WO2009129783A2 - Method for protecting a metal from corrosion - Google Patents

Method for protecting a metal from corrosion Download PDF

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Publication number
WO2009129783A2
WO2009129783A2 PCT/DE2009/000516 DE2009000516W WO2009129783A2 WO 2009129783 A2 WO2009129783 A2 WO 2009129783A2 DE 2009000516 W DE2009000516 W DE 2009000516W WO 2009129783 A2 WO2009129783 A2 WO 2009129783A2
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WO
WIPO (PCT)
Prior art keywords
metal
corrosion
steel
coating material
mixtures
Prior art date
Application number
PCT/DE2009/000516
Other languages
German (de)
French (fr)
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WO2009129783A8 (en
WO2009129783A3 (en
Inventor
Christine Breyer
Stefan Goedicke
Stefan Sepeur
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Nano-X Gmbh
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Publication of WO2009129783A2 publication Critical patent/WO2009129783A2/en
Publication of WO2009129783A3 publication Critical patent/WO2009129783A3/en
Publication of WO2009129783A8 publication Critical patent/WO2009129783A8/en

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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/038—Anticorrosion agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the invention relates to a method for protecting a metal from corrosion.
  • Another approach to protecting metals from corrosion is to apply metallic coatings to the metal, such as by electroplating chrome, nickel, brass, etc. This creates good corrosion-resistant materials that are also visually appealing. However, this corrosion protection has no high temperature resistance and the materials are also poor or not deformable.
  • metal can be protected from corrosion by zinc paints, zinc dust coatings, galvanic zinc, but the zinc coating is not hard and not high temperature resistant.
  • JP 62-103305 A describes the application of nickel and cobalt powder with an organic binder and the subsequent sintering thereof. According to EP 0 459 637 B1, it is known to bind metal particles with an organic polymer and then sinter them.
  • the object of the invention is therefore to provide a method for protecting a metal from corrosion, with the good ductility and high temperature resistance of the corrosion-protected metal can be achieved.
  • a coating material which a. low-melting metal pigments whose melting point is less than 1000 ° C, b. one or more alloying elements and c.
  • the coating material is subjected to a temperature treatment at temperatures above the softening point of the metal pigment used, whereby the metal pigments combine with the alloying constituent (s) to form a new alloy.
  • the formation of alloy results in a change in the melting point and in the boiling point of the metal pigment used, the aim being predominantly to increase the melting point and boiling point "in situ.”
  • the alloy can also be formed as a gradient in the edge region of the pigments used.
  • the metal is steel or iron.
  • the coating material is applied by wet-chemical method or powder coating on the metal.
  • the electrochemical potential of the layer is less noble than the electrochemical potential of the metal, resulting in cathodic corrosion protection.
  • aluminum is included as a low melting point metal in the layer.
  • Aluminum has a higher melting point and is less noble than zinc, but aluminum is not suitable as a sacrificial element for cathodic corrosion protection of steel. This is related to the passivation of aluminum, which leads to the fact that the reaction rate of the oxidation of aluminum is so severely limited already after the coating with a dense monomolecular oxide skin that a further reaction practically does not take place.
  • a suitable alloying element it is possible to produce layers in which the passivation is eliminated and thus have both the good high-temperature resistance known from aluminum layers on steel and active cathodic protection against corrosion.
  • the low-melting metal pigments are selected from the group consisting of zinc, tin, lead, aluminum, magnesium, calcium, strontium, barium, sodium, potassium, lithium, bismuth, indium, cerium, tellurium, silver, Brass, bronze, nickel silver, mercury or mixtures thereof.
  • Pigments are understood as meaning particles having a particle size of from 100 ⁇ m to 500 ⁇ m, in particular from 1 ⁇ m to 100 ⁇ m.
  • the invention further includes that the alloying elements salts or nanoparticles of refractory metals (which melt due to the nanoparticulate again at lower temperatures), such as copper, iron, beryllium, cobalt, nickel, chromium, niobium, vanadium, molybdenum, manganese, tantalum, Osmium, tungsten, titanium, zirconium, gold, platinum or mixtures thereof.
  • alloying elements salts or nanoparticles of refractory metals (which melt due to the nanoparticulate again at lower temperatures), such as copper, iron, beryllium, cobalt, nickel, chromium, niobium, vanadium, molybdenum, manganese, tantalum, Osmium, tungsten, titanium, zirconium, gold, platinum or mixtures thereof.
  • the alloying elements During the softening of the low-melting metal pigments, the alloying elements increasingly diffuse deep into their surface with increasing temperature and lead to alloy formation starting at the surface of the particles up to complete penetration of the particles with sufficient treatment temperature and time.
  • the resulting alloys are composed of the corresponding high and low melting alloy components.
  • the compositions of some of the emerging alloys fall under the well-known names bronze, brass, hydronalium, titanium zinc, nickel silver, Tombak, etc., others are previously known under no name designation.
  • the binder comprises organic-inorganic compounds, in particular oligo- and polysiloxanes, from hydrolysis and condensation of alkylalkoxysilanes or alkoxysilanes or mixtures thereof, silicones or silicone resins, organically modified silicone resins or inorganic compounds, in particular silicates, polyphosphates, aluminosilicates, Metals, metal alkoxides and their condensation products; Contains or consists of metal oxides or metal salts.
  • the present invention is thus characterized in that no purely organic binders are used as in the prior art, but inorganic binders. It is not necessary to burn out the binder completely. Likewise, there is no sintering process after the expulsion of the binder.
  • the process of the present invention can be used to produce high temperature resistant anticorrosion coatings in the field of protection against scaling and corrosion of semi-finished products such as steel billets, billets, wires and tapes during and after manufacture and processing, anti-scaling in sheet and bulk warm and warm forging, e.g. Tempering or forging, the scale and corrosion protection of steel parts and semi-finished products during and after the tempering, e.g. Air, oil and water curing can be used.
  • semi-finished products such as steel billets, billets, wires and tapes during and after manufacture and processing
  • anti-scaling in sheet and bulk warm and warm forging e.g. Tempering or forging
  • the scale and corrosion protection of steel parts and semi-finished products during and after the tempering e.g. Air, oil and water curing can be used.
  • Zinkflake AT for example standard Zinkflake AT, from Eckart
  • 100 g of zinc particles are made up with 300 g of 20% strength copper (H) nitrate solution in l% aqueous sulfuric acid while stirring uniformly.
  • the addition of the copper (II) nitrate solution takes place slowly and in portions due to the strong heat of reaction.
  • the uniform stirring ensures that the entire zinc surface is evenly covered by copper. It is stirred for another 30 min. Thereafter, the supernatant solution is decanted off and the metal powder is dried in a circulating air oven at 100 ° C. for approx.
  • tetrabutyl orthotitanate 100 g are added with stirring to the dried metal particles and stirring is continued until a homogeneous particle distribution is achieved.
  • dilute with a suitable organic solvent e.g., ethanol.
  • the mixture is applied by means of a compressed air spray gun in the wet film on a steel sheet and baked for 10 min at 250 ° C as a layer.
  • the metal particles are transformed into an alloy of zinc and copper, which is also reflected in a brass-like hue of the layer after cooling to room temperature.
  • the metallic hybrid layer provides corrosion protection for the coated steel sheet.
  • the coating solution is applied by means of a Drucklufit spray gun in a wet film on a steel plate and baked for 10 min at 25O 0 C as a layer.
  • the metal particles are transformed into an aluminum-nickel alloy, which by Burning out the organic constituents of the silicone resin remaining SiO 2 matrix is attached to the steel substrate.
  • the hybrid layer formed provides corrosion protection for the coated steel sheet.
  • aluminum paste for example Stapa Metallux 2000, Eckart
  • 50 g of 1-butanol and homogeneously dispersed after addition of 150 g of tetrabutyl orthotitanate 100 g of aluminum paste (for example Stapa Metallux 2000, Eckart) are pasted with 50 g of 1-butanol and homogeneously dispersed after addition of 150 g of tetrabutyl orthotitanate.
  • 10 g of tetra-n-tin-butylate with stirring.
  • the aluminum pigments are held in suspension by continuous gentle stirring and applied to a steel tube with a brush in a covering layer.
  • the layer is dried for about 2 h at room temperature.
  • the coated steel tube is heated in an induction furnace under nitrogen atmosphere to about 800 ° C, held for 5 min at 800 ° C and then cooled back to room temperature.
  • the resulting metal-non-metal hybrid layer contains particles of an aluminum-tin alloy and protects the steel pipe from corrosion up to temperatures of> 500 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention relates to a method for protecting a metal from corrosion, characterised in that a coating material is applied to the metal, containing a. low-melting metal pigments, the melting point of which is less than 1,000°C, b. one or more alloying elements, c. organic/inorganic compositions containing binders, in particular, oligo- and poly-siloxanes from the hydrolysis and condensation of alkylalkoxysiloxanes or alkoxysilanes or mixtures thereof, silicones or silicone resins, organically-modified silicone resins or inorganic compounds, in particular, silicate, polyphosphate, aluminosilicate, metals, metal alkoxides and the condensation products thereof; metal oxides or metal salts, the coating material is subjected to a thermal treatment at temperatures above the softening point of the metal pigment used, wherein the metal pigment combines with the alloying agent(s) to give a new alloy.

Description

BESCHREIBUNG DESCRIPTION
Verfahren zum Schützen eines Metalls vor KorrosionMethod of protecting a metal from corrosion
Die Erfindung betrifft ein Verfahren zum Schützen eines Metalls vor Korrosion.The invention relates to a method for protecting a metal from corrosion.
Insbesondere im Temperaturbereich von 450 bis 1.100°C besteht eine Vielzahl von Anwendungsmöglichkeiten für Normalstahl. Da Normalstahl gerade bei diesen erhöhten Temperaturen der Korrosion unterliegt, jedoch kein aktiver Korrosionsschutz für Normalstahl bekannt ist, weicht man häufig auf Edelstahl aus, beispielsweise im Maschinenbau oder bei Auspuffanlagen. Dieser ist jedoch relativ schwer verformbar und zudem teuer.Especially in the temperature range of 450 to 1100 ° C, there are a variety of applications for mild steel. Since normal steel is subject to corrosion especially at these elevated temperatures, but no active corrosion protection for normal steel is known, one often deviates from stainless steel, for example in mechanical engineering or in exhaust systems. However, this is relatively difficult to deform and also expensive.
Ein anderer Ansatz, Metalle vor Korrosion zu schützen, besteht darin, metallische Überzüge auf dem Metall aufzubringen, beispielsweise durch galvanisches Aufbringen von Chrom, Nickel, Messing, usw. Hierdurch werden gut korrosionsbeständige Werkstoffe geschaffen, die zudem optisch ansprechend sind. Allerdings weist dieser Korrosionsschutz keine hohe Temperaturbeständigkeit auf und die Werkstoffe sind ebenfalls schlecht oder nicht verformbar.Another approach to protecting metals from corrosion is to apply metallic coatings to the metal, such as by electroplating chrome, nickel, brass, etc. This creates good corrosion-resistant materials that are also visually appealing. However, this corrosion protection has no high temperature resistance and the materials are also poor or not deformable.
Weiterhin kann Metall durch Zinkfarben, Zinkstaubbeschichtungen, galvanisches Verzinken vor Korrosion geschützt werden, wobei jedoch die Zinkbeschichtung nicht hart und nicht hochtemperaturfest ist.Furthermore, metal can be protected from corrosion by zinc paints, zinc dust coatings, galvanic zinc, but the zinc coating is not hard and not high temperature resistant.
Aus der DE 24 48 738 Al ist ein Verfahren zur Herstellung eines metallischen Verbundwerkstoffes auf einem metallischen Träger bekannt, bei dem feinteiliges Metallpulver mit mindestens einer weiteren metallischen Ausgangskomponente überzogen wird und das überzogene Metallpulver in einem organischen Bindemittel angeteigt und nach dem Austreiben des Bindemittels gesintert und verformt wird.From DE 24 48 738 Al a method for producing a metallic composite material on a metallic carrier is known in which finely divided metal powder is coated with at least one other metallic starting component and the coated metal powder pasted in an organic binder and sintered after the expulsion of the binder and is deformed.
Die JP 62-103305 A beschreibt das Auftragen von Nickel und Kobaltpulver mit einem organischen Bindemittel und das anschließende Sintern derselben. Gemäß der EP 0 459 637 Bl ist es bekannt, Metallpartikel mit einem organischen Polymer zu binden und anschließend zu sintern.JP 62-103305 A describes the application of nickel and cobalt powder with an organic binder and the subsequent sintering thereof. According to EP 0 459 637 B1, it is known to bind metal particles with an organic polymer and then sinter them.
Aufgabe der Erfindung ist es somit, ein Verfahren zum Schützen eines Metalls vor Korrosion zu schaffen, mit dem eine gute Verformbarkeit und hohe Temperaturbeständigkeit des korrosionsgeschützten Metalls erreichbar ist.The object of the invention is therefore to provide a method for protecting a metal from corrosion, with the good ductility and high temperature resistance of the corrosion-protected metal can be achieved.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daßThis object is achieved in that
• auf das Metall ein Beschichtungsmaterial aufgetragen wird, welches a. niedrigschmelzende Metallpigmente, deren Schmelztemperatur weniger als 1.0000C beträgt, b. ein oder mehrere Legierungselemente und c. Bindemittel enthaltend organisch-anorganische Verbindungen, insbesondere Oligo- und Polysiloxane, aus Hydrolyse und Kondensation von Alkylalkoxysilanen bzw. Alkoxysilanen bzw. Mischungen hieraus, Silikone oder Silikonharze, organisch modifizierte Silikonharze oder anorganische Verbindungen, insbesondere Silikate, Polyphosphate, Aluminosilikate, Metalle, Metallalkoxide und deren Kondensationsprodukte; Metalloxide oder Metallsalze, enthält,On the metal a coating material is applied, which a. low-melting metal pigments whose melting point is less than 1000 ° C, b. one or more alloying elements and c. Binder containing organic-inorganic compounds, in particular oligo- and polysiloxanes, from hydrolysis and condensation of alkylalkoxysilanes or alkoxysilanes or mixtures thereof, silicones or silicone resins, organically modified silicone resins or inorganic compounds, in particular silicates, polyphosphates, aluminosilicates, metals, metal alkoxides and their condensation products; Metal oxides or metal salts, contains,
• das Beschichtungsmaterial einer Temperaturbehandlung bei Temperaturen oberhalb des Erweichungspunktes des eingesetzten Metallpigmentes unterzogen wird, wobei sich die Metallpigmente mit dem bzw. den Legierungsbestandteilen zu einer neuen Legierung verbinden.The coating material is subjected to a temperature treatment at temperatures above the softening point of the metal pigment used, whereby the metal pigments combine with the alloying constituent (s) to form a new alloy.
Aus Untersuchungen zu Korrosionsschutzbeschichtungen bei Raumtemperatur ist bekannt, daß durch die Umhüllung von Metallpartikeln wie Zink mit anorganischen Matrices wie etwa Titanoxid (TiO2) deutlich bessere Ergebnisse im Korrosionsschutz als mit reinen Zinkschichten erzielt werden können. Um dieses Grundprinzip auf den Hochtemperaturbereich zu übertragen, ist es notwendig, eine temperaturbeständige anorganische Schutzschicht auf den Metallpartikeln abzuscheiden und nicht etwa wie im Fallen von pulvermetallurgischen Schichten das organische Matrixmaterial komplett herauszubrennen.From studies on corrosion protection coatings at room temperature, it is known that the coating of metal particles such as zinc with inorganic matrices such as titanium oxide (TiO 2 ) significantly better results in corrosion protection than with pure zinc layers can be achieved. To transfer this basic principle to the high-temperature range, it is necessary to deposit a temperature-resistant inorganic protective layer on the metal particles and not as in Falling powder metallurgical layers completely burn out the organic matrix material.
Bei dem erfindungsgemäßen Verfahren erfolgt durch die Legierungsbildung eine Veränderung des Schmelzpunktes und des Siedepunktes des eingesetzten Metallpigmentes, wobei überwiegend eine „in situ" Schmelzpunkt- und Siedepunkterhöhung angestrebt wird. Die Legierung kann auch als Gradient im Randbereich der eingesetzten Pigmente entstehen.In the process according to the invention, the formation of alloy results in a change in the melting point and in the boiling point of the metal pigment used, the aim being predominantly to increase the melting point and boiling point "in situ." The alloy can also be formed as a gradient in the edge region of the pigments used.
Es liegt im Rahmen der Erfindung, daß das Metall Stahl oder Eisen ist.It is within the scope of the invention that the metal is steel or iron.
Erfindungsgemäß ist vorgesehen, daß das Beschichtungsmaterial durch naßchemische Verfahren oder Pulverlackierung auf das Metall aufgetragen wird.According to the invention it is provided that the coating material is applied by wet-chemical method or powder coating on the metal.
hi einer besonderen Ausführungsform ist das elektrochemische Potential der Schicht unedler als das elektrochemische Potential des Metalls, so daß sich ein kathodischer Korrosionsschutz ergibt.In a particular embodiment, the electrochemical potential of the layer is less noble than the electrochemical potential of the metal, resulting in cathodic corrosion protection.
Das bedeutet am Beispiel von Zink, daß ein Zinkpartikel durch Wärmebehandlung der bis dahin nicht „fertigen" Schicht mit einem höher schmelzenden Metall wie z.B. Kupfer eine Legierung eingeht, die je nach Temperatur und Dauer der Temperatureinwrrkung nur an der Oberfläche des Zinkpartikels vorliegt oder diesen vollständig durchdringt. Die Metallegierung hat einen höheren Schmelz- und Siedepunkt als das Zink, was dazu führt, daß das Zink nicht wie in Form von reinem Zink bei 908°C verdampft, sondern als Legierung eine höhere Temperaturbeständigkeit aufweist. Dadurch wird die mögliche Verarbeitungs- und Gebrauchstemperatur der während der Wärmebehandlung in ihren Endzustand überführten Schicht erhöht und somit deren Anwendungsmöglichkeiten erweitert. Soll, wie am Beispiel von Zink, die Schicht nach der Wärmebehandlung als Beschichtung auf Stahl einen aktiven kathodischen Korrosionsschutz aufweisen, so darf der Anteil eines edleren Legierungselements, wie z.B. Kupfer, eine bestimmte Menge nicht überschreiten, so daß das elektrochemische Standardpotential der Legierung nicht höher wird als das des Redox-Paares Fe2+/Fe. In einem anderen Beispiel ist Aluminium als niedrig schmelzendes Metall in der Schicht enthalten. Aluminium hat einen höheren Schmelzpunkt und ist unedler als Zink, aber dennoch eignet sich Aluminium nicht als Opferelement für einen kathodischen Korrosionsschutz von Stahl. Dies hängt mit der Passivierung von Aluminium zusammen, die dazu fuhrt, daß die Reaktionsgeschwindigkeit der Oxidation von Aluminium bereits nach der Belegung mit einer dichten monomolekularen Oxidhaut so stark eingeschränkt ist, daß eine weitere Reaktion praktisch nicht stattfindet. Durch Legierung mit einem geeigneten Legierungselement können Schichten erzeugt werden, in denen die Passivierung aufgehoben wird und die somit sowohl die von Aluminiumschichten auf Stahl bekannte gute Hochtemperaturbeständigkeit als auch aktiven kathodischen Korrosionsschutz aufweisen.This means using the example of zinc that a zinc particle by heat treatment of the hitherto not "finished" layer with a higher melting metal such as copper enters an alloy that is present depending on the temperature and duration of Temperaturinwrrkung only on the surface of the zinc particle or this completely The metal alloy has a higher melting and boiling point than the zinc, which results in the zinc not evaporating at 908 ° C as in the form of pure zinc but exhibiting higher temperature resistance as an alloy If, as with the example of zinc, the layer after the heat treatment as a coating on steel has an active cathodic protection against corrosion, the proportion of a nobler alloying element, eg Copper, a e do not exceed a certain amount, so that the standard electrochemical potential of the alloy is not higher than that of the redox couple Fe 2+ / Fe. In another example, aluminum is included as a low melting point metal in the layer. Aluminum has a higher melting point and is less noble than zinc, but aluminum is not suitable as a sacrificial element for cathodic corrosion protection of steel. This is related to the passivation of aluminum, which leads to the fact that the reaction rate of the oxidation of aluminum is so severely limited already after the coating with a dense monomolecular oxide skin that a further reaction practically does not take place. By alloying with a suitable alloying element, it is possible to produce layers in which the passivation is eliminated and thus have both the good high-temperature resistance known from aluminum layers on steel and active cathodic protection against corrosion.
Im Rahmen der Erfindung ist vorgesehen, daß die niedrigschmelzenden Metallpigmente ausgewählt sind aus der Gruppe bestehend aus Zink, Zinn, Blei, Aluminium, Magnesium, Calcium, Strontium, Barium, Natrium, Kalium, Lithium, Wismut, Indium, Cer, Tellur, Silber, Messing, Bronze, Neusilber, Quecksilber oder Mischungen hiervon.In the context of the invention, it is provided that the low-melting metal pigments are selected from the group consisting of zinc, tin, lead, aluminum, magnesium, calcium, strontium, barium, sodium, potassium, lithium, bismuth, indium, cerium, tellurium, silver, Brass, bronze, nickel silver, mercury or mixtures thereof.
Besonders geeignet sind Zink, Aluminium, Zinn, Magnesium oder Mischungen hiervon. Unter Pigmenten werden Partikel einer Partikelgröße von 100 im bis 500 μm, insbesondere im Bereich von 1 μm bis 100 μm verstanden.Particularly suitable are zinc, aluminum, tin, magnesium or mixtures thereof. Pigments are understood as meaning particles having a particle size of from 100 μm to 500 μm, in particular from 1 μm to 100 μm.
Zur Erfindung gehörig ist weiterhin, daß die Legierungselemente Salze oder Nanopartikel von hochschmelzenden Metallen (welche aufgrund der Nanopartikularität wieder bei niedrigeren Temperaturen schmelzen), wie Kupfer, Eisen, Beryllium, Kobalt, Nickel, Chrom, Niob, Vanadium, Molybdän, Mangan, Tantal, Osmium, Wolfram, Titan, Zirkonium, Gold, Platin oder Mischungen hiervon sind.The invention further includes that the alloying elements salts or nanoparticles of refractory metals (which melt due to the nanoparticulate again at lower temperatures), such as copper, iron, beryllium, cobalt, nickel, chromium, niobium, vanadium, molybdenum, manganese, tantalum, Osmium, tungsten, titanium, zirconium, gold, platinum or mixtures thereof.
Bevorzugt werden Kupfer-, Eisen-, Nickel-, Chrom-, Titan- und Zirkoniumnanopartikel verwendet.Preference is given to using copper, iron, nickel, chromium, titanium and zirconium nanoparticles.
Die Legierungselemente diffundieren bei der Erweichung der niedrig schmelzenden Metallpigmente mit steigender Temperatur zunehmend tief in deren Oberfläche ein und fuhren zu einer Legierungsbildung beginnend an der Oberfläche der Partikel bis hin zur vollständigen Durchdringung der Partikel bei ausreichender Behandlungstemperatur und -zeit. Die resultierenden Legierungen setzen sich zusammen aus den entsprechenden hoch- und niedrigschmelzenden Legierungsbestandteilen. Die Zusammensetzungen einiger der neu entstehenden Legierungen fallen dabei unter die bekannten Bezeichnungen Bronze, Messing, Hydronalium, Titanzink, Neusilber, Tombak, usw., andere sind bisher unter keiner Namensbezeichnung bekannt.During the softening of the low-melting metal pigments, the alloying elements increasingly diffuse deep into their surface with increasing temperature and lead to alloy formation starting at the surface of the particles up to complete penetration of the particles with sufficient treatment temperature and time. The resulting alloys are composed of the corresponding high and low melting alloy components. The compositions of some of the emerging alloys fall under the well-known names bronze, brass, hydronalium, titanium zinc, nickel silver, Tombak, etc., others are previously known under no name designation.
Erfindungsgemäß ist vorgesehen, daß das Bindemittel organisch-anorganische Verbindungen, insbesondere Oligo- und Polysiloxane, aus Hydrolyse und Kondensation von Alkylalkoxysilanen bzw. Alkoxysilanen bzw. Mischungen hieraus, Silikone oder Silikonharze, organisch modifizierte Silikonharze oder anorganische Verbindungen, insbesondere Silikate, Polyphosphate, Aluminosilikate, Metalle, Metallalkoxide und deren Kondensationsprodukte; Metalloxide oder Metallsalze enthält oder aus diesen besteht. Die vorliegende Erfindung ist somit dadurch gekennzeichnet, daß keine rein organischen Bindemittel wie im Stand der Technik verwendet werden, sondern anorganische Bindemittel. Es ist nicht erforderlich, das Bindemittel vollständig auszubrennen. Ebenfalls erfolgt kein Sintervorgang nach dem Austreiben des Bindemittels.According to the invention, the binder comprises organic-inorganic compounds, in particular oligo- and polysiloxanes, from hydrolysis and condensation of alkylalkoxysilanes or alkoxysilanes or mixtures thereof, silicones or silicone resins, organically modified silicone resins or inorganic compounds, in particular silicates, polyphosphates, aluminosilicates, Metals, metal alkoxides and their condensation products; Contains or consists of metal oxides or metal salts. The present invention is thus characterized in that no purely organic binders are used as in the prior art, but inorganic binders. It is not necessary to burn out the binder completely. Likewise, there is no sintering process after the expulsion of the binder.
Das erfindungsgemäße Verfahren kann zum Herstellen von hochtemperaturbeständigen Korrosionsschutzschichten im Bereich des Schutzes vor Verzunderung und Korrosion von Halbzeugen wie Stahlknüppeln, -Brammen, -Drähten, und -Bändern während und nach der Herstellung und Verarbeitung, des Verzunderungsschutzes bei der Blech- und Massivwarmund Halbwarmumformung, z.B. Formhärten oder Schmieden, des Zunder- und Korrosionsschutzes von Stahlteilen und -halbzeugen bei und nach der Vergütung, z.B. Luft-, Öl- und Wasserhärtung verwendet werden. Weitere Einsatzgebiete liegen im Korrosionsschutz von Stahl und Stahlbauteilen bei dauerhafter Temperaturbelastung wie beispielsweise in Verbrennungsmotoren, im Abgasstrang von Verbrennungsmotoren aller Art in Fahrzeugen, Schiffen und Fluggeräten, in Brennräumen sowie Abgasanlagen von Öfen, Heizanlagen, Müll- und sonstigen Verbrennungsanlagen sowie Kraftwerken sowie auf Stahlteilen in der Peripherie solcher Anlagen.The process of the present invention can be used to produce high temperature resistant anticorrosion coatings in the field of protection against scaling and corrosion of semi-finished products such as steel billets, billets, wires and tapes during and after manufacture and processing, anti-scaling in sheet and bulk warm and warm forging, e.g. Tempering or forging, the scale and corrosion protection of steel parts and semi-finished products during and after the tempering, e.g. Air, oil and water curing can be used. Further areas of application are the corrosion protection of steel and steel components under permanent temperature load such as internal combustion engines, in the exhaust system of internal combustion engines of all kinds in vehicles, ships and aircraft, in combustion chambers and exhaust systems of ovens, heating systems, waste and other incinerators and power plants as well as on steel parts the periphery of such systems.
Nachfolgend wird die Erfindung anhand von Ausfuhrungsbeispielen näher erläutert. Beispiele 1 :The invention will be explained in more detail with reference to exemplary embodiments. Examples 1:
100 g Zinkpartikel (z.B. Standard Zinkflake AT, Fa. Eckart) werden unter gleichmäßigem Rühren mit 300 g 20%iger Kupfer(H)-Nitratlösung in l%iger wässriger Schwefelsäure angepastet. Die Zugabe der Kupfer(II)-Nitratlösung erfolgt aufgrund der starken Reaktionswärme langsam und portionsweise. Durch das gleichmäßige Rühren wird sichergestellt, daß die gesamte Zinkoberfläche gleichmäßig von Kupfer bedeckt wird. Es wird noch 30 min weitergerührt. Danach wird die überstehende Lösung abdekantiert und das Metallpulver ca. Ih im Umluftofen bei 100°C getrocknet.100 g of zinc particles (for example standard Zinkflake AT, from Eckart) are made up with 300 g of 20% strength copper (H) nitrate solution in l% aqueous sulfuric acid while stirring uniformly. The addition of the copper (II) nitrate solution takes place slowly and in portions due to the strong heat of reaction. The uniform stirring ensures that the entire zinc surface is evenly covered by copper. It is stirred for another 30 min. Thereafter, the supernatant solution is decanted off and the metal powder is dried in a circulating air oven at 100 ° C. for approx.
Zu den getrockneten Metallpartikeln wird unter Rühren 100 g Tetrabutylorthotitanat gegeben und so lange weitergerührt, bis eine homogene Partikelverteilung erreicht wird. Gegebenenfalls wird mit einem geeigneten organischen Lösemittel (z.B. Ethanol) verdünnt. Die Mischung wird mittels einer Druckluft-Lackierpistole im Naßfilm auf ein Stahlblech aufgetragen und 10 min bei 250°C als Schicht eingebrannt.100 g of tetrabutyl orthotitanate are added with stirring to the dried metal particles and stirring is continued until a homogeneous particle distribution is achieved. Optionally, dilute with a suitable organic solvent (e.g., ethanol). The mixture is applied by means of a compressed air spray gun in the wet film on a steel sheet and baked for 10 min at 250 ° C as a layer.
Bei einer nachfolgend durchgeführten 30-minütigen Wärmebehandlung bei 700°C wandeln sich die Metallpartikel in eine Legierung aus Zink und Kupfer um, was sich auch in einem messingartigen Farbton der Schicht nach Abkühlen auf Raumtemperatur widerspiegelt. Die metallische Hybridschicht bietet einen Korrosionsschutz für das beschichtete Stahlblech.In a subsequent heat treatment at 700 ° C. for 30 minutes, the metal particles are transformed into an alloy of zinc and copper, which is also reflected in a brass-like hue of the layer after cooling to room temperature. The metallic hybrid layer provides corrosion protection for the coated steel sheet.
Beispiel 2:Example 2:
100 g Aluminiumpulver (z.B. MEP 103, Fa. Mepura) werden in 150g 1-Butanol dispergiert. Zu der Dispersion werden 20 g Nickel(II)-nitrat unter Rühren zugegeben und ca. Ih gleichmäßig gerührt. Zu der Reaktionsmischung werden 200 g Silikonharzbindemittel Silres HK 46 (Fa. Wacker) gegeben und durch 2h weiteres Rühren eine homogene Beschichtungslösung hergestellt.100 g of aluminum powder (for example MEP 103, Mepura) are dispersed in 150 g of 1-butanol. To the dispersion, 20 g of nickel (II) nitrate are added with stirring and stirred for Ih uniformly. 200 g of silicone resin binder Silres HK 46 (from Wacker) are added to the reaction mixture, and a homogeneous coating solution is prepared by further stirring 2 h.
Die Beschichtungslösung wird mittels einer Drucklufit-Lackierpistole im Naßfilm auf ein Stahlblech aufgetragen und 10 min bei 25O0C als Schicht eingebrannt. Bei einer nachfolgend durchgeführten 5-minütigen Wärmebehandlung bei 900°C wandeln sich die Metallpartikel in eine Aluminium-Nickel-Legierung um, welche durch die nach Herausbrennen der organischen Bestandteile des Silikonharzes verbleibenden SiO2-Matrix an den Stahluntergrund angebunden wird.The coating solution is applied by means of a Drucklufit spray gun in a wet film on a steel plate and baked for 10 min at 25O 0 C as a layer. In a subsequent 5-minute heat treatment at 900 ° C, the metal particles are transformed into an aluminum-nickel alloy, which by Burning out the organic constituents of the silicone resin remaining SiO 2 matrix is attached to the steel substrate.
Die gebildete Hybridschicht bietet einen Korrosionsschutz für das beschichtete Stahlblech.The hybrid layer formed provides corrosion protection for the coated steel sheet.
Beispiel 3:Example 3:
100 g Aluminiumpaste (z.B. Stapa Metallux 2000, Fa. Eckart) werden mit 50 g 1-Butanol angepastet und nach Zugabe von 150g Tetrabutylorthotitanat homogen dispergiert. Zu dem Ansatz werden 10 g Tetra-n-Zinnbutylat unter Rühren zugegeben. Die Aluminiumpigmente werden durch stetiges leichtes Rühren in der Schwebe gehalten und mit einem Pinsel in einer deckenden Schicht auf ein Stahlrohr aufgetragen. Die Schicht wird ca. 2 h bei Raumtemperatur angetrocknet. Anschließend wird das beschichtete Stahlrohr in einem Induktionsofen unter Stickstoffatmosphäre auf ca. 800°C erwärmt, 5 min bei 800°C gehalten und anschließend auf Raumtemperatur rückgekühlt.100 g of aluminum paste (for example Stapa Metallux 2000, Eckart) are pasted with 50 g of 1-butanol and homogeneously dispersed after addition of 150 g of tetrabutyl orthotitanate. To the batch is added 10 g of tetra-n-tin-butylate with stirring. The aluminum pigments are held in suspension by continuous gentle stirring and applied to a steel tube with a brush in a covering layer. The layer is dried for about 2 h at room temperature. Subsequently, the coated steel tube is heated in an induction furnace under nitrogen atmosphere to about 800 ° C, held for 5 min at 800 ° C and then cooled back to room temperature.
Die dabei gebildete Metall-Nichtmetall-Hybridschicht enthält Partikel aus einer Aluminium- Zinn-Legierung und schützt das Stahlrohr bis zu Temperaturen von >500°C vor Korrosion. The resulting metal-non-metal hybrid layer contains particles of an aluminum-tin alloy and protects the steel pipe from corrosion up to temperatures of> 500 ° C.

Claims

PATENTANSPRÜCHE
1. Verfahren zum Schützen eines Metalls vor Korrosion, dadurch gekennzeichnet, daß1. A method for protecting a metal from corrosion, characterized in that
• auf das Metall ein Beschichtungsmaterial aufgetragen wird, welches a. niedrigschmelzende Metallpigmente, deren Schmelztemperatur weniger als 1.0000C beträgt, b. ein oder mehrere Legierungselemente und c. Bindemittel enthaltend organisch-anorganische Verbindungen, insbesondere Oligo- und Polysiloxane, aus Hydrolyse und Kondensation von Alkylalkoxysilanen bzw. Alkoxysilanen bzw. Mischungen hieraus, Silikone oder Silikonharze, organisch modifizierte Silikonharze oder anorganische Verbindungen, insbesondere Silikate, Polyphosphate, Aluminosilikate, Metalle, Metallalkoxide und deren Kondensationsprodukte; Metalloxide oder Metallsalze, enthält,On the metal a coating material is applied, which a. low-melting metal pigments whose melting point is less than 1000 ° C, b. one or more alloying elements and c. Binder containing organic-inorganic compounds, in particular oligo- and polysiloxanes, from hydrolysis and condensation of alkylalkoxysilanes or alkoxysilanes or mixtures thereof, silicones or silicone resins, organically modified silicone resins or inorganic compounds, in particular silicates, polyphosphates, aluminosilicates, metals, metal alkoxides and their condensation products; Metal oxides or metal salts, contains,
• das Beschichtungsmaterial einer Temperaturbehandlung bei Temperaturen oberhalb des Erweichungspunktes des eingesetzten Metallpigmentes unterzogen wird, wobei sich die Metallpigmente mit dem bzw. den Legierungsbestandteilen zu einer neuen Legierung verbinden.The coating material is subjected to a temperature treatment at temperatures above the softening point of the metal pigment used, whereby the metal pigments combine with the alloying constituent (s) to form a new alloy.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Metall Stahl ist.2. The method according to claim 1, characterized in that the metal is steel.
3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Beschichtungsmaterial durch naßchemische Verfahren oder Pulverlackierung auf das Metall aufgetragen wird.3. The method according to claim 1, characterized in that the coating material is applied by wet-chemical method or powder coating on the metal.
4. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, das elektrochemische Potential der Schicht unedler als das elektrochemische Potential des Metalls, so daß sich ein kathodischer Korrosionsschutz ergibt.4. The method according to claim 1, characterized in that the electrochemical potential of the layer is less noble than the electrochemical potential of the metal, so that there is a cathodic protection against corrosion.
5. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die niedrigschmelzenden Metallpigmente ausgewählt sind aus der Gruppe bestehend aus Zink, Zinn, Blei, Aluminium, Magnesium, Calcium, Strontium, Barium, Natrium, Kalium, Lithium, Wismut, Indium, Cer, Tellur, Silber, Messing, Bronze, Neusilber, Quecksilber oder Mischungen hiervon.5. The method according to claim 1, characterized in that the low-melting metal pigments are selected from the group consisting of zinc, tin, lead, aluminum, magnesium, calcium, strontium, barium, sodium, potassium, lithium, Bismuth, indium, cerium, tellurium, silver, brass, bronze, nickel silver, mercury or mixtures thereof.
6. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Legierungselemente Salze oder Nanopartikel von hochschmelzenden Metallen, wie Kupfer, Eisen, Beryllium, Kobalt, Nickel, Chrom, Mob, Vanadium, Molybdän, Mangan, Tantal, Osmium, Wolfram, Titan, Zirkonium, Gold, Platin oder Mischungen hiervon sind.6. The method according to claim 1, characterized in that the alloying elements salts or nanoparticles of refractory metals, such as copper, iron, beryllium, cobalt, nickel, chromium, Mob, vanadium, molybdenum, manganese, tantalum, osmium, tungsten, titanium, zirconium , Gold, platinum or mixtures thereof.
7. Verwendung des Verfahrens gemäß den Ansprüchen 1 bis 6 zum Herstellen von hochtemperaturbeständigen Korrosionsschutzschichten im Bereich des Schutzes vor Verzunderung und Korrosion von Halbzeugen, insbesondere Stahlknüppeln, -Brammen, - Drähten, und -Bändern während und nach der Herstellung und Verarbeitung, des Verzunderungsschutzes bei der Blech- und Massivwarm- und Halbwarmumformung, inbesondere Formhärten oder Schmieden, des Zunder- und Korrosionsschutzes von Stahlteüen und -halbzeugen bei und nach der Vergütung, insbesondere Luft-, Öl- und Wasserhärtung, des Korrosionsschutzes von Stahl und Stahlbauteilen bei dauerhafter Temperaturbelastung, insbesondere in Verbrennungsmotoren, im Abgasstrang von Verbrennungsmotoren aller Art in Fahrzeugen, Schiffen und Fluggeräten, in Brenriräumen sowie Abgasanlagen von Öfen, Heizanlagen, Müll- und sonstigen Verbrennungsanlagen sowie Kraftwerken sowie auf Stahlteilen in der Peripherie solcher Anlagen. 7. Use of the method according to claims 1 to 6 for the manufacture of high temperature resistant corrosion protection layers in the field of protection against scaling and corrosion of semi-finished products, especially steel billets, rams, - wires, and bands during and after the manufacture and processing of the Verzunderungsschutzes the sheet metal and massive warm and warm forging, in particular mold hardening or forging, the scale and corrosion protection of Stahlteüen and semi-finished products during and after the annealing, in particular air, oil and water hardening, the corrosion protection of steel and steel components under permanent temperature load, in particular in internal combustion engines, in the exhaust system of internal combustion engines of all kinds in vehicles, ships and aircraft, in break rooms and exhaust systems of furnaces, heating plants, waste incinerators and other incinerators and power plants, as well as on steel parts in the periphery of such plants.
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