EP0161667B1 - Process for the treatment of metal surfaces - Google Patents
Process for the treatment of metal surfaces Download PDFInfo
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- EP0161667B1 EP0161667B1 EP85105917A EP85105917A EP0161667B1 EP 0161667 B1 EP0161667 B1 EP 0161667B1 EP 85105917 A EP85105917 A EP 85105917A EP 85105917 A EP85105917 A EP 85105917A EP 0161667 B1 EP0161667 B1 EP 0161667B1
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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 the corrosion-protective treatment of 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, after a coating treatment with a clear organic varnish or printing on the outer surface, make them suitable as attractive packaging.
- 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 into a cup and in deep drawing and smoothing to form the final shape.
- drawing lubricants such as water or aqueous emulsions that 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 oils, cooling lubricants and other contaminants are removed first in a cleaner with a low concentration and then in a cleaner with a higher concentration.
- the containers are then passed through one or more water rinse stages, whereupon they are completely dried in a drying oven.
- the outer surface is first provided with a basecoat or a decorative print and after drying with an outer layer of can lacquer. 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 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 10 to 5000 ppm aluminum ions, 10 to 200 ppm fluoride ions and up to 1000 ppm ions of at least one of the Contains metals titanium, zirconium and / or hafnium and which has a pH of 2 to 5.5.
- 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 may be above the solubility limit. 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 e.g. As boron, silicon, aluminum, zircon, hafnium and / or titanium can be used.
- a maximum fluoride concentration of 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.
- 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.
- the solution holds hydrogen ions in such an amount that a pH of 2 to 5.5 results.
- 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 batch and supplement concentrate contain about 1 to 25, preferably 2.5 to 10, g / 1 aluminum, 0.1 to 5 g / l fluoride and up to 10 g / 1 titanium, zirconium and / or hafnium.
- the pH of the concentrate is usually in the range from 0 to 4.
- the aqueous acidic treatment solution is applied to 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 process 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 spray process 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 used to rinse with water in the fifth stage and with deionized water in the sixth stage before drying takes place in a convection 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 pH was approximately 0.7.
- the treatment solution was obtained by adding 3 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 subjected to the alkaline cleaning, water rinsing, and 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 treated 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 according to Example 2, with the exception that the pH of the aqueous acidic solution of stage 3 was set to 3.5. After the final rinsing treatment, the cans were dried in an oven at 193 ° C. for 3 minutes. 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 in Example 2, with the exception that the pH of the acidic treatment solution was set to 5.5 in stage 3. After drying in the oven, the cans were shiny and without significant discoloration. Only some of the cans showed local discolouration on the floor curvature, 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 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 first-mentioned solutions, the zircon was introduced as potassium fluorozirconate, the hafnium as hafnium dioxide (Hf0 2 ) 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.
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- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur korrosionsschützenden Behandlung von Metalloberflächen aus Eisen und Stahl mit fluoridhaltigen Lösungen.The invention relates to a method for the corrosion-protective treatment of 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, after a coating treatment with a clear organic varnish or printing on the outer surface, make them suitable as attractive packaging.
Die Verfahrensfolge bei der Herstellung von Schwarzblechbehältern besteht üblicherweise im Abwickeln des mit einer Schutzölschichtversehenen 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, Schutzöle, 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 into a cup and in deep drawing and smoothing to form the final shape. In addition, cooling lubricants such as water or aqueous emulsions that 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 oils, cooling lubricants and other contaminants are removed first in a cleaner with a low concentration and then in a cleaner with a higher concentration. The containers are then passed through one or more water rinse stages, whereupon they are completely dried in a drying oven. This is followed by a one- 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 lacquer. 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.When manufacturing 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. Inadvertent stoppage of the production line, where the containers remain in the 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 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 10 bis 5000 ppm Aluminiumionen, 10 bis 200 ppm Fluoridionen und bis 1000 ppm Ionen mindestens eines der Metalle Titan, Zirkon und/oder Hafnium 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 10 to 5000 ppm aluminum ions, 10 to 200 ppm fluoride ions and up to 1000 ppm ions of at least one of the Contains metals titanium, zirconium and / or hafnium and which has a pH of 2 to 5.5.
Zwar ist es bekannt, auf Metalloberflächen saure Lösungen, die Fluorid in Form komplexer Verbindungen, wie BF4-, TiFs 2-, SiF6 2-, A1F6 3-, und heterozyklische Stickstoffverbindung enthalten [JP-A-59-74 281, CA 101 (1984) 59039b] oder aber saure Pasten, die u.a. Aluminiumverbindung und Fluorid enthalten (EP-A-58 257) aufzubringen. Jedoch werden hierbei gänzlich andersartige Ziele verfolgt. Im ersten Fall sollen Zinn oder Zinnlegierungen von Kupfersubstraten entfernt werden. Im zweiten Fall ist beabsichtigt, Metalloberflächen von Oxid- oder Zunderschichten zu befreien.It is known that acidic solutions on metal surfaces which contain fluoride in the form of complex compounds such as BF 4 , TiF s 2 , SiF 6 2 , A1F 6 3 and heterocyclic nitrogen compound [JP-A-59-74 281 , CA 101 (1984) 59039b] or acidic pastes which contain, inter alia, aluminum compound and fluoride (EP-A-58 257). However, completely different goals are pursued here. In the first case, tin or tin alloys should be removed from copper substrates. In the second case, the intention is to remove oxide or scale layers from metal surfaces.
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, kann ggf. über der Löslichkeitsgrenze liegen. 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 may be above the solubility limit. 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. Eine Fluoridkonzentration von maximal 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.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 e.g. As boron, silicon, aluminum, zircon, hafnium and / or titanium can be used. A maximum fluoride concentration of 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.
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 Kalimfluorozirkonat (K2ZrF6) wird bevorzugt eingesetzt, zumal hierdurch Zirkon und Fluor gleichzeitig eingebracht werden.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.
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.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 holds 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 around 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/1 Aluminium, 0,1 bis 5 g/I Fluorid sowie 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 batch and supplement concentrate contain about 1 to 25, preferably 2.5 to 10, g / 1 aluminum, 0.1 to 5 g / l fluoride and up to 10 g / 1 titanium, zirconium 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 intergriert 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 applied to 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 process 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 spray process 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 used to rinse with water in the fifth stage and with deionized water in the sixth stage before drying takes place in a convection 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.
Es wurde ein zur Verdünnung mit Wasser geeignetes Konzentrat, enthaltend
- 6,5 g/I Fluorborsäure (HBF4)
- 8 g/1 Kaliumfluorozirkonat (K2ZrF6)
- 130 g/1 Aluminiumsulfathydrat (Al2(SO4)3. 14 H20 Rest Wasser
- 6.5 g / l fluoroboric acid (HBF 4 )
- 8 g / 1 potassium fluorozirconate (K 2 ZrF 6 )
- 130 g / 1 of aluminum sulfate hydrate (Al 2 (SO 4) 3. 14, H 2 0 balance water
Die Behandlungslösung wurde durch Zusatz von 3 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 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.
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 subjected to the alkaline cleaning, water rinsing, and 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 treated 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.
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 ist.Black tin cans were treated according to the procedure according to Example 2, with the exception that the pH of the aqueous acidic solution of stage 3 was set to 3.5. After the final rinsing treatment, the cans were dried in an oven at 193 ° C. for 3 minutes. The cans showed a brown-golden discoloration, which is intolerable if only a final treatment with a clear varnish is provided.
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 in Example 2, with the exception that the pH of the acidic treatment solution was set to 5.5 in stage 3. After drying in the oven, the cans were shiny and without significant discoloration. Only some of the cans showed local discolouration on the floor curvature, 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.
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.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 first-mentioned solutions, the zircon was introduced as potassium fluorozirconate, the hafnium as hafnium dioxide (Hf0 2 ) 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.
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. Es wurden Korrosion und Aussehen der Dosen nach einem Anlagenstillstand bewertet. Die Ergebnisse sind in Tabelle 2 zusammengestellt.In this example, the effect of pH on the appearance of the can was evaluated, using two different treatment solutions with identical conditions with regard to contact time of 5 seconds, temperature of 49 ° C. and fluoride concentration of 100 ppm (introduced as HBF 4 ). 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. Corrosion and appearance of the cans after a plant shutdown were assessed. The results are summarized in Table 2.
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.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 of zircon, with a treatment duration 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)
Priority Applications (1)
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AT85105917T ATE38254T1 (en) | 1984-05-18 | 1985-05-14 | METHOD OF TREATMENT OF METAL SURFACES. |
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US611663 | 1984-05-18 | ||
US06/611,663 US4496404A (en) | 1984-05-18 | 1984-05-18 | Composition and process for treatment of ferrous substrates |
Publications (2)
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EP0161667A1 EP0161667A1 (en) | 1985-11-21 |
EP0161667B1 true EP0161667B1 (en) | 1988-10-26 |
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US (1) | US4496404A (en) |
EP (1) | EP0161667B1 (en) |
JP (1) | JPS60255986A (en) |
AT (1) | ATE38254T1 (en) |
AU (1) | AU576574B2 (en) |
BR (1) | BR8502349A (en) |
CA (1) | CA1264538A (en) |
DE (2) | DE3565863D1 (en) |
ES (1) | ES543711A0 (en) |
GB (1) | GB2158845B (en) |
MX (1) | MX164560B (en) |
NZ (1) | NZ212007A (en) |
ZA (1) | ZA853561B (en) |
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JP2541269B2 (en) * | 1987-08-27 | 1996-10-09 | 日本板硝子株式会社 | Method of manufacturing oxide thin film |
DE3829154A1 (en) * | 1988-08-27 | 1990-03-01 | Collardin Gmbh Gerhard | CHROME-FREE METHOD FOR PRE-TREATING METALLIC SURFACES BEFORE COATING WITH ORGANIC MATERIALS |
US5073196A (en) * | 1989-05-18 | 1991-12-17 | Henkel Corporation | Non-accelerated iron phosphating |
DE4017187A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | METHOD FOR REFILLING CONVERSION LAYERS |
DE3924984A1 (en) * | 1989-07-28 | 1991-01-31 | Metallgesellschaft Ag | METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS |
DE4017186A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | GENERATION OF CONVERSION OVERHEADS ON ZINC OR ZINC ALLOY SURFACES |
US5294266A (en) * | 1989-07-28 | 1994-03-15 | Metallgesellschaft Aktiengesellschaft | Process for a passivating postrinsing of conversion layers |
BE1005463A3 (en) * | 1990-11-03 | 1993-08-03 | Glaverbel | Production reflecting objects. |
KR100292447B1 (en) * | 1991-08-30 | 2001-06-01 | 웨인 씨. 제쉬크 | Method of forming protective modified coating on metal substrate surface |
US5281282A (en) * | 1992-04-01 | 1994-01-25 | Henkel Corporation | Composition and process for treating metal |
SG54220A1 (en) * | 1992-04-01 | 1998-11-16 | Henkel Corp | Composition and process for treating metal |
DE19510825A1 (en) * | 1995-03-24 | 1996-09-26 | Henkel Kgaa | Anticorrosive cleaner for tinned steel |
US5641542A (en) * | 1995-10-11 | 1997-06-24 | Betzdearborn Inc. | Chromium-free aluminum treatment |
US5840772A (en) * | 1996-09-18 | 1998-11-24 | Ppg Industries, Inc. | Methods of recycling and compositions used therein |
JP4099307B2 (en) * | 2000-04-20 | 2008-06-11 | 日本ペイント株式会社 | Non-chromium anti-rust treatment agent for aluminum, anti-rust treatment method and anti-rust treated aluminum products |
KR100466418B1 (en) * | 2000-11-25 | 2005-01-13 | 주식회사 포스코 | Tin plate with good sulphide stain protection, corrosion resistance and paintability, and a method for manufacturing it |
US7611588B2 (en) * | 2004-11-30 | 2009-11-03 | Ecolab Inc. | Methods and compositions for removing metal oxides |
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GB947658A (en) * | 1960-07-25 | 1964-01-22 | Polychrome Corp | Planographic printing plate and method for preparing same |
US3160506A (en) * | 1962-10-19 | 1964-12-08 | Polychrome Corp | Planographic printing plate and method for preparing same |
US3539403A (en) * | 1966-12-07 | 1970-11-10 | Collardin Gmbh Gerhard | Solutions for the deposition of protective layers on zinc surfaces and process therefor |
US3539402A (en) * | 1967-02-16 | 1970-11-10 | Collardin Gmbh Gerhard | Solutions for the deposition of protective surface layers on iron and zinc and process therefor |
DE1933013C3 (en) * | 1969-06-28 | 1978-09-21 | Gerhard Collardin Gmbh, 5000 Koeln | Process for the production of protective layers on aluminum, iron and zinc by means of solutions containing complex fluorides |
US4017334A (en) * | 1973-10-04 | 1977-04-12 | Oxy Metal Industries Corporation | Process for treating aluminum cans |
FR2417537A1 (en) * | 1978-02-21 | 1979-09-14 | Parker Ste Continentale | COMPOSITION BASED ON HAFNIUM TO INHIBIT CORROSION OF METALS |
US4273592A (en) * | 1979-12-26 | 1981-06-16 | Amchem Products, Inc. | Coating solution for metal surfaces |
US4370177A (en) * | 1980-07-03 | 1983-01-25 | Amchem Products, Inc. | Coating solution for metal surfaces |
DE3105508A1 (en) * | 1981-02-14 | 1982-09-02 | Metallgesellschaft Ag, 6000 Frankfurt | Stain and rust removal paste for metals |
US4457790A (en) * | 1983-05-09 | 1984-07-03 | Parker Chemical Company | Treatment of metal with group IV B metal ion and derivative of polyalkenylphenol |
-
1984
- 1984-05-18 US US06/611,663 patent/US4496404A/en not_active Expired - Lifetime
-
1985
- 1985-05-07 CA CA000480961A patent/CA1264538A/en not_active Expired - Lifetime
- 1985-05-07 NZ NZ212007A patent/NZ212007A/en unknown
- 1985-05-09 AU AU42230/85A patent/AU576574B2/en not_active Ceased
- 1985-05-10 ZA ZA853561A patent/ZA853561B/en unknown
- 1985-05-14 DE DE8585105917T patent/DE3565863D1/en not_active Expired
- 1985-05-14 ES ES543711A patent/ES543711A0/en active Granted
- 1985-05-14 DE DE19853517280 patent/DE3517280A1/en not_active Withdrawn
- 1985-05-14 EP EP85105917A patent/EP0161667B1/en not_active Expired
- 1985-05-14 AT AT85105917T patent/ATE38254T1/en not_active IP Right Cessation
- 1985-05-15 GB GB08512285A patent/GB2158845B/en not_active Expired
- 1985-05-17 JP JP60105722A patent/JPS60255986A/en active Pending
- 1985-05-17 BR BR8502349A patent/BR8502349A/en not_active IP Right Cessation
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Publication number | Publication date |
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US4496404A (en) | 1985-01-29 |
CA1264538A (en) | 1990-01-23 |
GB2158845A (en) | 1985-11-20 |
JPS60255986A (en) | 1985-12-17 |
EP0161667A1 (en) | 1985-11-21 |
AU4223085A (en) | 1985-11-21 |
MX164560B (en) | 1992-08-26 |
NZ212007A (en) | 1988-09-29 |
GB2158845B (en) | 1987-11-04 |
ATE38254T1 (en) | 1988-11-15 |
ZA853561B (en) | 1985-12-24 |
DE3517280A1 (en) | 1985-11-28 |
DE3565863D1 (en) | 1988-12-01 |
ES8603589A1 (en) | 1986-01-01 |
BR8502349A (en) | 1986-01-21 |
GB8512285D0 (en) | 1985-06-19 |
AU576574B2 (en) | 1988-09-01 |
ES543711A0 (en) | 1986-01-01 |
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