EP0162875B1 - Corrosion inhibitors for aluminium - Google Patents
Corrosion inhibitors for aluminium Download PDFInfo
- Publication number
- EP0162875B1 EP0162875B1 EP84904122A EP84904122A EP0162875B1 EP 0162875 B1 EP0162875 B1 EP 0162875B1 EP 84904122 A EP84904122 A EP 84904122A EP 84904122 A EP84904122 A EP 84904122A EP 0162875 B1 EP0162875 B1 EP 0162875B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- combination
- amino
- aluminium
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
Definitions
- the invention relates to the use of a combination of 3-amino-5-alkyl-1,2,4-triazoles and aminotrimethylenephosphonic acid in a weight ratio of 10: 1 to 1: 1 as a corrosion inhibitor for aluminum in aqueous, acid-reacting systems.
- alkali silicates or sodium benzoate.
- suitable additives such as alkali silicates or sodium benzoate.
- alkali silicates show a good activity in the neutral range and especially in the case of alkali silicates in the basic range.
- alkali silicates are unusable, while the desired protection can only be achieved with sodium benzoate at high concentrations.
- FR-A-2 014 864 describes a method for preventing the corrosion of aluminum and aluminum alloys in hydrochloric acid solutions at temperatures between 0 and 30 ° C.
- the hydrochloric acid solutions which have an HCI concentration of 0.1 to 12 percent by weight, a soluble aminomethylenephosphonic acid or its salts in an amount of 0.5 to 20 percent by weight, based on the HCI content.
- the aminomethylenephosphonic acid to be used contains at least two phosphonic acid groups in the molecule as well as a characteristic group of the general formula -N (CH 2 -PO 3 H 2 ) 2 .
- Aminotri- (methylenephosphonic acid or ethylenediaminetetra- (methylenephosphonic acid) are preferably used.
- inhibitors known per se for other metals can also be used.
- EP-A-25 863 relates to the use of 3-amino-5-alkyl-1,2,4-triazoles - preferably having 5 to 7 carbon atoms in the alkyl radical - as corrosion inhibitors for non-ferrous metals, such as copper, brass, bronze or the like, in aqueous systems in the pH range from 6 to 10. These compounds are added to the aqueous systems in an amount of 0.05 to 10 g / m 3 , preferably 0.1 to 0.5 g / m 3 . In addition, additional stone protection and dispersing agents and / or complexing phosphonic acids can be used.
- Suitable phosphonic acids are 1-hydroxyethane-1,1-disphosphonic acid, aminotrimethylene phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, their water-soluble salts or mixtures of these compounds.
- 3-amino-5-alkyl-1, 2,4-triazoles are suitable for this purpose, the alkyl radical of which has 2 to 10, preferably 7 to 9, carbon atoms.
- aminotrimethylenephosphonic acid has also proven to be particularly suitable, while such effects are not obtained with other commercially available phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid.
- the mixtures of 3-amino-5-alkyl-1,2,4-triazoles and aminotrimethylenephosphonic acid described are used in amounts of 50 to 1,000 g / m 3 , preferably 200 to 500 g / m 3 .
- aminoalkyl-1,2,4-triazoles which are used are prepared by methods known per se, for example by reacting fatty acid with aminoguanidine hydrogen carbonate. However, the preparation of these compounds is not the subject of this application.
- the corrosion protection properties are determined in the manner described below.
- test strips 80 x 15 x 1 mm are hung in a 1-1 test vessel containing 800 ml of test water and a defined amount of substance to be examined, and in it for 18 hours at room temperature and 80 revolutions per minute leave.
- test water used as the corrosive medium was produced in accordance with DIN 51360/2 and adjusted to a pH of 1 using concentrated sulfuric acid.
- the table below shows the inhibitors used, their concentration and the corrosion protection achieved in%.
- the data given under order number 7 corresponds to the object of registration.
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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)
Abstract
Description
Gegenstand der Erfindung ist die Verwendung einer Kombination aus 3-Amino-5-alkyl-1,2,4-triazolen und Aminotrimethylenphosphonsäure im Gewichtsverhältnis von 10 : 1 bis 1 : 1 als Korrosionsinhibitor für Aluminium in wäßrigen, sauer reagierenden Systemen.The invention relates to the use of a combination of 3-amino-5-alkyl-1,2,4-triazoles and aminotrimethylenephosphonic acid in a weight ratio of 10: 1 to 1: 1 as a corrosion inhibitor for aluminum in aqueous, acid-reacting systems.
Es ist bekannt, die Korrosion von Aluminium in wäßrigen Systemen durch geeignete Zusätze, wie Alkalisilikate oder Natriumbenzoat, herabzusetzen. Derartige Verbindungen zeigen eine gute Wirksamkeit im neutralen und insbesondere bei Alkalisilikaten im basischen Bereich. Im sauren Bereich dagegen sind Alkalisilikate unbrauchbar, während mit Natriumbenzoat nur mit hohen Konzentrationen der angestrebte Schutz erreichbar ist.It is known to reduce the corrosion of aluminum in aqueous systems by means of suitable additives, such as alkali silicates or sodium benzoate. Such compounds show a good activity in the neutral range and especially in the case of alkali silicates in the basic range. In the acidic range, however, alkali silicates are unusable, while the desired protection can only be achieved with sodium benzoate at high concentrations.
Ferner wird in der FR-A-2 014 864 ein Verfahren zur Verhinderung der Korrosion von Aluminium und Aluminiumlegierungen in salzsauren Lösungen bei Temperaturen zwischen 0 und 30°C beschrieben. Hierbei setzt man den salzsauren Lösungen, die eine HCI-Konzentration von 0,1 bis 12 Gewichtsprozent aufweisen, eine lösliche Aminomethylenphosphonsäure oder deren Salze in einer Menge von 0,5 bis 20 Gewichtsprozent, bezogen auf den HCI-Gehalt, zu. Die zu verwendende Aminomethylenphosphonsäure enthält im Molekül mindestens zwei Phosphonsäuregruppen sowie eine charakteristische Gruppe der allgemeinen Formel -N(CH2-PO3H2)2. Bevorzugt werden Aminotri-(methylenphosphonsäure oder Ethylendiamintetra-(methylenphos- phonsäure) eingesetzt. Daneben können auch an sich bekannte Inhibitoren für andere Metalle verwendet werden.Furthermore, FR-A-2 014 864 describes a method for preventing the corrosion of aluminum and aluminum alloys in hydrochloric acid solutions at temperatures between 0 and 30 ° C. Here, the hydrochloric acid solutions, which have an HCI concentration of 0.1 to 12 percent by weight, a soluble aminomethylenephosphonic acid or its salts in an amount of 0.5 to 20 percent by weight, based on the HCI content. The aminomethylenephosphonic acid to be used contains at least two phosphonic acid groups in the molecule as well as a characteristic group of the general formula -N (CH 2 -PO 3 H 2 ) 2 . Aminotri- (methylenephosphonic acid or ethylenediaminetetra- (methylenephosphonic acid) are preferably used. In addition, inhibitors known per se for other metals can also be used.
Gegenstand der EP-A-25 863 ist die Verwendung von 3-Amino-5-alkyl-1,2,4-triazolen - mit vorzugsweise 5 bis 7 C-Atomen im Alkylrest - als Korrosionsinhibitoren für Buntmetalle, wie Kupfer, Messing, Bronze oder dergleichen, in wäßrigen Systemen im pH-Bereich von 6 bis 10. Diese Verbindungen werden den wäßrigen Systemen in einer Menge von 0,05 bis 10 g/m3, vorzugsweise 0,1 bis 0,5 g/m3, zugesetzt. Daneben können zusätzliche Steinschutz- und Dispergiermittel und/oder komplexierende Phosphonsäuren Verwendung finden. Als Phosphonsäuren kommen beispielsweise 1-Hydroxyethan-1,1-disphosphonsäure, Aminotrimethylenphosphonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure, deren wasserlösliche Salze oder Gemische dieser Verbindungen in Frage.EP-A-25 863 relates to the use of 3-amino-5-alkyl-1,2,4-triazoles - preferably having 5 to 7 carbon atoms in the alkyl radical - as corrosion inhibitors for non-ferrous metals, such as copper, brass, bronze or the like, in aqueous systems in the pH range from 6 to 10. These compounds are added to the aqueous systems in an amount of 0.05 to 10 g / m 3 , preferably 0.1 to 0.5 g / m 3 . In addition, additional stone protection and dispersing agents and / or complexing phosphonic acids can be used. Examples of suitable phosphonic acids are 1-hydroxyethane-1,1-disphosphonic acid, aminotrimethylene phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, their water-soluble salts or mixtures of these compounds.
Demgegenüber wurde nun gefunden, daß man als Korrosionsinhibitor für Aluminium in wäßrigen Systemen über einen weiten sauren Bereich (pH 1 bis 6) die eingangs beschriebene Kombination mit ausgezeichneten Ergebnissen verwenden kann.In contrast, it has now been found that the corrosion inhibitor for aluminum in aqueous systems over a wide acidic range (pH 1 to 6) can be used with the combination described above with excellent results.
Insbesondere sind hierfür 3-Amino-5-alkyl-1 ,2,4-triazole geeignet, deren Alkylrest 2 bis 10, vorzugsweise 7 bis 9, C-Atome aufweist.In particular, 3-amino-5-alkyl-1, 2,4-triazoles are suitable for this purpose, the alkyl radical of which has 2 to 10, preferably 7 to 9, carbon atoms.
Ferner ist die Verwendung einer Kombination bevorzugt, in welcher 3-Amino-5-alkyl-1,2,4-triazole und Aminotrimethylenphosphonsäure im Gewichtsverhältnis 5 : 1 vorliegen.Furthermore, the use of a combination is preferred in which 3-amino-5-alkyl-1,2,4-triazoles and aminotrimethylenephosphonic acid are present in a weight ratio of 5: 1.
Dabei tritt überraschenderweise ein synergistischer Effekt ein, indem mit der beanspruchten Kombination erheblich bessere Ergebnisse als mit den einzelnen Komponenten erzielt werden. Darüber hinaus hat sich auch Aminotrimethylenphosphonsäure als besonders geeignet erwiesen, während man mit anderen handelsüblichen Phosphonsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure oder 2-Phosphonobutan-1,2,4-tricarbonsäure, derartige Effekte nicht erhält.Surprisingly, a synergistic effect occurs in that considerably better results are achieved with the claimed combination than with the individual components. In addition, aminotrimethylenephosphonic acid has also proven to be particularly suitable, while such effects are not obtained with other commercially available phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid.
Die Verwendung der beschriebenen Gemische aus 3-Amino-5-alkyl-1,2,4-triazolen und Aminotrimethylenphosphonsäure erfolgt in Mengen von 50 bis 1.000 g/m3, vorzugsweise 200 bis 500 g/m3.The mixtures of 3-amino-5-alkyl-1,2,4-triazoles and aminotrimethylenephosphonic acid described are used in amounts of 50 to 1,000 g / m 3 , preferably 200 to 500 g / m 3 .
Die Herstellung der Aminoalkyl-1,2,4-triazole, die zur Anwendung gelangen, erfolgt nach an sich bekannten Methoden, so beispielsweise durch Umsetzung von Fettsäure mit Aminoguanidin-hydrogen-carbonat. Die Herstellung dieser Verbindungen ist jedoch nicht Gegenstand dieser Anmeldung.The aminoalkyl-1,2,4-triazoles which are used are prepared by methods known per se, for example by reacting fatty acid with aminoguanidine hydrogen carbonate. However, the preparation of these compounds is not the subject of this application.
Die Bestimmung der Korrosionsschutzeigenschaften erfolgt in der nachstehend beschriebenen Weise.The corrosion protection properties are determined in the manner described below.
Je drei sorgfältig vorbehandelte und gewogene Teststreifen (80 x 15 x 1 mm) werden in ein 1-1-Prüfgefäß, das 800 ml Testwasser und eine definierte Menge an zu untersuchender Substanz enthält, gehängt und 18 Stunden bei Raumtemperatur und 80 Umdrehungen pro Minute darin belassen.Three carefully pretreated and weighed test strips (80 x 15 x 1 mm) are hung in a 1-1 test vessel containing 800 ml of test water and a defined amount of substance to be examined, and in it for 18 hours at room temperature and 80 revolutions per minute leave.
Aus dem Gewichtsverlust wurde der Korrosionsschutzwert S, bezogen auf eine Blindprobe, berechnet.
- a - Gewichtsverlust Probe
- b - Gewichtsverlust Blindwert
- a - weight loss sample
- b - Weight loss blank
Das als korrosives Medium benutzte Versuchswasser wurde nach DIN 51360/2 hergestellt und mit konzentrierter Schwefelsäure auf einen pH-Wert von 1 eingestellt.The test water used as the corrosive medium was produced in accordance with DIN 51360/2 and adjusted to a pH of 1 using concentrated sulfuric acid.
In der nachstehenden Tabelle sind jeweils die verwendeten Inhibitoren, deren Konzentration sowie der erzielte Korrosionsschutz in % wiedergegeben. Die unter der laufenden Nummer 7 angegebenen Daten entsprechen dem Anmeldungsgegenstand.
In der Tabelle bedeuten:
- HAT - 3-Heptyl-5-amino-1,2,4-triazol
- HEDP = 1-Hydroxyethan-1,1-diphosphonsäure
- ATMP = Aminotrimethylenphosphonsäure
- PBTC = 2-Phosphonobutan-1,2,4-tricarbonsäure
- HAT - 3-heptyl-5-amino-1,2,4-triazole
- HEDP = 1-hydroxyethane-1,1-diphosphonic acid
- ATMP = aminotrimethylenephosphonic acid
- PBTC = 2-phosphonobutane-1,2,4-tricarboxylic acid
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84904122T ATE40839T1 (en) | 1983-11-14 | 1984-11-02 | CORROSION INHIBITORS FOR ALUMINUM. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833341152 DE3341152A1 (en) | 1983-11-14 | 1983-11-14 | CORROSION INHIBITORS FOR ALUMINUM |
| DE3341152 | 1983-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0162875A1 EP0162875A1 (en) | 1985-12-04 |
| EP0162875B1 true EP0162875B1 (en) | 1989-02-15 |
Family
ID=6214286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84904122A Expired EP0162875B1 (en) | 1983-11-14 | 1984-11-02 | Corrosion inhibitors for aluminium |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4647429A (en) |
| EP (1) | EP0162875B1 (en) |
| JP (1) | JPS61500447A (en) |
| DE (2) | DE3341152A1 (en) |
| WO (1) | WO1985002207A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904901A (en) * | 1984-12-03 | 1990-02-27 | Lumel, Inc. | Electrolumescent panels |
| DE19701031C2 (en) * | 1997-01-15 | 1998-12-10 | Henkel Kgaa | Use of 3-amino-5-alkyl-1,2,4-triozoles as silver protection agents |
| DE19758262A1 (en) * | 1997-12-31 | 1999-07-08 | Henkel Kgaa | Granular component containing alkylaminotriazole for use in machine dishwashing detergents (MGSM) and process for its production |
| JP2010070790A (en) * | 2008-09-17 | 2010-04-02 | Chiyoda Chemical Kk | Discoloration preventing treatment method for aluminum-based metal |
| US9243333B2 (en) * | 2012-09-27 | 2016-01-26 | The United States Of America, As Represented By The Secretary Of The Navy | Coated aluminum alloy pigments and corrosion-resistant coatings |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3553101A (en) * | 1968-05-17 | 1971-01-05 | Exxon Research Engineering Co | Prevention of corrosion using heterocyclic nitrogen compounds |
| GB1222133A (en) * | 1968-05-25 | 1971-02-10 | Geigy Uk Ltd | Inhibition of corrosion of copper and its alloys using 3-amino-1:2:4-triazole |
| AT276897B (en) * | 1968-08-01 | 1969-12-10 | Henkel & Cie Gmbh | Prevention of corrosion of aluminum and aluminum alloys in hydrochloric acid solutions |
| DE1917686A1 (en) * | 1969-04-05 | 1970-10-08 | Benckiser Knapsack Gmbh | Method of treating water baths |
| US3935125A (en) * | 1974-06-25 | 1976-01-27 | Chemed Corporation | Method and composition for inhibiting corrosion in aqueous systems |
| US4317744A (en) * | 1979-04-25 | 1982-03-02 | Drew Chemical Corporation | Corrosion inhibitor |
| DE2934461A1 (en) * | 1979-08-25 | 1981-03-26 | Henkel KGaA, 40589 Düsseldorf | CORROSION INHIBITORS FOR COLORED METALS |
| US4409121A (en) * | 1980-07-21 | 1983-10-11 | Uop Inc. | Corrosion inhibitors |
| GB2094776B (en) * | 1981-03-11 | 1984-05-16 | Dearborn Chemicals Ltd | Prevention of corrosion in aqueous systems |
| US4452758A (en) * | 1981-07-08 | 1984-06-05 | Basf Wyandotte Corporation | Compositions and process for inhibiting corrosion of aluminum |
-
1983
- 1983-11-14 DE DE19833341152 patent/DE3341152A1/en not_active Withdrawn
-
1984
- 1984-11-02 JP JP59504352A patent/JPS61500447A/en active Pending
- 1984-11-02 WO PCT/EP1984/000347 patent/WO1985002207A1/en active IP Right Grant
- 1984-11-02 DE DE8484904122T patent/DE3476774D1/en not_active Expired
- 1984-11-02 EP EP84904122A patent/EP0162875B1/en not_active Expired
- 1984-11-02 US US06/757,839 patent/US4647429A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3476774D1 (en) | 1989-03-23 |
| US4647429A (en) | 1987-03-03 |
| DE3341152A1 (en) | 1985-05-23 |
| JPS61500447A (en) | 1986-03-13 |
| EP0162875A1 (en) | 1985-12-04 |
| WO1985002207A1 (en) | 1985-05-23 |
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