EP0099598A1 - Solution for the anti-corrosive treatment of metallic surfaces, and concentrate for preparing it - Google Patents
Solution for the anti-corrosive treatment of metallic surfaces, and concentrate for preparing it Download PDFInfo
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- EP0099598A1 EP0099598A1 EP83200876A EP83200876A EP0099598A1 EP 0099598 A1 EP0099598 A1 EP 0099598A1 EP 83200876 A EP83200876 A EP 83200876A EP 83200876 A EP83200876 A EP 83200876A EP 0099598 A1 EP0099598 A1 EP 0099598A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting 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
- C23F11/12—Oxygen-containing compounds
- C23F11/124—Carboxylic acids
Definitions
- the invention relates to an aqueous treatment liquid for corrosion protection of metal surfaces containing salts of one or more aliphatic carboxylic acids with 6 to 10 carbon atoms (component a) and salts of one or more polyoxycarboxylic acids with 6 to 8 carbon atoms (component b). and a concentrate for their manufacture.
- corrosion-protecting additives To protect metallic surfaces against corrosion when in contact with aqueous liquids or when storing metal parts after treatment with aqueous liquids, it is customary to add corrosion-protecting additives to the water.
- various metals are often to be protected by an addition.
- anti-corrosion additives must be readily soluble and stable in water of various degrees of hardness and insensitive to elevated temperatures. They should have a protective effect even at low doses. On the other hand, they must not be toxic, harmful to sewage or irritating to the skin and must not have a strong intrinsic odor.
- EP-PS 0 020 042 describes a corrosion protection agent which contains 5 to 20% by weight of aliphatic monobasic acid with 8 to 20 C atoms, 0 to 4% by weight of lubricant, 10 to 35% by weight of aromatic mono- or Polycarboxylic acid and an amine, which forms a water-soluble salt with the aliphatic and aromatic acid.
- an anticorrosive agent which contains 50 to 100 parts of a salt of a saturated carboxylic acid having 6 to 18 carbon atoms with an amine having 6 to 12 carbon atoms and 20 to 200 parts Alkali metal benzoate and 1 to 50 parts of alkanolamide as a reaction product of ethanolamine and a saturated fatty acid having 6 to 18 carbon atoms.
- an aqueous treatment liquid for corrosion protection of metal surfaces which contains a reaction product of aliphatic carboxylic acids with 6 to 10 carbon atoms and of polyoxycarboxylic acids, such as gluconic acid or tartaric acid, with an alkanolamine.
- treatment fluids for corrosion protection of metals can reduce the corrosion of steel and cast iron, but do not adequately protect other metals.
- Corrosion protection agents based on mercaptobenzthiazole or benzotriazole are common for copper and brass. However, their effect is greatly reduced in numerous mixtures for the corrosion protection of steel.
- multimetal systems e.g. used in hydraulics or in the cooling of large internal combustion engines, including oil emulsions.
- oil emulsions have many disadvantages that limit their use.
- the emulsion decomposes in hard water, the concentrate is flammable and it is not possible to drain it without prior special processing (separation of oil).
- the object of the invention is to provide an aqueous treatment liquid for corrosion protection of metal surfaces or a concentrate for their production, which does not have the known, in particular the aforementioned disadvantages.
- the aqueous treatment liquid mentioned at the outset is designed in accordance with the invention in such a way that it has an additional salt content of one or more aromatic monocarboxylic acids (component c) and the salt-forming cations are predominantly alkali ions.
- the combination of the components of the treatment liquid has a synergistic effect in that significantly better corrosion protection values are obtained than can be achieved with one of the components alone or in combination with only one further component. It is also surprising that - to use organic inhibitors in the form of alkanolamine salts of the acids, contrary to the usual recommendation - especially alkaline salts are effective in the present case 'particularly.
- the molar ratio of the individual components can vary within a wide range and essentially depends on the metals to be protected against corrosion.
- the concentration used and the conditions of use also play a certain role.
- the aqueous treatment liquid contains as component a) salt of caprylic acid and / or xthylhexanoic acid, as component b) salt of gluconic acid and / or heptonic acid and as component c) salt of benzoic acid.
- ammonium ion content should not exceed 20% of the total cation content.
- a further improvement in the properties can be achieved if the treatment liquids according to the invention have an addition of nonionic surfactants with a cloud point below 30 ° C.
- nonionic surfactants are water soluble at low temperatures. When the cloud point is reached, the solutions begin to become cloudy and the foaming effect of the surfactant solution is noticeably reduced.
- These surfactants improve the wetting of the metal surface, so that the treatment liquid can also act on moderately greased or contaminated parts.
- Polyglycol ethers of fatty alcohols, fatty amines and polyamines and polyglycol esters of fatty acids which have been reacted with ethylene oxide and propylene oxide have proven particularly useful. High-molecular block polymers made of polypropylene glycol, condensed with polyethylene oxide, and made of polyethylene glycol, condensed with propylene oxide have an optimal effect.
- corrosion inhibitors for individual metals can also be introduced into the treatment liquids according to the invention, provided that they are compatible with one another in aqueous solution and do not impair the corrosion protection of other metals.
- corrosion inhibitors are, for example, boric acid esters, higher salts Carboxylic acids, salts of amino acids, salts of sulfonamido carboxylic acids and fatty acid alkanolamides.
- Treatment liquids containing mercaptobenzthiazole, benzotriazole and their derivatives are particularly advantageous for the treatment of copper or brass.
- biocides such as phenol derivatives, formaldehyde-releasing compounds, triazines and quaternary ammonium compounds.
- the most favorable values with regard to corrosion protection are achieved when the treatment liquids with which the metals are in contact with components a), b) and c) in a total amount of 0.2 to 4% by weight, preferably 0.5 to 2% by weight.
- the pH of the ready-to-use treatment liquid is expediently in the range from 7 to 10, preferably 8 to 9.
- the easiest way to prepare the salts used in the treatment liquid is to simply mix the organic acids with alkalis and water at temperatures of 40 to 90 ° C.
- the treatment fluids for corrosion protection can be made from a solid salt mixture.
- a liquid concentrate is preferred for the batch, since the treatment liquid can be prepared from it in the simplest manner by dilution.
- Concentrates which contain components a), b) and c) in a total concentration of 30 to 80% by weight, dissolved in water, are particularly suitable.
- the surfactant content of the concentrate is 0.5 to 10 G ew .-%, preferably 1 to 4 wt .-%.
- Sample sheets (100x20x1 mm) made of steel, aluminum, copper, brass (70/30) and zinc in water of 22.4 ° dH (adjusted with calcium chloride) were immersed in half with the addition of corrosion inhibitors and covered in beakers, covered with watch glass, Stored for 28 days at a temperature of 35 ° C. After the test, the samples were rinsed, dried and the weight difference determined.
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Abstract
Description
Die Erfindung betrifft eine wäßrige Behandlungsflüss.igkeit zum Korrosionsschutz von Metalloberflächen mit einem Gehalt an Salzen einer oder mehrerer aliphatischer Carbonsäuren mit 6 bis 10 C-Atomen (Komponente a) sowie Salzen einer oder mehrerer Polyoxycarbonsäuren mit 6 bis 8 C-Atomen (Komponente b) sowie ein Konzentrat zu deren Herstellung.The invention relates to an aqueous treatment liquid for corrosion protection of metal surfaces containing salts of one or more aliphatic carboxylic acids with 6 to 10 carbon atoms (component a) and salts of one or more polyoxycarboxylic acids with 6 to 8 carbon atoms (component b). and a concentrate for their manufacture.
Zum Schutz metallischer Oberflächen gegen Korrosion bei Kontakt mit wäßrigen Flüssigkeiten oder beim Lagern von Metallteilen nach einer Behandlung mit wäßrigen Flüssigkeiten ist es üblich, dem Wasser korrosionsschützende Zusätze zuzugeben. Da-bei sollen durch einen Zusatz häufig verschiedene Metalle geschützt werden. So wird z.B. in geschlossenen Heiz- oder Kühlkreisläufen oder bei Anwendung von wäßrigen Hydraulikflüssigkeiten verlangt, daß neben Stahl und Gußeisen auch Aluminium, Kupfer, Messing, Zink und andere Metalle bzw. Metallegierungen vor Korrosion geschützt werden. Darüber hinaus müssen korrosionsschützende Zusätze in Wasser verschiedener Härtegrade gut löslich und beständig sowie gegen erhöhte Temperaturen unempfindlich sein. Sie sollen schon bei niedriger Dosierung schützend wirken. Hingegen dürfen sie nicht giftig, abwasserschädlich oder hautreizend sein und keinen starken Eigengeruch besitzen.To protect metallic surfaces against corrosion when in contact with aqueous liquids or when storing metal parts after treatment with aqueous liquids, it is customary to add corrosion-protecting additives to the water. In addition, various metals are often to be protected by an addition. For example, in closed heating or cooling circuits or when using aqueous hydraulic fluids, aluminum, copper, brass, zinc and other metals or metal alloys are protected against corrosion in addition to steel and cast iron. In addition, anti-corrosion additives must be readily soluble and stable in water of various degrees of hardness and insensitive to elevated temperatures. They should have a protective effect even at low doses. On the other hand, they must not be toxic, harmful to sewage or irritating to the skin and must not have a strong intrinsic odor.
Zum Korrosionsschutz einzelner Metalle sind verschiedene wasserlösliche Behandlungsflüssigkeiten bekannt. Für Stahl und Grauguß werden z.B. Lösungen von Nitrit, insbesondere Natriumnitrit, in alkalischer Einstellung angewendet. Als organische Stoffe werden in der Fachliteratur z.B. Benzoate, Borsäureester, Seifen, Salze von Aminosäuren und von Sulfonamidocarbonsäuren, erwähnt. Sie werden überwiegend als Alkanolaminsalze eingesetzt.Various water-soluble treatment liquids are known for the corrosion protection of individual metals. For steel and cast iron, e.g. Solutions of nitrite, especially sodium nitrite, applied in an alkaline setting. The organic literature uses e.g. Benzoates, boric acid esters, soaps, salts of amino acids and of sulfonamidocarboxylic acids. They are mainly used as alkanolamine salts.
Die EP-PS 0 020 042 beschreibt ein Korrosionsschutzmittel, das 5 bis 20 Gew.-% aliphatische monobasische Säure mit 8 bis 20 C-Atomen, 0 bis 4 Gew.-% Schmiermittel, 10 bis 35 Gew.-% aromatische Mono- oder Polycarbonsäure und ein Amin, das mit der aliphatischen und aromatischen Säure ein wasserlösliches Salz bildet, enthält.EP-PS 0 020 042 describes a corrosion protection agent which contains 5 to 20% by weight of aliphatic monobasic acid with 8 to 20 C atoms, 0 to 4% by weight of lubricant, 10 to 35% by weight of aromatic mono- or Polycarboxylic acid and an amine, which forms a water-soluble salt with the aliphatic and aromatic acid.
Gemäß US-PS 3 573 225 kommt ein korrosionsschützendes Mittel zum Einsatz, das einen Gehalt an 50 bis 100 Teilen eines Salzes einer gesättigten Carbonsäure mit 6 bis 18 C-Atomen mit einem Amin mit 6 bis 12 C-Atomen, an 20 bis 200 Teilen Alkalimetallbenzoat sowie an 1 bis 50 Teilen Alkanolamid als Reaktionsprodukt aus Äthanolamin und einer gesättigten Fettsäure mit 6 bis 18 C-Atomen aufweist.According to US Pat. No. 3,573,225, an anticorrosive agent is used which contains 50 to 100 parts of a salt of a saturated carboxylic acid having 6 to 18 carbon atoms with an amine having 6 to 12 carbon atoms and 20 to 200 parts Alkali metal benzoate and 1 to 50 parts of alkanolamide as a reaction product of ethanolamine and a saturated fatty acid having 6 to 18 carbon atoms.
Schließlich ist aus der DE-OS 26 14 234 eine wäßrige Behandlungsflüssigkeit zum Korrosionsschutz von Metalloberflächen bekannt, die ein Umsetzungsprodukt von aliphatischen Carbonsäuren mit 6 bis 10 C-Atomen und von Polyoxycarbonsäuren, wie Gluconsäure oder Weinsäure, mit einem Alkanolamin enthält.Finally, from DE-OS 26 14 234 an aqueous treatment liquid for corrosion protection of metal surfaces is known, which contains a reaction product of aliphatic carboxylic acids with 6 to 10 carbon atoms and of polyoxycarboxylic acids, such as gluconic acid or tartaric acid, with an alkanolamine.
Die genannten Behandlungsflüssigkeiten zum Korrosionsschutz von Metallen können zwar die Korrosion von Stahl und Gußeisen verringern, schützen aber andere Metalle nur ungenügend.The above-mentioned treatment fluids for corrosion protection of metals can reduce the corrosion of steel and cast iron, but do not adequately protect other metals.
So ist Aluminium praktisch nur durch Chromate oder Silikate, die aber nur bei einem hohen pH-Wert und in weichem Wasser als Lösung beständig sind, schützbar. Auch für Zink haben sich im praktischen Einsatz nur Chromate bewährt. Zwar ist aus der US-PS 4 093 780 zur Verhinderung der Weißrostbildung auf Zink die Eignung von Estern der Thioglykolsäure bekannt, jedoch stören bei der Anwendung die schlechte Wasserlöslichkeit und der starke Geruch der Ester erheblich. Zum Schutz anderer Metalle ist dieses Mittel nicht geeignet.So aluminum is practically only by chromates or silicates, which, however, only at a high pH value and in soft water Solution are stable, can be protected. In practice, only chromates have also proven themselves for zinc. Although the suitability of esters of thioglycolic acid is known from US Pat. No. 4,093,780 for preventing the formation of white rust on zinc, the poor solubility in water and the strong odor of the esters considerably interfere with use. This agent is not suitable for protecting other metals.
Für Kupfer und Messing sind Korrosionsschutzmittel auf Basis von Mercaptobenzthiazol oder Benzotriazol üblich. Deren Wirkung läßt aber in zahlreichen Mischungen zum Korrosionsschutz von Stahl stark nach.Corrosion protection agents based on mercaptobenzthiazole or benzotriazole are common for copper and brass. However, their effect is greatly reduced in numerous mixtures for the corrosion protection of steel.
Über den Schutz von Multimetallsystemen ist vergleichsweise wenig veröffentlicht worden. Eine Ubersicht ist beispielsweise durch J. Weber "Die Inhibierung der Korrosion in industriellen Kühlsystemen" in Werkstoff und Korrosion 30 (1979), Seiten 713 bis 722 gegeben. Für mehrere Metalle, wie Stahl, Gußeisen, Aluminium, Kupfer, Messing, Zink, bewähren sich nach diesen Angaben nur Chromate, die aber wegen ihrer Giftigkeit nicht in größerem Maße anwendbar sind.Comparatively little has been published on the protection of multimetal systems. An overview is given, for example, by J. Weber "The inhibition of corrosion in industrial cooling systems" in Material and Corrosion 30 (1979), pages 713 to 722. For several metals, such as steel, cast iron, aluminum, copper, brass, zinc, according to this information only chromates are effective, but because of their toxicity they cannot be used to a greater extent.
Neben wäßrigen Behandlungsflüssigkeiten zum Korrosionsschutz von Metalloberflächen werden zum Schutz von Multimetallsystemen, z.B. in der Hydraulik oder bei der Kühlung großer Verbrennungsmotoren, auch ölemulsionen eingesetzt. Sie haben jedoch viele Nachteile, die ihre Anwendung begrenzen. In hartem Wasser zersetzt sich die Emulsion, das Konzentrat ist entflammbar und das Ablassen ist ohne vorherige spezielle Aufarbeitung (Abscheiden von öl) nicht möglich.In addition to aqueous treatment fluids to protect metal surfaces from corrosion, multimetal systems, e.g. used in hydraulics or in the cooling of large internal combustion engines, including oil emulsions. However, they have many disadvantages that limit their use. The emulsion decomposes in hard water, the concentrate is flammable and it is not possible to drain it without prior special processing (separation of oil).
Aufgabe der Erfindung ist es, eine wäßrige Behandlungsflüssigkeit zum Korrosionsschutz von Metalloberflächen bzw. eines Konzentrats zu deren Herstellung bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile nicht aufweist.The object of the invention is to provide an aqueous treatment liquid for corrosion protection of metal surfaces or a concentrate for their production, which does not have the known, in particular the aforementioned disadvantages.
Die Aufgabe wird gelöst, indem die eingangs genannte wäßrige Behandlungsflüssigkeit entsprechend der Erfindung derart ausgestaltet wird, daß sie einen zusätzlichen Gehalt an Salz einer oder mehrerer aromatischer Monocarbonsäuren (Komponente c) aufweist und die salzbildenden Kationen überwiegend Alkaliionen sind.The object is achieved in that the aqueous treatment liquid mentioned at the outset is designed in accordance with the invention in such a way that it has an additional salt content of one or more aromatic monocarboxylic acids (component c) and the salt-forming cations are predominantly alkali ions.
Uberraschenderweise zeigt die Kombination der Bestandteile der Behandlungsflüssigkeit einen synergistischen Effekt, indem entscheidend bessere Korrosionsschutzwerte erhalten werden, als mit einem der Bestandteile allein oder in Kombination mit nur einem weiteren Bestandteil erzielbar sind. Überraschend ist auch, daß - entgegen der üblichen Empfehlung, organische Inhibitoren in Form von Alkanolaminsalzen der Säuren einzusetzen - im vorliegenden Falle' gerade Alkalisalze besonders wirksam sind.Surprisingly, the combination of the components of the treatment liquid has a synergistic effect in that significantly better corrosion protection values are obtained than can be achieved with one of the components alone or in combination with only one further component. It is also surprising that - to use organic inhibitors in the form of alkanolamine salts of the acids, contrary to the usual recommendation - especially alkaline salts are effective in the present case 'particularly.
Das molare Verhältnis der einzelnen Komponenten kann sich in breiten Grenzen bewegen und hängt im wesentlichen von den vor Korrosion zu schützenden Metallen ab. Auch.die angewendete Konzentration und die Anwendungsbedingungen spielen eine gewisse Rolle.The molar ratio of the individual components can vary within a wide range and essentially depends on the metals to be protected against corrosion. The concentration used and the conditions of use also play a certain role.
Eine bevorzugte Ausgestaltung der Erfindung besteht in einer Behandlungsflüssigkeit, in der die Salze in einem molaren Verhältnis von
- Komponente a) zu Komponente b) wie 10:1 bis 1:5, vorzugsweise 4:1 bis 1:2,
- Komponente a) zu Komponente c) wie 5:1 bis 1:5, vorzugsweise 2:1 bis 1:2,
- Komponente b) zu Komponente c) wie 5:1 bis 1:10, vorzugsweise 2:1 bis 1:4 enthalten sind.
- Component a) to component b) as 10: 1 to 1: 5, preferably 4: 1 to 1: 2,
- Component a) to component c) as 5: 1 to 1: 5, preferably 2: 1 to 1: 2,
- Component b) to component c) as 5: 1 to 1:10, preferably 2: 1 to 1: 4 are included.
Besonders gute Ergebnisse werden erhalten, wenn die wäßrige Behandlungsflüssigkeit als Komponente a) Salz von Caprylsäure und/oder Xthylhexansäure, als Komponente b) Salz von Gluconsäure und/oder Heptonsäure sowie als Komponente c) Salz von Benzoesäure enthält.Particularly good results are obtained if the aqueous treatment liquid contains as component a) salt of caprylic acid and / or xthylhexanoic acid, as component b) salt of gluconic acid and / or heptonic acid and as component c) salt of benzoic acid.
Weiterhin wurde gefunden, daB, um einen optimalen Korrosionsschutz zu erreichen, der Gehalt an Ammoniumionen nicht mehr als 20 % des Gesamtkationengehaltes betragen sollte.It was also found that, in order to achieve optimum protection against corrosion, the ammonium ion content should not exceed 20% of the total cation content.
Eine weitere Verbesserung der Eigenschaften kann erzielt werden, wenn die erfindungsgemäßen Behandlungsflüssigkeiten einen Zusatz von nichtionogenen Tensiden mit einem Trübungspunkt unter 30 °C aufweisen. Solche Tenside sind bei tiefen Temperaturen wasserlöslich. Bei Erreichen des Trübungspunktes beginnen die Lösungen trübe zu werden und die Schaumwirkung der Tensidlösung verringert sich merklich. Durch diese Tenside wird die Benetzung der Metalloberfläche verbessert, so daß die Behandlungsflüssigkeit auch auf mäßig befetteten oder verschmutzten Teilen wirken kann. Besonders bewährt haben sich Polyglykoläther von Fettalkoholen, Fettaminen und Polyaminen sowie Polyglykolester von Fettsäuren, die mit Äthylenoxid und Propylenoxid umgesetzt wurden. Eine optimale Wirkung zeigen hochmolekulare Blockpolymere aus Polypropylenglykol, kondensiert mit Polyäthylenoxid, und aus Polyäthylenglykol, kondensiert mit Propylenoxid.A further improvement in the properties can be achieved if the treatment liquids according to the invention have an addition of nonionic surfactants with a cloud point below 30 ° C. Such surfactants are water soluble at low temperatures. When the cloud point is reached, the solutions begin to become cloudy and the foaming effect of the surfactant solution is noticeably reduced. These surfactants improve the wetting of the metal surface, so that the treatment liquid can also act on moderately greased or contaminated parts. Polyglycol ethers of fatty alcohols, fatty amines and polyamines and polyglycol esters of fatty acids which have been reacted with ethylene oxide and propylene oxide have proven particularly useful. High-molecular block polymers made of polypropylene glycol, condensed with polyethylene oxide, and made of polyethylene glycol, condensed with propylene oxide have an optimal effect.
In die erfindungsgemäßen Behandlungsflüssigkeiten können auch andere an sich bekannte Korrosionsinhibitoren für einzelne Metalle, soweit sie in wäßriger Lösung miteinander verträglich sind und nicht den Korrosionsschutz bei anderen Metallen verschlechtern, zusätzlich eingebracht werden. Solche Korrosionsinhibitoren sind beispielsweise Borsäureester, Salze höherer Carbonsäuren, Salze von Aminosäuren, Salze von Sulfonamidocarbonsäuren und Fettsäurealkanolamide. Speziell zur Behandlung von Kupfer oder Messing sind Behandlungsflüssigkeiten mit einem Gehalt an Mercaptobenzthiazol, Benzotriazol und deren Abkömmlinge vorteilhaft.Other known corrosion inhibitors for individual metals can also be introduced into the treatment liquids according to the invention, provided that they are compatible with one another in aqueous solution and do not impair the corrosion protection of other metals. Such corrosion inhibitors are, for example, boric acid esters, higher salts Carboxylic acids, salts of amino acids, salts of sulfonamido carboxylic acids and fatty acid alkanolamides. Treatment liquids containing mercaptobenzthiazole, benzotriazole and their derivatives are particularly advantageous for the treatment of copper or brass.
Um die wäßrigen Behandlungsflüssigkeiten vor einem Befall durch Mikroorganismen zu schützen, ist es häufig vorteilhaft, geeignete Biozide, wie Phenolderivate, Formaldehyd abspaltende Verbindungen, Triazine und quartäre Ammoniumverbindungen zuzugeben.In order to protect the aqueous treatment liquids from attack by microorganisms, it is often advantageous to add suitable biocides, such as phenol derivatives, formaldehyde-releasing compounds, triazines and quaternary ammonium compounds.
Die günstigsten Werte hinsichtlich Korrosionsschutz werden erzielt, wenn die Behandlungsflüssigkeiten, mit denen die Metalle in Berührung stehen, die Komponenten a), b) und c) in einer Gesamtmenge von 0,2 bis 4 Gew.-%, vorzugsweise von 0,5 bis 2 Gew.-%, vorliegen.The most favorable values with regard to corrosion protection are achieved when the treatment liquids with which the metals are in contact with components a), b) and c) in a total amount of 0.2 to 4% by weight, preferably 0.5 to 2% by weight.
Der pH-Wert der gebrauchsfertigen Behandlungsflüssigkeit liegt zweckmäßigerweise im Bereich von 7 bis 10, vorzugsweise 8 bis 9.The pH of the ready-to-use treatment liquid is expediently in the range from 7 to 10, preferably 8 to 9.
Die in der Behandlungsflüssigkeit eingesetzten Salze werden am einfachsten durch einfaches Mischen der organischen Säuren mit Alkalien und Wasser bei Temperaturen von 40 bis 90 °C hergestellt.The easiest way to prepare the salts used in the treatment liquid is to simply mix the organic acids with alkalis and water at temperatures of 40 to 90 ° C.
Grundsätzlich können die Behandlungsflüssigkeiten zum Korrosionsschutz aus einem festen Salzgemisch hergestellt werden. Bevorzugt ist jedoch für den Ansatz ein flüssiges Konzentrat, da sich hieraus durch Verdünnen in einfachster Weise die Behandlungsflüssigkeit herstellen läßt. Konzentrate, die die Komponenten a), b) und c) in einer Gesamtkonzentration von 30 bis 80 Gew.-%, in Wasser gelöst, enthalten, sind besonders geeignet. Zweckmäßigerweise beträgt der Tensidgehalt des Konzentrates 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 4 Gew.-%.In principle, the treatment fluids for corrosion protection can be made from a solid salt mixture. However, a liquid concentrate is preferred for the batch, since the treatment liquid can be prepared from it in the simplest manner by dilution. Concentrates which contain components a), b) and c) in a total concentration of 30 to 80% by weight, dissolved in water, are particularly suitable. Conveniently, the surfactant content of the concentrate is 0.5 to 10 G ew .-%, preferably 1 to 4 wt .-%.
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.
In den nachstehenden Versuchen wurde die Korrosionsschutzwirkung der erfindungsgemäßen Behandlungsflüssigkeit (Beispiele 9 bis 11) im Vergleich zu Einzelkomponenten sowie anderen Zusammensetzungen dargelegt (Beispiel 1 bis 8 und 12).In the experiments below, the anti-corrosion effect of the treatment liquid according to the invention (Examples 9 to 11) was demonstrated in comparison to individual components and other compositions (Examples 1 to 8 and 12).
Zur Prüfung wurde eine modifizierte Methode so, wie sie im 'Fünften Bericht über Anforderungen und Prüfungen schwer entflammbarer Flüssigkeiten zur hydraulischen Kraftübertragung und Steuerung', Luxemburg 1974, ausgegeben von der Kommission der europäischen Gemeinschaften, vorgeschlagen ist, angewendet.A modified method as proposed in the 'Fifth Report on Requirements and Tests for Flammable Liquids for Hydraulic Power Transmission and Control', Luxembourg 1974, issued by the Commission of the European Communities, was used for testing.
Es wurden Probebleche (100x20x1 mm) aus Stahl, Aluminium, Kupfer, Messing (70/30) und Zink in Wasser von 22,4 °dH (mit Calciumchlorid eingestellt) mit Zugabe von Korrosionsinhibitoren zur Hälfte getaucht und in Bechergläsern, mit Uhrglas bedeckt, 28 Tage bei einer Temperatur von 35 °C gelagert. Nach der Prüfung wurden die Proben gespült, getrocknet und die Gewichtsdifferenz ermittelt.Sample sheets (100x20x1 mm) made of steel, aluminum, copper, brass (70/30) and zinc in water of 22.4 ° dH (adjusted with calcium chloride) were immersed in half with the addition of corrosion inhibitors and covered in beakers, covered with watch glass, Stored for 28 days at a temperature of 35 ° C. After the test, the samples were rinsed, dried and the weight difference determined.
Der Hemmwert der Zusätze wurde nach der folgenden Formel errechnet:
- M1 ... Abtrag in Wasser ohne Zusatz
- M2 ... Abtrag in inhibierter Lösung
- M 1 ... removal in water without additives
- M 2 ... removal in inhibited solution
Die errechneten Hemmwerte für in Wasser und in verschiedenen Behandlungsflüssigkeiten geprüfte Probebleche sind in der nachstehenden Tabelle zusammengefaßt. Die Konzentration der einzelnen zugesetzten Korrosionsinhibitoren sind in Spalte 3 aufgeführt.
Claims (15)
enthält.2. Treatment liquid according to claim 1, characterized in that it contains the salts in a molar ratio of
contains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3223940 | 1982-06-26 | ||
| DE19823223940 DE3223940A1 (en) | 1982-06-26 | 1982-06-26 | TREATMENT LIQUID FOR CORROSION PROTECTION OF METAL SURFACES AND CONCENTRATE FOR THEIR PRODUCTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0099598A1 true EP0099598A1 (en) | 1984-02-01 |
Family
ID=6166954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83200876A Withdrawn EP0099598A1 (en) | 1982-06-26 | 1983-06-15 | Solution for the anti-corrosive treatment of metallic surfaces, and concentrate for preparing it |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0099598A1 (en) |
| JP (1) | JPS5925977A (en) |
| AU (1) | AU561560B2 (en) |
| BR (1) | BR8303394A (en) |
| CA (1) | CA1219119A (en) |
| DE (1) | DE3223940A1 (en) |
| GB (1) | GB2122598B (en) |
| NZ (1) | NZ204711A (en) |
| ZA (1) | ZA834632B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206144A1 (en) * | 1985-06-20 | 1986-12-30 | Henkel Kommanditgesellschaft auf Aktien | Aqueous compositions for the Hilite and flux process, and their use |
| EP0479470A1 (en) * | 1990-10-01 | 1992-04-08 | Texaco Development Corporation | Corrosion-inhibited antifreeze/coolant composition |
| FR2687412A1 (en) * | 1992-02-14 | 1993-08-20 | Atochem Elf Sa | Corrosion-inhibiting composition based on carboxylic acid and its application for inhibiting corrosion |
| WO1995002712A2 (en) * | 1993-07-16 | 1995-01-26 | Henkel Kommanditgesellschaft Auf Aktien | Use of carboxylic acids in agents for the treatment of metal surfaces |
| US5507861A (en) * | 1992-02-14 | 1996-04-16 | Elf Atochem S.A. And Haber Partners Sarl | Carboxylic acid-based corrosion-inhibiting composition and application thereof in corrosion prevention |
| EP1148154A1 (en) * | 1999-01-07 | 2001-10-24 | Otsuka Kagaku Kabushiki Kaisha | Surface-treating agent for magnesium-based part and method of surface treatment |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647392A (en) * | 1985-12-27 | 1987-03-03 | Texaco Inc. | Monobasic-dibasic acid/salt antifreeze corrosion inhibitor |
| US4851145A (en) * | 1986-06-30 | 1989-07-25 | S.A. Texaco Petroleum Nv | Corrosion-inhibited antifreeze/coolant composition |
| DE4007985A1 (en) * | 1989-03-17 | 1990-10-04 | Mitsubishi Electric Corp | Aq. compsn. contg. fatty acid amide and saccharide |
| DE69220209T2 (en) * | 1992-04-06 | 1997-10-02 | Texaco Services Europ Ltd | Anticorrosive antifreeze |
| US5997763A (en) * | 1998-04-27 | 1999-12-07 | Shell Oil Company | Corrosion inhibiting antifreeze compositions containing various carboxylic acids |
| US9700425B1 (en) | 2011-03-20 | 2017-07-11 | Nuvasive, Inc. | Vertebral body replacement and insertion methods |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2529178A (en) * | 1947-12-06 | 1950-11-07 | W H And L D Betz | Method for obtaining corrosion and tuberculation inhibition in water systems |
| FR1139139A (en) * | 1955-12-29 | 1957-06-25 | Anti-rust product | |
| GB910138A (en) * | 1959-11-10 | 1962-11-07 | Ici Ltd | Improvements in and relating to the prevention of corrosion in cooling systems |
| US3405072A (en) * | 1966-01-05 | 1968-10-08 | Continental Can Co | Method of inhibiting corrosion of aqueous mediums by addition of lithium salts of organic acids |
| DE1936990A1 (en) * | 1967-10-09 | 1971-02-04 | Exxon Research Engineering Co | Method and device for preventing corrosion |
| FR2346465A1 (en) * | 1976-04-02 | 1977-10-28 | Parker Ste Continentale | ANTI-CORROSION AGENT FOR METAL SURFACES |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE480466A (en) * | 1943-11-04 | |||
| GB855442A (en) * | 1957-05-22 | 1960-11-30 | Ici Ltd | Improvements in or relating to anti-rusting agents |
| GB838258A (en) * | 1958-03-14 | 1960-06-22 | Ici Ltd | Improvements in and relating to the prevention of corrosion in cooling systems |
| NL242077A (en) * | 1958-03-27 | |||
| GB961409A (en) * | 1961-05-24 | 1964-06-24 | United States Borax Chem | Corrosion inhibitor compositions |
-
1982
- 1982-06-26 DE DE19823223940 patent/DE3223940A1/en not_active Withdrawn
-
1983
- 1983-06-15 EP EP83200876A patent/EP0099598A1/en not_active Withdrawn
- 1983-06-22 CA CA000430914A patent/CA1219119A/en not_active Expired
- 1983-06-23 GB GB08317084A patent/GB2122598B/en not_active Expired
- 1983-06-24 ZA ZA834632A patent/ZA834632B/en unknown
- 1983-06-24 BR BR8303394A patent/BR8303394A/en unknown
- 1983-06-27 NZ NZ204711A patent/NZ204711A/en unknown
- 1983-06-27 JP JP58115734A patent/JPS5925977A/en active Pending
- 1983-06-27 AU AU16295/83A patent/AU561560B2/en not_active Ceased
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2529178A (en) * | 1947-12-06 | 1950-11-07 | W H And L D Betz | Method for obtaining corrosion and tuberculation inhibition in water systems |
| FR1139139A (en) * | 1955-12-29 | 1957-06-25 | Anti-rust product | |
| GB910138A (en) * | 1959-11-10 | 1962-11-07 | Ici Ltd | Improvements in and relating to the prevention of corrosion in cooling systems |
| US3405072A (en) * | 1966-01-05 | 1968-10-08 | Continental Can Co | Method of inhibiting corrosion of aqueous mediums by addition of lithium salts of organic acids |
| DE1936990A1 (en) * | 1967-10-09 | 1971-02-04 | Exxon Research Engineering Co | Method and device for preventing corrosion |
| FR2346465A1 (en) * | 1976-04-02 | 1977-10-28 | Parker Ste Continentale | ANTI-CORROSION AGENT FOR METAL SURFACES |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206144A1 (en) * | 1985-06-20 | 1986-12-30 | Henkel Kommanditgesellschaft auf Aktien | Aqueous compositions for the Hilite and flux process, and their use |
| EP0479470A1 (en) * | 1990-10-01 | 1992-04-08 | Texaco Development Corporation | Corrosion-inhibited antifreeze/coolant composition |
| FR2687412A1 (en) * | 1992-02-14 | 1993-08-20 | Atochem Elf Sa | Corrosion-inhibiting composition based on carboxylic acid and its application for inhibiting corrosion |
| US5507861A (en) * | 1992-02-14 | 1996-04-16 | Elf Atochem S.A. And Haber Partners Sarl | Carboxylic acid-based corrosion-inhibiting composition and application thereof in corrosion prevention |
| WO1995002712A2 (en) * | 1993-07-16 | 1995-01-26 | Henkel Kommanditgesellschaft Auf Aktien | Use of carboxylic acids in agents for the treatment of metal surfaces |
| WO1995002712A3 (en) * | 1993-07-16 | 1995-06-22 | Henkel Kgaa | Use of carboxylic acids in agents for the treatment of metal surfaces |
| EP1148154A1 (en) * | 1999-01-07 | 2001-10-24 | Otsuka Kagaku Kabushiki Kaisha | Surface-treating agent for magnesium-based part and method of surface treatment |
| EP1148154A4 (en) * | 1999-01-07 | 2002-09-25 | Otsuka Kagaku Kk | Surface-treating agent for magnesium-based part and method of surface treatment |
| US6569264B1 (en) | 1999-01-07 | 2003-05-27 | Otsuka Kagaku Kabushiki Kaisha | Surface-treating agent for magnesium-based part and method of surface treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA834632B (en) | 1984-03-28 |
| AU561560B2 (en) | 1987-05-14 |
| BR8303394A (en) | 1984-02-07 |
| DE3223940A1 (en) | 1983-12-29 |
| AU1629583A (en) | 1984-01-05 |
| CA1219119A (en) | 1987-03-17 |
| GB2122598A (en) | 1984-01-18 |
| GB2122598B (en) | 1985-07-10 |
| NZ204711A (en) | 1986-02-21 |
| JPS5925977A (en) | 1984-02-10 |
| GB8317084D0 (en) | 1983-07-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): BE DE FR IT SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19840727 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: HOCH, HELMUT Inventor name: RONES, JOSEF Inventor name: MOELLER, SIEGFRIED Inventor name: FISCHER, FRANZ |