EP1373599A2 - Produit d'addition, preparation et utilisation dudit produit en tant qu'inhibiteur de corrosion - Google Patents

Produit d'addition, preparation et utilisation dudit produit en tant qu'inhibiteur de corrosion

Info

Publication number
EP1373599A2
EP1373599A2 EP02729987A EP02729987A EP1373599A2 EP 1373599 A2 EP1373599 A2 EP 1373599A2 EP 02729987 A EP02729987 A EP 02729987A EP 02729987 A EP02729987 A EP 02729987A EP 1373599 A2 EP1373599 A2 EP 1373599A2
Authority
EP
European Patent Office
Prior art keywords
acid
corrosion
addition product
use according
product according
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.)
Withdrawn
Application number
EP02729987A
Other languages
German (de)
English (en)
Inventor
Andreas Hartwig
Kerstin Albinsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE10143521A external-priority patent/DE10143521B4/de
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1373599A2 publication Critical patent/EP1373599A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • 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
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines

Definitions

  • the invention relates to an addition product, its production from one or more organic bases and one or more of the acids hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid and its use as a corrosion inhibitor, in particular for protecting light metals.
  • Conversion baths with the corrosion inhibitors hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid are used for corrosion protection of light metals or light metal alloys.
  • the light metals are treated by immersing them in the acid bath for a certain time. This creates a conversion layer that protects the treated metal from corrosion.
  • the protective effect can be extended if the metal to be protected has a coating, e.g. a varnish or adhesive, which is a reservoir for the inhibiting ions. If the coating is damaged, the inhibitor can be detached from the coating by adding water and transported to the injured area in order to have an inhibiting effect there.
  • Corrosion protection pigments such as zinc phosphate or barium metaborate are usually added as inhibitors for this purpose.
  • Metal salts of hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid can also be incorporated into polymers in the form of pigments.
  • the abovementioned salts have the disadvantage that they do not have a high solubility in water and are therefore poorly suited for rapid protection of an injured part of the metal.
  • the potential for action of these salts is lower than that of the particularly effective chromates.
  • Chromates are known to be particularly effective inhibitors. This makes it possible to use relatively poorly soluble chromates as inhibitors. Chromates used particularly frequently are zinc chromate, barium chromate and strontium chromate, and also mixtures of these compounds.
  • the object of the present invention is to overcome the disadvantages of the prior art and to provide corrosion inhibitors which ensure rapid and permanent inhibition of corrosion processes.
  • the addition products according to the invention can be prepared by means of an acid-base reaction from hexafluorosilicic acid, hexafluorotitanic acid and / or hexafluorozirconic acid with one or more organic bases.
  • Organic bases for the purposes of this invention are generally understood to mean organic compounds which, when reacted with inorganic acids, such as, in particular, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, give salts or salt-like compounds.
  • inorganic acids such as, in particular, hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, give salts or salt-like compounds.
  • an organic base is preferably understood to mean organic nitrogen-containing compounds. Furthermore, due to the better handling of these, particularly non-cydic bases with a molecular weight that is greater than 105 g * mol "1 and cydic bases with a molecular weight that is greater than 70 g * mol _1 are to be understood.
  • the addition products according to the invention offer the advantage over metal salts of hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid in that they not only inhibit the anodic partial reaction but also, due to the organic component of the addition product according to the invention, inhibit the cathodic partial reaction of a corrosion process and thus result in an increased corrosion inhibition.
  • Impurities or nobler light metal alloy components mostly act as cathode; the anodic partial reaction takes place at the base points of the alloy, usually phases with a high proportion of light metals.
  • the starting point of the corrosion is usually a point at which the coating of the light metal or the light metal alloy has been damaged.
  • the addition products according to the invention also have the advantage over metal salts of hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid that they are more soluble in aqueous media.
  • the anion SiF 6 2 ' , TiF 6 2 " or ZrF 6 2' required for the anodic inhibition is made available more quickly and can be released from the coating more quickly by means of added water and transported to the injured area in order to have an inhibiting effect there.
  • the addition products according to the invention also have the advantage that they are not carcinogens such as hexavalent chromate compounds or toxic heavy metal compounds such as barium salts.
  • the addition products according to the invention can be incorporated into polymers and are therefore used to produce protective layers with an inhibitory effect can.
  • the basic constituents of paints, adhesives, primers, paints or potting compounds are to be mentioned as polymers.
  • the addition to a polymer has the advantage that a reservoir of the corrosion inhibitor is made available, which prevents corrosion under the polymer when corrosive media diffuse in or at points of injury.
  • Examples of polymers are epoxy resins, urethanes, acrylates, alkyd resins or polyvinyl acetate and their copolymers.
  • inhibitors according to the invention can not only be incorporated into polymers but, like hexafluorosilicic acid, hexafluorotitanic acid or hexafluorozirconic acid, can also be used in conversion baths and other liquids for the treatment of light metal surfaces.
  • Preferred organic bases for the preparation of the addition products according to the invention are heterocyclic nitrogen compounds.
  • Polymeric and non-polymeric heterocyclic nitrogen compounds form stable complexes with heavy metals.
  • the cathodic partial reaction of the corrosion process is blocked by the complex formation.
  • Heterocyclic nitrogen compounds which are good complexing agents with metals are therefore preferred for the preparation of the corrosion inhibitors according to the invention.
  • Heterocycles, which form stable complexes with impurities or nobler alloy components such as copper, which frequently occurs in light metal alloys, are particularly advantageous.
  • Organic bases which have at least two heteroatoms (such as N, O, S) in one or two heterocyclic rings are used to produce particularly strongly inhibiting addition products.
  • Preferred organic bases are heterocyclic nitrogen compounds such as e.g. substituted and unsubstituted 1, 2,4-triazoles, 1 H-
  • Benzotriazoles benzothiazoles, benzimidazoles, benzoxazoles, 2,2'-bichinolines, nitrones, 2,5-dimercapto-1, 3,4-thiadiazoles and 2,9-dimethylphenanthrolines.
  • heterocyclic nitrogen compounds with a particularly strongly inhibiting action are, for example, 1 H-benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, benzothiazole, 2-alkylbenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole succinic acid, benzimidazole, 2-alkylbenzimidazole, 2- (5-aminopentyl) benzimidazole, benzoxazole and 2-mercaptobenzoxazole.
  • Heterocycles with alkyl side groups reduce the water solubility and thus improve the long-term effect of the corrosion inhibitor.
  • Particularly preferred organic bases are furthermore compounds such as substituted and unsubstituted phthalocyanines, chlorines and porphyrins. Due to the formation of very stable complexes with a large number of metals and thus the strong corrosion-inhibiting effect, these compounds are particularly suitable for the preparation of the addition products according to the invention.
  • the organic base for producing the addition products according to the invention is a polymer with one or more basic groups.
  • the above-mentioned heterocydic groups are in particular the basic group
  • the addition products according to the invention also include those which are prepared from polymeric bases whose basic groups are only partially protonated.
  • Copolymers can also be used as polymers.
  • derivatives of the corresponding monomeric organic bases which have a vinyl group can be polymerized together with a comonomer in order to obtain suitable polymers.
  • the choice of the comonomer can, for example, influence the solubility in water or the compatibility with constituents of a polymer matrix into which the addition product is to be incorporated.
  • the water solubility can be reduced by increasing the proportion of the alkyl side groups of the polymer and thus the long-term effect can be improved when used as a corrosion inhibitor; by using vinylimidazole monomers, the water solubility can be increased and a good short-term effect can be achieved.
  • Polymers are advantageously also used when, in addition to corrosion-inhibiting properties, it is also desirable that a proton buffer permanently fixed in the polymer is present. This binds the acid formed during corrosion. A strong buffer effect is achieved by using addition products in which not all basic groups are protonated.
  • Phosphates, borates, vanadates, molybdates, tungstates and / or phosphonates are used.
  • the use of the addition products according to the invention in combination with previously known corrosion inhibitors or anti-corrosion pigments is particularly preferred when a synergistic effect results in the specific application. This is the case, for example, if the cathodic partial reaction of the corrosion process is sufficient even through a small amount of the addition product according to the invention is inhibited, but this amount is not sufficient to inhibit the anodic partial reaction. In such a case, a previously known inhibitor is used according to the invention, which is able to inhibit the anodic partial reaction.
  • the combination with known corrosion inhibitors offers the advantage that mixtures of different inhibitors can be produced that have a wide range
  • Addition products according to the invention with a high solubility in water and known corrosion inhibitors or addition products according to the invention with a moderate solubility in water give mixtures which have both a rapid anticorrosive action (primary action) and a long-term action (secondary action).
  • the addition products according to the invention are particularly suitable for use as corrosion inhibitors.
  • the corrosion-inhibiting effect of the addition products according to the invention is e.g. demonstrated that the addition products are dissolved in water together with a corrosive substance and the resulting solution is allowed to act on the metals to be protected.
  • the content of the corrosive substance is chosen higher than that of the inhibitor.
  • the addition products according to the invention are advantageously incorporated into one or more polymers.
  • Such compositions are used to produce protective layers with an inhibitory effect.
  • polymers are to be understood as meaning paints, adhesives, primers, casting compounds, sealing compounds, paints and / or anti-corrosion primers.
  • the addition to a polymer has the advantage that a reservoir of the corrosion inhibitor is provided which prevents corrosion under the polymer when corrosive media diffuse in or at points of injury.
  • polymers are epoxy resins, urethanes, acrylates, alkyd resins or polyvinyl acetate and their copolymers.
  • the corrosion-inhibiting addition products can also be used in protective layers of any kind.
  • the addition products according to the invention are furthermore advantageously used in conversion baths. However, they can be used in general in aqueous solutions for the treatment of light metal surfaces.
  • Partial reaction can take place through the organic bases of the conversion layer.
  • the inhibitors according to the invention can also be prepared intermediately by introducing the corresponding components into the bath.
  • the addition products according to the invention are preferably used for the corrosion protection of components made of aluminum, magnesium, zinc and / or alloys of these elements and in particular for the corrosion protection of components made of copper-containing light metal alloys.
  • alloys are: the aluminum alloys AA2024, AC120 and the magnesium alloys AM50. Due to their high strength, the copper-containing aluminum alloys are widely used in aircraft construction. The corrosion protection of components for aircraft construction is therefore a preferred area of application for the inhibitors according to the invention.
  • the corrosion inhibitors according to the invention can be used here both in treatment liquids for the components and in paints, primers, adhesives, sealants or casting compounds.
  • Another preferred area of application of the corrosion inhibitors according to the invention is the corrosion protection of components which are exposed to the weather.
  • this includes components for motor vehicle construction.
  • Components which have a light metal and / or a light metal alloy and corrosion-inhibiting constituents are also claimed, the latter comprising one or more bases, preferably bases described in more detail above, which inhibit the partial cathodic reaction of the corrosion process on this component.
  • Components with a a composition containing a corrosion inhibitor are not claimed.
  • Example 3 The synthesis is carried out as described in Example 1, using 1 15 g of a 60% hexafluorotitanic acid instead of hexafluorosilicic acid.
  • Example 3 The synthesis is carried out as described in Example 1, using 1 15 g of a 60% hexafluorotitanic acid instead of hexafluorosilicic acid.
  • the synthesis is carried out as described in Example 1, 193 g of a 45% strength hexafluorozirconic acid being used instead of the hexafluorosilicic acid.
  • the corrosion-inhibiting properties are tested in comparison with the conventional inhibitors sodium chromate, barium metaborate and yttrium vanadate. For comparison, the corrosive effect of a sodium chloride solution not provided with an inhibitor is determined.
  • the corrosion-inhibiting properties are tested based on the cataplasm test.
  • the metal sample is first degreased with methyl ethyl ketone, sanded with 100 grit sandpaper and cleaned again with methyl ethyl ketone.
  • the sample is wrapped with cotton wool and soaked in the test solution.
  • the sample prepared in this way is stored in a tightly closed vessel for 1344 hours (8 weeks) at 60 ° C.
  • the test solution consists of 1% by weight of sodium chloride as a corrosive substance and 0.1% by weight of the respective corrosion inhibitor in demineralized water.
  • Aluminum AA2024 format 20 X 80 X 1 mm
  • aluminum AC120 format 25 X 100 X1 mm
  • magnesium AM50 format (25 X 100 X 3 mm) were used as samples.
  • commercially available corrosion inhibitors and a Solution without corrosion inhibitor tested as comparative examples The evaluation is based on the corroded area and the number of pitting spots formed. The results are summarized in the following table:

Landscapes

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

Abstract

Produit d'addition qui peut être préparé à l'aide d'une réaction acide-base à partir d'acide hexafluorosilicique et / ou d'acide hexafluorotitanique et / ou d'acide hexafluorozirconique et d'une ou plusieurs bases organiques. La présente invention concerne également un procédé de préparation dudit produit ainsi que son utilisation. Les produits d'addition selon la présente invention, qui garantissent une inhibition rapide et durable des processus de corrosion, sont particulièrement adaptés pour inhiber la corrosion des métaux légers.
EP02729987A 2001-03-16 2002-03-11 Produit d'addition, preparation et utilisation dudit produit en tant qu'inhibiteur de corrosion Withdrawn EP1373599A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10112850 2001-03-16
DE10112850 2001-03-16
DE10143521A DE10143521B4 (de) 2001-03-16 2001-09-05 Additionsprodukt, seine Herstellung und seine Verwendung als Korrosionsinhibitor
DE10143521 2001-09-05
PCT/EP2002/002658 WO2002090619A2 (fr) 2001-03-16 2002-03-11 Produit d'addition, preparation et utilisation dudit produit en tant qu'inhibiteur de corrosion

Publications (1)

Publication Number Publication Date
EP1373599A2 true EP1373599A2 (fr) 2004-01-02

Family

ID=26008801

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02729987A Withdrawn EP1373599A2 (fr) 2001-03-16 2002-03-11 Produit d'addition, preparation et utilisation dudit produit en tant qu'inhibiteur de corrosion

Country Status (3)

Country Link
US (1) US20040168748A1 (fr)
EP (1) EP1373599A2 (fr)
WO (1) WO2002090619A2 (fr)

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TW200417419A (en) * 2002-12-24 2004-09-16 Nippon Paint Co Ltd Chemical conversion coating agent and surface-treated metal
US20040170840A1 (en) * 2002-12-24 2004-09-02 Nippon Paint Co., Ltd. Chemical conversion coating agent and surface-treated metal
US7510612B2 (en) 2002-12-24 2009-03-31 Nippon Paint Co., Ltd. Chemical conversion coating agent and surface-treated metal
ES2387805T3 (es) * 2003-02-25 2012-10-02 Chemetall Gmbh Procedimiento para revestir superficies metálicas con una composición rica en polímeros
BRPI0513094A (pt) * 2004-08-03 2008-04-29 Chemetall Gmbh processo para proteção de uma superfìcie metálica com um revestimento inibidor de corrosão
US20080127859A1 (en) * 2004-11-10 2008-06-05 Thomas Kolberg Method for Coating Metallic Surfaces with an Aqueous Multi-Component Composition
US8101014B2 (en) * 2004-11-10 2012-01-24 Chemetall Gmbh Process for coating metallic surfaces with a multicomponent aqueous composition
US20060099332A1 (en) 2004-11-10 2006-05-11 Mats Eriksson Process for producing a repair coating on a coated metallic surface
US20080138615A1 (en) * 2005-04-04 2008-06-12 Thomas Kolberg Method for Coating Metallic Surfaces with an Aqueous Composition and Said Composition
US9347134B2 (en) 2010-06-04 2016-05-24 Prc-Desoto International, Inc. Corrosion resistant metallate compositions
US10329674B2 (en) 2016-12-01 2019-06-25 Vitech International, Inc. Fluorinated acid compounds, compositions and methods of use

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Also Published As

Publication number Publication date
US20040168748A1 (en) 2004-09-02
WO2002090619A3 (fr) 2003-10-16
WO2002090619A2 (fr) 2002-11-14

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