling attack on those containing aluminum Surfaces that also cause a correspondingly lower sludge formation. In addition, it was possible to ensure with the method according to the invention that due to the fact that there is less and less precipitated on the phosphated surface deposited particles after the subsequent painting no annoying Markings such as Roughness, streaking or other irregularities were recognizable.
- a standard phosphating solution with the following composition was prepared from pa chemicals: Zn 1.5 g / l Mn 1.0 g / l Ni 1.0 g / l P 2 O 5 14.0 g / l NO 3 3.0 g / l SiF 6 1.0 g / l FS 2.0 Free acid.
- This entry corresponds to approx. 40 bodies per hour with 50% aluminum surface area and a pickling attack of approx. 1 g / m 2 during the contact time.
- Al (ppm) ((((200m 3 - partial flow) • conc. Al in ppm after 1 h + (partial flow • rest Al in ppm after precipitation)) / 200) + Al in ppm from entry via pickling attack / h.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- ing And Chemical Polishing (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Behandeln bzw. Vorbehandeln von Teilen mit Aluminium-Oberflächen.The invention relates to a method for treating or pretreating parts with aluminum surfaces.
Phosphatierverfahren für Aluminium und Aluminiumlegierungen sind grundsätzlich bekannt. In der industriellen Praxis haben sich dabei Fluorid-modifizierte Phosphatierverfahren mit mindestens 150 mg/l freiem Fluorid besonders bewährt. Diese Verfahren sind insbesondere in der Automobilindustrie von Bedeutung und werden vor allem verwendet, wenn ein Mix von Substraten aus verschiedenen Metallen bzw. Legierungen durch die Anlagen gegeben wird.Phosphating processes for aluminum and aluminum alloys are fundamental known. In industrial practice, fluoride has been modified Phosphating process with at least 150 mg / l free fluoride especially proven. These processes are particularly important in the automotive industry are mainly used when a mix of substrates from different Metals or alloys are given by the plants.
Diese Verfahren haben jedoch die schwerwiegenden Nachteile, daß aufgrund des hohen Fluoridgehaltes größere Mengen an Kryolith (Na3AlF6) oder/und an verwandten Fällungsprodukten im Phosphatierungsbad ausgeschieden werden und daß sich Anteile der Fällungsprodukte auch auf der phosphatierten Oberfläche abscheiden, ohne durch einfache Spülvorgänge von dort entfernt werden zu können, wobei eine erhöhte Rauheit auf der vorbehandelten Oberfläche erzeugt wird, die sich auch nach der nachfolgenden Lackierung mit ihrer Rauheit störend auswirkt.However, these processes have the serious disadvantages that, owing to the high fluoride content, larger amounts of cryolite (Na 3 AlF 6 ) and / or related precipitation products are excreted in the phosphating bath and that portions of the precipitation products are also deposited on the phosphated surface without simple rinsing processes to be able to be removed from there, an increased roughness being produced on the pretreated surface, which also has a disruptive effect on its roughness after the subsequent coating.
DE-A1-197 35 314 beschreibt ein Verfahren zur Vorbehandlung von Bauteilen mit Aluminium-Oberflächen - ggfs. in Gegenwart von Magnesium-, Stahl- oder/und Zink-Oberflächen - in einer Phosphatierungsanlage, in der die Bauteile mit einer Entfettungslösung entfettet, durch Behandeln mit einer Fluorid enthaltenden Phosphatierungslösung phosphatiert und anschließend durch Behandeln mit einer Passivierungslösung passiviert werden. Der Anteil der Aluminium- oder/und der Magnesium-Oberfläche an der gesamten zu behandelnden Oberfläche der Bauteile beträgt hierbei mindestens 10 %. Hierbei soll das Fluorid der Phosphatierungslösung ausschließlich als komplexgebundenes Fluorid zugesetzt werden und soll der Gehalt der hieraus gebildeten freien Fluorid-lonen in der Phosphatierungslösung zur Phosphatierung der Stahl- und/oder Zink-Oberflächen ohne Phosphatierung der Aluminium- oder/und Magnesium-Oberflächen auf weniger als 100 mg/l gehalten werden. Außerdem soll die Passivierungslösung so zusammengesetzt sein, daß sie die phosphatierten Stahl- oder/und Zink-Oberflächen passiviert und auf den Aluminium- oder/und Magnesium-Oberflächen eine Konversionsschicht ausbildet.DE-A1-197 35 314 describes a method for pretreating components with Aluminum surfaces - possibly in the presence of magnesium, steel and / or zinc surfaces - In a phosphating plant in which the components with a Degreasing solution degreased by treatment with a fluoride-containing Phosphating solution phosphated and then by treatment with a Passivation solution to be passivated. The proportion of aluminum or / and Magnesium surface on the entire surface of the components to be treated is at least 10%. Here, the fluoride of the phosphating solution The content should only be added as complex-bound fluoride the free fluoride ions formed therefrom in the phosphating solution Phosphating of the steel and / or zinc surfaces without phosphating the Aluminum and / or magnesium surfaces kept at less than 100 mg / l become. In addition, the passivation solution should be composed so that it the phosphated steel and / or zinc surfaces passivated and on the Aluminum or / and magnesium surfaces forms a conversion layer.
Dieses Verfahren hat jedoch den Nachteil, daß es nur bei vergleichsweise geringen Flächenanteilen an Aluminium-Oberflächen, meistens nur bis zu etwa 20 Flächen-% aller zu behandelnden Oberflächen an dem Mix der Substrate, eingesetzt werden kann. Außerdem hat es die Nachteile, daß Kryolith oder/und verwandte Fällungsprodukte weiterhin im Vorbehandlungsbad gebildet werden und daß die Schichtbildungsreaktionen insbesondere auf Eisen- und Stahl-Oberflächen bei einem erhöhten Aluminiumgehalt der Phosphatierungslösung beeinträchtigt werden, so daß nicht mehr der gesamte Mix aus Substraten von verschiedenen Metall- und Legierungsoberflächen im Bad gleichmäßig gut beschichtet werden kann.However, this method has the disadvantage that it is only comparatively small Area shares on aluminum surfaces, mostly only up to about 20% by area of all surfaces to be treated on the mix of substrates can. It also has the disadvantages that cryolite or / and related ones Precipitation products continue to be formed in the pretreatment bath and that the Layering reactions, especially on iron and steel surfaces in one increased aluminum content of the phosphating solution are affected, so that no longer the entire mix of substrates made of different metal and Alloy surfaces can be coated equally well in the bathroom.
EP-A2-0 454 361 beschreibt ein Zinkphosphatierungsverfahren, bei dem Körper mit metallischen Oberflächen in ein Zinkphosphatierbad getaucht werden, das neben einem Fluoridkomplex einen Gehalt an einfachem Fluorid im Bereich von 200 bis 300 mg/L enthält und bei dem das molare Verhältnis der Gehalte an Komplexfluorid zu einfachem Fluorid ≥ 0,01 gehalten wird, und bei dem die Körper danach mit einer zweiten Zinkphosphatierungslösung besprüht werden, die einen Gehalt an einfachem Fluorid von ≤ 500 mg/L, jedoch einem höheren Gehalt als bei der ersten Zinkphosphatierungslösung, aufweist. Hierbei kann ein externer Fällungsbehälter eingesetzt werden.EP-A2-0 454 361 describes a zinc phosphating process in which the body is involved metallic surfaces are immersed in a zinc phosphating bath, which is next to a fluoride complex has a content of simple fluoride in the range from 200 to 300 mg / L contains and in which the molar ratio of the contents of complex fluoride to simple fluoride ≥ 0.01, and then the body with a second zinc phosphating solution are sprayed, which contains simple Fluoride ≤ 500 mg / L, but a higher content than the first Zinc phosphating solution. An external precipitation container can be used here be used.
EP-A2-0 434 358 lehrt ein ähnliches Zinkphosphatierungsverfahren, bei dem derartige Körper nur einmal mit einer Zinkphosphatlösung in Kontakt gebracht werden, wobei diese Lösung einen Gehalt an einfachem Fluorid im Bereich von 200. bis 500 mg/L aufweist und bei der das molare Verhältnis der Gehalte an Komplexfluorid zu einfachem Fluorid im Bereich von 0,01 bis 0,5 gehalten wird. EP-A2-0 434 358 teaches a similar zinc phosphating process in which such bodies are brought into contact with a zinc phosphate solution only once with a solution of simple fluoride in the range of 200. up to 500 mg / L and at which the molar ratio of the contents Complex fluoride to simple fluoride is kept in the range of 0.01 to 0.5.
Aufgabe der Erfindung ist es, die Nachteile des Standes der Technik zu überwinden und insbesondere ein Verfahren zum Phosphatieren von Aluminium und Aluminium-haltigen Legierungen vorzuschlagen, das auch bei erhöhten Anteilen an Aluminium-haltigen Oberflächen der zu behandelnden oder der vorzubehandelnden Bauteile eine gute, in industriellem Maßstab aufbringbare Konversionsschicht oder/und eine entsprechende Passivierungsschicht auf den Oberflächen von Aluminium oder Aluminium-haltigen Legierungen - ggfs. in einem Mix von Substraten aus verschiedenen Metallen bzw. Legierungen - aufzubringen gestattet.The object of the invention is to overcome the disadvantages of the prior art and in particular a process for phosphating aluminum and aluminum-containing To propose alloys, even with increased proportions of aluminum-containing Surfaces of the components to be treated or pre-treated a good conversion layer that can be applied on an industrial scale or / and one appropriate passivation layer on the surfaces of aluminum or Alloys containing aluminum - possibly in a mix of substrates different metals or alloys - allowed to apply.
Die Aufgabe wird gelöst durch ein Verfahren zur Behandlung oder zur Vorbehandlung von Teilen, Profilen, Bändern oder Drähten mit Oberflächen von Aluminium bzw. Aluminium-haltigen Legierungen - ggfs. in Anwesenheit von Oberflächen von weiteren Metallen bzw. Legierungen - mit einer Fluorid und Phosphat enthaltenden sauren wässerigen Lösung, dadurch gekennzeichnet, daß das Fluorid zumindest teilweise als freies Fluorid in der Lösung vorliegt und daß die Gehalte im Bad der Phosphatierungslösung
- an freiem Fluorid im Konzentrationsbereich von 6 bis 120 mg/l Ffrei und
- an Aluminium im Konzentrationsbereich kleiner oder gleich 100 mg/l Al-lonen (einschließlich komplexgebundenem Al)
- free fluoride in the concentration range from 6 to 120 mg / l F free and
- on aluminum in the concentration range less than or equal to 100 mg / l Al ions (including complex-bound Al)
Alternativ oder gleichzeitig kann bei dem erfindungsgemäßen Verfahren dafür gesorgt werden, daß steigende Gehalte an Aluminium in der Phosphatierungslösung in einer gesonderten Zone des Phosphatierungsbades auf Gehalte kleiner oder gleich 100 mg/l Al-lonen abgesenkt werden.Alternatively or simultaneously, the method according to the invention can be used for this be ensured that increasing levels of aluminum in the phosphating solution in a separate zone of the phosphating bath to contents less than or be reduced to 100 mg / l Al ions.
Durch den Beizangriff wird Aluminium an der metallischen Oberfläche angelöst, und ein Aluminiumgehalt wird in die Phosphatierungslösung aufgenommen. Ein gewisser Aluminiumgehalt kann aber auch aus anderen Quellen in die Phosphatierungslösung kommen wie z.B. aus eingetragenen Chemikalien der Nachspüllösung. Der Aluminiumgehalt kann vorwiegend oder gänzlich durch Fällung, aber teilweise auch durch-Komplexierung gesenkt werden. Der Gehalt an freiem Fluorid in der Phosphatierungslösung wird vorzugsweise in einem Bereich von 6 bis 120 mg/l, besonders bevorzugt in einem Bereich von 10 bis 80 mg/l, ganz besonders bevorzugt in einem Bereich von 20 bis 50 mg/l gehalten. Der Aluminiumgehalt in der Phosphatierungslösung wird vorzugsweise bei Werten ≤ 80 mg/l, besonders bevorzugt ≤ 60 mg/l, ganz besonders bevorzugt ≤ 30 mg/l gehalten.The pickling attack dissolves aluminum on the metallic surface, and an aluminum content is taken up in the phosphating solution. Someone specific Aluminum content can also be from other sources in the phosphating solution come like from registered chemicals of the rinse solution. The Aluminum content can be predominantly or entirely by precipitation, but also partially be lowered by complexation. The free fluoride content in the Phosphating solution is preferably in a range from 6 to 120 mg / l, particularly preferably in a range from 10 to 80 mg / l, very particularly preferably kept in a range of 20 to 50 mg / l. The aluminum content in the Phosphating solution is preferred especially at values ≤ 80 mg / l preferably ≤ 60 mg / l, very particularly preferably ≤ 30 mg / l.
Das erfindungsgemäße Verfahren zeichnet sich auch dadurch aus, daß in dem Fällungsbehälter oder in der gesonderten Zone des Bades durch Zugabe von Alkali-lonen, Fluorid-Komplexe oder/und Fluorid-lonen Aluminium in der Phosphatierungslösung gefällt wird, insbesondere mit Na- oder K-lonen oder mit mindestens einem leicht dissoziierenden Fluorid wie z.B. NaF, NH4F, NaHF2 bzw. KF. Der AlFx-Komplex kann hierbei bereits vorkomplexiert vorhanden sein. Es ist vorteilhaft, das erfindungsgemäße Verfahren so zu steuern, daß trotz der F-Zugabe keine Erhöhung des Gehalts an freiem Fluorid im Bad erfolgt. Die Gehalte an Alkali-lonen im Phosphatierungsbad betragen vorzugsweise 1 bis 20 g/l und werden bevorzugt auch in diesem Bereich gehalten, insbesondere bei 3 bis 10 g/l. Grundsätzlich kann der Gehalt an Alkali-lonen auch weit über der Konzentration von 20 g/l liegen, z.B. bei 30 g/l. Bei einer derart hohen Alkalikonzentratiori kann jedoch in vielen Fällen eine Instabilität des Bades auftreten. Bei einer Mischung verschiedener Alkali-lonen nebeneinander ist ein dominierender Gehalt an Natrium- oder/und Kalium-lonen bevorzugt.The process according to the invention is also characterized in that aluminum is precipitated in the phosphating solution in the precipitation tank or in the separate zone of the bath by adding alkali metal ions, fluoride complexes and / or fluoride ions, in particular with Na or K Ion or with at least one easily dissociating fluoride such as NaF, NH 4 F, NaHF 2 or KF. The AlF x complex can already be pre-complexed. It is advantageous to control the process according to the invention in such a way that, despite the F addition, there is no increase in the free fluoride content in the bath. The contents of alkali ions in the phosphating bath are preferably 1 to 20 g / l and are preferably also kept in this range, in particular 3 to 10 g / l. In principle, the alkali ion content can also be far above the concentration of 20 g / l, for example 30 g / l. With such a high alkali concentration, instability of the bath can occur in many cases. In the case of a mixture of different alkali ions next to one another, a dominant content of sodium and / or potassium ions is preferred.
Hierdurch wird bewirkt, daß der ausgefällte Kryolith und die verwandten Fällungsprodukte wie z.B. K2NaAlF6 nicht oder kaum mehr in dem Phosphatierungsbad auftreten, sondern weitgehend oder (fast) ausschließlich in der gesonderten Zone des Bades oder im Fällungsbehälter. Dadurch können sich die Fällungsprodukte nicht mehr oder kaum noch auf der zu beschichtenden Oberfläche absetzen.This has the effect that the precipitated cryolite and the related precipitation products such as K 2 NaAlF 6 do not or hardly occur in the phosphating bath, but largely or (almost) exclusively in the separate zone of the bath or in the precipitation container. As a result, the precipitation products can no longer or hardly settle on the surface to be coated.
Vorteilhafterweise beträgt die Konzentration an freiem Fluorid der Phosphatierungslösung im Phosphatierungsbad 8 bis 80 mg/l und insbesondere 10 bis 50 mg/l bzw. im Fällungsbehälter oder in der gesonderten Zone des Badbehälters 5 bis 500 mg/l freies Fluorid, insbesondere 20 bis 200 mg/l, besonders bevorzugt 30 bis 120 mg/l. Es ist daher auch bevorzugt, diese Gehalte in diesen Konzentrationen zu halten. Da üblicherweise unter 5 mg/l kein Beizangriff auf Aluminium durch freies Fluorid auftritt und da dieser Beizangriff benötigt wird, da die nachfolgende Passivierung z.B. mit Chromat-haltigen Verbindungen, Titanfluorid, Zinkonfluorid, löslicher Seltenerd-Verbindung - insbesondere einer Cer-haltigen Verbindung, wobei Scandium, Yttrium und Lanthan im Begriff Seltenerdelement enthalten sind -, auf Basis Silan, selbst organisierender Moleküle auf Basis Phosphonat, in Lösungsmittel löslichem oder/und dispergierbarem Polymer allein nicht für eine Passivierung ausreicht, ist ein geringer Mindestgehalt an freiem Fluorid in der Phosphatierungslösung erforderlich. Andererseits bildet sich in vielen Fällen bei Gehalten oberhalb von 120 mg/l freiem Fluorid eine geschlossene Phosphatschicht aus dem Phosphatierungsbad auf den metallischen Oberflächen aus, falls der Gehalt an mit dem Phosphat mitgefällten Kationen wie Zn, Cu, Ni, Fe, Mn usw. nicht sehr gering ist. Die Ausbildung einer Phosphatschicht auf den Aluminium-Oberflächen ist aus Gründen des Korrosionsschutzes nicht zwingend erforderlich. Daher wird ein Gehalt an freiem Fluorid oberhalb von 120 mg/l üblicherweise nicht gewählt werden, obwohl auch oberhalb dieses Wertes erfindungsgemäß gearbeitet werden kann, weil zudem ein höherer Chemikalienverbrauch und eine größere Mengen an ausgefälltem Schlamm aus Kryolith oder/und verwandten Fällungsprodukten verursacht wird. Außerdem ist es bevorzugt, einen Konzentrationsunterschied an freiem Fluorid zwischen Phosphatierungsbad und Fällungsbehälter bzw. gesonderter Zone im Bad von 30 bis 60 mg/l einzustellen und aufrechtzuerhalten.The concentration of free fluoride is advantageously Phosphating solution in the phosphating bath 8 to 80 mg / l and in particular 10 up to 50 mg / l or in the precipitation tank or in the separate zone of the bath tank 5 to 500 mg / l free fluoride, in particular 20 to 200 mg / l, particularly preferably 30 up to 120 mg / l. It is therefore also preferred to have these levels in these concentrations to keep. Since usually below 5 mg / l there is no pickling attack on aluminum by free Fluoride occurs and because this pickling attack is needed as the subsequent one Passivation e.g. with chromate-containing compounds, titanium fluoride, zinc fluoride, soluble rare earth compound - especially a cerium-containing compound, wherein Scandium, yttrium and lanthanum are contained in the term rare earth element -, on Based on silane, self-organizing molecules based on phosphonate, in solvent soluble or / and dispersible polymer alone not for passivation is sufficient, a low minimum level of free fluoride in the Phosphating solution required. On the other hand, in many cases Keep a closed phosphate layer above 120 mg / l free fluoride from the phosphating bath on the metallic surfaces if the content not very much on cations co-precipitated with the phosphate such as Zn, Cu, Ni, Fe, Mn etc. is low. The formation of a phosphate layer on the aluminum surfaces is not absolutely necessary for reasons of corrosion protection. Therefore, a Content of free fluoride above 120 mg / l is usually not chosen, although it is also possible to work according to the invention above this value because also higher chemical consumption and a larger amount of precipitated Sludge from cryolite and / or related precipitation products is caused. It is also preferred to have a concentration difference in free fluoride between the phosphating bath and the precipitation tank or separate zone in the bath adjust and maintain from 30 to 60 mg / l.
In vielen Fällen wird das erfindungsgemäße Verfahren so genutzt werden, daß die Verweilzeit der Phosphatierungslösung im Fällungsbehälter oder in der gesonderten Fällungszone bis zu 1 h beträgt, oft bis zu 0,5 h. Der Volumenstrom vom Bad zum Fällungsbehälter und zurück wird entsprechend den gewählten Volumina bzw. Teilvolumina sowie dem gewünschten Aluminium-Gehalt im Phosphatierungsbad eingestellt.In many cases, the inventive method will be used so that the Residence time of the phosphating solution in the precipitation tank or in the separate one Precipitation zone is up to 1 h, often up to 0.5 h. The volume flow from the bathroom to the Precipitation container and back is according to the selected volumes or Partial volumes and the desired aluminum content in the phosphating bath set.
Der Begriff "Teil" im Sinne dieser Anmeldung umfaßt alle Arten und Formen von Blechen, Band- und Profilabschnitten, Formkörpem, Halbzeugen, Bauteilen, Baugruppen usw.The term "part" in the sense of this application encompasses all types and forms of Sheets, strip and profile sections, shaped bodies, semi-finished products, components, Assemblies etc.
Üblicherweise werden die zu behandelnden bzw. vorzubehandelnden Teile, Profile, Bänder oder/und Drähte bei dem erfindungsgemäßen Verfahren vor dem Beizen/Phosphatieren gereinigt, gespült und ggf. getrennt von den Spül- und Reinigungsstufen mit einer Aktivierungslösung, z.B. auf Basis kolloidal verteiltem Titanphosphat in Kontakt gebracht.The parts, profiles, to be treated or pretreated are usually Tapes and / or wires in the method according to the invention before pickling / phosphating cleaned, rinsed and, if necessary, separated from the rinsing and Cleaning stages with an activation solution, e.g. based on colloidal distribution Titanium phosphate contacted.
Die behandelten bzw. vorbehandelten Teile, Profile, Bänder oder/und. Drähte können nach dem Beizen/Phosphatieren gespült oder/und passiviert werden, insbesondere mit einer Passivierungslösung auf Basis einer Chromat-haftigen Verbindung, Titanfluorid, Zirkonfluorid, löslicher Seltenerd-Verbindung - insbesondere Cer-haltiger Verbindung, selbst organisierender Moleküle z.B. auf Basis Phosphonat, auf Basis Silan, in Lösungsmittel löslichem oder/und dispergierbarem Polymer. The treated or pretreated parts, profiles, strips or / and. Wires can rinsed and / or passivated after pickling / phosphating, in particular with a passivation solution based on a chromate-containing compound, Titanium fluoride, zirconium fluoride, soluble rare earth compound - especially cerium-containing Connection, self-organizing molecules e.g. based on phosphonate, based Silane, solvent-soluble and / or dispersible polymer.
Die behandelten bzw. vorbehandelten oder/und passivierten Teile, Profile, Bänder oder/und Drähte können nach dem Beizen/Phosphatieren bzw. nach dem Passivieren getrocknet werden. In manchen Fällen wie z.B. bei dem unmittelbar anschließender Elektrotauchfackienrng ist jedoch eine Trocknung nicht erforderlich.The treated or pretreated and / or passivated parts, profiles, strips or / and wires can be after pickling / phosphating or after Passivation can be dried. In some cases such as at the immediate subsequent electrodeposition, however, drying is not necessary.
Die Fällung des Aluminiums kann unter Normaldruck und bei einer Temperatur im Bereich von Raumtemperatur bis 70 °C erfolgen, insbesondere bei einer Temperatur im Bereich von 40 bis 60 °C. Bei dem erfindungsgemäßen Verfahren kann die Ausbildung der Konversions- bzw. Passivierungsschicht unter Normaldruck und bei einer Temperatur von Raumtemperatur bis 70 °C erfolgen, vorzugsweise bei 35 bis 60 °C. Der pH-Wert liegt üblicherweise in dem Bereich von 2 bis 4. Der pH-Wert von Phosphatierungsbädem liegt grundsätzlich immer im Bereich um pH 3 herum. Bei Werten von pH ≥ 4,0 ist das Bad üblicherweise instabil, während bei Werten von pH ≤ 2,0 das Bad so stabil ist, daß üblicherweise keine gute Schichtbildung auftritt, weil die ph-Wert-Verschiebung an der frisch gebeizten metallischen Oberfläche nicht zu einem Abscheiden der Konversionsschicht ausreicht.The precipitation of the aluminum can be carried out under normal pressure and at a temperature in the Range from room temperature to 70 ° C, especially at one temperature in the range of 40 to 60 ° C. In the method according to the invention, the Formation of the conversion or passivation layer under normal pressure and at a temperature from room temperature to 70 ° C, preferably at 35 to 60 ° C. The pH is usually in the range of 2 to 4. The pH of Phosphating baths are always in the range around pH 3. at Values of pH ≥ 4.0 are usually unstable, while values of pH ≤ 4.0 2.0 the bath is so stable that usually no good layer formation occurs because the The pH value shift on the freshly pickled metallic surface does not increase a separation of the conversion layer is sufficient.
Schließlich können die behandelten bzw. vorbehandelten oder/und passivierten Teile, Profile, Bänder oder/und Drähte mit einem Lack, mit einer andersartigen organischen Beschichtung, mit einer Folie oder/und mit einer Klebstoffschicht beschichtet, ggf. bedruckt und ggf. umgeformt werden, wobei die derart beschichteten Metallteile zusätzlich mit anderen Teilen zusammengeklebt, zusammengeschweißt oder/und anderweitig miteinander verbunden werden können.Finally, the treated or pretreated and / or passivated parts, Profiles, tapes and / or wires with a varnish, with a different organic Coating, coated with a film or / and with an adhesive layer, if necessary printed and possibly formed, the metal parts coated in this way additionally glued, welded together and / or with other parts can otherwise be connected.
Die derart erfindungsgemäß hergestellten Produkte lassen sich in der Automobilindustrie, in der Luftfahrtindustrie, im Apparate- und Maschinenbau, in der Möbelindustrie, im Bauwesen, für Haushaltsgeräte, Elektrogeräte, Meßgeräte, Kontrotteinrichtungen, Prüfeinrichtungen, Konstruktionselemente, Gehäuse, Verkleidungen, Regale, Gestelle, Rahmen, Raumteiler, Trennwände, Verblendungen, Beleuchtungskörper, Leitplanken, Heizkörper- oder Zaunelemente sowie Kleinteile, insbesondere für Karosserieteile bzw. Karosserien, verwenden. The products thus produced according to the invention can be found in the Automotive industry, in the aviation industry, in apparatus and mechanical engineering, in the Furniture industry, construction, for household appliances, electrical appliances, measuring devices, Control devices, test devices, construction elements, housings, Cladding, shelves, frames, frames, room dividers, partitions, facings, Lighting fixtures, crash barriers, radiator or fence elements as well as small parts, especially for body parts or bodies.
Figur 1 zeigt ein Fließbild, welches ein mögliches von mehreren Prinzipien der separaten Aluminium-Abscheidung schematisch darstellt.FIG. 1 shows a flow diagram which shows one possible of several principles of separate aluminum deposition schematically.
Das erfindungsgemäße Phosphatierverfahren hat gegenüber bisher beschriebenen und praktizierten Verfahren den Vorteil, daß der Kryolith oder/und verwandte Fällungsprodukte enthaltende Schlamm weitgehend in einer gesonderten Fällungszone oder in einem gesonderten Fällungsbehälter anfällt und von dort entsorgt werden kann. Außerdem ist es mit dem erfindungsgemäßen Verfahren möglich, unterschiedliche metallische Substrate in einem Mix zu behandeln bzw. vorzubehandeln, ohne daß es zu Beeinträchtigungen der Schichtbildung z.B. auf Stahl kommt. Aufgrund der verringerten Gehalte an freiem Fluorid in der Phosphatierungslösung tritt auch ein geringerer Beizangriff auf Aluminium-haltigen Oberflächen auf, der auch eine entsprechend geringere Schlammbildung bedingt. Außerdem konnte mit dem erfindungsgemäßen Verfahren sichergestellt werden, daß aufgrund nur noch weniger auf der phosphatierten Oberfläche mitgefällter und abgelagerter Partikel nach der anschließenden Lackierung keine störenden Markierungen wie z.B. Rauheit, Schlierenbildung bzw. sonstige Ungleichmäßigkeiten erkennbar waren.The phosphating process according to the invention has been described in comparison with previously and practiced methods the advantage that the cryolite or / and related Sludge containing precipitation products largely in a separate Precipitation zone or in a separate precipitation container and from there can be disposed of. It is also with the method according to the invention possible to treat different metallic substrates in one mix or pretreatment without affecting the layer formation e.g. on Steel is coming. Due to the reduced levels of free fluoride in the Phosphating solution also occurs less pickling attack on those containing aluminum Surfaces that also cause a correspondingly lower sludge formation. In addition, it was possible to ensure with the method according to the invention that due to the fact that there is less and less precipitated on the phosphated surface deposited particles after the subsequent painting no annoying Markings such as Roughness, streaking or other irregularities were recognizable.
Es war überraschend, daß sich weitgehend stabile Badverhältnisse in Bezug auf den Gehalt an freiem Fluorid und an Aluminium im Phosphatierungsbad sowie in der gesonderten Zone bzw. im Fällungsbehälter trotz der sehr unterschiedlichen Konzentrationen dieser Gehalte verwirklichen ließen.It was surprising that largely stable bath conditions with regard to the Free fluoride and aluminum content in the phosphating bath and in the separate zone or in the precipitation container despite the very different Concentrations of these levels were achieved.
Der Gegenstand der Erfindung wird im folgenden anhand von einem Ausführungsbeispiel näher erläutert.The object of the invention is described below with reference to a Embodiment explained in more detail.
Um die geeigneten Fällungsbedingungen für Aluminium-haltige Phosphatierungslösungen in einem erfindungsgemäßen Phosphatierbad zu ermitteln, wurden folgende Versuche durchgeführt. Hierbei wurden vor allem die Einflüsse der Konzentrationen von freiem Fluorid, Natrium sowie komplex gebundenem Fluorid auf die Geschwindigkeit der Aluminiumfällung untersucht.To find the suitable precipitation conditions for aluminum-containing To determine phosphating solutions in a phosphating bath according to the invention, the following tests were carried out. The influences of the Concentrations of free fluoride, sodium and complex bound fluoride investigated the rate of aluminum precipitation.
Um eventuell existierende Wechselwirkungen der signifikanten Parameter besser erkennen zu können, wurde eine Computer-unterstützte Versuchsplanung herangezogen. Verwendet wurde das Programm Stavex 4.3.To better possibly existing interactions of the significant parameters To be able to recognize, was a computer-assisted test planning used. The Stavex 4.3 program was used.
- Fluoridmessung:Fluoride measurement:
- Orion Model 960 mit lonen-selktiver ElektrodeOrion Model 960 with ion-selective electrode
- Aluminium:Aluminum:
- ICP.ICP.
Aus p.a.-Chemikalien wurde eine Standardphosphatierungslösung mit folgender
Zusammensetzung hergestellt:
Ausgehend von dieser Lösung wurden lonen von SiF6 und Na sowie der Anteil des freien Fluorides in weiteren Ansätzen variiert.Starting from this solution, ions of SiF 6 and Na and the proportion of free fluoride were varied in further batches.
Es wurden 0,5 l der oben beschriebenen Phosphatierungslösung in einen Kunststoffbecher gefüllt, und mit einer 24 %-igen H2SiF6-Lösung wurde der ggf. gewünschte höhere Gehalt an Silikofluorid eingestellt, wobei die Korrektur des Gehaltes an Freier Säure mit einem NaOH-Zusatz vorgenommen wurde. Der Na-Gehalt wurde mittels NaNO3, der entsprechende Gehalt an freiem Fluorid wurde mittels einer verdünnten Ammoniumbifluorid-Lösung eingestellt. Nun wurden mit einer verdünnten Aluminiumnitrat-Lösung 20 mg/l Aluminium dem Bad zugegeben. Nach 0, 15, 30 und 60 Minuten wurde das freie Fluorid gemessen, und es wurde eine Probe der Lösung zwecks Aluminiumbestimmung gezogen.0.5 l of the phosphating solution described above was poured into a plastic beaker, and the desired higher content of silicofluoride was adjusted with a 24% H 2 SiF 6 solution, the correction of the free acid content using NaOH - Additional was made. The Na content was adjusted using NaNO 3 , the corresponding free fluoride content was adjusted using a dilute ammonium bifluoride solution. Now 20 mg / l aluminum were added to the bath with a dilute aluminum nitrate solution. After 0, 15, 30 and 60 minutes the free fluoride was measured and a sample of the solution was taken for aluminum determination.
Um eine Nachfällung des Aluminiums in der gezogenen Probe zu verhindern, wurde wie folgt vorgegangen: 5 ml der mittels Membranfilter filtrierten Probe wurden in eine stark salzsaure VE-Wasser-Lösung gegeben und mit VE-Wasser auf 50 ml aufgefüllt. Diese Lösung wurde mittels ICP auf ihren Aluminiumgehalt untersucht.To prevent reprecipitation of the aluminum in the sample taken, proceed as follows: 5 ml of the sample filtered using a membrane filter were placed in a added strongly hydrochloric acid demineralized water solution and made up to 50 ml with demineralized water. This solution was examined for its aluminum content by means of ICP.
Die Ergebnisse sind in Tabelle 1 zusammengestellt. The results are summarized in Table 1.
Beim Versuch 1 zeigte sich über die Zeit von 5 Tagen keine Ausfällung des
Aluminiums. Bei den Versuchen 4, 8 und 15 ergab sich eine drastische Verminderung
des Aluminiumgehalts sogar innerhalb von 15 Minuten. Erhöhte Alkaligehalte sind in
Verbindung mit erhöhten Gehalten an freiem Fluorid zu bevorzugen. SiF6 wurde
wegen der Stabilität der Phosphatierungslösung und für die Verwendbarkeit für einen
Mix verschiedenartiger metallischer Oberflächen, insbesondere für die Vermeidung
der Stippenbildung auf verzinkten oder Zink-haltigen Oberflächen, zugegeben.In
Nach Auswertung der in Beispiel 1 gefundenen Werte läßt sich folgende beispielhafte Berechnung durchführen:After evaluating the values found in Example 1, the following are exemplary Carry out calculation:
Dieser Eintrag entspricht ca. 40 Karossen pro Stunde mit 50- % Aluminium-Oberflächenanteil und einem Beizangriff von ca. 1 g/m2 während der Kontaktzeit.This entry corresponds to approx. 40 bodies per hour with 50% aluminum surface area and a pickling attack of approx. 1 g / m 2 during the contact time.
Berechnungsformel für die stationäre Konzentration des Aluminiums in der
Phosphatienrngslösung:
Hieraus wurde geschlossen, daß es nötig ist, daß der zu behandelnde Volumenstrom mindestens 0,5 Beckenvolumina pro Stunde beträgt, um einen genügend hohen Anteil an gelöstem Aluminium erfassen zu können. Dies ergibt bei einer durchschnittlichen Verweilzeit von 30 min ein Volumen des Reaktionsbeckens von 50 m3. Ein Restgehalt an Aluminium im Auslauf des Behandlungsbecken von ca. 5 ppm ergibt einen theoretischen stationären Gehalt an Aluminium im Behandlungsbad von ca. 25 ppm. Da aber auch im Behandlungsbad (siehe z.B. Versuch 3 aus Tabelle 1) mit einer teilweisen Fällung des Aluminiums zu rechnen ist, wird sich der tatsächliche Gehalt an gelöstem Aluminium auf einen tieferen Wert einstellen: Ca. 20 % der gesamten Fällungsprodukte treten im Phosphatierbad auf und ergaben ca. 20 ppm Al-Gehalt in der Phosphatierungslösung des Bades im stationären Zusand. Ca. 80 % der gesamten Fällungsprodukte fielen im Fällungsbehälter aus.From this it was concluded that it is necessary for the volume flow to be treated to be at least 0.5 pool volumes per hour in order to be able to detect a sufficiently high proportion of dissolved aluminum. With an average residence time of 30 min, this results in a volume of the reaction basin of 50 m 3 . A residual aluminum content in the outlet of the treatment pool of approx. 5 ppm results in a theoretical stationary aluminum content in the treatment bath of approx. 25 ppm. However, since a partial precipitation of the aluminum can also be expected in the treatment bath (see, for example, experiment 3 from table 1), the actual content of dissolved aluminum will set itself to a lower value: approx. 20% of the total precipitation products occur in the phosphating bath and resulted in approx. 20 ppm Al content in the phosphating solution of the bath in stationary condition. Approximately 80% of the total precipitation products failed in the precipitation container.
Claims (13)
- Method for the treatment or pretreatment of parts, sections, strips or wires with surfaces of aluminium or alloys containing aluminium - if applicable in the presence of surfaces of further metals or alloys - with an acid aqueous solution containing fluoride and phosphate, characterised in that the fluoride is at least partly present in the solution as free fluoride, and in that, in the bath of the phosphatizing solution,the free-fluoride content is maintained at a concentration in the range from 6 to 120 mg/l Ffree, andthe aluminium content is maintained at a concentration in the range of ≤ 100 mg/l Al ions (including complex-bound A1)
- Method according to claim 1, modified in that in a separate zone of the phosphatizing bath increasing aluminium contents in the phosphatizing solution are decreased to contents ≤ 100 mg/l Al ions.
- Method according to claim 1 or 2, characterised in that, in the tank or in the separate zone of the bath, aluminium is precipitated in the phosphatizing solution by adding alkali ions, fluoride complexes and/or fluoride ions, in particular by means of Na or K ions or by means of at least one easily dissociating fluoride such as, for example, NaF, NH4F, NaHF2 or KF.
- Method according to one of the preceding claims, characterised in that the alkali ion content in the bath is maintained at a concentration in the range from 1 to 20 g/l.
- Method according to one of the preceding claims, characterised in that the free-fluoride concentration in the precipitation tank or in the separate zone of the bath container is 5 to 500 mg/l free fluoride.
- Method according to one of the preceding claims, characterised in that the dwell time of the phosphatizing solution in the precipitation tank or in the separate precipitation zone is up to 1 h.
- Method according to one of the preceding claims, characterised in that prior to pickling/phosphatizing, the parts, sections, strips and/or wires to be treated or pretreated are cleaned, rinsed and, if applicable separately from the rinsing and cleaning stages, brought into contact with an activating solution, for example on the basis of colloidally dispersed titanium phosphate.
- Method according to one of the preceding claims, characterised in that after pickling/phosphatizing, the treated or pretreated parts, sections, strips and/or wires are rinsed and/or passivated, in particular by means of a passivating solution on the basis of a chromate-containing compound, titanium fluoride, zirconium fluoride, silane, self-organizing molecules for example on the basis of phosphonate, a polymer soluble and/or dispersible in solvent, a soluble rare-earth compound - in particular a soluble cerium-containing compound, in which case the term rare-earth element is also to include scandium, yttrium and lanthanum.
- Method according to one of the preceding claims, characterised in that the treated or pretreated and/or passivated parts, sections, strips and/or wires are dried after pickling/phosphatizing or after passivation.
- Method according to one of the preceding claims, characterised in that the precipitation of the aluminium is effected under normal pressure and at a temperature in the range from room temperature to 70°C.
- Method according to one of the preceding claims, characterised in that the formation of the conversion or passivation layer is effected under normal pressure and at a temperature from room temperature to 70°C.
- Method according to one of the preceding claims, characterised in that the treated or pretreated and/or passivated parts, sections, strips and/or wires are coated with a lacquer, with another kind of organic coating, with a film and/or with an adhesive layer, if applicable printed and if applicable reshaped, where the metal parts coated in this way can in addition be bonded, welded and/or otherwise connected together with other parts.
- Use of the products produced in accordance with the method according to claims 1 to 12 in the automotive industry, in the aeronautical industry, in apparatus and machine construction, in the furniture industry, in the building trade, for household appliances, electrical appliances, measuring instruments, control devices, testing devices, construction elements, housings, panellings, shelf systems, racks, frames, dividers, partitions, trim panels, lighting fixtures, crash barriers, radiator or fence elements as well as small parts, in particular for car body parts or car bodies.
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DE10026850A DE10026850A1 (en) | 2000-05-31 | 2000-05-31 | Process for treating or pretreating components with aluminum surfaces |
DE10026850 | 2000-05-31 | ||
PCT/EP2001/005756 WO2001092597A2 (en) | 2000-05-31 | 2001-05-19 | Method for treating or pre-treating components comprising aluminium surfaces |
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EP (1) | EP1290242B1 (en) |
JP (1) | JP2003535220A (en) |
AT (1) | ATE260349T1 (en) |
AU (1) | AU7633701A (en) |
DE (2) | DE10026850A1 (en) |
ES (1) | ES2215920T3 (en) |
WO (1) | WO2001092597A2 (en) |
ZA (1) | ZA200209670B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MXPA03006677A (en) | 2001-02-16 | 2003-10-24 | Henkel Kgaa | Process for treating multi-metal articles. |
US6793738B2 (en) * | 2002-03-28 | 2004-09-21 | General Electric Company | Method for processing acid treatment solution, solution processed thereby, and method for treating articles therewith |
AU2003250917A1 (en) | 2002-07-10 | 2004-02-02 | Chemetall Gmbh | Method for coating metallic surfaces |
DE102010030697A1 (en) | 2010-06-30 | 2012-01-05 | Henkel Ag & Co. Kgaa | Process for the selective phosphating of a composite metal construction |
CN102094195B (en) * | 2011-01-14 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Phosphating method of surface of metal material |
EP2915903B1 (en) * | 2014-03-05 | 2018-02-21 | The Boeing Company | Chromium-free conversion coating |
EP3682042B1 (en) * | 2017-09-14 | 2021-11-10 | Chemetall GmbH | Method for pretreating aluminum materials, particularly aluminum wheels |
JP7394761B2 (en) * | 2017-12-12 | 2023-12-08 | ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Boric acid-free composition for removing deposits containing cryolite |
DE102020116345B3 (en) * | 2020-06-22 | 2021-04-08 | Möller Chemie GmbH & Co. KG | Process for the regeneration of an exhausted treatment liquid containing sulfuric acid from aluminum refining |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5200000A (en) * | 1989-01-31 | 1993-04-06 | Nihon Parkerizing Co., Ltd. | Phosphate treatment solution for composite structures and method for treatment |
KR100197145B1 (en) * | 1989-12-19 | 1999-06-15 | 후지이 히로시 | Method for phosphating metal surface with zinc phosphate |
JPH07100870B2 (en) * | 1990-04-24 | 1995-11-01 | 日本ペイント株式会社 | Method for treating zinc phosphate coating on metal surface |
JP2794013B2 (en) * | 1990-10-24 | 1998-09-03 | 日本パーカライジング株式会社 | Phosphate chemical conversion treatment solution for iron-aluminum metal sheet metal construction |
JPH07173643A (en) * | 1993-12-21 | 1995-07-11 | Mazda Motor Corp | Method for phosphating metal surface and phosphating solution |
-
2000
- 2000-05-31 DE DE10026850A patent/DE10026850A1/en not_active Withdrawn
-
2001
- 2001-05-19 JP JP2002500786A patent/JP2003535220A/en active Pending
- 2001-05-19 EP EP01953946A patent/EP1290242B1/en not_active Expired - Lifetime
- 2001-05-19 WO PCT/EP2001/005756 patent/WO2001092597A2/en active IP Right Grant
- 2001-05-19 AU AU76337/01A patent/AU7633701A/en not_active Abandoned
- 2001-05-19 US US10/258,893 patent/US20030150527A1/en not_active Abandoned
- 2001-05-19 ES ES01953946T patent/ES2215920T3/en not_active Expired - Lifetime
- 2001-05-19 AT AT01953946T patent/ATE260349T1/en not_active IP Right Cessation
- 2001-05-19 DE DE50101560T patent/DE50101560D1/en not_active Expired - Fee Related
-
2002
- 2002-11-28 ZA ZA200209670A patent/ZA200209670B/en unknown
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2006
- 2006-07-07 US US11/483,111 patent/US20070119520A1/en not_active Abandoned
Also Published As
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WO2001092597A2 (en) | 2001-12-06 |
EP1290242A2 (en) | 2003-03-12 |
US20070119520A1 (en) | 2007-05-31 |
WO2001092597B1 (en) | 2002-05-23 |
WO2001092597A3 (en) | 2002-04-25 |
ATE260349T1 (en) | 2004-03-15 |
ES2215920T3 (en) | 2004-10-16 |
AU7633701A (en) | 2001-12-11 |
JP2003535220A (en) | 2003-11-25 |
DE50101560D1 (en) | 2004-04-01 |
DE10026850A1 (en) | 2001-12-06 |
ZA200209670B (en) | 2003-11-28 |
US20030150527A1 (en) | 2003-08-14 |
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