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EP1226031B1 - Method for producing multi-phase composite materials - Google Patents

Method for producing multi-phase composite materials Download PDF

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Publication number
EP1226031B1
EP1226031B1 EP00951429A EP00951429A EP1226031B1 EP 1226031 B1 EP1226031 B1 EP 1226031B1 EP 00951429 A EP00951429 A EP 00951429A EP 00951429 A EP00951429 A EP 00951429A EP 1226031 B1 EP1226031 B1 EP 1226031B1
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EP
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Prior art keywords
aluminum
composite material
intermediate layer
base material
aluminium
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German (de)
French (fr)
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EP1226031A2 (en
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Jutta KLÖWER
Katja Brune
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VDM Metals GmbH
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ThyssenKrupp VDM GmbH
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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
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • Aluminum-containing nickel-based alloys and stainless steels are often used as carrier films in automotive exhaust gas catalysts, as electrical heating conductors, as components in industrial furnaces, in plant construction and in gas turbines because of their excellent oxidation resistance and because of their heat resistance.
  • Typical examples are nickel-based alloys with 1 to 3 mass% aluminum and 15 to 30% chromium as defined by the materials 2.4633 and 2.4851 (DIN material number) and UNS 07214 (Unified Numbering System of ASTM).
  • DIN material number Denst material number
  • UNS 07214 Unified Numbering System of ASTM
  • EP 0511 699 B1 describes a process for producing aluminum-alloyed iron-chromium foils, in which an Fe-Cr steel is provided with a thin layer of aluminum. The resulting composite material is rolled to the desired final dimension or to an intermediate dimension, the final, homogeneous material being adjusted by diffusion annealing.
  • US-A-5,336,139 describes a method in which a composite is made by roll cladding with aluminum.
  • the base material is a ferritic iron-based alloy.
  • ferritic materials often do not have the heat resistance required for many high-temperature applications. If high heat resistance combined with good heat resistance is required, austenitic steels or nickel-based alloys must be used. Austenitic materials, however, have so far not been able to be produced using such processes, since the Diffusion annealing must be carried out at a temperature at which the aluminum coating is already melting.
  • the invention is therefore based on the object of developing an economical method with which high aluminum contents can be achieved to produce heat-resistant austenitic materials.
  • the object is achieved by a method for producing a composite material with high heat and abrasion resistance, in that a base material made of an austenitic nickel, cobalt or iron-based alloy on one or both sides with an intermediate layer made of a ferritic, a chromium content between (in wt. %) Containing 8 and 25%, chromium steel, to which a layer of aluminum or an aluminum alloy is applied on one or both sides, and this composite material formed from the base material, intermediate layer and aluminum layer by cold and / or hot forming to the desired intermediate - Or brought final dimension and then diffusion annealed at a temperature above 600 ° C.
  • EP-A-874 062 describes the production of heat-resistant heating wire or heating tape by applying a powder mixture, each consisting of half of chromium and aluminum, to a base material made of austenitic steel and subsequent annealing in a vacuum at 1100 ° C.
  • An outer layer of Al and Al-iron alloy forms over an intermediate layer of ferritic stainless steel with AlFe and AlNi particles distributed therein.
  • the method according to the invention is distinguished in that an intermediate layer made of a ferritic chromium steel with a chromium content between 8 and 25% by mass is applied between the aluminum coating and the base material. It has surprisingly been found that when an intermediate layer made of a ferritic chromium steel is used, the aluminum first penetrates into the intermediate layer and there immediately forms high-melting iron-aluminum and iron-chromium and iron-chromium-aluminum compounds before the aluminum melts he follows. The diffusion annealing can take place at temperatures above 600 ° C.
  • the intermediate layer can consist of a sheet, tape, foil or, in the case of round cross sections, a tube. It is also possible to combine the intermediate layer and the aluminum layer by first coating a chrome steel with an aluminum layer by fire-aluminizing or cladding and then cladding this two-phase composite onto the base material. Alternatively, the composite of base material and chrome steel or the composite of aluminum and chrome steel can also be produced directly using the continuous casting process.
  • the thickness of the intermediate layer made of chrome steel, base material and aluminum layer is determined in each case according to the desired thickness and desired properties of the aluminum-rich outer layer.
  • This method also has the advantage that special alloy elements, for example oxygen-affine elements, which improve the heat resistance and the adhesion of the protective oxide layers (yttrium, hafnium, zirconium, titanium, silicon, cerium, lanthanum) can be introduced into the intermediate layer and thus close to the surface To be available.
  • special alloy elements for example oxygen-affine elements, which improve the heat resistance and the adhesion of the protective oxide layers (yttrium, hafnium, zirconium, titanium, silicon, cerium, lanthanum) can be introduced into the intermediate layer and thus close to the surface To be available.
  • Another advantage of this method is that by choosing suitable combinations of base material, intermediate layer and support material, materials with a wide range of property combinations can be produced. This means that special requirements for the strength and physical properties of the base material can be combined with special requirements for surface properties such as hardness, corrosion resistance and abrasion resistance.
  • Another advantage of the method according to the invention is to produce sheets or tubes with aluminum enrichment on one side. From this results there is the possibility of producing semi-finished products for components that have different material requirements due to different process media on both sides (e.g. in heat exchangers).
  • the composite material according to the invention can be used for tools for cutting, cutting and grinding.
  • Figures 1 to 4 show design examples for the production of a multi-phase composite material with high aluminum contents, as will be explained in more detail in the following examples.
  • Fig. 1 shows the structure of the different materials before the diffusion annealing.
  • the thicknesses of the base material, intermediate layer and aluminum layer are determined depending on the desired ratio of the aluminum-rich zone and the base material.
  • the intermediate layer consists of a chrome steel with a chrome content between 8 and 25% by mass.
  • the aluminum pad consists of an aluminum-silicon alloy or pure aluminum.
  • a composite material consisting of a fire-aluminum chromium steel (Fe-Cr18) with additions of yttrium and hafnium was chosen as the cladding.
  • the individual layers of the composite are joined together by cold rolling.
  • Cold rolling is carried out to the desired final dimension or an intermediate dimension with or without intermediate annealing.
  • the aluminum penetrates completely into the intermediate layer and partially into the base material. A connection is created between the base material and the support, as shown in Fig. 2 . Diffusion pores occurring in the interface can be eliminated by further reshaping.
  • the width of the aluminum-rich zone is determined by the time and temperature for the diffusion annealing.
  • the material is produced by cold rolling and annealing the composite as described in Example 1.
  • the material is produced by cold rolling and annealing the composite as described in Example 1.
  • the one-sided plating of corrosion-resistant materials acc. Fig. 3 comes into question for semi-finished products made of typical corrosion-resistant stainless steels, pure nickel, Ni-Cu alloys and nickel-based alloys, which are exposed to an aggressive aqueous medium (acids or alkalis, sea water) on one side and to a hot process gas on the other side.
  • the aluminum-rich surface layer protects the corrosion-resistant material on the process gas side against high-temperature corrosion.
  • the material is produced by cold rolling and annealing the composite as described in Example 1.
  • Manufacture of a semi-finished product with a round cross-section (tube or rod) with high aluminum contents near the surface by applying aluminum or aluminum-silicon on one side to a corrosion-resistant, heat-resistant or high-temperature-resistant material.
  • a tube or a rod is produced by the usual methods of tube or rod production (for example extrusion, cold hammering, vocationalage or drawing) as shown in Fig. 4 Composite of base material, Fe-Cr intermediate layer and aluminum layer. The diffusion annealing is carried out as described in Example 1.
  • Example 1 The preparation is carried out as described in Example 1.
  • the composite material is rolled onto thin foils with or without intermediate annealing.
  • the diffusion annealing is carried out as indicated in Example 1.
  • the annealing times and annealing temperatures are chosen so that a homogeneous aluminum content is obtained over the entire film cross section, with the exception of a thin edge zone with an increased aluminum content.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Coating With Molten Metal (AREA)
  • Metal Rolling (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Laminated Bodies (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention relates to a method for producing heat and corrosion-resistant austenitic steel, nickel alloys and cobalt alloys. Said method enables the production of austenitic materials with a significantly higher aluminium content in the border area, in comparison to those in prior art and thus with both a significantly greater heat-resistance and a significantly greater abrasion-resistance.

Description

Als Trägerfolien in Automobilabgaskatalysatoren, als elektrische Heizleiter, als Komponenten in Industrieöfen, im Anlagenbau und in Gasturbinen werden oft aluminiumhaltige Nickelbasislegierungen und Edelstähle wegen ihrer ausgezeichneten Oxidationsbeständigkeit und wegen ihrer Warmfestigkeit eingesetzt. Typische Beispiele sind Nickelbasislegierungen mit 1 bis 3 Masse% Aluminium und 15 bis 30 % Chrom wie sie durch die Werkstoffe 2.4633 und 2.4851 (DIN Werkstoffnummer) und UNS 07214 (Unified Numbering System der ASTM) definiert sind. Bei hohen thermischen Beanspruchungen und/oder geringen Wanddicken reicht jedoch der Aluminiumgehalt in diesen Werkstoffen nicht aus, um über einen langen Zeitraum eine Aluminiumoxidschicht auszubilden. Es bilden sich dann lokal Chromoxide, die bei hohen Temperaturen zu lokaler Korrosion führen. Darüber hinaus dampfen Chromoxide bei Temperaturen oberhalb von 1000 °C ab und können z. B. in Industrieöfen zu einer Kontamination des Glühgutes führen.Aluminum-containing nickel-based alloys and stainless steels are often used as carrier films in automotive exhaust gas catalysts, as electrical heating conductors, as components in industrial furnaces, in plant construction and in gas turbines because of their excellent oxidation resistance and because of their heat resistance. Typical examples are nickel-based alloys with 1 to 3 mass% aluminum and 15 to 30% chromium as defined by the materials 2.4633 and 2.4851 (DIN material number) and UNS 07214 (Unified Numbering System of ASTM). With high thermal stresses and / or small wall thicknesses, however, the aluminum content in these materials is not sufficient to form an aluminum oxide layer over a long period of time. Chromium oxides then form locally, which lead to local corrosion at high temperatures. In addition, chromium oxides evaporate at temperatures above 1000 ° C and can e.g. B. in industrial furnaces lead to contamination of the annealing material.

Eine Anhebung des Aluminiumgehaltes in Knetlegierungen auf mehr als 5 Masse% war bisher wegen der mit einem hohen Aluminiumgehalt verbundenen Umformprobleme nicht möglich. Die z. B. in G. Sauthoff, "Intermetallics", VCH Weinheim, beschriebenen Entwicklungen der hochaluminiumhaltigen "Aluminide" mit bis zu 25 Masse% Aluminium führten zwar zu Werkstoffen mit den gewünschten hohen Aluminiumgehalten; diese Werkstoffe haben jedoch andere Nachteile, wie z. B. eine geringe Warmfestigkeit und eine sehr schlechte Kalt- und Warmumformbarkeit.Up to now, an increase in the aluminum content in wrought alloys to more than 5 mass% was not possible due to the forming problems associated with a high aluminum content. The z. For example, developments described in G. Sauthoff, "Intermetallics", VCH Weinheim, of the high-aluminum-containing "aluminides" with up to 25% by mass of aluminum lead to materials with the desired high aluminum contents; however, these materials have other disadvantages, such as. B. a low heat resistance and a very poor cold and hot formability.

Die Notwendigkeit hoher Atuminiumgehalte zur Gewährleistung einer ausreichenden Hochtemperatur- und Korrosionsbeständigkeit führte auf der anderen Seite zur Entwicklung von aluminiumhaltigen Schutzschichten (NiCrAIY-Schichten), die beispielsweise zur Beschichtung von Hochtemperaturkomponenten in Gasturbinen eine weite Verbreitung gefunden haben. Beschichtete Werkstoffe sind jedoch als Halbzeuge nicht verarbeitbar, so daß diese nur begrenzt einsetzbar sind.On the other hand, the need for high aluminum contents to ensure sufficient high temperature and corrosion resistance led to the development of aluminum-containing protective layers (NiCrAIY layers), which are used, for example, to coat High temperature components in gas turbines have found widespread use. However, coated materials cannot be processed as semi-finished products, so that they can only be used to a limited extent.

Zur Umgehung dieser Probleme wird in EP 0511 699 B1 ein Verfahren zur Herstellung aluminiumlegierter Eisen-Chrom-Folien beschrieben, in dem ein Fe-Cr-Stahl mit einer dünnen Schicht aus Aluminium versehen wird. Der so entstandene Verbundwerkstoff wird an die gewünschte Endabmessung oder an eine Zwischenabmessung gewalzt, wobei der endgültige, homogene Werkstoff durch eine Diffusionsglühung eingestellt wird.To avoid these problems, EP 0511 699 B1 describes a process for producing aluminum-alloyed iron-chromium foils, in which an Fe-Cr steel is provided with a thin layer of aluminum. The resulting composite material is rolled to the desired final dimension or to an intermediate dimension, the final, homogeneous material being adjusted by diffusion annealing.

Die US-A-5,336,139 beschreibt ein Verfahren, bei dem ein Verbundwerkstoff durch Walzplattieren mit Aluminium hergestellt wird.US-A-5,336,139 describes a method in which a composite is made by roll cladding with aluminum.

Ein ähnliches Verfahren, mit etwas anderer Legierungszusammensetzung beschreibt die EP O 861 916 A1.A similar process, with a slightly different alloy composition, is described in EP O 861 916 A1.

Die DE 196 52 399 A1 beschreibt ein Verfahren zur Herstellung von Eisen-Chrom-Aluminiumlegierungen für Katalysator- und Heizleiterfolien, in dem ein Eisen-Chrom-Band mit einer Aluminium-Silizium-Legierung feueraluminiert wird und nach dem Walzen an End- oder Zwischenabmessung durch eine Diffusionsglühung ein neuer, aluminiumhaltiger Werkstoff gebildet wird.DE 196 52 399 A1 describes a process for the production of iron-chromium-aluminum alloys for catalyst and heating conductor foils, in which an iron-chromium strip is fire-aluminized with an aluminum-silicon alloy and after rolling to final or intermediate dimensions a diffusion annealing a new, aluminum-containing material is formed.

Diese Verfahren sind geeignet, wenn es sich bei dem Basismaterial um eine ferritische Eisenbasislegierung handelt. Ferritische Werkstoffe verfügen jedoch oft nicht über eine für viele Hochtemperaturanwendungen erforderliche Warmfestigkeit. Ist eine hohe Warmfestigkeit in Verbindung mit einer guten Hitzebeständigkeit gefordert, so müssen austenitische Stähle oder Nickelbasislegierungen eingesetzt werden. Austenitische Werkstoffe können jedoch bisher nicht mit derartigen Verfahren hergestellt werden, da die Diffusionsglühung bei einer Temperatur durchgeführt werden muß, bei der es bereits zu einem Aufschmelzen der Aluminiumauflage kommt.These methods are suitable if the base material is a ferritic iron-based alloy. However, ferritic materials often do not have the heat resistance required for many high-temperature applications. If high heat resistance combined with good heat resistance is required, austenitic steels or nickel-based alloys must be used. Austenitic materials, however, have so far not been able to be produced using such processes, since the Diffusion annealing must be carried out at a temperature at which the aluminum coating is already melting.

Der Erfindung liegt demzufolge die Aufgabe zugrunde, ein wirtschaftliches Verfahren zu entwickeln, mit dem sich zur Darstellung hitzebeständiger austenitischer Werkstoffe hohe Aluminiumgehalte realisieren lassen.The invention is therefore based on the object of developing an economical method with which high aluminum contents can be achieved to produce heat-resistant austenitic materials.

Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung eines Verbundwerkstoffes mit hoher Hitze- und Abrasionsbeständigkeit, indem ein Grundwerkstoff aus einer austenitischen Nickel-, Kobalt- oder Eisenbasislegierung ein- oder beidseitig mit einer Zwischenschicht aus einem ferritischen, einen Chromgehalt zwischen (in Gew.-%) 8 und 25 % beinhaltenden, Chromstahl versehen wird, auf welche ein- oder beiseitig eine Schicht aus Aluminium bzw. einer Aluminiumlegierung aufgebracht wird, und dieser aus Grundwerkstoff, Zwischenschicht und Aluminiumauflage gebildete Werkstoffverbund durch Kalt- und/oder Warmformgebung an die gewünschte Zwischen- oder Endabmessung gebracht und anschließend bei einer Temperatur oberhalb von 600°C diffusionsgeglüht wird.The object is achieved by a method for producing a composite material with high heat and abrasion resistance, in that a base material made of an austenitic nickel, cobalt or iron-based alloy on one or both sides with an intermediate layer made of a ferritic, a chromium content between (in wt. %) Containing 8 and 25%, chromium steel, to which a layer of aluminum or an aluminum alloy is applied on one or both sides, and this composite material formed from the base material, intermediate layer and aluminum layer by cold and / or hot forming to the desired intermediate - Or brought final dimension and then diffusion annealed at a temperature above 600 ° C.

Vorteilhafte Weiterbildungen des erfindungsgemäßen Verfahrens sind den zugehörigen Unteransprüchen zu entnehmen.Advantageous developments of the method according to the invention can be found in the associated subclaims.

EP-A-874 062 beschreibt die Herstellung von hitzebeständigem Heizdraht oder von Heizband durch Auftragen einer je zur Hälfte aus Chrom und Aluminium bestehenden Pulvermischung auf einem Grundmaterial aus austenitischem, Stahl und anschließendes Glühen in Vakuum bei 1100°C. Es bildet sich eine äußere Schicht aus Al und Al-Eisenlegierung über einer Zwischenschicht aus ferritischem rostfreiem Stahl mit darin verteilten AlFe - und AlNi-Teilchen.EP-A-874 062 describes the production of heat-resistant heating wire or heating tape by applying a powder mixture, each consisting of half of chromium and aluminum, to a base material made of austenitic steel and subsequent annealing in a vacuum at 1100 ° C. An outer layer of Al and Al-iron alloy forms over an intermediate layer of ferritic stainless steel with AlFe and AlNi particles distributed therein.

Das erfindungsgemäße Verfahren ist dadurch ausgezeichnet, dass eine Zwischenschicht aus einem ferritischen Chromstahl mit einem Chromgehalt zwischen 8 und 25 Masse% zwischen der Aluminiumauflage und dem Grundwerkstoff aufgebracht wird. Es hat sich überraschend gezeigt, daß bei Verwendung einer Zwischenlage aus einem ferritischem Chromstahl das Aluminium zunächst in die Zwischenschicht eindringt und dort sofort hochschmelzende Eisen-Aluminiun und Eisen-Chrom und Eisen-Chrom-Aluminium-Verbindungen bildet, bevor ein Aufschmelzen des Aluminiums erfolgt. Die Diffusionsglühung kann so bei Temperaturen oberhalb von 600 °C erfolgen.The method according to the invention is distinguished in that an intermediate layer made of a ferritic chromium steel with a chromium content between 8 and 25% by mass is applied between the aluminum coating and the base material. It has surprisingly been found that when an intermediate layer made of a ferritic chromium steel is used, the aluminum first penetrates into the intermediate layer and there immediately forms high-melting iron-aluminum and iron-chromium and iron-chromium-aluminum compounds before the aluminum melts he follows. The diffusion annealing can take place at temperatures above 600 ° C.

Die Zwischenschicht kann aus einem Blech, Band, Folie oder, im Falle runder Querschnitte, aus einem Rohr bestehen. Es ist auch möglich, Zwischenschicht und Aluminiumauflage zu kombinieren, indem zunächst ein Chromstahl durch Feueraluminieren oder Plattieren mit einer Aluminiumauflage beschichtet wird und dieser Zweiphasenverbund dann auf den Grundwerkstoff plattiert wird. Alternativ kann der Verbund aus Grundwerkstoff und Chromstahl oder der Verbund aus Aluminium und Chromstahl auch direkt im Stranggießverfahren hergestellt werden. Die Dicke von Zwischenlage aus Chromstahl, Grundwerkstoff und Aluminiumschicht wird jeweils nach gewünschter Dicke und gewünschten Eigenschaften der aluminiumreichen Randschicht bestimmt.The intermediate layer can consist of a sheet, tape, foil or, in the case of round cross sections, a tube. It is also possible to combine the intermediate layer and the aluminum layer by first coating a chrome steel with an aluminum layer by fire-aluminizing or cladding and then cladding this two-phase composite onto the base material. Alternatively, the composite of base material and chrome steel or the composite of aluminum and chrome steel can also be produced directly using the continuous casting process. The thickness of the intermediate layer made of chrome steel, base material and aluminum layer is determined in each case according to the desired thickness and desired properties of the aluminum-rich outer layer.

Vorteilhaft bei diesem Verfahren ist auch, dass sich Sonderlegierungselemente, zum Beispiel sauerstoffaffine Elemente, die die Hitzebeständigkeit und die Haftung der schützenden Oxidschichten verbessern (Yttrium, Hafnium, Zirkonium, Titan, Silizium, Cer, Lanthan) in die Zwischenlage einbringen lassen und damit oberflächennah zur Verfügung stehen.This method also has the advantage that special alloy elements, for example oxygen-affine elements, which improve the heat resistance and the adhesion of the protective oxide layers (yttrium, hafnium, zirconium, titanium, silicon, cerium, lanthanum) can be introduced into the intermediate layer and thus close to the surface To be available.

Vorteilhaft bei diesem Verfahren ist ebenfalls, dass sich durch Wahl geeigneter Kombinationen aus Grundwerkstoff, Zwischenschicht und Auflagewerkstoff Werkstoffe mit einem weitem Spektrum von Eigenschaftskombinationen herstellen lassen. So können besondere Anforderungen an die Festigkeit und an physikalische Eigenschaften des Grundwerkstoffes mit besonderen Anforderungen an Oberflächeneigenschaften wie Härte, Korrosionsbeständigkeit und Abrasionsbeständigkeit kombiniert werden.Another advantage of this method is that by choosing suitable combinations of base material, intermediate layer and support material, materials with a wide range of property combinations can be produced. This means that special requirements for the strength and physical properties of the base material can be combined with special requirements for surface properties such as hardness, corrosion resistance and abrasion resistance.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, Bleche oder Rohre mit einseitiger Aluminiumanreicherung herzustellen. Hieraus ergibt sich die Möglichkeit, Halbzeuge für solche Komponenten zu erzeugen, bei denen wegen unterschiedlicher Prozessmedien auf beiden Seiten (z. B. in Wärmetauschern) unterschiedliche Anforderungen an den Werkstoff gestellt werden.Another advantage of the method according to the invention is to produce sheets or tubes with aluminum enrichment on one side. From this results there is the possibility of producing semi-finished products for components that have different material requirements due to different process media on both sides (e.g. in heat exchangers).

Neben der Herstellung von Halbzeugen in Form von Blechen, Bändern, Folien, Rohren, Stangen und Drähten kann der erfindungsgemäße Verbundwerkstoff eingesetzt werden für Werkzeuge zum Trennen, Schneiden und Mahlen.In addition to the production of semi-finished products in the form of sheets, strips, foils, tubes, rods and wires, the composite material according to the invention can be used for tools for cutting, cutting and grinding.

Darüber hinaus sind Anwendungsgebiete im Kraftfahrzeugbau, bei Schiffsmotoren und Flugzeugtriebwerken sowie im Industrieofen- und Anlagenbau gegeben, in denen der Verbundwerkstoff als Halbzeuge zum Einsatz gebracht wird.In addition, there are areas of application in motor vehicle construction, ship engines and aircraft engines as well as in industrial furnace and plant construction, in which the composite material is used as semi-finished products.

Die Abbildungen 1 bis 4 zeigen Ausführungbeispiele für die Herstellung eines Mehrphasenverbundwerkstoffes mit hohen Aluminiumgehalten, wie sie in den folgenden Beispielen näher erläutert werden.Figures 1 to 4 show design examples for the production of a multi-phase composite material with high aluminum contents, as will be explained in more detail in the following examples.

Beispiel 1: Example 1 :

Herstellung eines hochhitzebeständigen und hochwarmfesten Werkstoffes durch beidseitiges Plattieren (oder Feueraluminieren) einer warmfesten Nickelbasislegierung mit Aluminium oder Aluminium-Silizium.Manufacture of a highly heat-resistant and highly heat-resistant material by cladding (or fire aluminum) on both sides of a heat-resistant nickel-based alloy with aluminum or aluminum-silicon.

Abb. 1 zeigt den Aufbau der verschiedenen Werkstoffe vor der Diffusionsglühung. Die Dicken von Grundwerkstoff, Zwischenlage und Aluminiumauflage werden je nach gewünschtem Verhältnis von aluminiumreicher Zone und Grundwerkstoff festgelegt. Die Zwischenlage besteht aus einem Chromstahl mit einem Chromgehalt zwischen 8 und 25 Masse %. Die Aluminiumauflage besteht aus einer Aluminium-Siliziumlegierung oder aus Reinaluminium. Fig. 1 shows the structure of the different materials before the diffusion annealing. The thicknesses of the base material, intermediate layer and aluminum layer are determined depending on the desired ratio of the aluminum-rich zone and the base material. The intermediate layer consists of a chrome steel with a chrome content between 8 and 25% by mass. The aluminum pad consists of an aluminum-silicon alloy or pure aluminum.

Im Beispiel wurde ein Verbundwerkstoff bestehend aus einem feueraluminierten Chromstahl (Fe-Cr18) mit Zusätzen von Yttrium und Hafnium als Plattierauflage gewählt.In the example, a composite material consisting of a fire-aluminum chromium steel (Fe-Cr18) with additions of yttrium and hafnium was chosen as the cladding.

Die einzelnen Schichten des Werkstoffverbundes werden durch Kaltwalzen miteinander verbunden. Das Kaltwalzen erfolgt an die gewünschte Endabmessung oder eine Zwichenabmessung mit oder ohne Zwischenglühung.The individual layers of the composite are joined together by cold rolling. Cold rolling is carried out to the desired final dimension or an intermediate dimension with or without intermediate annealing.

Bei der Diffusionsglühung bei einer Temperatur von etwa 1100 °C dringt das Aluminium vollständig in die Zwischenlage und teilweise in den Grundwerkstoff ein. Zwischen Grundwerkstoff und Auflage entsteht eine Verbindung, wie in Abb. 2 dargestellt. Auftretende Diffusionsporen in der Grenzfläche können durch eine weitere Umformung beseitigt werden.During diffusion annealing at a temperature of around 1100 ° C, the aluminum penetrates completely into the intermediate layer and partially into the base material. A connection is created between the base material and the support, as shown in Fig. 2 . Diffusion pores occurring in the interface can be eliminated by further reshaping.

Die Breite der aluminiumreichen Zone wird durch Zeit und Temperatur für die Diffusionsglühung festgelegt.The width of the aluminum-rich zone is determined by the time and temperature for the diffusion annealing.

Für dieses Verfahren bieten sich insbesondere hochwarmfeste und hitzebeständige Legierungen mit unzureichender Zunderbeständigkeit bei sehr hohen Temperaturen an. Hierzu gehören alle Nickel- und Kobaltbasislegierungen, die Chromoxidschichten bei hohen Temperaturen bilden wie die Werkstoffe 2.4816, 2.4855, 2.4663, 2.4856, 2.4665, 2.4665. 2.4964, 2.4683 und 2.4650 an (Angaben: DIN-Werkstoffnummern).Highly heat-resistant and heat-resistant alloys with inadequate scale resistance at very high temperatures are particularly suitable for this process. This includes all nickel and cobalt-based alloys that form chrome oxide layers at high temperatures, such as materials 2.4816, 2.4855, 2.4663, 2.4856, 2.4665, 2.4665. 2.4964, 2.4683 and 2.4650 (information: DIN material numbers).

Beispiel 2:Example 2:

Herstellung eines hochhitzebeständigen und hochwarmfesten Werkstoffes durch beidseitiges Plattieren oder Feueraluminieren eines Edelstahles mit Aluminium oder Aluminium-Silizium.Manufacture of a highly heat-resistant and heat-resistant material by cladding or fire-aluminizing a stainless steel with aluminum or aluminum-silicon on both sides.

Die Herstellung des Werkstoffes durch Kaltwalzen und Glühen des Werkstoffverbundes erfolgt wie unter Beispiel 1 beschrieben.The material is produced by cold rolling and annealing the composite as described in Example 1.

Für das ein- oder beidseitige Plattieren von Edelstählen bieten sich zum Beispiel warmfeste Stähle vom Typ 1.4876 an, deren Hochtemperaturkorrosionsbeständigkeit in heißen Prozessgasen durch die aluminiumhaltige Randzone signifikant verbessert wird.For the one-sided or double-sided cladding of stainless steels, there are, for example, heat-resistant steels of type 1.4876, whose high-temperature corrosion resistance in hot process gases is significantly improved by the aluminum-containing edge zone.

Beispiel 3:Example 3:

Herstellung eines korrosions- und hitzebeständigen Verbundwerkstoffes durch einseitiges Plattieren oder Aluminieren eines korrosionsbeständigen Werkstoffes mit Aluminium oder Aluminium-Silizium.Manufacture of a corrosion and heat-resistant composite material by one-sided plating or aluminizing a corrosion-resistant material with aluminum or aluminum-silicon.

Die Herstellung des Werkstoffes durch Kaltwalzen und Glühen des Werkstoffverbundes erfolgt wie unter Beispiel 1 beschrieben.The material is produced by cold rolling and annealing the composite as described in Example 1.

Das einseitige Plattieren von korrosionsbeständigen Werkstoffen gem. Abb. 3 kommt in Frage für Halbzeuge aus typischen korrosionsbeständigen Edelstählen, Reinnickel, Ni-Cu-Legierungen und Nickelbasislegierungen, die auf einer Seite einem aggressiven wäßrigem Medium (Säuren oder Alkalien, Seewasser) und auf der anderen Seite einem heißen Prozessgas ausgesetzt sind. Die aluminiumreiche Randschicht schützt den korrosionsbeständigen Werkstoff auf der Prozessgasseite gegen Hochtemperaturkorrosion.The one-sided plating of corrosion-resistant materials acc. Fig. 3 comes into question for semi-finished products made of typical corrosion-resistant stainless steels, pure nickel, Ni-Cu alloys and nickel-based alloys, which are exposed to an aggressive aqueous medium (acids or alkalis, sea water) on one side and to a hot process gas on the other side. The aluminum-rich surface layer protects the corrosion-resistant material on the process gas side against high-temperature corrosion.

Beispiel 4:Example 4:

Herstellung eines Fe-Ni-Werkstoffes mit geringem Ausdehnungskoeffizienten bei gleichzeitgig hoher Hitzebeständigkeit. Nach dem beschriebenen Verfahren ist es möglich, Halbzeuge aus Werkstoffen vom Typ Fe-Ni36 (1.3912) zu erzeugen, welche auch bei hohen Temperaturen noch einsetzbar ist. Üblicherweise ist die Verwendbarkeit dieser Werkstoffe auf Temperaturen unterhalb von 600 °C beschränkt.Manufacture of an Fe-Ni material with a low coefficient of expansion and high heat resistance. According to the described process, it is possible to produce semi-finished products from Fe-Ni36 (1.3912), which can still be used even at high temperatures. The usability of these materials is usually limited to temperatures below 600 ° C.

Die Herstellung des Werkstoffes durch Kaltwalzen und Glühen des Werkstoffverbundes erfolgt wie unter Beispiel 1 beschrieben.The material is produced by cold rolling and annealing the composite as described in Example 1.

Beispiel 5:Example 5:

Herstellung eines Halbzeuges mit rundem Querschnitt (Rohr oder Stange) mit hohen Aluminiumgehalten im oberflächennahen Bereich durch einseitiges Aufbringen von Aluminium oder Aluminium-Silizium auf einen korrosionsbeständigen, hitzebeständigen oder hochwarmfesten Werkstoff.Manufacture of a semi-finished product with a round cross-section (tube or rod) with high aluminum contents near the surface by applying aluminum or aluminum-silicon on one side to a corrosion-resistant, heat-resistant or high-temperature-resistant material.

Die Herstellung eines Rohres oder einer Stange erfolgt durch die üblichen Verfahren der Rohr- oder Stangenfertigung (beispielsweise Strangpressen, Kalthämmern, Pilgern oder Ziehen) des in Abb. 4 dargestellten Werkstoffverbundes aus Grundwerkstoff, Fe-Cr-Zwischenschicht und Aluminiumauflage. Die Diffusionsglühung erfolgt wie in Beispiel 1 beschrieben.A tube or a rod is produced by the usual methods of tube or rod production (for example extrusion, cold hammering, pilgrimage or drawing) as shown in Fig. 4 Composite of base material, Fe-Cr intermediate layer and aluminum layer. The diffusion annealing is carried out as described in Example 1.

Für dieses Verfahren sind alle in den Beispielen 1-4 aufgeführten Werkstoffe geeignet.All of the materials listed in Examples 1-4 are suitable for this process.

Beispiel 6:Example 6:

Herstellung dünner Folien aus einem hitzebeständigen und warmfesten Werkstoff durch ein- oder beidseitiges Aufbringen von Aluminium oder Aluminium-Silizium auf einen korrosionsbeständigen, hitzebeständigen oder hochwarmfesten Werkstoff.Production of thin foils from a heat-resistant and heat-resistant material by applying aluminum or aluminum-silicon on one or both sides to a corrosion-resistant, heat-resistant or high-temperature-resistant material.

Die Herstellung erfolgt wie unter Beispiel 1 beschrieben. Der Werkstoffverbund wird mit oder ohne Zwischenglühung an dünne Folien gewalzt. Die Diffusionsglühung wird, wie im Beispiel 1 angegeben, durchgeführt. Die Glühzeiten und Glühtemperaturen werden aber so gewählt, daß sich ein homogener Aluminiumgehalt über den gesamten Folienquerschnitt einstellt, mit Ausnahme einer dünnen Randzone mit erhöhtem Aluminiumgehalt.The preparation is carried out as described in Example 1. The composite material is rolled onto thin foils with or without intermediate annealing. The diffusion annealing is carried out as indicated in Example 1. The annealing times and annealing temperatures are chosen so that a homogeneous aluminum content is obtained over the entire film cross section, with the exception of a thin edge zone with an increased aluminum content.

Für dieses Verfahren sind alle in den Beispielen 1-4 beschriebenen Werkstoffe geeignet.All of the materials described in Examples 1-4 are suitable for this process.

Claims (9)

  1. A method for producing a composite material having a high heat and abrasion stability, wherein a base material composed of an austenitic nickel, cobalt or iron master alloy is coated on one or two sides with an intermediate layer of a ferritic chromium steel having a chromium content comprised between (in % by mass) 8 and 25%, onto which an aluminium or aluminium alloy layer is applied on one or on both sides, and this composite material composed of base material, intermediate layer and aluminium coating is shaped into the desired intermediate or final dimension by cold and/or hot forming and is afterwards homogenized at a temperature of above 600°C.
  2. A method according to claim 1, characterized in that a sheet metal, a band, a foil or, in case of round sections, a tube is used as intermediate layer.
  3. A method according to claim 1 or 2, characterized in that the intermediate layer and the aluminium coating are combined, such that at first the chromium steel is coated with the aluminium coating by fire aluminizing or plating and then this two phase compound is applied, in particular plated onto the base material.
  4. A method according to claim 1, characterized in that the compound composed of base material and chromium steel or the compound composed of chromium steel and aluminium is formed by continuous casting.
  5. A method according to one of the claims 1 through 4, characterized in that one or more of the oxygen affine elements cerium, lanthanum, hafnium, zirconium, silicium, titanium, yttrium, calcium or magnesium is or are added to the ferritic chromium steel, wherein the total content of these elements does not exceed 0.5% (in % by mass).
  6. Use of the composite material formed according to one of the claims 1 through 5 for producing semi-finished products in form of tubes, bands, foils, sheet metals, rods and wires.
  7. Use of the composite material formed according to one of the claims 1 through 5 for producing separating, cutting and grinding tools.
  8. Use of the composite material formed according to one of the claims 1 through 5 for producing semi-finished products for motor vehicles, ship motors and aircraft driving gears.
  9. Use of the composite material formed according to one of the claims 1 through 5 for producing semi-finished products for use in the construction of industrial furnaces and installations.
EP00951429A 1999-09-03 2000-07-22 Method for producing multi-phase composite materials Expired - Lifetime EP1226031B1 (en)

Applications Claiming Priority (3)

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DE19942234A DE19942234C1 (en) 1999-09-03 1999-09-03 Process for the production of multi-phase composite materials and use of the composite material
DE19942234 1999-09-03
PCT/EP2000/007045 WO2001017767A2 (en) 1999-09-03 2000-07-22 Method for producing multi-phase composite materials

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DE10137823C2 (en) * 2001-08-02 2003-08-21 Thyssenkrupp Stahl Ag Process for making strips from a metallic composite
US8333592B2 (en) * 2005-12-06 2012-12-18 Andrew Warburton Swan Video-captured model vehicle simulator
DE102006041324A1 (en) * 2006-09-01 2008-03-06 Rolls-Royce Deutschland Ltd & Co Kg Method for joining thick-walled components made from creep-resistant materials used in the construction of a driving gear comprises cleaning the connecting surfaces and treating with an activating agent and further processing
DE102009025197B4 (en) * 2008-10-01 2012-11-08 Thyssenkrupp Vdm Gmbh Process for the production of composite metal semi-finished products
DE102016201337A1 (en) * 2016-01-29 2017-08-03 Bayerische Motoren Werke Aktiengesellschaft Hydrogen-carrying steel component for use in motor vehicles, motor vehicle with hydrogen-carrying steel component and method for producing a hydrogen-carrying steel component

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US336139A (en) * 1886-02-16 Method of operating proportional water meters
US4705727A (en) * 1985-10-11 1987-11-10 Pfizer Inc. Composite material for induction heating
DE69203926T2 (en) * 1991-04-29 1995-12-07 Gen Motors Corp Thin sheets of iron-chromium coated with aluminum, with additions of rare earth metals or yttrium.
EP0672520B1 (en) * 1994-03-18 1999-03-03 Clad Lizenz AG Multilayered, cold formable and deep drawable metal composites
DE4434801A1 (en) * 1994-09-29 1996-04-04 Kolbenschmidt Ag Plain bearing material
US5976708A (en) * 1995-11-06 1999-11-02 Isuzu Ceramics Research Institute Co., Ltd. Heat resistant stainless steel wire
DE19652399A1 (en) * 1996-12-17 1998-06-18 Krupp Vdm Gmbh Production of multicomponent foil
FR2760244B1 (en) * 1997-02-28 1999-04-09 Usinor PROCESS FOR THE MANUFACTURE OF A FERRITIC STAINLESS STEEL STRAP WITH A HIGH ALUMINUM CONTENT FOR USE IN PARTICULAR FOR A MOTOR VEHICLE EXHAUST CATALYST SUPPORT
SE9702909L (en) * 1997-08-12 1998-10-19 Sandvik Ab Use of a ferritic Fe-Cr-Al alloy in the manufacture of compound tubes, as well as compound tubes and the use of the tubes

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ATE249337T1 (en) 2003-09-15
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