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EP0058711B1 - Process and product for the passivation of iron and steel surfaces - Google Patents

Process and product for the passivation of iron and steel surfaces Download PDF

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Publication number
EP0058711B1
EP0058711B1 EP81902484A EP81902484A EP0058711B1 EP 0058711 B1 EP0058711 B1 EP 0058711B1 EP 81902484 A EP81902484 A EP 81902484A EP 81902484 A EP81902484 A EP 81902484A EP 0058711 B1 EP0058711 B1 EP 0058711B1
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Prior art keywords
acid
weight
treated
phosphonic
maleic acid
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German (de)
French (fr)
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EP0058711A1 (en
Inventor
Hermann Drosdziok
Jürgen Geke
Hans-Günther GERMSCHEID
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors

Definitions

  • the invention relates to a method and means for passivating iron and steel surfaces chemically with the aid of aqueous solutions which react weakly alkaline and contain a combination of certain corrosion-inhibiting substances.
  • Passivation agents are also used as an additive to pressure baths, quenching water, such as for induction hardening, cooling circuits, such as in engine test benches, and also as hydraulic fluids.
  • passivation A number of methods are known for passivation. For example, it can be carried out with oils or fats or also corresponding plastic emulsions, although undesirable layers often form. It is therefore often advisable to passivate the metal surfaces with aqueous solutions that contain appropriate chemical additives.
  • Such corrosion inhibiting passivating agents for iron surfaces are, for example, alkali nitrites, alkali chromates, soaps, benzoates and alkanolamines. Alkanol amide salts of maleic acid have also been used for the passivation of iron and steel surfaces (see; e.g. EP-A-0002780).
  • Suitable maleic acid monoalkylamides are both amides with straight-chain and branched alkyl radicals having 6 to 14 carbon atoms, preferably having 8 to 10 carbon atoms.
  • Suitable alkanolamines are short-chain compounds such as mono-, di- and triisopropanolamine, n-propanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine and preferably mono-, di- and triethanolamine, in particular as Mixture, into consideration.
  • Suitable complexing phosphonic acids are: 1-hydroxyalkyl-1,1-diphosphonic acids, 1-aminoalkyl-1,1-diphosphonic acid, phosphonocarboxylic acids, such as in particular 2-phosphono-1,2,4-tricarboxylic acid and / or Phosphonic acids of the general formula in the means.
  • 1-Hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and nitrilotrimethylenephosphonic acid have preferably proven successful.
  • the phosphonic acids can also be used as alkali salts or alkanolamine salts.
  • the free phosphonic acids can also be added to the corresponding solutions. In such a case, an excess of alkanolamine in the solution can then be used to adjust the pH to 7.5 to 10.5.
  • An essential feature of the combination according to the invention is the weight ratio of maleic acid monoalkylamide to alkanolamine, which should be 1 0.3 to 1:10 and preferably 1: to 1: 4.
  • the weight ratio of maleic acid monoalkylamide to phosphonic acid is the process according to the invention 1: 0.01 to 1: 0.5 and preferably 1: 0.1 to 1: 0.5.
  • a further increase in the addition of phosphonic acid is possible, but does not bring any additional synergistic effects.
  • the pH of the solution from 7.5 to 10.5 which is suitable for carrying out the process is not already achieved by the alkalinity of the substances used, it can be adjusted by adding a small amount of alkali.
  • the metal surfaces made of iron or steel can be treated at elevated temperatures between 30 and 100 ° C., but preferably at room temperature.
  • the agents can also contain further substances.
  • surfactants preferably nonionic low-foaming surfactants. Especially if cleaning is desired at the same time as the passivation or if greased or partially greased parts are to be treated in one operation.
  • low-foaming nonionic surfactants the addition products of ethylene or propylene oxide onto polypropylene glycol or polyethylene glycol and addition products of ethylene and / or propylene oxide onto mono- or polyalcohols, mono- or polyamines, fatty acids, amides and alkylphenols with an alkyl radical of preferably 8 to 20, in particular 12 to 18 carbon atoms.
  • the concentration in the aqueous passivation solution is between 0.005 to 0.3 percent by weight.
  • agents according to the invention may also be expedient in some cases to add builders, which increase the action of the surfactants, to the agents according to the invention in order to enhance the cleaning action.
  • builders which increase the action of the surfactants, to the agents according to the invention in order to enhance the cleaning action.
  • Ortho- or polymer phosphates and / or borates should be mentioned in particular.
  • a builder content in amounts of 0.2 to 2 percent by weight, based on the aqueous solution, is preferred.
  • the agents according to the invention can also contain alkanolamine soaps of short-chain fatty acids - d. H. of fatty acids with 6 to 12 carbon atoms -, for example caprylic or isononanoic acid, which reinforce the corrosion protection effect in a manner known per se and act as a solubilizer and as a foam regulator.
  • the solutions according to the invention may optionally also contain preservatives for preventing bacterial decomposition, such as chlorophenols, diphenyl derivatives, hexahydrotriazine derivatives and / or for non-ferrous metal inhibition, benztriazole, mercaptobenztriazole and lignin sulfonate in amounts of about 0.05 to 0.1 percent by weight.
  • preservatives for preventing bacterial decomposition such as chlorophenols, diphenyl derivatives, hexahydrotriazine derivatives and / or for non-ferrous metal inhibition, benztriazole, mercaptobenztriazole and lignin sulfonate in amounts of about 0.05 to 0.1 percent by weight.
  • agents used contain the components mentioned in the stated amounts. If desired, however, the corresponding agents can also be prepared in concentrated form in order to be diluted to the stated concentration immediately before use.
  • the corrosion protection obtained with the solutions according to the invention is considerably higher than the sum of the properties of the individual substances and exceeds the passivating agents used hitherto.
  • the outstanding corrosion protection properties of the method according to the invention were tested in the corrosion protection test according to DIN 51 360/2 with cast chips GG 30 at an exposure time of 2 hours.
  • the test solutions were prepared at room temperature with 20 ° hard water.
  • the pH of all test solutions was between 8.5 and 10.5; Test and comparison solution were adjusted to the same pH.
  • the concentration of the respective combination was 1, 1.5 and 2% in the DIN tests.
  • the comparative tests are listed under a) and the solutions according to the invention under b).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Metal surfaces are treated with 0,5 to 5% by weight of aqueous solutions (pH 7.5 to 10.5) containing a combination of anticorrosive substances giving a clear aqueous solution. This combination includes: a) one or several alkylamides of n-monomaleic or isomaleic acid with 6 to 14, preferably 8 to 10 carbon atoms. b) one or several alkanolamines, preferably mono-, di and/or triethanolamine and c) complexing phosphonic oxides, preferably 1-hydroxy-alkyl-1, 1-diphosphonic oxyde, 1-aminoalkyl-1 acid, 1-diphosphonic, phosphonocarbonic acid and/or a phosphonic acid having the formula: (FORMULA) Preferred phosphonic acids are 1-hydroxyethane-1, 1-diphosphonic, 2-phosphonobutane-1,2,4-tricarbonic and/or nitrilotrimethylenphosphonic acid. The ratio a:b in the solutions has to be from 1:0,3 to 1:10, the ratio a:c has to be from 1:0.01 to 1:0,5. The solutions may further contain surfactants, preferably phosphates and/or borates. These solutions provide a better protection against corrosion than that obtained with the means used heretofore.

Description

Gegenstand der Erfindung sind ein Verfahren und Mittel zum Passivieren von Eisen- und Stahloberflächen auf chemischem Wege mit Hilfe wäßriger Lösungen, die schwach alkalisch reagieren und eine Kombination bestimmter korrosionsinhibierender Substanzen enthalten.The invention relates to a method and means for passivating iron and steel surfaces chemically with the aid of aqueous solutions which react weakly alkaline and contain a combination of certain corrosion-inhibiting substances.

Es ist häufig erforderlich, zur Vermeidung unerwünschter Korrosionserscheinungen Eisen- und Stahloberflächen zu passivieren. Dies erfolgt beispielsweise bei oder nach Reinigungsoperationen, bei der Metallbearbeitung oder Zwischenlagerung vor einer weiteren Bearbeitung der Metalle. Ebenfalls werden Passivierungsmittel als Zusatz zu Abdrückbädern, Abschreckwässern, wie zum Beispiel bei der Induktionshärtung, Kühlkreisläufen, wie bei Motorenprüfständen, und auch als Hydraulikflüssigkeiten verwendet.It is often necessary to passivate iron and steel surfaces to avoid undesirable corrosion. This takes place, for example, during or after cleaning operations, during metal processing or intermediate storage before further processing of the metals. Passivation agents are also used as an additive to pressure baths, quenching water, such as for induction hardening, cooling circuits, such as in engine test benches, and also as hydraulic fluids.

Für die Passivierung ist eine Reihe von Methoden bekannt. So kann sie beispielsweise mit Ölen oder Fetten oder auch entsprechenden Kunststoffemulsionen vorgenommen werden, wobei sich allerdings häufig unerwünschte Schichten bilden. Deshalb ist es oft zweckmäßig, die Metalloberflächen mit wäßrigen Lösungen, die entsprechende chemische Zusätze enthalten, zu passivieren. Derartige die Korrosion inhibierende Passivierungsmittel für Eisenoberflächen sind beispielsweise Alkalinitrite, Alkalichromate, Seifen, Benzoate und Alkanolamine. Auch wurden Alkanol-amid salze vo: Malein amid säuren schon für die Passivierung von Eisen- und Stahloberflächen eingesetzt (Sieh ; z. B. EP-A-0002780).A number of methods are known for passivation. For example, it can be carried out with oils or fats or also corresponding plastic emulsions, although undesirable layers often form. It is therefore often advisable to passivate the metal surfaces with aqueous solutions that contain appropriate chemical additives. Such corrosion inhibiting passivating agents for iron surfaces are, for example, alkali nitrites, alkali chromates, soaps, benzoates and alkanolamines. Alkanol amide salts of maleic acid have also been used for the passivation of iron and steel surfaces (see; e.g. EP-A-0002780).

Es wurde nun überraschenderweise gefunden, daß hinsichtlich des Korrosionsschutzes eine starke synergistische Wirkung auftritt, wenn man sich des nachstehend beschriebenen Verfahrens zum Passivieren von Eisen- und Stahloberflächen auf chemischem Wege mit Hilfe wäßriger Lösungen, die alkalisch reagieren und eine Kombination bestimmter korrosionsinhibierender Substanzen enthalten, bedient.It has now surprisingly been found that a strong synergistic effect occurs with regard to corrosion protection if one uses the process described below for passivating iron and steel surfaces by chemical means with the aid of aqueous solutions which have an alkaline reaction and contain a combination of certain corrosion-inhibiting substances .

Das neue Verfahren ist dadurch gekennzeichnet, daß die Metalloberflächen mit 0,5 bis 5 gewichtsprozentigen Lösungen behandelt werden, deren pH-Wert zwischen 7,5 und 10,5 liegt und die eine in Wasser klar lösliche Kombination aus

  • a) einem oder mehreren Maleinsäuremonoalkylamiden,
  • b) einem oder mehreren Alkanolaminen,
  • c) einer oder mehrerer Phosphonsäuren, die komplexierende Eigenschaften haben,

enthalten, wobei das Gewichtsverhältnis Maleinsäuremonoalkylamid zu Alkanolamin 1 : 0,3 bis 1 : 10 und das Gewichtsverhältnis Maleinsäuremonoalkylamid zu Phosphonsäure 1 : 0,01 bis 1 : 0,5 beträgt.The new method is characterized in that the metal surfaces are treated with 0.5 to 5 percent by weight solutions, the pH value of which is between 7.5 and 10.5 and which is a combination which is clearly soluble in water
  • a) one or more maleic acid monoalkylamides,
  • b) one or more alkanolamines,
  • c) one or more phosphonic acids which have complexing properties,

included, the weight ratio maleic monoalkylamide to alkanolamine 1: 0.3 to 1:10 and the weight ratio maleic monoalkylamide to phosphonic acid is 1: 0.01 to 1: 0.5.

Als Maleinsäuremonoalkylamide kommen sowohl Amide mit geradkettigen als auch verzweigten Alkylresten mit 6 bis 14 Kohlenstoffatomen, vorzugsweise mit 8 bis 10 Kohlenstoffatomen in Betracht.Suitable maleic acid monoalkylamides are both amides with straight-chain and branched alkyl radicals having 6 to 14 carbon atoms, preferably having 8 to 10 carbon atoms.

Als geeignete Alkanolamine kommen kurzkettige Verbindungen wie Mono-, Di- und Triisopropanolamin, n-Propanolamin, N,N,N',N'-Tetrakis-(2-hydroxyethyl)-ethylendiamin und vorzugsweise Mono-, Di-und Triethanolamin, insbesondere als Gemisch, in Betracht.Suitable alkanolamines are short-chain compounds such as mono-, di- and triisopropanolamine, n-propanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine and preferably mono-, di- and triethanolamine, in particular as Mixture, into consideration.

Als geeignete komplexierende Phosphonsäuren sind zu nennen : 1-Hydroxy-alkyl-1,1-diphosphon- säuren, 1-Aminoalkyl-1,1-diphosphonsäure, Phosphonocarbonsäuren, wie insbesondere 2-Phosphono-1,2,4-tricarbonsäure und/oder Phosphonsäuren der allgemeinen Formel

Figure imgb0001
in der
Figure imgb0002
bedeutet.Suitable complexing phosphonic acids are: 1-hydroxyalkyl-1,1-diphosphonic acids, 1-aminoalkyl-1,1-diphosphonic acid, phosphonocarboxylic acids, such as in particular 2-phosphono-1,2,4-tricarboxylic acid and / or Phosphonic acids of the general formula
Figure imgb0001
in the
Figure imgb0002
means.

Vorzugsweise haben sich 1-Hydroxyethan-1,1-diphosphonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure und Nitrilotrimethylenphosphonsäure bewährt. Die Phosphonsäuren können im übrigen auch als Alkalisalze oder Alkanolaminsalze eingesetzt werden. Es kann den entsprechenden Lösungen aber auch die freien Phosphonsäuren hinzugefügt werden. In einem solchen Falle kann dann durch einen Überschuß an Alkanolamin in der Lösung diese auf den pH-Wert 7,5 bis 10,5 eingestellt werden.1-Hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and nitrilotrimethylenephosphonic acid have preferably proven successful. The phosphonic acids can also be used as alkali salts or alkanolamine salts. However, the free phosphonic acids can also be added to the corresponding solutions. In such a case, an excess of alkanolamine in the solution can then be used to adjust the pH to 7.5 to 10.5.

Ein wesentliches Merkmal der erfindungsgemäßen Kombination ist das Gewichtsverhältnis von Maleinsäuremonoalkylamid zu Alkanolamin, welches 1 0,3 bis 1 : 10 und vorzugsweise 1 : bis 1 :4 betragen soll. Das Gewichtsverhältnis von Maleinsäuremonoalkylamid zu Phosphonsäure beträgt bei dem erfindungsgemäßen Verfahren 1 : 0,01 bis 1 : 0,5 und vorzugsweise 1 : 0,1 bis 1 : 0,5. Eine weitere Erhöhung des Phosphonsäurezusatzes ist zwar möglich, bringt aber keine zusätzlichen synergistischen Effekte.An essential feature of the combination according to the invention is the weight ratio of maleic acid monoalkylamide to alkanolamine, which should be 1 0.3 to 1:10 and preferably 1: to 1: 4. The weight ratio of maleic acid monoalkylamide to phosphonic acid is the process according to the invention 1: 0.01 to 1: 0.5 and preferably 1: 0.1 to 1: 0.5. A further increase in the addition of phosphonic acid is possible, but does not bring any additional synergistic effects.

Falls der für die Durchführung des Verfahrens geeignete pH-Wert der Lösung von 7,5 bis 10,5 nicht bereits durch die Alkalität der verwendeten Substanzen erzielt wird, kann er durch einen geringen Zusatz an Alkali eingestellt werden.If the pH of the solution from 7.5 to 10.5 which is suitable for carrying out the process is not already achieved by the alkalinity of the substances used, it can be adjusted by adding a small amount of alkali.

Die Behandlung der Metalloberflächen aus Eisen oder Stahl kann bei erhöhten Temperaturen zwischen 30 und 100 °C, vorzugsweise jedoch bei Raumtemperatur, erfolgen.The metal surfaces made of iron or steel can be treated at elevated temperatures between 30 and 100 ° C., but preferably at room temperature.

Die Mittel können zusätzlich zu den bereits erwähnten Komponenten noch weitere Substanzen enthalten. Insbesondere kommen dabei Tenside, vorzugsweise nichtionogene schaumschwache Tenside, in Betracht. Insbesondere dann, wenn gleichzeitig mit der Passivierung eine Reinigung erwünscht ist oder befettete oder teilbefettete Teile gleichzeitig in einem Arbeitsgang behandelt werden sollen.In addition to the components already mentioned, the agents can also contain further substances. In particular, surfactants, preferably nonionic low-foaming surfactants, are suitable. Especially if cleaning is desired at the same time as the passivation or if greased or partially greased parts are to be treated in one operation.

Als schaumschwache nichtionogene Tenside sind zu nennen : die Anlagerungsprodukte von Ethylen- oder Propylenoxid an Polypropylenglykol beziehungsweise Polyethylenglykol sowie Anlagerungsprodukte von Ethylen- und/oder Propylenoxid an Mono- oder Polyalkohole, Mono- oder Polyamine, Fettsäuren, Amide und Alkylphenole mit einem Alkylrest von vorzugsweise 8 bis 20, insbesondere 12 bis 18 C-Atomen.The following are low-foaming nonionic surfactants: the addition products of ethylene or propylene oxide onto polypropylene glycol or polyethylene glycol and addition products of ethylene and / or propylene oxide onto mono- or polyalcohols, mono- or polyamines, fatty acids, amides and alkylphenols with an alkyl radical of preferably 8 to 20, in particular 12 to 18 carbon atoms.

Soweit Tenside Anwendung finden, liegt die Konzentration in der wäßrigen Passivierungslösung zwischen 0,005 bis 0,3 Gewichtsprozent.If surfactants are used, the concentration in the aqueous passivation solution is between 0.005 to 0.3 percent by weight.

Schließlich kann es in manchen Fällen auch zweckmäßig sein, zur Verstärkung der Reinigungswirkung den erfindungsgemäßen Mitteln sogennante Builder, die die Wirkung der Tenside verstärken, zuzusetzen. Insbesondere sind zu nennen Ortho- oder Polymerphosphate und/oder Borate. Bevorzugt ist ein Gehalt an Buildern in Mengen von 0,2 bis 2 Gewichtsprozent, bezogen auf die wäßrige Lösung. Die erfindungsgemäßen Mittel können weiterhin noch Alkanolaminseifen kurzkettiger Fettsäuren - d. h. von Fettsäuren mit 6 bis 12 C-Atomen -, beispielsweise Capryl- oder Isononansäure, enthalten, die in an sich bekannter Weise die Korrosionsschutzwirkung verstärken und als Lösungsvermittler sowie als Schaumregulator wirken. Auch können die erfindungsgemäßen Lösungen gegebenenfalls noch Konservierungsmittel zur Verhinderung der bakteriellen Zersetzung, wie beispielsweise Chlorphenole, Diphenylderivate, Hexahydrotriazinderivate und/oder zur Buntmetallinhibierung Benztriazol, Mercaptobenztriazol und Ligninsulfonat in Mengen von etwa 0,05 bis 0,1 Gewichtsprozent enthalten.Finally, it may also be expedient in some cases to add builders, which increase the action of the surfactants, to the agents according to the invention in order to enhance the cleaning action. Ortho- or polymer phosphates and / or borates should be mentioned in particular. A builder content in amounts of 0.2 to 2 percent by weight, based on the aqueous solution, is preferred. The agents according to the invention can also contain alkanolamine soaps of short-chain fatty acids - d. H. of fatty acids with 6 to 12 carbon atoms -, for example caprylic or isononanoic acid, which reinforce the corrosion protection effect in a manner known per se and act as a solubilizer and as a foam regulator. The solutions according to the invention may optionally also contain preservatives for preventing bacterial decomposition, such as chlorophenols, diphenyl derivatives, hexahydrotriazine derivatives and / or for non-ferrous metal inhibition, benztriazole, mercaptobenztriazole and lignin sulfonate in amounts of about 0.05 to 0.1 percent by weight.

Die zur Anwendung gelangenden Mittel enthalten die genannten Komponenten in den angegebenen Mengen. Gewünschtenfalls können jedoch auch die entsprechenden Mittel in konzentrierter Form hergestellt werden, um unmittelbar vor der Verwendung auf die genannte Konzentration verdünnt zu werden.The agents used contain the components mentioned in the stated amounts. If desired, however, the corresponding agents can also be prepared in concentrated form in order to be diluted to the stated concentration immediately before use.

Der Korrosionsschutz, der mit den erfindungsgemäßen Lösungen erhalten wird, ist erheblich höher als die Summe der Eigenschaften der Einzelsubstanzen und übertrifft die bisher verwendeten Passivierungsmittel.The corrosion protection obtained with the solutions according to the invention is considerably higher than the sum of the properties of the individual substances and exceeds the passivating agents used hitherto.

BeispieleExamples

Die hervorragenden korrosionsschützenden Eigenschaften des erfindungsgemäßen Verfahrens wurden im Korrosionsschutztest nach DIN 51 360/2 mit Gußspänen GG 30 bei Expositionszeiten von 2 Stunden getestet. Die Prüflösungen wurden bei Raumtemperatur mit 20° hartem Wasser angesetzt. Der pH-Wert aller Testlösungen lag zwischen 8,5 und 10,5 ; Test- und Vergleichslösung wurden auf den gleichen pH-Wert eingestellt. Die Konzentration der jeweiligen Kombination betrug bei den DIN-Testen 1, 1,5 und 2%. In der Tabelle sind unter a) die Vergleichsversuche, unter b) die erfindungsgemäßen Lösungen aufgeführt.The outstanding corrosion protection properties of the method according to the invention were tested in the corrosion protection test according to DIN 51 360/2 with cast chips GG 30 at an exposure time of 2 hours. The test solutions were prepared at room temperature with 20 ° hard water. The pH of all test solutions was between 8.5 and 10.5; Test and comparison solution were adjusted to the same pH. The concentration of the respective combination was 1, 1.5 and 2% in the DIN tests. In the table, the comparative tests are listed under a) and the solutions according to the invention under b).

(Siehe Tabellen, Seite 4 ff.)(See tables, page 4 ff.)

Figure imgb0003
Figure imgb0003
Figure imgb0004
Figure imgb0004

  • 8. Aktivsubstanzen der Rezeptur in Gewichtsteilen
    • 10 Monoethanolamin
    • 10 Diethanolamin
    • 10 Triethanolamin
    • 5 Maleinsäuremono-2-ethylhexylamid
    • 2 Maleinsäuremonodecylamid
    • 7 Caprylsäure
    • 1 1-Hydroxyethan-1.1-diphosphonsäure, 60%ig
    • 1 Aminotrimethylenphosphonsäure, 50 %ig
    • 2 nichtionogenes Tensid (Anlagerungsprodukt von Ethylenoxid an Polyethylenglykol)
    • 1 Phosphonobutantricarbonsäure, 50 %ig
    8. Active ingredients of the formulation in parts by weight
    • 10 monoethanolamine
    • 10 diethanolamine
    • 10 triethanolamine
    • 5 maleic acid mono-2-ethylhexylamide
    • 2 maleic acid monodecylamide
    • 7 caprylic acid
    • 1 1-hydroxyethane-1,1-diphosphonic acid, 60%
    • 1 aminotrimethylenephosphonic acid, 50%
    • 2 non-ionic surfactant (adduct of ethylene oxide with polyethylene glycol)
    • 1 phosphonobutane tricarboxylic acid, 50%
  • 9. Aktivsubstanzen der Rezeptur in Gewichtsteilen
    • 10 Maleinsäuremono-2-ethylhexylamid
    • 30 Diethanolamin
    • 5 Caprylsäure
    • 31-Hydroxyethan-1.1-diphosphonsäure, 60 %ig
    • 2 nichtionogenes Tensid (Anlagerungsprodukt von Ethylenoxid an Polyethylenglykol)
    9. Active ingredients of the formulation in parts by weight
    • 10 maleic acid mono-2-ethylhexylamide
    • 30 diethanolamine
    • 5 caprylic acid
    • 31-hydroxyethane-1,1-diphosphonic acid, 60%
    • 2 non-ionic surfactant (adduct of ethylene oxide with polyethylene glycol)
  • 10. Aktivsubstanzen der Rezeptur in Gewichtsteilen
    • 10 Borsäure
    • 5 Monoethanolamin
    • 6,6 Maleinsäuremono-2-ethylhexylamid
    • 20 Diethanolamin
    • 3,3 Caprylsäure
    • 2 1-Hydroxyethan-1.1-diphosphonsäure
    • 1,3 nichtionogenes Tensid (Anlagerungsprodukt von Ethylenoxid an Polyethylenglykol)
    10. Active ingredients of the formulation in parts by weight
    • 10 boric acid
    • 5 monoethanolamine
    • 6.6 maleic acid mono-2-ethylhexylamide
    • 20 diethanolamine
    • 3.3 caprylic acid
    • 2 1-hydroxyethane-1,1-diphosphonic acid
    • 1.3 non-ionic surfactant (adduct of ethylene oxide with polyethylene glycol)
Korrosionstest nach DIN 51 360/2Corrosion test according to DIN 51 360/2

Beurteilung der Rostbildung in Korrosionsgraden 0-4, 0 = keine Korrosion, 4 = starke KorrosionAssessment of rust formation in degrees of corrosion 0-4, 0 = no corrosion, 4 = severe corrosion

(Siehe Tabelle, Seite 7 f.)(See table, page 7 f.)

Figure imgb0005
Figure imgb0005

Claims (18)

1. A process for passivating iron and steel surfaces using aqueous, alkaline reacting solutions containing corrosion inhibitors, characterized in that the metal surface is treated with 0.5 to 5 % by weight solutions containing a combination, clearly soluble in water, of
a) one or more maleic acid monoalkyl amides,
b) one or more alkanolamines,
c) one or more phosphonic acids having complexing properties,

the ratio by.weight of maleic acid monoalkyl amide to alkanolamines amounting to between 1 : 0.3 and 1 : 10 and the ratio by weight of maleic acid monoalkyl amide to phosphonic acid to between 1 : 0.01 and 1 : 0.5 and the solution having a pH-value of from 7.5 to 10.5.
2. A process as claimed in Claim 1, characterized in that the metal surface is treated with a solution containing maleic acid mono-n- or -iso-alkyl amides containing from 6 to 14 and preferably from 8 to 10 carbon atoms in the alkyl radical.
3. A process as claimed in Claims 1 and 2, characterized in that the metal surface is treated with a solution containing mono-, di- and/or triethanolamine.
4. A process as claimed in Claims 1 to 3, characterized in that the metal surface is treated with a solution containing as phosphonic acid 1-hydroxyalkyl-1,1-diphosphonic acid, 1-aminoalkyl-1,1-diphosphonic acid, phosphonocarboxylic acid and/or a phosphonic acid corresponding to the following formula
Figure imgb0010
in which
Figure imgb0011
5. A process as claimed in Claims 1 to 4, characterized in that the metal surface is treated with a solution containing as phosphonic acid 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1, 2,4-tricarboxylic acid and/or nitrilotrimethylene phosphonic acid.
6. A process as claimed in Claims 1 to 5, characterized in that the metal surface is treated with a solution in which the ratio by weight of maleic acid monoalkyl amide to alkanolamines is from 1 1 to 1 : 4.
7. A process as claimed in Claims 1 to 6, characterized in that the metal surface is treated with a solution in which the ratio by weight of maleic acid monoalkyl amide to phosphonic acid amounts to between 1 : 0.1 and 1 : 0.5.
8. A process as claimed in Claims 1 to 7, characterized in that the metal surface is treated with a solution which additionally contains surfactants, preferably nonionic surfactants, in quantities of from 0.005 to 0.3 % by weight, based on the aqueous solution.
9. A process as claimed in Claims 1 to 8, characterized in that the metal surface is treated with a solution which additionally contains builders, preferably phosphates and/or borates, in quantities of from 0.2 to 2 % by weight, based on the aqueous solution.
10. An agent for passivating iron and steel surfaces based on aqueous, alkaline reacting solutions containing corrosion inhibitors, characterized in that the solutions contain a combination, clearly soluble in water, of
a) one or more maleic acid monoalkyl amides,
b) one or more alkanolamines,
c) one or more phosphonic acids having complexing properties,

in total quantities of from 0.5 to 5 % by weight, the ratio by weight of maleic acid monoalkyl amide to alkanolamine amounting to between 1 : 0.3 and 1 : 10 and the ratio by weight of maleic acid monoalkyl amide to phosphonic acid to between 1 : 0.01 and 1 : 0.5 and the solutions having pH-values in the range from 7.5 to 10.5.
11. An agent as claimed in Claim 10, characterized in that it contains maleic acid mono-n- or -iso-alkyl amides containing from 6 to 14 and preferably from 8 to 10 carbon atoms in the alkyl radical.
12. An agent as claimed in Claims 10 and 11, characterized in that it contains mono-, di- and/or triethanolamine.
13. An agent as claimed in Claims 10 to 12, characterized in that it contains as phosphonic acid 1-hydroxyalkyl-1,1-diphosphonic acid, 1-aminoalkyl-1,1-diphosphonic acid, phosphonocarboxylic acid and/or a phosphonic acid corresponding to the following formula
Figure imgb0012
in which
Figure imgb0013
14. An agent as claimed in Claims 10 to 13, characterized in that it contains as phosphonic acid 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and/or nitrilotrimethylene phosphonic acid.
15. An agent as claimed in Claims 10 to 14, characterized in that the ratio by weight of maleic acid monoalkyl amide to alkanolamines amounts to between 1 : 1 and 1 :4.
16. A process as claimed in Claims 10 to 15, characterized in that the ratio by weight of maleic acid monoalkyl amide to phosphonic acid amounts to between 1 : 0.1 and 1 : 0.5.
17. An agent as claimed in Claims 10 to 16, characterized in that it additionally contains surfactants, preferably nonionic surfactants, in quantities of from 0.005 to 0.3% by weight, based on the aqueous solution.
18. An agent as claimed in Claims 10 to 17, characterized in that it additionally contains builders, preferably phosphates and/or borates, in quantities of from 0.2 to 2 % by weight, based on the aqueous solution.
EP81902484A 1980-08-27 1981-08-19 Process and product for the passivation of iron and steel surfaces Expired EP0058711B1 (en)

Priority Applications (1)

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AT81902484T ATE7932T1 (en) 1980-08-27 1981-08-19 PROCESSES AND MEANS FOR PASSIVATING IRON AND STEEL SURFACES.

Applications Claiming Priority (2)

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DE3032226 1980-08-27
DE19803032226 DE3032226A1 (en) 1980-08-27 1980-08-27 METHOD AND MEANS FOR PASSIVATING IRON AND STEEL SURFACES

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EP0058711B1 true EP0058711B1 (en) 1984-06-13

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JP (1) JPH0132313B2 (en)
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FR (1) FR2489372B1 (en)
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EP0364030A1 (en) * 1988-10-11 1990-04-18 Calgon Corporation Synergistic compositions and method for inhibiting carbon steel corrosion in aqueous systems
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EP1652969A1 (en) * 2004-10-28 2006-05-03 Henkel Kommanditgesellschaft auf Aktien Deruster composition and method
CN105986277A (en) * 2015-02-03 2016-10-05 上海立昌环境工程有限公司 Preparation of non-phosphorus neutral rust remover and application thereof
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JP6566740B2 (en) * 2015-06-24 2019-08-28 日本パーカライジング株式会社 Water-based metal surface treatment agent, film production method, and metal material with film
US10443135B1 (en) 2018-05-11 2019-10-15 Macdermid Enthone Inc. Near neutral pH pickle on multi-metals
CN109504959B (en) * 2018-12-17 2021-04-23 熊映明 Aluminum alloy spraying pretreatment chrome-free passivation line cleaning water reverse series water saving configuration
CN109518173B (en) * 2018-12-17 2021-04-23 熊映明 Aluminum alloy powder spraying pretreatment chromizing line cleaning water reverse series water saving configuration

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WO1982000665A1 (en) 1982-03-04
IT1137644B (en) 1986-09-10
JPS57501289A (en) 1982-07-22
ES504978A0 (en) 1982-08-16
IT8123630A0 (en) 1981-08-25
US4437898A (en) 1984-03-20
ZA815967B (en) 1982-09-29
EP0058711A1 (en) 1982-09-01
MX157164A (en) 1988-10-31
BR8108760A (en) 1982-07-06
FR2489372A1 (en) 1982-03-05
JPH0132313B2 (en) 1989-06-30
DE3032226A1 (en) 1982-04-01
IT8123630A1 (en) 1983-02-25
DE3164174D1 (en) 1984-07-19
ES8206660A1 (en) 1982-08-16
CA1169337A (en) 1984-06-19
BE890068A (en) 1981-12-16
FR2489372B1 (en) 1986-04-11

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