EP0103234A2 - Process for densifying anodically produced oxide layers on aluminium or aluminium alloys - Google Patents
Process for densifying anodically produced oxide layers on aluminium or aluminium alloys Download PDFInfo
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- EP0103234A2 EP0103234A2 EP83108560A EP83108560A EP0103234A2 EP 0103234 A2 EP0103234 A2 EP 0103234A2 EP 83108560 A EP83108560 A EP 83108560A EP 83108560 A EP83108560 A EP 83108560A EP 0103234 A2 EP0103234 A2 EP 0103234A2
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
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- the invention relates to a method for compacting anodically produced oxide layers on aluminum or aluminum alloys by treatment with aqueous solutions at elevated temperatures, the occurrence of disruptive aluminum hydroxide coatings (sealing coatings) on the surfaces being prevented.
- Anodically produced oxide layers are often applied to aluminum surfaces for the purpose of corrosion protection. These oxide layers protect the aluminum surfaces from the effects of weather and other corrosive media. Furthermore, the anodic oxide layers are also applied in order to obtain a harder surface and thus to achieve increased wear resistance of the aluminum. Due to the intrinsic color of the oxide layers and their partially easy coloring, particularly decorative effects can be achieved. 1
- anodic oxide layers on aluminum For applying.
- the oxide layers are produced with direct current in solutions of sulfuric acid (direct current-sulfuric acid method).
- These layers can be subsequently colored by dipping in solutions of a suitable dye or by alternating current treatment in an electrolyte containing metal salts.
- solutions of organic acids such as, in particular, sulfophthalic acid, are also frequently used for the application of the oxide layers or sulfanilic acid or these mixed with sulfuric acid. The latter methods are known as color anodization methods.
- these anodically applied oxide layers do not meet all requirements with regard to corrosion protection, since they have a porous structure. For this reason, it is necessary to densify the oxide layers. This densification is often carried out with hot or boiling water and referred to as "sealing". This closes the pores and thus significantly increases the protection against corrosion.
- the so-called sealing coating is formed on the entire surface.
- This consists of hydrated aluminum oxide and is not touch-proof, so that the decorative effect of the layer is adversely affected. It also reduces the adhesive strength when gluing such aluminum parts and, due to the increased effective surface area, promotes later contamination and corrosion. For these reasons, it was previously necessary to remove the covering by hand, mechanically or chemically.
- the object of the present invention is to further improve the previous methods of operation and to make them even safer in order to arrive at an improved method for compacting anodic oxide layers on aluminum or aluminum alloys.
- phosphinocarboxylic acids used in the process according to the invention can be prepared by known processes.
- reaction products of hypophosphorous acid are used, such as those used in the reaction with acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, maleic acid, glutaronic acid, citraconic acid, itaconic acid, 2-butene-2-carboxylic acid, dimethyl maleic acid, 2-methylene glutaric acid, butene polycarboxylic acids and ethylene tetracarboxylic acids, ethylene tetracarboxylic acids, ethylene tetracarboxylic acids and ethylene tetracarboxylic acids, ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids Cinnamic acid are created.
- reaction products with hypophosphorous acid derived from higher unsaturated carboxylic acids can also be used.
- their use in terms of optimal bath management becomes increasingly complex.
- their water-soluble salts in which all or part of the acidic protons have been replaced, for example, by alkali metal, ammonium, alkaline earth metal, alkylammonium or alkanolammonium ions, can also be used for carrying out the process.
- the salts are used in an amount that corresponds to 0.0005 to 0.5 g / 1 of the free acids.
- a preferred embodiment of the method is that the compression is carried out in solutions which contain the reaction products formed in the addition of 2-8 molecules of acrylic acid to the two PH functions of the hypophosphorous acid or their water-soluble salts in an amount of 0.0005 to 0.5 g / 1 included.
- a further embodiment of the method consists in that the compression is carried out in solutions which contain the reaction products obtained in the reaction of maleic acid with hypophosphorous acid or their water-soluble salts.
- the solutions of the acids or salts according to the invention are adjusted to a pH of 4 to 8, preferably 5 to 6. This setting can be made with ammonia or acetic acid.
- the compression with the solutions according to the invention is carried out at temperatures between 90 ° C. and the boiling point. In general, a temperature of 95 to 100 ° C is maintained.
- the compression time is within the usual range and is approximately 1.5 to 3.5 min / ⁇ m layer thickness of the anodic oxide layer.
- Additives known per se, such as nickel or cobalt acetate, can also be added to the compression solutions for this purpose in small amounts between 0.0001 and 0.5 g / l.
- the new process makes it possible to prevent the formation of sealing deposits without the anodic oxide layer is impaired or the quality of compaction is reduced. Due to the special properties of the active ingredients used, the risk of unintentional harmful overdosing is greatly reduced. Rinsing after compaction or spraying to remove any residue from the surface is not required. The appearance of the surface is not influenced by the method according to the invention; the effects that were achieved by pretreatment and anodization are retained.
- the designation of the aluminum alloys was made in accordance with DIN 1725.
- the quality of the oxide layers was determined by the apparent conductance or y-value according to DIN 50 949 and by the loss factor d according to ISO / TC 79 / SC2 (ALL-1) Doc. 65 E.
- the quality of the compression was also checked using the chromophosphoric acid test (ISO 3210).
- Al 99.5 An alkaline degreased and pickled aluminum sheet (Al 99.5) was compressed after the anodic oxidation using the direct current sulfuric acid method (layer thickness 20 ⁇ m) in a solution containing 0.01 g / 1 of a reaction product of 2 mol maleic acid in deionized water Contained 1 mol of hypophosphorous acid and adjusted to pH 5.8 with ammonia.
- the reaction product of 2 moles of maleic acid with 1 mole of hypophosphorous acid was prepared by adding 45 g of sodium hypophosphite monohydrate to 100 g of maleic acid dissolved in 250 ml of water. The reaction mixture was heated to 60 ° C and 8 g of ammonium persulfate in small portions over 4 hours let drip in water. The reaction e g Mixing was maintained for 2 more hours at 60 ° C. The solution thus obtained was used for the experiments without isolation of the reaction product, the active substance content resulting from the raw materials used.
- the anodized aluminum was densified for 60 min. performed at 98 ° C. After that, the sheets showed no sealing coating. The layer thickness remained unchanged at 20 ⁇ m. The dielectric loss factor was 0.42 and the admittance had dropped from over 400 to 12.5 ⁇ S. A weight loss of 12.9 mg / dm 2 was found in the chromophosphoric acid test.
- Alkaline degreased and pickled profiles made of the alloy AlMgSi 0.5 were anodized using the direct current sulfuric acid-oxalic acid method (layer thickness 19 ⁇ m) and colored bronze electrolytically in a tin-containing coloring electrolyte. The profiles were then compacted for a time corresponding to 3 min / ⁇ m layer thickness at 98 ° C. in a solution adjusted to pH 6.0, which solution had been obtained in deionized water 0.001 g / l of a reaction product of hypophosphorous acid with 8 mol of acrylic acid.
- Profiles made from the alloy AlMgSi 0.5 degreased and pickled by the usual method were anodized using the direct current sulfuric acid method (layer thickness 18-21 ⁇ m). These were at a pH Value of 5.8 (adjusted with ammonia or acetic acid) in solutions which contain the reaction products of hypophosphorous acid with itaconic acid, citraconic acid or 1-butene-2,3,4-tricarboxylic acid listed in the table - prepared according to that in Example 1 mentioned processes - contained in the specified amounts, at 97 - 100 ° C for 60 min. condensed.
- the table shows the deposit-preventing effect and the 'influence of the substances' on the layer quality, expressed according to the results of the admittance measurement of the dielectric loss factor and the weight loss in the chromium-phosphoric acid test.
- the sealing coating is prevented and the layer quality is not impaired.
- Comparative experiments with cyclohexane hexacarboxylic acid and phosphonobutane-2,3,4-tricarboxylic acid were included in the table, which show that, although the sealing coating is prevented in the comparison substances, severe layer damage occurs even at the higher concentrations.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zum Verdichten von anodisch erzeugten Oxidschichten auf Aluminium oder Aluminiumlegierungen durch Behandlung mit wäßrigen Lösungen bei erhöhten Temperaturen, wobei das Auftreten von störenden Aluminiumhydroxidbelägen (Sealingbelägen) auf den Oberflächen verhindert wird.The invention relates to a method for compacting anodically produced oxide layers on aluminum or aluminum alloys by treatment with aqueous solutions at elevated temperatures, the occurrence of disruptive aluminum hydroxide coatings (sealing coatings) on the surfaces being prevented.
Auf Aluminiumoberflächen werden zum Zwecke des Korrosionsschutzes vielfach anodisch erzeugte Oxidschichten aufgebracht. Diese Oxidschichten schützen die Aluminiumoberflächen vor den Einflüssen der Witterung und anderer korrodierender Medien. Ferner werden die anodischen Oxidschichten auch aufgebracht, um eine härtere Oberfläche zu erhalten und damit eine erhöhte Verschleißfestigkeit des Aluminiums zu erreichen. Durch die Eigenfarbe der Oxidschichten bzw. ihre teilweise leichte Einfärbbarkeit lassen sich besonders dekorati- .ve Effekte erzielen. 1Anodically produced oxide layers are often applied to aluminum surfaces for the purpose of corrosion protection. These oxide layers protect the aluminum surfaces from the effects of weather and other corrosive media. Furthermore, the anodic oxide layers are also applied in order to obtain a harder surface and thus to achieve increased wear resistance of the aluminum. Due to the intrinsic color of the oxide layers and their partially easy coloring, particularly decorative effects can be achieved. 1
Für das Aufbringen von. anodischen Oxidschichten auf Aluminium sind eine Reihe von Verfahren bekannt. Beispielsweise erfolgt die Erzeugung der Oxidschichten mit Gleichstrom in Lösungen von Schwefelsäure (Gleichstrom-Schwefelsäure-Verfahren).For applying. A number of methods are known for anodic oxide layers on aluminum. For example, the oxide layers are produced with direct current in solutions of sulfuric acid (direct current-sulfuric acid method).
Diese Schichten können durch Tauchen in Lösungen eines geeigneten Farbstoffes oder durch eine Wechselstrombehandlung in einem metallsalzhaltigen Elektrolyten nachträglich eingefärbt werden. Häufig werden für das Aufbringen der Oxidschichten jedoch auch Lösungen organischer Säuren, wie insbesondere Sulfophtalsäure bzw. Sulfanilsäure oder aber diese im Gemisch mit Schwefelsäure, verwendet. Die zuletzt genannten Verfahren sind als Farbanodisationsverfahrenbekarint.These layers can be subsequently colored by dipping in solutions of a suitable dye or by alternating current treatment in an electrolyte containing metal salts. However, solutions of organic acids, such as, in particular, sulfophthalic acid, are also frequently used for the application of the oxide layers or sulfanilic acid or these mixed with sulfuric acid. The latter methods are known as color anodization methods.
Diese anodisch aufgebrachten Oxidschichten erfüllen aber nicht alle Anforderungen im Hinblick auf den Korrosionsschutz, da sie eine poröse Struktur aufweisen. Aus diesem Grunde ist es erforderlich, die Oxidschichten nachzuverdichten. Diese Nachverdichtung wird vielfach mit heißem bzw. siedendem Wasser vorgenommen und als "Sealing" bezeichnet. Hierdurch werden die Poren verschlossen und damit der Korrosionsschutz erheblich erhöht.However, these anodically applied oxide layers do not meet all requirements with regard to corrosion protection, since they have a porous structure. For this reason, it is necessary to densify the oxide layers. This densification is often carried out with hot or boiling water and referred to as "sealing". This closes the pores and thus significantly increases the protection against corrosion.
Bei der Nachverdichtung anodisch aufgebrachter Oxidschichten werden aber nicht nur die Poren verschlossen, sondern es bildet sich auch- auf der gesamten Fläche ein mehr oder weniger starker samtartiger Belag, der sogenannte Sealingbelag. Dieser besteht aus hydratisiertem Aluminiumoxid und ist nicht griffest, so daß der dekorative Effekt der Schicht hierdurch beeinträchtigt wird. Ferner vermindert er die Haftfestigkeit bei der verklebung solcher Aluminiumteile und fördert durch die vergrößerte effektive Oberfläche spätere Verschmutzung und Korrosion. Aus diesen Gründen war es bisher notwendig, den Belag von Hand mechanisch oder auf chemischem Wege zu entfernen.During the densification of anodically applied oxide layers, not only are the pores closed, but also a more or less strong velvety coating, the so-called sealing coating, is formed on the entire surface. This consists of hydrated aluminum oxide and is not touch-proof, so that the decorative effect of the layer is adversely affected. It also reduces the adhesive strength when gluing such aluminum parts and, due to the increased effective surface area, promotes later contamination and corrosion. For these reasons, it was previously necessary to remove the covering by hand, mechanically or chemically.
Es ist bereits bekannt, von verdichteten und mit Sealingbelag behafteten Oberflächen durch eine Mineralsäurenachbehandlung diesen Belag wieder abzulösen. Bei diesem Verfahren ist somit ein weiterer Behandlungsschritt notwendig, und es erfordert außerdem eine sehr sorgfältige Nachbehandlung mit der Mineralsäure, um eine Schichtschädigung auszuschließen.It is already known to detach this coating again from compacted surfaces which are covered with sealing coating by means of a mineral acid aftertreatment. A further treatment step is therefore necessary in this method, and it also requires a very careful aftertreatment with the mineral acid in order to rule out damage to the layer.
Weiterhin gehört es zum Stand der Technik, zur Verhinderung von Sealingbelägen eine Nachverdichtung mit Lösungen durchzuführen, die Nickelacetat und Ligninsulfonat enthalten. Nachteilig bei dieser Arbeitsweise ist unter anderem das Vergilben der erhaltenen Oxidschichten unter Lichteinfluß. Schließlich sind auch schon Verfahren beschrieben, bei denen zur Verhinderung der Sealingbeläge eine Heißwasserverdichtung unter Zusatz bestimmter Polyacrylate (DE-PS 19 38 039) oder -bestimmter Dextrine (DE-PS 19 44 452) erfolgt. Diese Verfahren haben sich gut bewährt. In manchen Fällen, insbesondere bei steigendem Molekulargewicht der verwendeten Wirkstoffe, können jedoch mehr oder weniger sichtbare Polymerfilme auf der Oberfläche entstehen. Diese sind unerwünscht. Auch hat man bereits beschrieben, Oxycarbonsäuren wie Citronensäure (DE-PS 21 62 674) sowie verschiedene Phosphonsäuren (DE-PS 22 -11 553) in kleinen Mengen als Sealingbelagverhinderer zu verwenden. Bei Einsatz dieser Substanzen hat sich jedoch gezeigt, daß insbesondere in großen, schlecht umgewälzten Bädern Schwierigkeiten mit der Uberdosierung des Wirkstoffs entstehen können. Es ist nämlich nicht immer problemlos, den Konzentrationsbereich einzuhalten, bei dem einerseits der Sealingbelag absolut sicher verhindert wird, ohne daß andererseits das Ergebnis der Kurzzeitprüfungen negativ beeinflußt wird. Obwohl die Gefahr der Uberdosierung durch die bereits bekannte Verwendung von bestimmten cycloaliphatischen oder aromatischen Polycarbonsäuren (DE-OS 26 50 989) weiter reduziert werden konnte, waren in der Praxis gelegentlich immer noch unbeabsichtigte Abweichungen von dem optimalen Konzentrationsbereich festzustellen.It is also part of the prior art to carry out post-compaction with solutions which contain nickel acetate and lignin sulfonate in order to prevent sealing deposits. One disadvantage of this procedure is the yellowing of the oxide layers obtained under the influence of light. Finally, processes have also been described in which hot water compaction is carried out with the addition of certain polyacrylates (DE-PS 19 38 039) or certain dextrins (DE-PS 19 44 452) to prevent the sealing coatings. These methods have worked well. In some cases, especially when the molecular weight of the active ingredients used increases, more or less visible polymer films can form on the surface. These are undesirable. It has also already been described to use oxycarboxylic acids such as citric acid (DE-PS 21 62 674) and various phosphonic acids (DE-PS 22 -11 553) in small quantities as a sealant inhibitor. When using these substances, however, it has been shown that difficulties can arise with overdosing of the active substance, particularly in large, poorly circulated baths. It is not always easy to adhere to the concentration range in which, on the one hand, the sealing coating is prevented with absolute certainty, without, on the other hand, the result of the short-term tests being adversely affected. Although the risk of overdosing could be further reduced by the already known use of certain cycloaliphatic or aromatic polycarboxylic acids (DE-OS 26 50 989), in practice there were still occasionally unintentional deviations from the optimal concentration range.
Dementsprechend stellt sich die vorliegende Erfindung die Aufgabe, die bisherigen Arbeitsweisen weiter zu verbessern und noch sicherer zu gestalten, um zu einem verbesserten Verfahren zum Verdichten von anodischen Oxidschichten auf Aluminium oder Aluminiumlegierungen zu gelangen.Accordingly, the object of the present invention is to further improve the previous methods of operation and to make them even safer in order to arrive at an improved method for compacting anodic oxide layers on aluminum or aluminum alloys.
Die Erfindung betrifft demgemäß ein Verfahren zum Verdichten von anodisch erzeugten Oxidschichten auf Aluminium oder Aluminiumlegierungen durch Behandlung mit wäßrigen Lösungen mit einem pH-Wert von 4 bis 8 bei Temperaturen zwischen 90°C und der Siedetemperatur, das dadurch gekennzeichnet ist, daß man die Verdichtung mit Lösungen durchführt, die 0,0005 bis 0,5 g/1 Phosphinocarbonsäuren, die bei der Umsetzung von hypophosphoriger Säure mit ungesättigten mono- oder polyfunktionellen Carbonsäuren der allgemeinen Formel I
- R1 Wasserstoff oder einen der Reste -CH3, -C2H5, -C3H7, -C4H9,
- R2, R3 und R4 Wasserstoff oder einen der Reste -CH3 -C 2H5, -COOH, -CH2-COOH, -CH2-CH2-COOH, bedeuten und wobei mindestens einer der Reste R1 bis R4 eine COOH-Gruppe darstellt oder enthält, im Molverhältnis 1 : 1 bis 1 : 8 gebildet werden, oder deren wasserlösliche Salze enthalten.
- R 1 is hydrogen or one of the radicals -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 ,
- R 2 , R 3 and R 4 are hydrogen or one of the radicals -CH 3 - C 2 H 5 , -C OO H, -CH 2 -COOH, -CH 2 -CH 2 -COOH, and at least one of the radicals R 1 to R 4 represents or contains a COOH group, are formed in a molar ratio of 1: 1 to 1: 8, or contain their water-soluble salts.
Die im erfindungsgemäßen Verfahren eingesetzten Phosphinocarbonsäuren können nach bekannten Verfahren hergestellt werden. Beispielsweise sei auf das allgemein bekannte Lehrbuch-Houben-Weyl, "Methoden der organischen Chemie" 4. Aufl., Bd. XII/1, Stuttgart 1963, S. 228 bis 229 verwiesen.The phosphinocarboxylic acids used in the process according to the invention can be prepared by known processes. For example, reference is made to the generally known textbook-Houben-Weyl, "Methods of Organic Chemistry" 4th edition, Vol. XII / 1, Stuttgart 1963, pp. 228 to 229.
Demgemäß finden Umsetzungsprodukte von hypophosphoriger Säure Verwendung, wie sie bei der Umsetzung mit Acrylsäure, Methacrylsäure, Ethylacrylsäure, Crotonsäure, Maleinsäure, Glutarconsäure, Citraconsäure, Itaconsäure, 2-Buten-2-carbonsäure, Dimethylmaleinsäure, 2-Methylenglutarsäure, Butenpolycarbonsäuren, Ethylentetracarbonsäure, Pentenpolycarbonsäuren und Zimtsäure entstehen. Erfindungsgemäß können auch von höheren ungesättigten Carbonsäuren abgeleitete Umsetzungsprodukte mit hypophosphoriger Säure verwendet werden. Mit steigendem Molekulargewicht wird deren Anwendung hinsichtlich einer optimalen Badführung jedoch zunehmend aufwendiger. Für die Durchführung des Verfahrens können außer den Säuren auch ihre wasserlöslichen Salze angewandt werden, bei denen alle oder ein Teil der sauren Protonen beispielsweise durch Alkali-, Ammonium-, Erdalkali-, Alkylammonium- oder Alkanolammoniumionen ersetzt wurden. Hierbei werden die Salze in einer Menge eingesetzt, die 0,0005 bis 0,5 g/1 der freien Säuren entspricht.Accordingly, reaction products of hypophosphorous acid are used, such as those used in the reaction with acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, maleic acid, glutaronic acid, citraconic acid, itaconic acid, 2-butene-2-carboxylic acid, dimethyl maleic acid, 2-methylene glutaric acid, butene polycarboxylic acids and ethylene tetracarboxylic acids, ethylene tetracarboxylic acids, ethylene tetracarboxylic acids and ethylene tetracarboxylic acids, ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids, and ethylene tetracarboxylic acids Cinnamic acid are created. According to the invention, reaction products with hypophosphorous acid derived from higher unsaturated carboxylic acids can also be used. With increasing molecular weight, however, their use in terms of optimal bath management becomes increasingly complex. In addition to the acids, their water-soluble salts, in which all or part of the acidic protons have been replaced, for example, by alkali metal, ammonium, alkaline earth metal, alkylammonium or alkanolammonium ions, can also be used for carrying out the process. The salts are used in an amount that corresponds to 0.0005 to 0.5 g / 1 of the free acids.
Eine bevorzugte Ausführungsform des Verfahrens besteht darin, daß man die Verdichtung in Lösungen durchführt, welche die bei der Anlagerung von 2 - 8 Molekülen Acrylsäure an die beiden P-H-Funktionen der hypophosphorigen Säure entstandenen Umsetzungsprodukte oder deren wasserlösliche Salze in einer Menge von 0,0005 bis 0,5 g/1 enthalten.A preferred embodiment of the method is that the compression is carried out in solutions which contain the reaction products formed in the addition of 2-8 molecules of acrylic acid to the two PH functions of the hypophosphorous acid or their water-soluble salts in an amount of 0.0005 to 0.5 g / 1 included.
Eine weitere Ausführungsform des Verfahrens besteht darin, daß die Verdichtung in Lösungen durchgeführt wird, die die bei der Umsetzung von Maleinsäure mit hypophosphoriger Säure erhaltenden Umsetzungsprodukte oder deren wasserlösliche Salze enthalten.A further embodiment of the method consists in that the compression is carried out in solutions which contain the reaction products obtained in the reaction of maleic acid with hypophosphorous acid or their water-soluble salts.
Als vorteilhaft hat es sich ebenfalls erwiesen, die Verdichtung in Lösungen durchzuführen, welche die bei der Umsetzung von hypophosphoriger Säure mit Itaconsäure erhaltenen Umsetzungsprpdukte oder deren wasserlösliche Salze enthalten.It has also proven to be advantageous to carry out the compression in solutions which contain the reaction products obtained in the reaction of hypophosphorous acid with itaconic acid or their water-soluble salts.
Eine ebenso günstige Ausführungsform des Verfahrens ist gegeben durch die Verwendung von Anlagerungsprodukten der 1-Buten-2,3,4-tricarbonsäure an hypophosphorige Säure oder deren wasserlösliche Salze.An equally favorable embodiment of the process is given by the use of addition products of 1-butene-2,3,4-tricarboxylic acid with hypophosphorous acid or its water-soluble salts.
Die Lösungen der erfindungsgemäßen Säuren bzw. Salze werden auf einen pH-Wert von 4 bis 8, vorzugsweise 5 bis 6, eingestellt. Diese Einstellung kann mit Ammoniak bzw. Essigsäure erfolgen. Für den Ansatz der Lösungen ist es vorteilhaft, wenn vollentsalztes bzw. destilliertes oder Kondenswasser verwendet wird.The solutions of the acids or salts according to the invention are adjusted to a pH of 4 to 8, preferably 5 to 6. This setting can be made with ammonia or acetic acid. For the preparation of the solutions, it is advantageous if demineralized or distilled water or condensed water is used.
Die Verdichtung mit den erfindungsmäßen Lösungen wird bei Temperaturen zwischen 90°C und der Siedetemperatur durchgeführt. Im allgemeinen wird eine Temperatur von 95 bis 100°C eingehalten. Die Verdichtungszeit hält sich hierbei in dem üblichen Rahmen und beträgt etwa 1,5 bis 3,5 min/µm Schichtdicke der anodischen Oxidschicht. Den Verdichtungslösungen können weiterhin auch noch für diese Zwecke an sich bekannte Zusätze wie Nickel- oder Kobaltacetat in kleinen Mengen zwischen 0,0001 und 0,5 g/1 zugesetzt werden. Durch das neue Verfahren ist es möglich, die Ausbildung von Sealingbelägen zu verhindern, ohne daß die anodische Oxidschicht beeinträchtigt oder die Qualität der Verdichtung herabgesetzt wird. Durch die besonderen Eigenschaften der verwendeten Wirkstoffe ist die Gefahr einer ünbeabsichtigten schädlichen Überdosierung stark reduziert. Eine Nachspülung nach der Verdichtung oder ein Absprühen, um irgendwelche Rückstände von der Oberfläche zu entfernen, sind nicht erforderlich. Das Aussehen der Oberfläche wird durch das erfindungsgemäße Verfahren nicht beeinflußt; es bleiben die Effekte erhalten, wie sie durch Vorbehandlung und Anodisation erzielt wurden.The compression with the solutions according to the invention is carried out at temperatures between 90 ° C. and the boiling point. In general, a temperature of 95 to 100 ° C is maintained. The compression time is within the usual range and is approximately 1.5 to 3.5 min / μm layer thickness of the anodic oxide layer. Additives known per se, such as nickel or cobalt acetate, can also be added to the compression solutions for this purpose in small amounts between 0.0001 and 0.5 g / l. The new process makes it possible to prevent the formation of sealing deposits without the anodic oxide layer is impaired or the quality of compaction is reduced. Due to the special properties of the active ingredients used, the risk of unintentional harmful overdosing is greatly reduced. Rinsing after compaction or spraying to remove any residue from the surface is not required. The appearance of the surface is not influenced by the method according to the invention; the effects that were achieved by pretreatment and anodization are retained.
In den nachfolgenden Beispielen wurde die Bezeichnung der Aluminiumlegierungen gemäß DIN 1725 vorgenommen. Die Qualität der Oxidschichten wurde durch den Scheinleitwert oder y-Wert nach DIN 50 949 und durch den Verlustfaktor d nach ISO/TC 79/SC2 (ALL-1) Dok.65 E bestimmt. Weiterhin wurde die Güte der Verdichtung mittels des Chromphosphorsäuretests (ISO 3210) geprüft.In the following examples, the designation of the aluminum alloys was made in accordance with DIN 1725. The quality of the oxide layers was determined by the apparent conductance or y-value according to DIN 50 949 and by the loss factor d according to ISO / TC 79 / SC2 (ALL-1) Doc. 65 E. The quality of the compression was also checked using the chromophosphoric acid test (ISO 3210).
Ein alkalisch entfettetes und gebeiztes Aluminiumblech (Al 99,5) wurde nach der anodischen Oxidation im Gleichstrom-Schwefelsäure-Verfahren (Schichtdicke 20 µm) in einer Lösung verdichtet, die in entionisiertem Wasser 0,01 g/1 eines Umsetzungsproduktes von 2 Mol Maleinsäure mit 1 Mol hypophosphoriger Säure enthielt und mit Ammoniak auf pH 5,8 eingestellt worden war.An alkaline degreased and pickled aluminum sheet (Al 99.5) was compressed after the anodic oxidation using the direct current sulfuric acid method (layer thickness 20 µm) in a solution containing 0.01 g / 1 of a reaction product of 2 mol maleic acid in deionized water Contained 1 mol of hypophosphorous acid and adjusted to pH 5.8 with ammonia.
Das Umsetzungsprodukt von 2 Mol Maleinsäure mit 1 Mol hypophosphoriger Säure wurde hergestellt, indem zu 100 g Maleinsäure, gelöst in 250 ml Wasser, 45 g Natriumhypophosphitmonohydrat gegeben wurde. Das Reaktionsgemisch wurde auf 60°C erwärmt und während 4 Stunden in kleinen Portionen 8 g Ammoniumpersulfat gelöst in Wasser zutropfen lassen. Das Reaktionsge-misch wurde für 2 weitere Stunden auf 60°C gehalten. Die so erhaltene Lösung wurde ohne Isolierung des Umsetzungsproduktes für-die Versuche verwendet, wobei sich der Aktivsubstanzgehalt aus den eingesetzten Rohstoffen ergab.The reaction product of 2 moles of maleic acid with 1 mole of hypophosphorous acid was prepared by adding 45 g of sodium hypophosphite monohydrate to 100 g of maleic acid dissolved in 250 ml of water. The reaction mixture was heated to 60 ° C and 8 g of ammonium persulfate in small portions over 4 hours let drip in water. The reaction e g Mixing was maintained for 2 more hours at 60 ° C. The solution thus obtained was used for the experiments without isolation of the reaction product, the active substance content resulting from the raw materials used.
Die Verdichtung des anodisierten Aluminiums wurde während 60 min. bei 98°C durchgeführt. Danach zeigten die Bleche, keinen Sealingbelag. Die Schichtdicke betrug unverändert 20 µm. Der dielektrische Verlustfaktor betrug 0,42, und der Scheinleitwert war von über 400 auf 12,5 µS abgefallen. Im Chromphosphorsäuretest wurde ein Gewichtsverlust von 12,9 mg/dm2 gefunden.The anodized aluminum was densified for 60 min. performed at 98 ° C. After that, the sheets showed no sealing coating. The layer thickness remained unchanged at 20 µm. The dielectric loss factor was 0.42 and the admittance had dropped from over 400 to 12.5 µS. A weight loss of 12.9 mg / dm 2 was found in the chromophosphoric acid test.
Praktisch identische Ergebnisse wurden nach entsprechender pH-Einstellung mit Essigsäure erhalten, wenn man von den äquivalenten Mengen der Natrium-, Kalium-, Ammonium-, Magnesium-, Calcium-, Tetramethylammonium-oder Alkanolaminsalzen des Umsetzungsproduktes von 2 Mol Maleinsäure mit 1 Mol hypophosphoriger Säure ausging.Practically identical results were obtained after appropriate pH adjustment with acetic acid if the equivalent amounts of the sodium, potassium, ammonium, magnesium, calcium, tetramethylammonium or alkanolamine salts of the reaction product of 2 mol of maleic acid with 1 mol of hypophosphorous acid ran out of.
Alkalisch entfettete und gebeizte Profile aus der Legierung AlMgSi 0,5 wurden nach dem Gleichstrom-Schwefelsäure-Oxalsäure-Verfahren anodisch oxidiert (Schichtdicke 19 µm) und in einem zinnhaltigen Färbeelektrolyten elektrolytisch bronze eingefärbt. Die Profile wurden darauf während einer 3 min./µm Schichtdicke entsprechenden Zeit bei 98°C in einer auf pH 6,0 eingestellten Lösung verdichtet, die in entionisiertem Wasser 0,001 g/1 eines Umsetzungsproduktes von hypophosphoriger Säure mit 8 Mol Acrylsäure erhalten worden war.Alkaline degreased and pickled profiles made of the alloy AlMgSi 0.5 were anodized using the direct current sulfuric acid-oxalic acid method (layer thickness 19 µm) and colored bronze electrolytically in a tin-containing coloring electrolyte. The profiles were then compacted for a time corresponding to 3 min / μm layer thickness at 98 ° C. in a solution adjusted to pH 6.0, which solution had been obtained in deionized water 0.001 g / l of a reaction product of hypophosphorous acid with 8 mol of acrylic acid.
Das Umsetzungsprodukt von Acrylsäure mit hypophosphoriger Säure wurde wie folgt hergestellt:
- Die Suspension von 100 g 50%iger hypophosphoriger Säure, 40, g Acrylsäure, 4. g Benzoylperoxid mit einem Gehalt von 25 % Wasser und 300 ml Wasser wurde unter Rühren vorsichtig auf 95 - 98°C erwärmt. Die einsetzende exotherme Reaktion wurde ohne weitere zusätzliche Erwärmung durch Zugabe von 340 g Acrylsäure während 45 min. in Gang gehalten. Nach vollständiger Zugabe und Nachlassen der exothermen Reaktion wurde die Mischung 3 Stunden bei 95 - 100°C gerührt. Die so erhaltene viskose Lösung, die rechnerisch 430 g Aktivsubstanz enthielt, wurde für die Versuche verwendet.
- The suspension of 100 g of 50% hypophosphorous acid, 40, g of acrylic acid, 4. g of benzoyl peroxide with a content of 25% water and 300 ml of water was carefully heated to 95-98 ° C. with stirring. The onset of exothermic reaction was without further heating by adding 340 g of acrylic acid for 45 min. kept going. After the addition and release of the exothermic reaction had ended, the mixture was stirred at 95-100 ° C. for 3 hours. The viscous solution thus obtained, which mathematically contained 430 g of active substance, was used for the experiments.
Nach der wie oben beschrieben durchgeführten Verdichtung zeigten die Profile keinen Sealingbelag oder sonstige sichtbare Ablagerungen auf der Oberfläche. Die Schichtdicke betrug nach wie vor 19 µm. Der Scheinleitwert war von über 400 auf 17 µS abgesunken. Der dielektrische Verlustfaktor betrug 0,45. Im Chrom-phosphorsäure-Test wurde ein Gewichtsverlust von 9,3 mg/dm2 gefunden.After the compaction was carried out as described above, the profiles showed no sealing coating or other visible deposits on the surface. The layer thickness was still 19 µm. The apparent conductance had dropped from over 400 to 17 µS. The dielectric loss factor was 0.45. A weight loss of 9.3 m g / d m 2 was found in the chromium-phosphoric acid test.
Die-gleichen Ergebnisse wurden erzielt, wenn das Umsetzungsprodukt von Acrylsäure mit hypophosphoriger Säure im Molverhältnis 4 : 1 oder äquivalente Mengen seines Natrium-, Kalium-, Ammonium-, Magnesium-, Kalzium-, Tetramethylammonium- oder Alkanolaminsalzes nach entsprechender pH-Einstellung eingesetzt wurden.The same results were obtained when the reaction product of acrylic acid with hypophosphorous acid in a molar ratio of 4: 1 or equivalent amounts of its sodium, potassium, ammonium, magnesium, calcium, tetramethylammonium or alkanolamine salt were used after appropriate pH adjustment .
Nach dem üblichen Verfahren entfettete und gebeizte Profile aus der Legierung AlMgSi 0,5 wurden nach dem Gleichstrom-Schwefelsäure-Verfahren anodisch oxidiert (Schichtdicke 18 - 21 µm). Diese wurden bei einem pH-Wert von 5,8 (eingestellt mit Ammoniak bzw. Essigsäure) in Lösungen, welche die in der Tabelle aufgeführten Umsetzungsprodukte von hypophosphoriger Säure mit Itaconsäure, Citraconsäure bzw. 1-Buten-2,3,4-tricarbonsäure - hergestellt nach dem in Beispiel 1 genannten Verfahren - in den angegebenen Mengen enthielten, bei 97 - 100°C 60 min. verdichtet.Profiles made from the alloy AlMgSi 0.5 degreased and pickled by the usual method were anodized using the direct current sulfuric acid method (layer thickness 18-21 µm). These were at a pH Value of 5.8 (adjusted with ammonia or acetic acid) in solutions which contain the reaction products of hypophosphorous acid with itaconic acid, citraconic acid or 1-butene-2,3,4-tricarboxylic acid listed in the table - prepared according to that in Example 1 mentioned processes - contained in the specified amounts, at 97 - 100 ° C for 60 min. condensed.
In der Tabelle sind die belagsverhindernde Wirkung und der' Einfluß der Substanzen 'auf die Schichtqualität, ausgedrückt nach den Ergebnissen der Scheinleitwertmessung des dielektrischen Verlustfaktors und des Gewichtsverlustes im Chrom-Phosphorsäure-Test, zusammengestellt. Bei der Verwendung der erfindungsgemäßen Verbindungen in entsprechenden Konzentrationen wird der Sealingbelag verhindert und die Schichtqualität nicht beeinträchtigt. In die Tabelle wurden Vergleichsversuche mit Cyclohexanhexacarbonsäure und Phosphonobu- tan-2,3,4-tricarbonsäure aufgenommen, die zeigen, daß bei den Vergleichssubstanzen zwar der Sealingbelag verhindert wird, jedoch bereits bei den höheren Konzentrationen eine starke Schichtschädigung eintritt.
Claims (7)
oder deren wasserlösliche Salze enthalten.Process for compacting anodically produced oxide layers on aluminum or aluminum alloys by treatment with aqueous solutions with a pH of 4 to 8 at temperatures between 90 ° C and the boiling temperature, which is characterized in that the densification is carried out with solutions which , 0005 to 0.5 g / 1 phosphinocarboxylic acids which in the reaction of hypophosphorous acid with unsaturated mono- or polyfunctional carboxylic acids of the general formula I
or contain their water-soluble salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83108560T ATE28218T1 (en) | 1982-09-09 | 1983-08-31 | PROCESS FOR DENSING ANODICALLY PRODUCED OXIDE COATINGS ON ALUMINUM OR ALUMINUM ALLOYS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3233411 | 1982-09-09 | ||
| DE19823233411 DE3233411A1 (en) | 1982-09-09 | 1982-09-09 | METHOD FOR COMPRESSING ANODICALLY PRODUCED OXIDE LAYERS ON ALUMINUM OR ALUMINUM ALLOYS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0103234A2 true EP0103234A2 (en) | 1984-03-21 |
| EP0103234A3 EP0103234A3 (en) | 1985-09-25 |
| EP0103234B1 EP0103234B1 (en) | 1987-07-08 |
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ID=6172769
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83108560A Expired EP0103234B1 (en) | 1982-09-09 | 1983-08-31 | Process for densifying anodically produced oxide layers on aluminium or aluminium alloys |
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| Country | Link |
|---|---|
| US (1) | US4445983A (en) |
| EP (1) | EP0103234B1 (en) |
| JP (1) | JPS5970797A (en) |
| AT (1) | ATE28218T1 (en) |
| AU (1) | AU565677B2 (en) |
| BR (1) | BR8304885A (en) |
| CA (1) | CA1212072A (en) |
| DE (2) | DE3233411A1 (en) |
| DK (1) | DK158748C (en) |
| ES (1) | ES8405450A1 (en) |
| GR (1) | GR79624B (en) |
| NO (1) | NO159945C (en) |
| PT (1) | PT77295B (en) |
| ZA (1) | ZA836673B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990007589A1 (en) * | 1989-01-05 | 1990-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Process for impregnating anodized aluminium surfaces |
| WO1997046738A1 (en) * | 1996-05-31 | 1997-12-11 | Henkel Kommanditgesellschaft Auf Aktien | Short-term heat-sealing of anodized metal surfaces with surfactant-containing solutions |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3917188A1 (en) * | 1989-05-26 | 1990-11-29 | Happich Gmbh Gebr | PROCESS FOR PRODUCING COLORED SURFACES ON PARTS OF ALUMINUM OR ALUMINUM ALLOYS |
| ES2081433T3 (en) * | 1990-04-25 | 1996-03-16 | Nalco Chemical Co | OLIGOMEROS OF PHOSPHINATES, COMPOSITIONS THAT CONTAIN THEM AND PROCEDURE FOR THEIR OBTAINING AND USE. |
| DE10161478A1 (en) * | 2001-12-14 | 2003-06-26 | Henkel Kgaa | Sealing anodized surface of metal, e.g. aluminum or alloy, uses solution containing lithium and/or magnesium ions, nonionic surfactant and cyclic polycarboxylic acid, maleic anhydride (co)polymer and/or phosphinocarboxylic acid copolymer |
| JP4936791B2 (en) * | 2006-05-22 | 2012-05-23 | 株式会社東芝 | Aeration-less water treatment system |
| US8609254B2 (en) | 2010-05-19 | 2013-12-17 | Sanford Process Corporation | Microcrystalline anodic coatings and related methods therefor |
| US8512872B2 (en) | 2010-05-19 | 2013-08-20 | Dupalectpa-CHN, LLC | Sealed anodic coatings |
| CN109518253B (en) * | 2017-09-18 | 2021-05-21 | 中铝材料应用研究院有限公司 | High-adhesion and corrosion-resistant anodic oxidation method based on aluminum alloy surface |
| CN109518252B (en) * | 2017-09-18 | 2021-05-21 | 中铝材料应用研究院有限公司 | High-adhesion and corrosion-resistant anodic oxidation method based on aluminum alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3634146A (en) * | 1969-09-04 | 1972-01-11 | American Cyanamid Co | Chemical treatment of metal |
| US3770513A (en) * | 1972-06-08 | 1973-11-06 | American Cyanamid Co | Chemical treatment of metal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3400023A (en) * | 1964-05-11 | 1968-09-03 | Kelite Corp | Composition for preservation of metals, process and article |
| US3813303A (en) * | 1971-04-14 | 1974-05-28 | Alusuisse | Method of treating an aluminum surface |
| US4293441A (en) * | 1979-03-12 | 1981-10-06 | Minnesota Mining And Manufacturing Company | Corrosion inhibiting heat transfer liquid |
-
1982
- 1982-09-09 DE DE19823233411 patent/DE3233411A1/en not_active Withdrawn
-
1983
- 1983-08-15 DK DK371883A patent/DK158748C/en not_active IP Right Cessation
- 1983-08-15 NO NO832927A patent/NO159945C/en unknown
- 1983-08-29 GR GR72322A patent/GR79624B/el unknown
- 1983-08-30 US US06/527,906 patent/US4445983A/en not_active Expired - Lifetime
- 1983-08-31 EP EP83108560A patent/EP0103234B1/en not_active Expired
- 1983-08-31 DE DE8383108560T patent/DE3372382D1/en not_active Expired
- 1983-08-31 AT AT83108560T patent/ATE28218T1/en not_active IP Right Cessation
- 1983-09-06 PT PT77295A patent/PT77295B/en not_active IP Right Cessation
- 1983-09-08 ZA ZA836673A patent/ZA836673B/en unknown
- 1983-09-08 BR BR8304885A patent/BR8304885A/en not_active IP Right Cessation
- 1983-09-08 AU AU18923/83A patent/AU565677B2/en not_active Ceased
- 1983-09-08 ES ES525508A patent/ES8405450A1/en not_active Expired
- 1983-09-08 CA CA000436312A patent/CA1212072A/en not_active Expired
- 1983-09-09 JP JP58167388A patent/JPS5970797A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3634146A (en) * | 1969-09-04 | 1972-01-11 | American Cyanamid Co | Chemical treatment of metal |
| US3770513A (en) * | 1972-06-08 | 1973-11-06 | American Cyanamid Co | Chemical treatment of metal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990007589A1 (en) * | 1989-01-05 | 1990-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Process for impregnating anodized aluminium surfaces |
| WO1997046738A1 (en) * | 1996-05-31 | 1997-12-11 | Henkel Kommanditgesellschaft Auf Aktien | Short-term heat-sealing of anodized metal surfaces with surfactant-containing solutions |
| US6059897A (en) * | 1996-05-31 | 2000-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Short-term heat-sealing of anodized metal surfaces with surfactant-containing solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0103234A3 (en) | 1985-09-25 |
| ES525508A0 (en) | 1984-06-01 |
| JPH0312159B2 (en) | 1991-02-19 |
| NO159945C (en) | 1989-02-22 |
| GR79624B (en) | 1984-10-31 |
| CA1212072A (en) | 1986-09-30 |
| EP0103234B1 (en) | 1987-07-08 |
| DK371883A (en) | 1984-03-10 |
| DK371883D0 (en) | 1983-08-15 |
| NO832927L (en) | 1984-03-12 |
| DK158748B (en) | 1990-07-09 |
| JPS5970797A (en) | 1984-04-21 |
| DE3372382D1 (en) | 1987-08-13 |
| ES8405450A1 (en) | 1984-06-01 |
| BR8304885A (en) | 1984-04-24 |
| US4445983A (en) | 1984-05-01 |
| ATE28218T1 (en) | 1987-07-15 |
| PT77295A (en) | 1983-10-01 |
| ZA836673B (en) | 1984-04-25 |
| NO159945B (en) | 1988-11-14 |
| PT77295B (en) | 1986-02-04 |
| DK158748C (en) | 1990-12-10 |
| DE3233411A1 (en) | 1984-03-15 |
| AU1892383A (en) | 1984-03-15 |
| AU565677B2 (en) | 1987-09-24 |
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