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EP0161667A1 - Process for the treatment of metal surfaces - Google Patents

Process for the treatment of metal surfaces Download PDF

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Publication number
EP0161667A1
EP0161667A1 EP85105917A EP85105917A EP0161667A1 EP 0161667 A1 EP0161667 A1 EP 0161667A1 EP 85105917 A EP85105917 A EP 85105917A EP 85105917 A EP85105917 A EP 85105917A EP 0161667 A1 EP0161667 A1 EP 0161667A1
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EP
European Patent Office
Prior art keywords
treatment
solution
ppm
metal surfaces
contact
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
Application number
EP85105917A
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German (de)
French (fr)
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EP0161667B1 (en
Inventor
Peter King
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Henkel Corp
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Parker Chemical Co
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Priority to AT85105917T priority Critical patent/ATE38254T1/en
Publication of EP0161667A1 publication Critical patent/EP0161667A1/en
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Publication of EP0161667B1 publication Critical patent/EP0161667B1/en
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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

Definitions

  • the invention relates to a method for treating metal surfaces made of iron and steel with fluoride-containing solutions.
  • containers made from low-carbon steel sheet - usually referred to as black sheet - are usually manufactured by pre-forming, deep drawing and smoothing.
  • Such containers have a desirable light gray glossy surface, which make them suitable as attractive packaging after a coating treatment with a clear organic lacquer or printing on the outer surface.
  • the process sequence in the manufacture of black plate containers usually consists in unwinding the black plate strip provided with a protective oil layer from the coil, in applying drawing lubricants, in a first preliminary deformation to a cup and in deep drawing and smoothing to form the final shape.
  • drawing lubricants such as water or aqueous emulsions, which facilitate the deep-drawing process, are usually used in the drawing and smoothing process.
  • the containers are then cut smooth in a trimmer and cleaned in a multi-stage washing process.
  • Lubricants, protective agents are first used in a cleaner with a low concentration and then in a cleaner with a higher concentration. oils, coolants and other contaminants removed.
  • the containers are then passed through one or more water rinsing stages, whereupon they are completely dried in a drying oven. This is followed by a single or multi-stage painting and decorative printing on the outer surface.
  • the outer surface is first provided with a basecoat or a decorative print and after drying with an outer layer of can paint. After it has hardened, it is coated internally with subsequent hardening. If the opacity of the selected paint is low, the container finally obtained must retain the shiny, light gray metallic appearance - as far as visible through the paint.
  • the object of the invention is to provide a method by means of which the aforementioned problems can be remedied. It should be able to be integrated as an integrable component in the multi-stage cleaning or rinsing process and retain the desirable light gray shiny metal surface at least until the final one Protection by painting or another type of surface treatment is guaranteed.
  • 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 metal surface is brought into contact with a solution which contains aluminum ions and up to 200 ppm of fluoride ions and which has a pH of 2 to 5.5 having.
  • a preferred embodiment of the invention consists in bringing the metal surfaces into contact with a solution which additionally contains up to 1000 ppm ions of at least one of the metals titanium, zirconium and / or hafnium.
  • the aluminum can be introduced into the solution intended for carrying out the process according to the invention in the form of any soluble and compatible aluminum salt.
  • Suitable salts are e.g. Aluminum fluoride, but especially aluminum sulfate hydrate.
  • the aluminum concentration is largely arbitrary and can exceed the solubility limit. Usually the concentration is in the range of 10 to 5000 ppm. Concentrations in the range of 25 to 250 ppm are preferred.
  • the fluoride can be introduced into the aqueous treatment solution as a simple fluorine compound, such as hydrofluoric acid, as a simple or bifluoride salt of alkali or ammonium.
  • a simple fluorine compound such as hydrofluoric acid
  • complex fluorides of, for example, boron, silicon, aluminum, zircon, hafnium and / or titanium can also be used.
  • the fluoride concentration can be approximately 5 to 200 ppm. A content of 10 to 150 ppm is preferred.
  • the fluoride concentration generally depends on the amount of aluminum present in the solution, the nature of the metal surface to be treated, the temperature of the treatment solution and the duration of the treatment.
  • the ions of at least one of the metals titanium, zirconium and hafnium can be introduced into the solution in the form of any compound which is soluble in the acidic aqueous medium, unless disturbing bath constituents are added.
  • Suitable compounds are, for example, potassium fluorotitanate, titanium zirconium fluoride, fluozirconic acid, ammonium or alkali fluorozirconates, zirconium fluoride, zirconium sulfate and hafnium oxide and hafnium acids and salts, for example hafnium nitrate, fluoride or chloride.
  • Alkali fluorozirconate in particular potassium fluorozirconate (K 2 ZrF 6 ) is preferably used, especially since zirconium and fluorine are introduced at the same time.
  • concentration of ions of at least one of the metals titanium, zirconium and hafnium can range up to 1000 ppm, those in the range from 40 to 320 ppm are preferred. The most common concentration in the working bath is around 80 ppm.
  • the solution contains hydrogen ions in such an amount that a pH of 2 to 5.5 results.
  • a pH of 2 to 5.5 results at pH values above 5.5.
  • no visible treatment or coating formation is obtained and consequently no corrosion protection is created.
  • the pH to be set depends on the duration of the treatment, the bath temperature and, for example, the spray pressure, but also on the concentration of the other bath components.
  • a pH value of 4.0 to 4.5 can achieve particularly favorable results.
  • the aqueous treatment solution is usually obtained from a concentrate by dilution with water.
  • Both the batch and the supplement concentrate contain about 1 to 25, preferably 2.5 to 10, g / l aluminum, 0.1 to 5 g / 1 fluoride and, in a preferred embodiment, up to 10 g / 1 Titanium, zircon and / or hafnium.
  • the pH of the concentrate is usually in the range from 0 to 4.
  • the aqueous acidic treatment solution is brought into contact with the surface of iron or steel at a temperature of 26.7 to 82 ° C., preferably 32.2 to 54 ° C.
  • the treatment time can be 2 seconds to 5 minutes, preferably 5 seconds to 1 minute.
  • the contact of the metal surface with the solution can take place in dipping, flooding and in particular in spraying.
  • the spray treatment is also advantageous because the conventional washing treatment into which the method according to the invention can be integrated, in particular because of the shape of the containers to be treated and the necessary thorough contact with the solution, is generally designed as a spraying method anyway.
  • the process according to the invention can be carried out in the second stage of a three-stage washing process, in the third stage of a five-stage washing process or in the fourth stage of a six-stage washing process.
  • the fourth stage is rinsed with water in the fifth stage and with deionized water in the sixth stage before drying takes place in a forced air oven.
  • the duration of the contact between the metal surface and the treatment solution is largely determined by the operation of the existing system. When setting the treatment temperature, too, you will usually follow the treatment temperatures otherwise prevailing in the system.
  • the treatment solution was obtained by adding 3 l of the aforementioned concentrate to 140 l of water.
  • the pH was adjusted to 3.8 to 4.5.
  • the treatment of a black sheet container was carried out in a five-stage washing plant with the stages of alkaline cleaning, water rinsing, treatment with the above-mentioned treatment solution for a period of 1 min, water rinsing and rinsing with demineralized water.
  • the container treated in this way with a remainder of water in the curved bottom was then dried at 163 ° C. No rust was visible on the surface of the container.
  • a continuous treatment line for black tin cans with the same treatment steps as above was stopped for half an hour. Thereafter, the cans in level 2 showed signs of rust, whereas the cans in levels 1, 3, 4 and 5 showed no visible rust.
  • black tin cans were used after the alkaline cleaning process gung, water rinsing, contacting with an aqueous solution which contained 200 ppm aluminum, 75 ppm HBF 4 , 80 ppm zirconium and had a pH of 4.4, water rinsing, rinsing with deionized water.
  • the individual treatment tanks were of practically the same length, so that the treatment times were practically the same at 40 seconds each.
  • the temperature of the solution applied in the third stage was 49 ° C.
  • Black tin cans were treated according to the procedure of Example 2, except that the pH of the aqueous acidic solution of Step 3 was adjusted to 3.5. After the final rinse treatment, the cans were oven-dried for 3 minutes at 193 ° C. The cans showed a brown-golden discoloration, which is intolerable if only a final treatment with a clear varnish is provided
  • Black tin cans were again treated according to the procedure of Example 2, with the exception that the pH of the acidic treatment solution in step 3 was set to 5.5. After drying in the oven, the cans were shiny and without significant discoloration. Only some of the cans showed local discolouration on the floor bulge, the edges and Contact surfaces of two neighboring cans. Some cans that had been removed from the system before the oven dried and therefore remained damp showed rust very quickly.
  • Example 1 a number of treatment solutions were prepared, which differed in the content of titanium, zirconium, hafnium. Finally, a solution was prepared as a control solution that contained only fluoride and was free of aluminum, zirconium, titanium and hafnium. In the former solutions, the zirconium was introduced as potassium fluorozirconate, the hafnium as hafnium dioxide (Hf02) and the titanium as hexafluorotitanic acid.
  • black tin cans were treated in a 19 liter spray tank for 1 min at 49 ° C. All treatment solutions had a pH of 4.3 and a fluoride content of 100 ppm (introduced as HBF 4 ). The aluminum and titanium, zirconium and / or hafnium content (in ppm) of the solution and the results obtained are shown in the table below. The appearance of the can jacket and the base of the can after drying in the oven were used for evaluation.
  • the effect of pH on the appearance of the can was assessed using two different treatments Solutions with identical conditions with regard to contact time of 5 sec, temperature of 49 ° C and fluoride concentration of 100 ppm (introduced as HBF 4 ) were used.
  • One of these solutions contained 200 ppm aluminum ions and none of the metals titanium, zircon and hafnium.
  • the second treatment solution contained 50 ppm zirconium and was free of aluminum.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Compounds Of Iron (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Saccharide Compounds (AREA)
  • Coating With Molten Metal (AREA)

Abstract

A composition and process for treating ferrous substrates including black plate container bodies to inhibit in-process corrosion or rusting of the surfaces thereof by contacting the ferrous substrate with aqueous acidic composition containing controlled effective amounts of aluminum, fluoride, optionally a second metal selected from the group consisting of zirconium, titanium, hafnium and mixtures thereof and hydrogen ions to provide a pH on the acid side.

Description

Die Erfindung betrifft ein Verfahren zur Behandlung von Metalloberflächen aus Eisen und Stahl mit fluoridhaltigen Lösungen.The invention relates to a method for treating metal surfaces made of iron and steel with fluoride-containing solutions.

Hierbei ist insbesondere an die Behandlung von Behältern, die aus niedriggekohltem Stahlblech - üblicherweise als Schwarzblech bezeichnet - gefertigt werden, gedacht. Sie werden üblicherweise durch Vorverformung, Tiefziehen und Glätten hergestellt. Derartige Behälter besitzen eine wünschenswerte hellgraue glänzende Oberfläche, die sie nach einer Überzugsbehandlung mit einem klaren organischen Lack oder Bedrucken auf der äußeren Oberfläche als attraktive Verpackung geeignet machen.In particular, the treatment of containers made from low-carbon steel sheet - usually referred to as black sheet - is considered. They are usually manufactured by pre-forming, deep drawing and smoothing. Such containers have a desirable light gray glossy surface, which make them suitable as attractive packaging after a coating treatment with a clear organic lacquer or printing on the outer surface.

Die Verfahrensfolge bei der Herstellung von Schwarzblechbehältern besteht üblicherweise im Abwickeln des mit einer Schutzölschicht versehenen Schwarzblechbandes vom Coil, im Aufbringen von Ziehschmiermitteln, in einer ersten vorläufigen Verformung zu einem Napf und im Tiefziehen und Glätten unter Ausbildung der endgültigen Form. Beim Zieh- und Glättvorgang werden gewöhnlich zusätzlich Kühlschmiermittel, wie Wasser oder wäßrige Emulsionen, die den Tiefziehprozeß erleichtern, eingesetzt. Anschließend werden die Behälter in einem Trimmer glattgeschnitten und in einem mehrstufigen Waschprozeß gereinigt. Hierbei werden zunächst in einem Reiniger mit geringer Konzentration und dann in einem Reiniger mit erhöhter Konzentration Schmiermittel, Schutz- öle, Kühlschmiermittel und andere Verunreinigungen entfernt. Die Behälter werden dann durch eine oder mehrere Wasserspülstufen geführt, worauf sie in einem Trockenofen vollständig getrocknet werden. Anschließend erfolgt eine ein- oder mehrstufige Lackierung und eine dekorative Bedruckung der äußeren Oberfläche. Hierbei wird üblicherweise zunächst die äußere Oberfläche mit einem Basislack oder einem dekorativen Druck und nach Trocknung mit einer äußeren Dosenlackschicht versehen. Nach dessen Härtung erfolgt eine Innenlackierung mit ebenfalls anschließender Härtung. Sofern die Deckkraft des gewählten Lackes gering ist, muß der schließlich erhaltene Behälter das glänzende, hellgraue metallische Aussehen - soweit durch den Lack sichtbar - beibehalten.The process sequence in the manufacture of black plate containers usually consists in unwinding the black plate strip provided with a protective oil layer from the coil, in applying drawing lubricants, in a first preliminary deformation to a cup and in deep drawing and smoothing to form the final shape. In addition, cooling lubricants, such as water or aqueous emulsions, which facilitate the deep-drawing process, are usually used in the drawing and smoothing process. The containers are then cut smooth in a trimmer and cleaned in a multi-stage washing process. Lubricants, protective agents are first used in a cleaner with a low concentration and then in a cleaner with a higher concentration. oils, coolants and other contaminants removed. The containers are then passed through one or more water rinsing stages, whereupon they are completely dried in a drying oven. This is followed by a single or multi-stage painting and decorative printing on the outer surface. Usually, the outer surface is first provided with a basecoat or a decorative print and after drying with an outer layer of can paint. After it has hardened, it is coated internally with subsequent hardening. If the opacity of the selected paint is low, the container finally obtained must retain the shiny, light gray metallic appearance - as far as visible through the paint.

Bei der Herstellung derartiger Behälter stellt man jedoch fest, daß oft während der Trocknung Roststellen auftreten, wenn in bestimmten Bereichen zuviel Wasser zurückgehalten wird. Dies gilt insbesondere für gewölbte Böden von Dosen, Ablaufkanten oder Berührungsstellen von zwei benachbarten Behältern. Dann müssen die Behälter verworfen - oder, was sehr aufwendig ist - überarbeitet werden. Unbeabsichtigter Stillstand der Produktionslinie, bei dem die Behälter für längere Zeit in Spülprozeßstufen verbleiben, verursacht häufig auch unansehnliche Rostflecken oder -streifen, die selbst durch den Lack sichtbar sind. Sie sind auch für eine geringe Lackhaftung verantwortlich und machen mithin das Erzeugnis unverkäuflich.In the manufacture of such containers, however, it is found that rust often occurs during drying if too much water is retained in certain areas. This applies in particular to curved floors of cans, drainage edges or contact points between two adjacent containers. Then the containers have to be discarded - or, which is very expensive - reworked. Unintentional stoppage of the production line, in which the containers remain in rinsing process stages for a long time, often also causes unsightly rust stains or streaks, which are even visible through the paint. They are also responsible for low paint adhesion and therefore make the product unsellable.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, mit dessen Hilfe die vorgenannten Probleme behoben werden können. Es soll als integrierbarer Bestandteil in den mehrstufigen Reinigungs- bzw. Spülprozeß eingegliedert werden können und die wünschenswerte hellgraue glänzende Metalloberfläche zumindest so lange bewahren, bis der endgültige Schutz durch Lackieren oder eine andersartige Oberflächenbehandlung gewährleistet ist.The object of the invention is to provide a method by means of which the aforementioned problems can be remedied. It should be able to be integrated as an integrable component in the multi-stage cleaning or rinsing process and retain the desirable light gray shiny metal surface at least until the final one Protection by painting or another type of surface treatment is guaranteed.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Metalloberfläche mit einer Lösung in Kontakt bringt, die Aluminiumionen und bis 200 ppm Fluoridionen enthält und die einen pH-Wert von 2 bis 5,5 aufweist.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 metal surface is brought into contact with a solution which contains aluminum ions and up to 200 ppm of fluoride ions and which has a pH of 2 to 5.5 having.

Eine bevorzugte Ausführungsform der Erfindung besteht darin, die Metalloberflächen mit einer Lösung in Berührung zu bringen, die zusätzlich bis 1000 ppm Ionen mindestens eines der Metalle Titan, Zirkon und/oder Hafnium enthält.A preferred embodiment of the invention consists in bringing the metal surfaces into contact with a solution which additionally contains up to 1000 ppm ions of at least one of the metals titanium, zirconium and / or hafnium.

Das Aluminium kann in die für die Durchführung des erfindungsgemäßen Verfahrens bestimmte Lösung in Form jedes löslichen und verträglichen Aluminiumsalzes eingebracht werden. Geeignete Salze sind z.B. Aluminiumfluorid, insbesondere aber Aluminiumsulfathydrat. Die Aluminiumkonzentration ist weitgehend beliebig und kann über die Löslichkeitsgrenze hinausgehen. Gewöhnlich liegt die Konzentration im Bereich von 10 bis 5000 ppm. Konzentrationen im Bereich von 25 bis 250 ppm sind bevorzugt.The aluminum can be introduced into the solution intended for carrying out the process according to the invention in the form of any soluble and compatible aluminum salt. Suitable salts are e.g. Aluminum fluoride, but especially aluminum sulfate hydrate. The aluminum concentration is largely arbitrary and can exceed the solubility limit. Usually the concentration is in the range of 10 to 5000 ppm. Concentrations in the range of 25 to 250 ppm are preferred.

Das Fluorid kann in die wäßrige Behandlungslösung als einfache Fluorverbindung, wie Fluorwasserstoffsäure, als einfaches oder Bifluoridsalz von Alkali oder Ammonium eingebracht werden. Es können ebenso komplexe Fluoride von z.B. Bor, Silizium, Aluminium, Zirkon, Hafnium und/oder Titan verwendet werden. Die Fluoridkonzentration kann ca. 5 bis 200 ppm betragen. Ein Gehalt von 10 bis 150 ppm ist bevorzugt. Die Fluoridkonzentration richtet sich im allgemeinen nach der in der Lösung vorhandenen Aluminiummenge, der Beschaffenheit der zu behandelnden Metalloberfläche, der Temperatur der Behandlungslösung und der Behandlungsdauer. Die Ionen mindestens eines der Metalle Titan, Zirkon und Hafnium können in die Lösung in Form jeder im sauren wäßrigen Medium löslichen Verbindung eingebracht werden, sofern nicht störende Badbestandteile zugeführt werden. Geeignete Verbindungen sind beispielsweise Kaliumfluorotitanat, Titanzirkonfluorid, Fluozirkonsäure, Ammonium- oder Alkalifluozirkonate, Zirkonfluorid, Zirkonsulfat sowie Hafniumoxid und Säuren und Salze des Hafniums, z.B. Hafniumnitrat, -fluorid oder -chlorid. Alkalifluorozirkonat, insbesondere Kaliumfluorozirkonat (K2ZrF6) wird bevorzugt eingesetzt, zumal hierdurch Zirkon und Fluor gleichzeitig eingebracht werden. Wenngleich die Konzentration an Ionen mindestens eines der Metalle Titan, Zirkon und Hafnium bis 1000 ppm reichen kann, sind solche im Bereich von 40 bis 320 ppm bevorzugt. Die gängigste Konzentration im arbeitenden Bad liegt etwa bei 80 ppm.The fluoride can be introduced into the aqueous treatment solution as a simple fluorine compound, such as hydrofluoric acid, as a simple or bifluoride salt of alkali or ammonium. Complex fluorides of, for example, boron, silicon, aluminum, zircon, hafnium and / or titanium can also be used. The fluoride concentration can be approximately 5 to 200 ppm. A content of 10 to 150 ppm is preferred. The fluoride concentration generally depends on the amount of aluminum present in the solution, the nature of the metal surface to be treated, the temperature of the treatment solution and the duration of the treatment. The ions of at least one of the metals titanium, zirconium and hafnium can be introduced into the solution in the form of any compound which is soluble in the acidic aqueous medium, unless disturbing bath constituents are added. Suitable compounds are, for example, potassium fluorotitanate, titanium zirconium fluoride, fluozirconic acid, ammonium or alkali fluorozirconates, zirconium fluoride, zirconium sulfate and hafnium oxide and hafnium acids and salts, for example hafnium nitrate, fluoride or chloride. Alkali fluorozirconate, in particular potassium fluorozirconate (K 2 ZrF 6 ) is preferably used, especially since zirconium and fluorine are introduced at the same time. Although the concentration of ions of at least one of the metals titanium, zirconium and hafnium can range up to 1000 ppm, those in the range from 40 to 320 ppm are preferred. The most common concentration in the working bath is around 80 ppm.

Neben den vorgenannten Badbestandteilen enthält die Lösung Wasserstoffionen in einer solchen Menge, daß ein pH-Wert von 2 bis 5,5 resultiert. Bei pH-Werten oberhalb 5,5 wird keine sichtbare Behandlung bzw. Überzugsausbildung erhalten und demzufolge kein Korrosionsschutz geschaffen. Im allgemeinen läßt sich sagen, daß der einzustellende pH-Wert von der Behandlungsdauer, der Badtemperatur und beispielsweise dem Spritzdruck, aber auch von der Konzentration der anderen Badbestandteile abhängt. Als Leitlinie gilt, daß bei einer Behandlungszeit von 30 sec bis 1 min bei einer Badtemperatur von etwa 49°C und normalem Spritzdruck ein pH-Wert von 4,0 bis 4,5 besonders günstige Ergebnisse erzielen läßt.In addition to the aforementioned bath components, the solution contains hydrogen ions in such an amount that a pH of 2 to 5.5 results. At pH values above 5.5, no visible treatment or coating formation is obtained and consequently no corrosion protection is created. In general, it can be said that the pH to be set depends on the duration of the treatment, the bath temperature and, for example, the spray pressure, but also on the concentration of the other bath components. As a guideline, with a treatment time of 30 seconds to 1 minute at a bath temperature of about 49 ° C and normal spray pressure, a pH value of 4.0 to 4.5 can achieve particularly favorable results.

Die wäßrige Behandlungslösung wird üblicherweise aus einem Konzentrat durch Verdünnen mit Wasser erhalten. Sowohl Ansatz- als auch Ergänzungskonzentrat enthalten etwa 1 bis 25, vorzugsweise 2,5 bis 10, g/l Aluminium, 0,1 bis 5 g/1 Fluorid sowie in bevorzugter Ausführungsform bis 10 g/1 Titan, Zirkon und/oder Hafnium. Der pH-Wert des Konzentrates liegt in der Regel im Bereich von 0 bis 4.The aqueous treatment solution is usually obtained from a concentrate by dilution with water. Both the batch and the supplement concentrate contain about 1 to 25, preferably 2.5 to 10, g / l aluminum, 0.1 to 5 g / 1 fluoride and, in a preferred embodiment, up to 10 g / 1 Titanium, zircon and / or hafnium. The pH of the concentrate is usually in the range from 0 to 4.

Die wäßrige saure Behandlungslösung wird auf die Oberfläche von Eisen oder Stahl mit einer Temperatur von 26,7 bis 82°C, vorzugsweise von 32,2 bis 54°C zur Einwirkung gebracht. Die Behandlungsdauer kann 2 sec bis 5 min, vorzugsweise 5 sec bis 1 min, betragen. Der Kontakt der Metalloberfläche mit der Lösung kann im Tauchen, Fluten und insbesondere im Spritzen erfolgen. Die Spritzbehandlung ist auch deswegen von Vorteil, weil die konventionelle Waschbehandlung, in die das erfindungsgemäße Verfahren integriert werden kann, insbesondere wegen der Form der zu behandelnden Behälter und des erforderlichen gründlichen Kontaktes mit der Lösung in der Regel ohnehin als Spritzverfahren konzipiert ist.The aqueous acidic treatment solution is brought into contact with the surface of iron or steel at a temperature of 26.7 to 82 ° C., preferably 32.2 to 54 ° C. The treatment time can be 2 seconds to 5 minutes, preferably 5 seconds to 1 minute. The contact of the metal surface with the solution can take place in dipping, flooding and in particular in spraying. The spray treatment is also advantageous because the conventional washing treatment into which the method according to the invention can be integrated, in particular because of the shape of the containers to be treated and the necessary thorough contact with the solution, is generally designed as a spraying method anyway.

Die Durchführung des erfindungsgemäßen Verfahrens kann in der zweiten Stufe eines dreistufigen Waschverfahrens, in der dritten Stufe eines fünfstufigen Waschverfahrens oder in der vierten Stufe eines sechsstufigen Waschverfahrens erfolgen. Im Falle des sechsstufigen Waschverfahrens wird nach dem erfindungsgemäßen Verfahren der vierten Stufe in der fünften Stufe mit Wasser und in der sechsten Stufe mit vollentsalztem Wasser gespült, bevor die Trocknung im Umluftofen geschieht. Die Dauer des Kontaktes zwischen Metalloberfläche und Behandlungslösung ist weitgehend durch die Arbeitsweise der vorhandenen Anlage bestimmt. Auch bei der Einstellung der Behandlungstemperatur wird man sich üblicherweise nach den ansonsten in der Anlage herrschenden Behandlungstemperaturen richten.The process according to the invention can be carried out in the second stage of a three-stage washing process, in the third stage of a five-stage washing process or in the fourth stage of a six-stage washing process. In the case of the six-stage washing process, the fourth stage is rinsed with water in the fifth stage and with deionized water in the sixth stage before drying takes place in a forced air oven. The duration of the contact between the metal surface and the treatment solution is largely determined by the operation of the existing system. When setting the treatment temperature, too, you will usually follow the treatment temperatures otherwise prevailing in the system.

Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.

Beispiel 1example 1

Es wurde ein zur Verdünnung mit Wasser geeignetes Konzentrat, enthaltend

  • 6,5 g/1 Fluoborsäure (HBF4) 8 g/1 Kaliumfluorozirkonat (K2ZrF6) 130 g/1 Aluminiumsulfathydrat (Al2(SO4)3.14 H2 0 Rest Wasser

hergestellt. Der pH-Wert betrug ca. 0,7.It contained a concentrate suitable for dilution with water
  • 6.5 g / 1 fluoboric acid (HBF 4 ) 8 g / 1 potassium fluorozirconate (K 2 ZrF 6 ) 130 g / 1 aluminum sulfate hydrate (Al 2 (SO 4 ) 3 .14 H 2 0 balance water

produced. The pH was approximately 0.7.

Die Behandlungslösung wurde durch Zusatz von 3 1 des vorgenannten Konzentrates zu 140 1 Wasser gewonnen. Der pH-Wert wurde auf 3,8 bis 4,5 eingestellt.The treatment solution was obtained by adding 3 l of the aforementioned concentrate to 140 l of water. The pH was adjusted to 3.8 to 4.5.

Die Behandlung eines Schwarzblechbehälters erfolgte in einer fünfstufigen Waschanlage mit den Stufen alkalische Reinigung, Wasserspülung, Behandlung mit der obengenannten Behandlungslösung während einer Dauer von 1 min, Wasserspülung und Spülung mit vollentsalztem Wasser. Der so behandelte Behälter mit einem Rest Wasser im gewölbten Boden wurde dann bei 163°C getrocknet. An der Behälteroberfläche war kein Rost sichtbar.The treatment of a black sheet container was carried out in a five-stage washing plant with the stages of alkaline cleaning, water rinsing, treatment with the above-mentioned treatment solution for a period of 1 min, water rinsing and rinsing with demineralized water. The container treated in this way with a remainder of water in the curved bottom was then dried at 163 ° C. No rust was visible on the surface of the container.

Eine kontinuierliche Behandlungslinie für Schwarzblechdosen mit den gleichen Behandlungsstufen wie vorstehend wurde für eine halbe Stunde angehalten. Danach zeigten die Dosen in der Stufe 2 Anflug von Rost, wohingegen die Dosen in den Stufen 1, 3, 4 und 5 keinen sichtbaren Rost aufwiesen.A continuous treatment line for black tin cans with the same treatment steps as above was stopped for half an hour. Thereafter, the cans in level 2 showed signs of rust, whereas the cans in levels 1, 3, 4 and 5 showed no visible rust.

Beispiel 2Example 2

In einer Pilotanlage der im Beispiel 1 genannten Art wurden Schwarzblechdosen nach dem Verfahrensgang alkalische Reinigung, Wasserspülung, Kontaktieren mit einer wäßrigen Lösung, die 200 ppm Aluminium, 75 ppm HBF4, 80 ppm Zirkon enthielt und einen pH-Wert von 4,4 aufwies, Wasserspülung, Spülung mit vollentsalztem Wasser behandelt. Die einzelnen Behandlungstanks waren von praktisch gleicher Länge, so daß die Behandlungszeiten mit jeweils 40 sec praktisch gleich waren. Die Temperatur der in der dritten Stufe applizierten Lösung betrug 49°C.In a pilot plant of the type mentioned in Example 1, black tin cans were used after the alkaline cleaning process gung, water rinsing, contacting with an aqueous solution which contained 200 ppm aluminum, 75 ppm HBF 4 , 80 ppm zirconium and had a pH of 4.4, water rinsing, rinsing with deionized water. The individual treatment tanks were of practically the same length, so that the treatment times were practically the same at 40 seconds each. The temperature of the solution applied in the third stage was 49 ° C.

Bei einem Stillstand der Anlage über einen Zeitraum von 35 min zeigten die mit der wäßrigen sauren Behandlungslösung behandelten Dosen keinerlei Rost. Demgegenüber zeigten die noch nicht nach dem erfindungsgemäßen Verfahren behandelten, also lediglich gereinigten und gespülten Dosen nahezu sofort Rost.When the system was at a standstill for 35 minutes, the cans treated with the aqueous acid treatment solution showed no rust. In contrast, the cans which had not yet been treated by the process according to the invention, ie only cleaned and rinsed, showed rust almost immediately.

Beispiel 3Example 3

Schwarzblechdosen wurden nach dem Verfahrensgang gemäß Beispiel 2 behandelt mit der Ausnahme, daß der pH-Wert der wäßrigen sauren Lösung der Stufe 3 auf 3,5 eingestellt war. Nach der abschließenden Spülbehandlung wurden die Dosen während 3 min bei 193°C im Ofen getrocknet. Die Dosen zeigten eine braun-goldene Verfärbung, was dann nicht tolerierbar ist, wenn nur eine Endbehandlung mit einem Klarlack vorgesehen istBlack tin cans were treated according to the procedure of Example 2, except that the pH of the aqueous acidic solution of Step 3 was adjusted to 3.5. After the final rinse treatment, the cans were oven-dried for 3 minutes at 193 ° C. The cans showed a brown-golden discoloration, which is intolerable if only a final treatment with a clear varnish is provided

Beispiel 4Example 4

Es wurden Schwarzblechdosen wiederum nach dem Verfahrensgang gemäß Beispiel 2 behandelt mit der Ausnahme, daß der pH-Wert der sauren Behandlungslösung in Stufe 3 auf 5,5 eingestellt war. Nach der Ofentrocknung waren die Dosen glänzend und ohne wesentliche Verfärbung. Lediglich einige der Dosen zeigten lokale Verfärbungen an der Bodenwölbung, den Kanten und Berührungsflächen zweier benachbarter Dosen. Einige Dosen, die der Anlage vor der Ofentrocknung entnommen worden waren und daher feucht blieben, zeigten recht schnell Rost.Black tin cans were again treated according to the procedure of Example 2, with the exception that the pH of the acidic treatment solution in step 3 was set to 5.5. After drying in the oven, the cans were shiny and without significant discoloration. Only some of the cans showed local discolouration on the floor bulge, the edges and Contact surfaces of two neighboring cans. Some cans that had been removed from the system before the oven dried and therefore remained damp showed rust very quickly.

Beispiel 5Example 5

Nach dem Schema des Beispiels 1 wurde eine Reihe von Behandlungslösungen angesetzt, die sich hinsichtlich des Gehaltes von Titan, Zirkon, Hafnium unterschieden. Schließlich wurde als Kontrollösung eine Lösung hergestellt, die nur Fluorid enthielt und frei von Aluminium, Zirkon, Titan und Hafnium war. Bei den erstgenannten Lösungen wurde das Zirkon als Kaliumfluorozirkonat, das Hafnium als Hafniumdioxid (Hf02) und das Titan als Hexafluorotitansäure eingebracht. Bei einem Verfahrensgang entsprechend Beispiel 1 wurden Schwarzblechdosen in einem 19 1 fassenden Spritztank während 1 min bei 49°C behandelt. Sämtliche Behandlungslösungen hatten einen pH-Wert von 4,3 und einen Gehalt an Fluorid von 100 ppm (eingebracht als HBF4). Der Gehalt der Lösung an Aluminium sowie an Titan, Zirkon und/oder Hafnium (in ppm) sowie die erzielten Ergebnisse sind in der nachfolgenden Tabelle angegeben. Zur Bewertung sind das Aussehen des Dosenmantels und des Dosenbodens nach der Ofentrocknung herangezogen worden.

Figure imgb0001
According to the scheme of Example 1, a number of treatment solutions were prepared, which differed in the content of titanium, zirconium, hafnium. Finally, a solution was prepared as a control solution that contained only fluoride and was free of aluminum, zirconium, titanium and hafnium. In the former solutions, the zirconium was introduced as potassium fluorozirconate, the hafnium as hafnium dioxide (Hf02) and the titanium as hexafluorotitanic acid. In a procedure similar to Example 1, black tin cans were treated in a 19 liter spray tank for 1 min at 49 ° C. All treatment solutions had a pH of 4.3 and a fluoride content of 100 ppm (introduced as HBF 4 ). The aluminum and titanium, zirconium and / or hafnium content (in ppm) of the solution and the results obtained are shown in the table below. The appearance of the can jacket and the base of the can after drying in the oven were used for evaluation.
Figure imgb0001

Bei einem weiteren Vergleichsversuch wurden wäßrige Lösungen eingesetzt, die frei von Fluorid waren und bei einem pH-Wert von 4,3 lediglich Aluminiumionen in einer Menge von 250 ppm enthielten. Bei Anwesenheit von überschüssigem Wasser im gewölbten Dosenboden wurde während der Ofentrocknung ein Rosten des Bodens festgestellt.In a further comparison experiment, aqueous solutions were used which were free of fluoride and only contained aluminum ions in an amount of 250 ppm at a pH of 4.3. In the presence of excess water in the vaulted can base, rusting of the base was found during oven drying.

Beispiel 6Example 6

In diesem Beispiel wurde der Effekt des pH-Wertes auf das Aussehen der Dose bewertet, wobei zwei unterschiedliche Behandlungslösungen mit identischen Bedingungen hinsichtlich Kontaktzeit von 5 sec, Temperatur von 49°C und Fluoridkonzentration von 100 ppm (eingebracht als HBF4) zum Einsatz kamen. Eine dieser Lösung enthielt 200 ppm Aluminiumionen und keines der Metalle Titan, Zirkon und Hafnium. Die zweite Behandlungslösung hatte einen Gehalt von 50 ppm Zirkon und war frei von Aluminium.In this example, the effect of pH on the appearance of the can was assessed using two different treatments Solutions with identical conditions with regard to contact time of 5 sec, temperature of 49 ° C and fluoride concentration of 100 ppm (introduced as HBF 4 ) were used. One of these solutions contained 200 ppm aluminum ions and none of the metals titanium, zircon and hafnium. The second treatment solution contained 50 ppm zirconium and was free of aluminum.

Es wurden Korrosion und Aussehen der Dosen nach einem Anlagenstillstand bewertet. Die Ergebnisse sind in Tabelle 2 zusammengestellt.

Figure imgb0002
Aus Tabelle 2 ergibt sich, daß bei einer Behandlungsdauer von 5 sec die besten Resultate mit Behandlungslösungen mit einem pH-Wert von über 2 und unter 4,6, die Aluminium enthalten und frei von Zirkon sind, erhalten werden.Corrosion and appearance of the cans after a plant shutdown were assessed. The results are summarized in Table 2.
Figure imgb0002
 It can be seen from Table 2 that the best results are obtained with treatment solutions with a pH of more than 2 and less than 4.6, which contain aluminum and are free from zircon, with a treatment time of 5 seconds.

Mit einer Zirkon enthaltenden Behandlungslösung (frei von Aluminium) werden die besten Ergebnisse bei einem pH-Wert im Bereich von oberhalb 3 und unterhalb 5 erzielt.The best results are achieved with a zirconium-containing treatment solution (free of aluminum) at a pH in the range from above 3 to below 5.

Die vorstehenden Beispiele veranschaulichen deutlich den Einfluß von Fluorid bei der Vermeidung bzw. starken Verminderung des Rostens bei Schwarzblechdosen und die Wirksamkeit des Aluminiums bei der Verhinderung einer Verfärbung der behandelten Dose.The above examples clearly illustrate the influence of fluoride in preventing or greatly reducing rust in black tin cans and the effectiveness of aluminum in preventing discoloration of the treated can.

Claims (8)

1. Verfahren zur Behandlung von Metalloberflächen aus Eisen oder Stahl mit fluoridhaltigen Lösungen, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die Aluminiumionen und bis 200 ppm Fluoridionen enthält und die einen pH-Wert von 2 bis 5,5 aufweist.1. A process for the treatment of metal surfaces made of iron or steel with fluoride-containing solutions, characterized in that the metal surfaces are brought into contact with a solution which contains aluminum ions and up to 200 ppm fluoride ions and which has a pH of 2 to 5.5 . 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die zusätzlich bis 1000 ppm Ionen mindestens eines der Metalle Titan, Zirkon und/oder Hafnium enthält.2. The method according to claim 1, characterized in that the metal surfaces are brought into contact with a solution which additionally contains up to 1000 ppm ions of at least one of the metals titanium, zirconium and / or hafnium. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die 10 bis 5000, vorzugsweise 25 bis 250 ppm Aluminiumionen enthält.3. The method according to claim 1 or 2, characterized in that the metal surfaces are brought into contact with a solution which contains 10 to 5000, preferably 25 to 250 ppm, aluminum ions. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die mindestens 10 ppm Fluoridionen enthält.4. The method according to claim 1, 2 or 3, characterized in that the metal surfaces are brought into contact with a solution which contains at least 10 ppm of fluoride ions. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die maximal 150 ppm Fluoridionen enthält.5. The method according to one or more of claims 1 to 4, characterized in that the metal surfaces are brought into contact with a solution which contains a maximum of 150 ppm fluoride ions. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Lösung in Kontakt bringt, die 40 bis 320 ppm Ionen mindestens eines der Metalle Titan, Zirkon, Hafnium enthält.6. The method according to one or more of claims 1 to 5, characterized in that the metal surfaces are brought into contact with a solution which contains 40 to 320 ppm ions of at least one of the metals titanium, zirconium, hafnium. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Metalloberflächen bei einer Temperatur von 26,7 bis 82°C, vorzugsweise 32,2 bis 54°C, mit der Lösung in Kontakt bringt.7. The method according to one or more of claims 1 to 6, characterized in that the metal surfaces are brought into contact with the solution at a temperature of 26.7 to 82 ° C, preferably 32.2 to 54 ° C. 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Metalloberflächen für eine Dauer von 2 sec bis 5 min, vorzugsweise 5 sec bis 1 min, mit der Lösung in Kontakt bringt.8. The method according to one or more of claims 1 to 7, characterized in that the metal surfaces are brought into contact with the solution for a duration of 2 sec to 5 min, preferably 5 sec to 1 min.
EP85105917A 1984-05-18 1985-05-14 Process for the treatment of metal surfaces Expired EP0161667B1 (en)

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EP0410497A1 (en) * 1989-07-28 1991-01-30 METALLGESELLSCHAFT Aktiengesellschaft Process for the passivate rinsing of phosphate coatings
EP0459550A1 (en) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Process for rinsing conversion coatings
EP0459549A1 (en) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Production of conversion coatings on zinc or zinc alloy surfaces
US5294266A (en) * 1989-07-28 1994-03-15 Metallgesellschaft Aktiengesellschaft Process for a passivating postrinsing of conversion layers
WO1996030558A1 (en) * 1995-03-24 1996-10-03 Henkel Kommanditgesellschaft Auf Aktien Corrosion protective cleaning agent for tin-plated steel
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EP0356855A3 (en) * 1988-08-27 1990-11-14 Gerhard Collardin Gmbh Pretreatment of metallic surfaces to be coated with organic materials without using chromium
EP0410497A1 (en) * 1989-07-28 1991-01-30 METALLGESELLSCHAFT Aktiengesellschaft Process for the passivate rinsing of phosphate coatings
US5294266A (en) * 1989-07-28 1994-03-15 Metallgesellschaft Aktiengesellschaft Process for a passivating postrinsing of conversion layers
EP0459550A1 (en) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Process for rinsing conversion coatings
EP0459549A1 (en) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Production of conversion coatings on zinc or zinc alloy surfaces
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US4496404A (en) 1985-01-29
ES543711A0 (en) 1986-01-01

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