EP0158287A2 - Process for treating aluminium surfaces - Google Patents

Process for treating aluminium surfaces Download PDF

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Publication number
EP0158287A2
EP0158287A2 EP85104110A EP85104110A EP0158287A2 EP 0158287 A2 EP0158287 A2 EP 0158287A2 EP 85104110 A EP85104110 A EP 85104110A EP 85104110 A EP85104110 A EP 85104110A EP 0158287 A2 EP0158287 A2 EP 0158287A2
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EP
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Prior art keywords
aluminum
coating
treatment liquid
water
aluminum alloy
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EP85104110A
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German (de)
French (fr)
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EP0158287B1 (en
EP0158287A3 (en
Inventor
Atsunori C/O Nihon Parkerizing. Ltd Yoshida
Hideaki C/O Nihon Parkerizing. Ltd Kaneko
Takao C/O Nihon Parkerizing. Ltd Ogino
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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Priority to AT85104110T priority Critical patent/ATE51039T1/en
Publication of EP0158287A2 publication Critical patent/EP0158287A2/en
Publication of EP0158287A3 publication Critical patent/EP0158287A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—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 solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic

Definitions

  • the invention relates to a method for the surface treatment of aluminum or aluminum alloys by means of an aqueous treatment liquid containing hexafluorosilicate.
  • a special case of the surface treatment of aluminum or aluminum alloys is the treatment of fins on heat exchangers, especially air conditioning units.
  • Most heat exchangers are designed for the purpose of increasing the heat output or the cooling effect in such a way that the heat-emitting or cooling surfaces are as large as possible.
  • the distance between the individual slats is chosen to be extremely small. If the heat exchanger is used for cooling purposes, atmospheric moisture condenses on the surface of the heat exchanger, in particular in the fins. Each The more hydrophobic the fin surfaces are, the easier the condensed water forms water drops, which clog the fin gaps, increase the resistance to air and thus reduce the heat exchange rate.
  • Another disadvantage is that the water droplets sticking in the lamellar gaps are blown into the air by the fan of the heat exchanger and are easily pressed out of the water collecting container attached at the bottom of the device. If necessary, the surroundings of the heat exchanger can be sprayed with water.
  • the silica particles or calcium carbonate particles are covered by the resin, so that the surface of the solid particles, which in themselves have hydrophilic properties, is shielded. A sufficiently hydrophilic layer cannot therefore be achieved.
  • the surface-active substance is easily washed off by water.
  • the methods according to 2. and 3. result in a hydrophilic coating, but have the disadvantage of poor adhesion and easy detachment.
  • the parts on the surface loosen easily and result in an easily swirlable powder.
  • they have the defect that the water glass, the lithium silicate, etc. is partially dissolved by the water condensed on a part of the heat exchanger, collects at the bottom of the fins, dries when the air conditioner is at a standstill and is whirled up as a powder when the device is restarted.
  • the object of the invention is to provide a process which avoids the disadvantages of the known processes, in particular those mentioned above, and with the aid of which it is possible to produce a uniform coating with good adhesive properties on surfaces of aluminum or aluminum alloys, which has a permanently hydrophilic property at a high surface Corrosion resistance mediates, and that works with a treatment liquid of increased duration.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid which contains complex-bound fluoride in the form of SiF 6 and additionally free fluoride and as an effective one Components contains.
  • a preferred embodiment of the invention consists in bringing the surface of aluminum or aluminum alloys into contact with a treatment liquid which acts as effective components contains.
  • concentrations of the active components are important insofar as, if the concentrations are too high, some of the components are only adsorptive on the surface is bound and is therefore easy to wipe off. In addition, the process becomes uneconomical in terms of costs. If, on the other hand, the concentrations of the individual components are too low, the individual components dissolve easily in the treatment liquid, but the speed of the coating formation decreases and the adhesion of the coating formed decreases.
  • the zinc concentration below 0.2 g / l the coating formation is slow and thus the layer formation is time-consuming.
  • the iron ions are less than 0.05 g / l, the adhesion of the coating will decrease. In particular, it is then difficult to form a coating with very good adhesion of more than 5 gjm2 of coating weight.
  • the components of the treatment liquid are normally added in the form of their soluble salts. They are present in the treatment liquid as salts or complex salts. Since some of these components have low solubility, the treatment liquids will generally be in the form of suspensions.
  • the zinc and iron components are most conveniently introduced via the fluorides, as a result of which the or some of the fluoride components are also introduced at the same time. If an iron pan is used as the container for the treatment liquid, a separate addition of iron salt may be dispensed with, provided that sufficient iron ions are supplied from the iron pan to the solution.
  • Sodium, potassium and lithium are generally used as the alkali metal.
  • Silicon and fluorine are the main components of the treatment liquid.
  • the fluorine ions etch the surface of the aluminum or aluminum alloy and accelerate the chemical reaction. They are also an integral part of the coating formed on contact with the treatment liquid. It generally contains 70% by weight Na 3 AlF 6 , 20% by weight Zn, 9% by weight Fe, balance Si.
  • the coating produced by the process according to the invention has a coating weight of generally 0.1-10 g / m 2 .
  • oxidizing agents which should not be introduced into the treatment liquid, are, for example, nitrate, chlorate, bromate, nitrite and organic nitro compounds.
  • a temperature of the treatment liquid of 40 - 100 ° C and a treatment time of at least 5 s is recommended for the treatment of the surface of aluminum or aluminum alloy.
  • the concentration of hydrogen ions in the treatment liquid corresponding to a pH value of 4-5 is optimal.
  • the pH is adjusted with acidic fluorides, hydrofluoric acid or - if the active components introduced lead to an acidic dispersion or solution - with caustic soda.
  • the contact between the metal surface and the treatment liquid takes place in a conventional manner, e.g. by dipping, flooding, spraying or roller application.
  • the coating of hydrophilic property and good corrosion resistance obtained in this way can be subjected to an aftertreatment with a solution containing chromate or chromic acid. This in particular improves the corrosion resistance even further.
  • the coating produced by the method according to the invention has the advantage, among other things, that it offers little resistance to sliding friction. If a certain coating weight is set, it is suitable as a lubricating layer for the cold forming of aluminum products.
  • the lubricating layer for plastic deformation must have good adhesion. Otherwise, damage to the material or the finished product can easily occur. Malfunctions can also occur if the material to be deformed gets caught in the deformation tools.
  • a coating weight of the lubricating layer for the plastic deformation or the cold deformation of 2-10 g / m 2 is required. To achieve even better lubrication performance, you can treat with lubricants such as metal soaps or lubricating oils.
  • the hydrophilic coating formed by the process according to the invention allows the condensed water to run off easily, so that the formation of water drops on the surface of the heat exchanger is made more difficult and the air resistance is reduced. This improves the heat exchange rate.
  • a suitable range of the coating weight is chosen, which is generally less than that of an intended plasti deformation. If - according to a preferred embodiment of the invention - rinsing with chromium VI-containing solutions is intended, the fermentable rinsing solutions can be used. This can be done, for example, by immersing in a treatment solution with 5 - 0.001% by weight chromic acid or spraying with such solutions. If necessary, a water rinse can follow.
  • the coating produced by the method according to the invention leads to dust nuisance when a heat exchanger is installed and in the initial phase of operation. Unlike conventional coatings, moisture and condensation do not affect the coating. An environmental impact both in the production area and during operation is prevented.
  • a treatment liquid was prepared so that the content was 6.8 g / l Na, 4.1 g / 1 Si, 17.1 g / 1 F, 0.77 g / l Zn and 0.5 g / l Fe at pH 4-5 gave.
  • Degreased and cleaned aluminum material A 1100 was immersed in the treatment liquid placed in a stainless steel tub and heated to 60 ° C for 10 sec, 15 sec, 30 sec, 1 min, 3 min, 5 min and 7 min, then rinsed with water and dried after draining the water. A uniform ash-gray coating was created.
  • the contact angle of a drop of water on the top area of the coated aluminum material measured with a goniometer.
  • corrosion resistance up to the formation of 5% "white rust” in hours was tested according to salt water spray test JIS-Z-2371 and the adhesion of the coating.
  • cellophane adhesive strips (Cellotape, Wz) were stuck on, then torn off and the percentage detachment of the coating determined. The results are shown in the table.
  • Aluminum material processed according to implementation examples 1-4 was immersed in a treatment solution with 1.5 g / l chromic acid (Parcolene 60 A from Nihon Parkerizing, Wz) at 50 ° C. bath temperature for 30 seconds after the coating had been formed. Then it was washed with water and dried after the water had run out. The same tests were carried out as in the aforementioned implementation examples. The test results are shown in the table.
  • 1.5 g / l chromic acid Parcolene 60 A from Nihon Parkerizing, Wz
  • the contact angle of a drop of water, the corrosion resistance and the coating adhesion were tested. The test results are shown in the table.
  • Aluminum material A 1100 was merely cleaned and then subjected to the aforementioned tests for determining the contact angle, the corrosion resistance and the coating adhesion. The results are shown in the table.
  • a temperature of 60 ° C. previously degreased and cleaned aluminum material A 5052 was immersed for 1, 3 or 5 minutes under the conditions of implementation example 1, then rinsed with water and dried after the water had run off.
  • Coatings with a coating weight of approx. 2.5 g / m 2 , approx. 5 g / m 2 and approx. 6 g / m 2 were formed , the adhesion of which was lower than when iron-containing treatment liquids were used. Removal of the coating occurred during deformation.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • ing And Chemical Polishing (AREA)
  • Conductive Materials (AREA)
  • Cookers (AREA)
  • Materials For Medical Uses (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

A composition and process useful in forming films on the surface of aluminum or its alloys is disclosed. The composition is an aqueous solution containing an alkali metal, silicon, fluorine, zinc and iron. The film is an adherent hydrophilic corrosion resistant film useful as such and/or as a lubricating film in metal forming.

Description

Die Erfindung betrifft ein Verfahren zur Oberflächenbehandlung von Aluminium oder Aluminiumlegierungen mittels einer Hexafluorosilikat enthaltenden wässrigen Behandlungsflüssigkeit.The invention relates to a method for the surface treatment of aluminum or aluminum alloys by means of an aqueous treatment liquid containing hexafluorosilicate.

Es gibt eine Vielzahl von Verfahren für die Oberflächenbehandlung von Aluminium oder Aluminiumlegierungen, die insbesondere auf die Vermittlung eines hohen Korrosionswiderstandes und eines dekorativen Aussehens zielen. Neben Verfahren mit anodischer Oxydation haben insbesondere Chromatierverfahren große Bedeutung erlangt.There are a large number of processes for the surface treatment of aluminum or aluminum alloys, which aim in particular to impart a high level of corrosion resistance and a decorative appearance. In addition to processes with anodic oxidation, chromating processes in particular have become very important.

Ein Spezialfall der Oberflächenbehandlung von Aluminium oder Aluminiumlegierungen besteht in der Behandlung von Lamellen von Wärmeaustauschern, insbesondere von Klimageräten. Hierbei ist jedoch ein zusätzlicher, sich aus den nachfolgenden Darlegungen ergebender Gesichtspunkt von besonderer Bedeutung. Die meisten Wärmeaustauscher sind zum Zwecke der Steigerung der Wärmeabgabe oder des Kühleffektes derart ausgelegt, daß die wärmeabgebenden oder kühlenden Flächen möglichst groß sind. Der Abstand zwischen den einzelnen Lamellen wird äußerst klein gewählt. Wird der Wärmeaustauscher zu Kühlzwecken verwendete kondensiert Luftfeuchtigkeit auf der Oberfläche des Wärmeaustauschers, insbesondere in den Lamellenspalten. Je hydrophober die Lamellenoberflächen sind, desto leichter bildet das Kondenswasser Wassertropfen, die die Lamellenspalten verstopfen, den Durchtrittswiderstand für Luft erhöhen und damit die Wärmeaustauschrate senken. Ein weiterer Nachteil ist, daß die in den Lamellenspalten haftenden Wassertropfen vom Ventilator des Wärmeaustauschers in die Luft geblasen und leicht aus dem im Gerät unten angebrachten Wasserauffangbehälter herausgedrückt werden. Gegebenenfalls kann dadurch die Umgebung des Wärmetauschers naßgespritzt werden.A special case of the surface treatment of aluminum or aluminum alloys is the treatment of fins on heat exchangers, especially air conditioning units. However, an additional point of view resulting from the following explanations is of particular importance. Most heat exchangers are designed for the purpose of increasing the heat output or the cooling effect in such a way that the heat-emitting or cooling surfaces are as large as possible. The distance between the individual slats is chosen to be extremely small. If the heat exchanger is used for cooling purposes, atmospheric moisture condenses on the surface of the heat exchanger, in particular in the fins. Each The more hydrophobic the fin surfaces are, the easier the condensed water forms water drops, which clog the fin gaps, increase the resistance to air and thus reduce the heat exchange rate. Another disadvantage is that the water droplets sticking in the lamellar gaps are blown into the air by the fan of the heat exchanger and are easily pressed out of the water collecting container attached at the bottom of the device. If necessary, the surroundings of the heat exchanger can be sprayed with water.

Auch bei Verwendung für Heizzwecke setzt sich im Winter an im Freien stehenden Geräten Reif-, Tau- und Nebelfeuchtigkeit an, welche die Heizwirkung verschlechtert. Von Zeit zu Zeit wird daher der Betrieb des Wärmeaustauschers umgekehrt, d.h. das im Freien stehende Gerät beheizt und die Feuchtigkeit beseitigt. Eine solche kurzzeitige und wirksame Beseitigung der Feuchtigkeit ist für die Funktion von kühlenden und heizenden Klimanalage unabdingbar.Even when used for heating purposes, frost, dew and fog moisture builds up on outdoor devices in winter, which worsens the heating effect. The operation of the heat exchanger is therefore reversed from time to time, i.e. the device is heated outdoors and the moisture is removed. Such a short-term and effective removal of moisture is essential for the function of cooling and heating air conditioning.

Um die Feuchtigkeit rasch zu entfernen, ist es deshalb wirkungsvoll, die Lamellenoberflächen der kühlenden Teile des Wärmeaustauschers hydrophil zu gestalten. Gleichzeitig wird dadurch das Sickervermögen des Wassers gesteigert. Eine alleinige Behandlung der Steigerung des Sickervermögens reicht jedoch im Hinblick auf den erforderlichen Korrosionsschutz nicht aus.In order to remove the moisture quickly, it is therefore effective to make the fin surfaces of the cooling parts of the heat exchanger hydrophilic. At the same time, the seepage capacity of the water is increased. Simply treating the increase in seepage capacity is not sufficient in terms of the required corrosion protection.

Bisher bekannte Verfahren, Lamellen von Wärmeaustauschern eine hydrophile Oberfläche zu verleihen, sind insbesondere:

  • 1. Einen Polymerharzüberzug zu bilden, der Kieselerdepartikel, Kalziumkarbonat oder ein oberflächenaktives Mittel enthält;
  • 2. auf einen durch anodische Oxydation erzeugten Überzug, einen Böhmitüberzug, einen Harzüberzug oder einen Chromatüberzug Wasserglas, Lithiumsilicat oder Kieselerdekolloid aufzutragen;
  • 3. unmittelbar auf die Aluminiumoberfläche Wasserglas, Lithiumsilikat, Kieselerdekolloid oder dergleichen aufzutragen.
Previously known methods of imparting a hydrophilic surface to fins of heat exchangers are in particular:
  • 1. Form a polymer resin coating containing silica particles, calcium carbonate or a surfactant;
  • 2. to apply water glass, lithium silicate or silica colloid to a coating produced by anodic oxidation, a boehmite coating, a resin coating or a chromate coating;
  • 3. Apply water glass, lithium silicate, silica colloid or the like directly to the aluminum surface.

Bei Mischüberzügen entsprechend 1. werden die Kieselerdepartikel oder Kalziumkarbonatpartikel durch das Harz bedeckt, so daß die Oberfläche der festen Partikel, die an sich hydrophile Eigenschaften besitzen, abgeschirmt wird. Eine ausreichend hydrophile Schicht läßt sich daher nicht erzielen. Bei Harzüberzügen mit oberflächenaktiven Stoffen wird der oberflächenaktive Stoff leicht durch Wasser abgewaschen. Die Verfahren entsprechend 2. und 3. ergeben zwar einen hydrophilen Überzug, haben aber den Nachteil schlechter Haftung und leichten Ablösens. Insbesondere lösen sich die an der Oberfläche befindlichen Teile leicht und ergeben ein leicht aufwirbelbares Pulver. Weiterhin haben sie den Mangel, daß das Wasserglas, das Lithiumsilikat usw. durch das an einem Teil des Wärmeaustauschers kondensierte Wasser teilweise gelöst wird, sich unten an den Lamellen sammelt, bei Stillstand des Klimagerätes antrocknet und bei Wiederinbetriebnahme des Gerätes als Pulver aufgewirbelt wird.In the case of mixed coatings corresponding to 1., the silica particles or calcium carbonate particles are covered by the resin, so that the surface of the solid particles, which in themselves have hydrophilic properties, is shielded. A sufficiently hydrophilic layer cannot therefore be achieved. In the case of resin coatings with surface-active substances, the surface-active substance is easily washed off by water. The methods according to 2. and 3. result in a hydrophilic coating, but have the disadvantage of poor adhesion and easy detachment. In particular, the parts on the surface loosen easily and result in an easily swirlable powder. Furthermore, they have the defect that the water glass, the lithium silicate, etc. is partially dissolved by the water condensed on a part of the heat exchanger, collects at the bottom of the fins, dries when the air conditioner is at a standstill and is whirled up as a powder when the device is restarted.

Aufgabe der Erfindung ist es, ein Verfahren bereitzustellen, das die Nachteile der bekannten, insbesondere vorgenannten Verfahren vermeidet und mit dessen Hilfe es gelingt, auf Oberflächen von Aluminium oder Aluminiumlegierungen einen gleichmäßigen Überzug mit guter Hafteigenschaft zu erzeugen, der der Oberfläche dauerhaft hydrophile Eigenschaft bei hoher Korrosionsbeständigkeit vermittelt, und das mit einer Behandlungsflüssigkeit erhöhter Einsatzdauer arbeitet.The object of the invention is to provide a process which avoids the disadvantages of the known processes, in particular those mentioned above, and with the aid of which it is possible to produce a uniform coating with good adhesive properties on surfaces of aluminum or aluminum alloys, which has a permanently hydrophilic property at a high surface Corrosion resistance mediates, and that works with a treatment liquid of increased duration.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man die Oberfläche von Aluminium oder Aluminiumlegierung mit einer Behandlungsflüssigkeit in Kontakt bringt, die komplex gebundenes Fluorid in Form von SiF6 sowie zusätzlich freies Fluorid und als wirksame Bestandteile

Figure imgb0001
enthält.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid which contains complex-bound fluoride in the form of SiF 6 and additionally free fluoride and as an effective one Components
Figure imgb0001
 contains.

Eine bevorzugte Ausführung der Erfindung besteht darin, die Oberfläche von Aluminium oder Aluminiumlegierungen mit einer Behandlungsflüssigkeit in Kontakt zu bringen, die als wirksame Bestandteile

Figure imgb0002
enthält.A preferred embodiment of the invention consists in bringing the surface of aluminum or aluminum alloys into contact with a treatment liquid which acts as effective components
Figure imgb0002
 contains.

Die Konzentrationen der wirksamen Bestandteile sind insofern von Bedeutung als bei zu hohen Konzentrationen ein Teil der Komponenten nur adsorptiv-auf der Oberfläehe gebunden wird und daher leicht abwischbar ist. Außerdem wird das Verfahren kostenmäßig unwirtschaftlich. Wenn hingegen die Konzentrationen der einzelnen Bestandteile zu gering sind, lösen sich die einzelnen Komponenten zwar leicht in der Behandlungsflüssigkeit auf, doch nimmt die Geschwindigkeit der Überzugsausbildung ab und die Haftung des gebildeten Überzuges läßt nach.The concentrations of the active components are important insofar as, if the concentrations are too high, some of the components are only adsorptive on the surface is bound and is therefore easy to wipe off. In addition, the process becomes uneconomical in terms of costs. If, on the other hand, the concentrations of the individual components are too low, the individual components dissolve easily in the treatment liquid, but the speed of the coating formation decreases and the adhesion of the coating formed decreases.

Liegt z.B. die Zinkkonzentration unter 0,2 g/l, ist die Überzugsausbildung langsam und damit die Schichtausbildung zeitaufwendig. Machen andererseits die Eisenionen weniger als 0,05 g/1 aus, läßt die Haftung des Überzuges nach. Insbesondere ist es dann schwierig, einen Überzug sehr guter Haftung von mehr als 5 gjm2 Überzugsgewicht zu bilden.For example, the zinc concentration below 0.2 g / l, the coating formation is slow and thus the layer formation is time-consuming. On the other hand, if the iron ions are less than 0.05 g / l, the adhesion of the coating will decrease. In particular, it is then difficult to form a coating with very good adhesion of more than 5 gjm2 of coating weight.

Die Komponenten der Behandlungsflüssigkeit werden normalerweise in Form ihrer löslichen Salze zugesetzt. Sie liegen in der Behandlungsfüssigkeit als Salze oder Komplexsalze vor. Da ein Teil dieser Komponenten geringe Löslichkeit besitzt, werden die Behandlungsflüssigkeiten im allgemeinen in Form von Suspensionen vorliegen.The components of the treatment liquid are normally added in the form of their soluble salts. They are present in the treatment liquid as salts or complex salts. Since some of these components have low solubility, the treatment liquids will generally be in the form of suspensions.

Die Einbringung der Zink- und Eisenkomponente geschieht am zweckmäßigsten über die Fluoride, wodurch gleichzeitig auch die oder ein Teil der Fluoridkomponente eingebracht wird. Sofern man als Behälter für die Behandlungsflüssigkeit eine Eisenwanne verwendet, kann gegebenenfalls auf eine gesonderte Zugabe von Eisensalz verzichtet werden, sofern aus der Eisenwanne hinreichend viel Eisenionen in die Lösung geliefert werden.The zinc and iron components are most conveniently introduced via the fluorides, as a result of which the or some of the fluoride components are also introduced at the same time. If an iron pan is used as the container for the treatment liquid, a separate addition of iron salt may be dispensed with, provided that sufficient iron ions are supplied from the iron pan to the solution.

Als Alkalimetall dient im allgemeinen Natrium, Kalium und Lithium.Sodium, potassium and lithium are generally used as the alkali metal.

Silicium und Fluor sind die Hauptbestandteile der Behandlungsflüssigkeit. Die Fluorionen ätzen die Oberfläche des Aluminiums bzw. der Aluminiumlegierung und beschleunigen die chemische Reaktion. Sie sind auch wesentlicher Bestandteil des beim Kontakt mit der Behandlungsflüssigkeit gebildeten Überzuges. Er enthält im allgemeinen 70 Gew.% Na3AlF6, 20 Gew.% Zn, 9 Gew.% Fe, Rest Si. Der mit dem erfindungsgemäßen Verfahren erzeugte Überzug weist ein Überzugsgewicht von im allgemeinen 0,1 - 10 g/m 2 auf.Silicon and fluorine are the main components of the treatment liquid. The fluorine ions etch the surface of the aluminum or aluminum alloy and accelerate the chemical reaction. They are also an integral part of the coating formed on contact with the treatment liquid. It generally contains 70% by weight Na 3 AlF 6 , 20% by weight Zn, 9% by weight Fe, balance Si. The coating produced by the process according to the invention has a coating weight of generally 0.1-10 g / m 2 .

Besondere Effekte hinsichtlich Überzugsausbildung werden erzielt, wenn - in weiterer vorteilhafter Ausgestaltung der Erfindung - man die Oberfläche von Aluminium oder Aluminiumlegierung mit einer Behandlungsflüssigkeit in Kontakt bringt, die frei von Oxydationsmitteln ist. Derartige Oxydationsmittel, die nicht in die Behandlungsflüssigkeit eingebracht werden sollten, sind beispielsweise Nitrat, Chlorat, Bromat, Nitrit und organische Nitroverbindungen.Special effects with regard to coating formation are achieved if - in a further advantageous embodiment of the invention - the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid which is free from oxidizing agents. Such oxidizing agents, which should not be introduced into the treatment liquid, are, for example, nitrate, chlorate, bromate, nitrite and organic nitro compounds.

Für die Behandlung der Oberfläche von Aluminium oder Aluminiumlegierung empfiehlt sich eine Temperatur der Behandlungsflüssigkeit von 40 - 100°C und eine Behandlungsdauer von mindestens 5 s. Die Konzentration der Wasserstoffionen in der Behandlungsflüssigkeit entsprechend einem pH-Wert von 4 - 5 ist optimal. Die Einstellung des pH-Wertes erfolgt mit sauren Fluoriden, Fluorwasserstoffsäure oder - falls die eingebrachten wirksamen Komponenten zu einer zu sauren Dispersion oder Lösung fuhren - mit Ätznatron.A temperature of the treatment liquid of 40 - 100 ° C and a treatment time of at least 5 s is recommended for the treatment of the surface of aluminum or aluminum alloy. The concentration of hydrogen ions in the treatment liquid corresponding to a pH value of 4-5 is optimal. The pH is adjusted with acidic fluorides, hydrofluoric acid or - if the active components introduced lead to an acidic dispersion or solution - with caustic soda.

Der Kontakt zwischen Metalloberfläche und Behandlungsflüssigkeit erfolgt auf herkömmliche Weise, z.B. durch Tauchen, Fluten, Spritzen oder Rollenauftrag.The contact between the metal surface and the treatment liquid takes place in a conventional manner, e.g. by dipping, flooding, spraying or roller application.

Im Anschluß an die Aufbringung des Überzuges wird üblicherweise gespült, um überschüssige Behandlungsflüssigkeit zu entfernen. Der auf diese Weise erhaltene Überzug von hydrophiler Eigenschaft sowie guter Korrosionsbeständigkeit kann in weiterer vorteilhafter Ausführung der Erfindung eine Nachbehandlung mit einer Chromat- oder Chromsäure-enthaltenen Lösung unterworfen werden. Hierdurch wird insbesondere die Korrosionsbeständigkeit nochmals verbessert.Following application of the coating, rinsing is usually carried out to remove excess treatment liquid. In a further advantageous embodiment of the invention, the coating of hydrophilic property and good corrosion resistance obtained in this way can be subjected to an aftertreatment with a solution containing chromate or chromic acid. This in particular improves the corrosion resistance even further.

Der mit dem erfindungsgemäßen Verfahren erzeugte Überzug besitzt unter anderem den Vorteil, daß er einer gleitenden Reibung wenig Widerstandskraft entgegensetzt. Bei Einstellung eines bestimmten Überzugsgewichts ist er als Schmierschicht für die Kaltverformung von Aluminiumerzeugnissen geeignet. Dabei muß die Schmierschicht für die plastische Verformung eine gute Haftfähigkeit besitzen. Andernfalls können leicht Beschädigungen am Material bzw. am fertigen Erzeugnis entstehen. Es kann auch zu Störungen dadurch kommen, daß das zu verformende Material in den Verformungswerkzeugen hängen bleibt. Im allgemeinen ist ein Überzugsgewicht der Schmierschicht für die plastische Verformung bzw. die Kaltverformung von 2 - 10 g/m2 erforderlich. Um noch bessere Schmierungsleistungen zu erzielen, kann mit Schmiermitteln, wie Metallseifen oder Schmierölen, nachbehandelt werden.The coating produced by the method according to the invention has the advantage, among other things, that it offers little resistance to sliding friction. If a certain coating weight is set, it is suitable as a lubricating layer for the cold forming of aluminum products. The lubricating layer for plastic deformation must have good adhesion. Otherwise, damage to the material or the finished product can easily occur. Malfunctions can also occur if the material to be deformed gets caught in the deformation tools. In general, a coating weight of the lubricating layer for the plastic deformation or the cold deformation of 2-10 g / m 2 is required. To achieve even better lubrication performance, you can treat with lubricants such as metal soaps or lubricating oils.

Der mit dem erfindungsgemäßen Verfahren gebildete hydrophile Überzug läßt das kondensierte Wasser leicht ablaufen, so daß die Bildung von Wassertropfen auf der Oberfläche des Wärmeaustauschers erschwert und der Luftdurchgangswiderstand vermindert werden. Hierdurch wird die Wärmeaustauschrate verbessert. Auch in diesem Falle wählt man einen geeigneten Bereich des Überzugsgewichts, der im allgemeinen geringer als bei einer vorgesehenen plastischen Verformung liegen wird. Sofern - entsprechend einer bevorzugten Ausgestaltung der Erfingung - eine Nachspülung mit Chrom VI-enthaltenden Lösungen beabsichtigt ist, können die gärgigen Nachspüllösungen verwendet werden. Dies geschient z.B. durch Eintauchen in eine Behandlungslösung mit 5 - 0,001 Gew.% Chromsäure oder eine Spritzbehandlung mit derartigen Lösungen. Gegebenenfalls kann sich eine Wasserspülung anschließen.The hydrophilic coating formed by the process according to the invention allows the condensed water to run off easily, so that the formation of water drops on the surface of the heat exchanger is made more difficult and the air resistance is reduced. This improves the heat exchange rate. In this case too, a suitable range of the coating weight is chosen, which is generally less than that of an intended plasti deformation. If - according to a preferred embodiment of the invention - rinsing with chromium VI-containing solutions is intended, the fermentable rinsing solutions can be used. This can be done, for example, by immersing in a treatment solution with 5 - 0.001% by weight chromic acid or spraying with such solutions. If necessary, a water rinse can follow.

Infolge seiner hervorragenden Haftung wird vermieden, daß der nach dem erfindungsgemäßen Verfahren erzeugte Überzug bei der Montage eines Wärmeaustauschers und in der Anfangsphase des Betriebes zu Staubbelästigungen führt. Anders als bei herkömmlichen Überzügen beeinträchtigen Feuchtigkeit und Kondenswasser den Überzug nicht. Eine Umweltbeeinträchtigung sowohl im Fertigungsbereich als auch während des Betriebes werden verhindert.As a result of its excellent adhesion, it is avoided that the coating produced by the method according to the invention leads to dust nuisance when a heat exchanger is installed and in the initial phase of operation. Unlike conventional coatings, moisture and condensation do not affect the coating. An environmental impact both in the production area and during operation is prevented.

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:

Durchführungsbeispiele 1 - 7Implementation examples 1 - 7

Es wurde eine Behandlungsflüssigkeit angesetzt, so daß sich ein Gehalt von 6,8 g/l Na, 4,1 g/1 Si, 17,1 g/1 F, 0,77 g/l Zn und 0,5 g/l Fe bei pH 4-5 ergab. In die in eine Edelstahlwanne gegebene und auf 60°C erwärmte Behandlungsflüssigkeit wurde zuvor entfettetes und gereinigtes Aluminiummaterial A 1100 jeweils für 10 sec, 15 sec, 30 sec, 1 min, 3 min, 5 min und 7 min eingetaucht, alsdann mit Wasser gespült und nach Ablaufen des Wassers getrocknet. Es entstand ein gleichmäßiger aschgrauer Überzug.A treatment liquid was prepared so that the content was 6.8 g / l Na, 4.1 g / 1 Si, 17.1 g / 1 F, 0.77 g / l Zn and 0.5 g / l Fe at pH 4-5 gave. Degreased and cleaned aluminum material A 1100 was immersed in the treatment liquid placed in a stainless steel tub and heated to 60 ° C for 10 sec, 15 sec, 30 sec, 1 min, 3 min, 5 min and 7 min, then rinsed with water and dried after draining the water. A uniform ash-gray coating was created.

Zur Ermittlung der hydrophilen Eigenschaften des Überzuges wurde der Randwinkel eines Wassertropfens auf der Ober- fläche des beschichteten Aluminiummaterials mit einem Goniometer gemessen. Außerdem wurde die Korrosionsbeständigkeit bis zur Bildung von 5 % "weißem Rost" in Stunden gemäß Salzwassersprühtest JIS-Z-2371 sowie die Haftung des Überzuges getestet. Zur Ermittlung der Haftung wurden Zellophanklebstreifen (Cellotape, Wz) aufgeklebt, dann abgerissen und die prozentuale Ablösung des Überzuges ermittelt. Die Ergebnisse zeigt die Tabelle.To determine the hydrophilic properties of the coating, the contact angle of a drop of water on the top area of the coated aluminum material measured with a goniometer. In addition, the corrosion resistance up to the formation of 5% "white rust" in hours was tested according to salt water spray test JIS-Z-2371 and the adhesion of the coating. To determine the adhesion, cellophane adhesive strips (Cellotape, Wz) were stuck on, then torn off and the percentage detachment of the coating determined. The results are shown in the table.

Durchführungsbeispiele 8 - 11Implementation examples 8 - 11

Nach den Durchführungsbeispielen 1 - 4 bearbeitetes Aluminiummaterial wurde nach der Überzugsausbildung in eine Behandlungslösung mit 1,5 g/1 Chromsäure (Parcolene 60 A der Nihon Parkerizing, Wz) bei 50°C Badtemperatur für 30 sec eingetaucht. Dann wurde mit Wasser gewaschen und nach Ablaufen des Wassers getrocknet. Es wurden die gleichen Versuche wie in den vorgenannten Durchführungsbeispielen vorgenommen. Die Versuchsergebnisse sind der Tabelle zu entnehmen.Aluminum material processed according to implementation examples 1-4 was immersed in a treatment solution with 1.5 g / l chromic acid (Parcolene 60 A from Nihon Parkerizing, Wz) at 50 ° C. bath temperature for 30 seconds after the coating had been formed. Then it was washed with water and dried after the water had run out. The same tests were carried out as in the aforementioned implementation examples. The test results are shown in the table.

Durchführungsbeispiele 12 - 17Implementation examples 12 - 17

Jeweils nach den oben beschriebenen Durchführungsbeispielen 4 - 7 behandeltes Aluminiummaterial wurde nach Überzugsausbildung in ein Schmiermittel mit Hauptbestandteil Natronseife (Bonderlube 235 der Nihon Parkerizing, Wz) bei 70°C für 1 - 2 min eingetaucht und dadurch etwa 10 g/m2 Schmiermittel aufgetragen. Danach erfolgte eine Kaltverformung zu Zylindern mit dem Ergebnis, daß jeweils Produkte mit einwandfreien Oberflächen erhalten wurden und daß ein Verkleben in den Verformungswerkzeugen praktisch nicht auftrat.In each case, aluminum material treated according to implementation examples 4-7 described above was immersed in a lubricant with a main component of sodium soap (Bonderlube 235 from Nihon Parkerizing, Wz) at 70.degree. C. for 1-2 minutes and thereby applied about 10 g / m 2 of lubricant. This was followed by cold forming into cylinders, with the result that products with perfect surfaces were obtained in each case and that there was practically no sticking in the forming tools.

Vergleichsbeispiel 1Comparative Example 1

Es wurde eine Behandlungsflüssigkeit entsprechend der von Durchführungsbeispiel 1, aus der das Eisen weggelassen war, benutzt und diese in eine Edelstahlwanne gefüllt. Bei einer Temperatur von 60°C wurde unter den Bedingungen des Durchführungsbeispiels 1 zuvor entfettetes und gereinigtes Aluminiummaterial A 1100 für 30 sec eingetaucht und ein Überzug gebildet. Ebenso wie in dem genannten Durchführungsbeispiel wurden der Randwinkel eines Wassertropfens, die Korrosionsbeständigkeit und die Überzugshaftung getestet. Die Versuchsergebnisse sind der Tabelle zu entnehmen.A treatment liquid corresponding to that of the implementation example 1, from which the iron was omitted, was used and this was filled into a stainless steel tub. At the temperature of 60 ° C., under the conditions of Implementation Example 1, previously degreased and cleaned aluminum material A 1100 was immersed for 30 seconds and a coating was formed. As in the implementation example mentioned, the contact angle of a drop of water, the corrosion resistance and the coating adhesion were tested. The test results are shown in the table.

Vergleichsbeispiel 2Comparative Example 2

Es wurde eine Behandlungsflüssigkeit entsprechend der von Durchführungsbeispiel 1, aus der das Zink weggelassen war, benutzt und diese in eine Edelstahlwanne gefüllt. Bei einer Badtemperatur von 60°C wurde unter den Bedingungen des Durchführungsbeispiels 1 zuvor entfettetes und gereinigtes Aluminiummaterial A 1100 für 15 min eingetaucht und ein Überzug gebildet. Die Ergebnisse der gleichen Tests wie im vorbeschriebenen Vergleichsbeispiel sind in der Tabelle angeführt.A treatment liquid corresponding to that of the implementation example 1, from which the zinc was omitted, was used and this was filled into a stainless steel tub. At a bath temperature of 60 ° C., previously degreased and cleaned aluminum material A 1100 was immersed for 15 minutes under the conditions of implementation example 1 and a coating was formed. The results of the same tests as in the comparative example described above are shown in the table.

Vergleichsbeispiel 3Comparative Example 3

Aluminiummaterial A 1100 wurde lediglich gereinigt und alsdann den vorgenannten Tests zur Bestimmung des Randwinkels, der Korrosionsbeständigkeit und der Überzugshaftung unterworfen. Die Ergebnisse enthält die Tabelle.Aluminum material A 1100 was merely cleaned and then subjected to the aforementioned tests for determining the contact angle, the corrosion resistance and the coating adhesion. The results are shown in the table.

Vergleichsbeispiel 4Comparative Example 4

Eine Behandlungsflüssigkeit mit der Zusammensetzung entsprechend Durchführungsbeispiel 1, bei der das Eisen weggelassen war, wurde in eine Edelstahlwanne gefüllt. Bei einer Temperatur von 60°C wurde unter den Bedingungen des Durchführungsbeispiels l zuvor entfettetes und gereinigtes Aluminiummaterial A 5052 jeweils für 1, 3 oder 5 min eingetaucht, dann mit Wasser gespült und nach Ablaufen des Wassers getrocknet. Es entstanden Überzüge eines Überzugs- gewichtes von ca. 2,5 g/m2, ca. 5 g/m2 und ca. 6 g/m2, deren Haftung geringer als bei Einsatz eisenenthaltender Behandlungsflüssigkeiten war. Bei Verformung traten Ablösungen des Überzuges auf.A treatment liquid having the composition according to the implementation example 1, in which the iron was omitted, was filled in a stainless steel tub. At a temperature of 60 ° C., previously degreased and cleaned aluminum material A 5052 was immersed for 1, 3 or 5 minutes under the conditions of implementation example 1, then rinsed with water and dried after the water had run off. Coatings with a coating weight of approx. 2.5 g / m 2 , approx. 5 g / m 2 and approx. 6 g / m 2 were formed , the adhesion of which was lower than when iron-containing treatment liquids were used. Removal of the coating occurred during deformation.

Die Nachbehandlung mit ca. 10 g/m2 Schmiermittel mit Hauptbestandteil Natronseife und die Kaltverformung, jeweils entsprechend Durchführungsbeispiel 12, führten zu dem Ergebnis, daß Beschädigungen an der Oberfläche des Aluminiummaterials auftraten. Darüber hinaus blieben an den Verformungswerkzeugen abgelöste Überzüge hängen, was eine häufige Reinigung erforderlich machte.

Figure imgb0003
The aftertreatment with about 10 g / m 2 of lubricant with the main constituent of sodium soap and the cold working, in each case in accordance with implementation example 12, led to the result that damage to the surface of the aluminum material occurred. In addition, detached coatings remained on the forming tools, which necessitated frequent cleaning.
Figure imgb0003

Claims (6)

l. Verfahren zur Oberflächenbehandlung von Aluminium oder Aluminiumlegierungen mittels einer Hexafluorosilikat enthaltenden wässrigen Behandlungsflüssigkeit, dadurch gekennzeichnet, daß man die Oberfläche von Aluminium oder Aluminiumlegierung mit einer Behandlungsflüssigkeit in Kontakt bringt, die komplex gebundenes Fluorid in Form von SiF6 sowie zusätzlich freies Fluorid und als wirksame Bestandteile
Figure imgb0004
enthält.l. Process for the surface treatment of aluminum or aluminum alloys by means of an aqueous treatment liquid containing hexafluorosilicate, characterized in that the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid which contains complex-bound fluoride in the form of SiF 6 and additionally free fluoride and as active constituents
Figure imgb0004
 contains. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Oberfläche von Aluminium oder Aluminiumlegierung mit einer Behandlungsflüssigkeit in Kontakt bringt, die
Figure imgb0005
enthält.2. The method according to claim 1, characterized in that the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid which
Figure imgb0005
 contains. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Oberfläche von Aluminium oder Aluminiumlegierung mit einer Behandlungsflüssigkeit in Kontakt bringt, die frei von Oxydationsmitteln ist.3. The method according to claim 1 or 2, characterized in that the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid which is free of oxidizing agents. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Oberfläche von Aluminium oder Aluminiumlegierung mit einer Behandlungsflüssigkeit bei einer Temperatur von 40 - 100°C während mindestens 5 sec in Kontakt bringt.4. The method according to claim 1, 2 or 3, characterized in that the surface of aluminum or aluminum alloy is brought into contact with a treatment liquid at a temperature of 40-100 ° C for at least 5 seconds. 5. Verfahren nach einem oder mehreren der Ansprüche 1 - 4, dadurch gekennzeichnet, daß man die Oberfläche von Aluminium oder Aluminiumlegierung in einer nachfolgenden Stufe mit einer Chrom VI enthaltenden Lösung nachbehandelt.5. The method according to one or more of claims 1-4, characterized in that the surface of aluminum or aluminum alloy is post-treated in a subsequent step with a chromium VI-containing solution. 6. Verfahren nach einem oder mehreren der Ansprüche 1 - 4, dadurch gekennzeichnet, daß man die Oberfläche von Aluminium oder Aluminiumlegierung in einer nachfolgenden Stufe mit Schmiermittel nachbehandelt.6. The method according to one or more of claims 1-4, characterized in that the surface of aluminum or aluminum alloy is aftertreated in a subsequent step with lubricant.
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US4650525A (en) 1987-03-17
PT80260B (en) 1987-03-16
AU4096885A (en) 1985-10-17
CA1240454A (en) 1988-08-16
DK163825B (en) 1992-04-06
PT80260A (en) 1985-05-01
ES8605869A1 (en) 1986-04-01
JPS60215772A (en) 1985-10-29
BR8501664A (en) 1985-12-10
AU577580B2 (en) 1988-09-29
GB2157325B (en) 1987-05-28
NZ211723A (en) 1988-02-12
EP0158287A3 (en) 1987-05-06

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