EP1922426A1 - Method for producing and using a nickel-based semi-finished product having a recrystallisation cube structure - Google Patents

Method for producing and using a nickel-based semi-finished product having a recrystallisation cube structure

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Publication number
EP1922426A1
EP1922426A1 EP06725088A EP06725088A EP1922426A1 EP 1922426 A1 EP1922426 A1 EP 1922426A1 EP 06725088 A EP06725088 A EP 06725088A EP 06725088 A EP06725088 A EP 06725088A EP 1922426 A1 EP1922426 A1 EP 1922426A1
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European Patent Office
Prior art keywords
semi
finished product
nickel
producing
strip
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EP06725088A
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German (de)
French (fr)
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EP1922426B1 (en
Inventor
Jörg EICKEMEYER
Dietmar Selbmann
Horst Wendrock
Bernhard Holzapfel
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Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
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Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the invention relates to a process for the production of nickel-based semi-finished products in strip or flat wire form with a recrystallization cube texture and the use of the semifinished product produced.
  • the semifinished product can be used in particular as a substrate for physico-chemical coatings with a high degree of microstructural alignment.
  • Such supports are suitable, for example, as substrates for ceramic coatings as used in the field of high temperature superconductivity. In this case, they are used in superconducting magnets, transformers, motors, tomographs or superconducting current paths.
  • Ni alloys with Mo and W (DE 100 05 861 C1). It has also been proposed to add such Ni alloys up to a maximum of 0.3 atom% Ag (DE 103 42 965.4).
  • Recrystallization is formed, have a structure with equiaxed grains, that is, based on the band level, they are about the same length and width.
  • grain extension in the longitudinal direction should be advantageous for current transport in superconductivity and result in higher transmittable currents (Hammerl, H. et al., Eur. Phys. Journal B (2002) 299-301).
  • Recrystallized nickel or its cubic texture alloys have grains which are approximately the same lengthwise in the longitudinal direction as in the transverse direction,
  • Nickel after cold working and recrystallization annealing, tends strongly to form a coarse grain structure, which is detrimental to obtaining the high grade cube texture.
  • Ni-tapes tend in the recrystallization heat treatment, especially at higher temperatures (800 to 115o C 0) strongly to the formation of grain boundaries trenches,
  • Grain boundary trench substrate material is poorly suited as a substrate for epitaxial layer depositions, for example for buffer layers and
  • the semi-finished product should have an elongated grain shape with stable cube texture, and the expanded grain should remain intact even after further thermal treatment at high temperatures for the purpose of oxide layer growth.
  • the method according to the invention is characterized in that initially a starting semi-finished product is produced by fusion metallurgy or powder metallurgy involving mechanical alloying, which consists of technically pure Ni or a Ni alloy, wherein an Ag addition in the microalloying range of at least 10 atomic ppm and a maximum of 1000 atomic ppm is contained.
  • This starting semifinished product is processed by means of a hot forming with subsequent cold working of> 50% thickness reduction to tape or flat wire with an intermediate dimension.
  • the semifinished product is annealed in the temperature range between 500 0 C and 85O 0 C annealed, the higher temperatures are used for the higher Ag contents, and then quenched. Subsequently, this intermediate is highly> 80% cold formed. Finally, a recrystallizing annealing treatment to achieve a complete cube texture is performed.
  • the final recrystallization annealing treatment is carried out depending on the alloy content in the nickel at temperatures of 500 0 C to 1200 0 C, preferably at 85O 0 C.
  • the semifinished product may advantageously be heat treated after or during the recrystallizing annealing for the purpose of growing a cube-textured NiO layer having a texture content of> 90% in an oxidizing atmosphere.
  • Ni alloy is used for the starting semi-finished product, which still contains Mo and / or W as alloying elements in addition to the Ag addition.
  • the formation of a high-grade cube texture is favored.
  • the expanded metal strip allows the growth of a highly cube textured NiO layer, which also has elongated grains.
  • the semifinished product can be used as a substrate for physico-chemical coatings with a high degree of microstructural orientation, in particular for producing wire-shaped or ribbon-shaped high-temperature superconductors.
  • Fig. 1 shows the stretched structure of nickel with 0.01 atom% of silver after hot rolling at 85O 0 C and then cold rolling with a thickness reduction of 85% and a tempering treatment with partial recrystallization at 55O 0 C for 30 min (longitudinal grinding, etched) ,
  • Fig. 2 shows elongated grains on the surface of a 80 micron thick band of nickel with 0.025 atom% of silver, which was subjected to an intermediate annealing at 65O 0 C for 30 minutes at 3 mm thickness, then was strongly cold formed at 80 microns thick and was finally annealed at 55O 0 C for 30 min (scanning electron micrograph).
  • Fig. 3 shows elongated grains with dice layer on the surface of an 80 micron thick band of nickel with 0.025 atom% of silver after a
  • Fig. 4 shows elongated grains with cube layer of nickel oxide on the surface of a 80 micron thick strip of nickel with 0.025 atom% of silver after an intermediate annealing at 65O 0 C over 30 min at 3 mm thickness, followed by strong cold forming at 80 microns thickness, the Texture annealing at 55O 0 C over 30 min and the oxidation in oxygen at
  • Example 1 Technically pure nickel, for example having a purity of 99.9 atomic percent nickel, is poured into a mold while 0.025 atomic percent silver is added. The ingot is rolled at 85O 0 C to the square dimension (22 x 22) mm 2 , homogenizing annealed and quenched. Subsequently, the square material is machined to obtain a defect-free surface for subsequent cold working by rolling. The cold rolling is first carried out with a rolling degree of over 50 percent thickness reduction of 20 mm to 3 mm thickness, in this case, 85% thickness reduction. The subsequent tempering at 65O 0 C for 30 min causes recrystallization with a proportion of elongated grains.
  • Fig. 1 shows a typical microstructure (nickel with 0.01 atomic percent silver). This structure with elongated grains serves as
  • Example 2 Technically pure nickel, for example having a purity of 99.9 atomic percent nickel, is melted by adding 0.01 atomic percent silver in a vacuum induction furnace and poured into a mold. The ingot is rolled at 900 ° C. to the square dimension (22 ⁇ 22) mm 2 , homogenized and quenched. Subsequently, the square material is machined to obtain a defect-free surface for subsequent cold working by rolling. Cold rolling is carried out with a rolling degree of over 50 percent thickness reduction, in this case 85%. The resulting nickel strip has a thickness of 3 mm. It is subsequently annealed min at 65O 0 C for 30 and quenched in water. The recrystallization produces a proportion of elongated grains.
  • the resulting nickel oxide layer has a structure with elongated grains, with a share of the cube layer of 97% (FIG. 4). The proportion of small-angle grain boundaries is 96%. This texture is rotated 45 ° from the texture of the nickel strip.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Metal Rolling (AREA)

Abstract

The invention relates to a method for producing and using a nickel-based semi-finished product embodied in the form of a strip or flat wire. The aim of said invention is to develop a method for producing a nickel-based semi-finished product which exhibits improved performance characteristics for the use in the form of a base for physical-chemical coatings provided with a high-quality intense microstructural orientation. Said semi-finished product should have an improved granular structure provided with a stable cube texture. For this purpose, the inventive method consists in producing an initial semi-finished product by means of a fusion or powder metallurgy process including mechanical alloys, wherein said semi-finished product comprises a technically pure Ni or the alloy thereof containing an Ag additive in a microalloy range which is equal to or greater than 10 atom ppm and is equal to or less than 1000 atom ppm, in shaping the initial semi-finished product in the form of a strip or flat wire by hot- and cold forming processes with a thickness reduction > 50 % associated with an intermediate measuring. During said intermediate measuring, the semi-finished product is softened by annealing at a temperature ranging from 500 to 850 °C, wherein the high temperatures are used for high Ag contents, and is subsequently quenched. Afterwards, the semi-finished product is exposed to the 80 % cold shaping. The inventive method also consists in carrying out a recrystallisation annealing treatment in such a way that the entire cubic texture is obtainable. The inventive semi-finished product is used in the form of a base for physical-chemical coatings provided with a high-quality intense microstructural orientation and for producing a high-temperature superconductor in the form of a flat wire or strip.

Description

Verfahren zur Herstellung und Verwendung von Halbzeug auf Nickelbasis mit RekristallisationswürfeltexturProcess for making and using nickel-based semifinished product with recrystallization cube texture
Technisches GebietTechnical area
Die Erfindung betrifft ein Verfahren zur Herstellung von Halbzeug auf Nickelbasis in Band- oder Flachdrahtform mit einer Rekristallisationswürfeltextur und die Verwendung des hergestellten Halbzeugs.The invention relates to a process for the production of nickel-based semi-finished products in strip or flat wire form with a recrystallization cube texture and the use of the semifinished product produced.
Das Halbzeug ist insbesondere einsetzbar als Unterlage für physikalisch-chemische Beschichtungen mit hochgradiger mikrostruktureller Ausrichtung. Solche Unterlagen sind zum Beispiel als Substrate für keramische Beschichtungen geeignet, wie sie auf dem Gebiet der Hochtemperatur-Supraleitung angewendet werden. Der Einsatz erfolgt in diesem Fall in supraleitenden Magneten, Transformatoren, Motoren, Tomographen oder supraleitenden Strombahnen.The semifinished product can be used in particular as a substrate for physico-chemical coatings with a high degree of microstructural alignment. Such supports are suitable, for example, as substrates for ceramic coatings as used in the field of high temperature superconductivity. In this case, they are used in superconducting magnets, transformers, motors, tomographs or superconducting current paths.
Stand der TechnikState of the art
Bekannt ist, dass polykristalline Metalle mit kubisch-flächenzentriertem Gitter, wie Nickel, Kupfer und Aluminium, nach vorausgegangener starker Kaltumformung durch Walzen bei der nachfolgenden Rekristallisation eine ausgeprägte Textur mit Würfellage ausbilden können (G. Wassermann: Texturen metallischer Werkstoffe, Springer, Berlin, 1939). Auf diese Weise texturierte Metallbänder, insbesondere Nickelbänder, werden auch als Unterlage für metallische Überzüge, keramische Pufferschichten und keramische Supraleiterschichten benutzt (US 5,741 ,377). Die Eignung solcher Metallbänder als Substratwerkstoff hängt maßgeblich vom erreichbaren Grad der Texturierung und der Stabilität der Textur im Bereich der Temperaturen ab, bei denen die Beschichtungsverfahren arbeiten. Es sind bereits texturierte Halbzeuge für die Herstellung von Hochtemperatur- Supraleitern bekannt, die aus Ni-Cr, Ni-Cr-V, Ni-Cu und ähnlichen Legierungen bestehen (US 5,964,966; US 6,106,615).It is known that polycrystalline metals with face-centered cubic lattice, such as nickel, copper and aluminum, after severe cold forming by rolling in the subsequent recrystallization form a pronounced texture with cube layer (G. Wassermann: textures of metallic materials, Springer, Berlin, 1939 ). Metal strips, in particular nickel strips, textured in this manner are also used as underlay for metallic coatings, ceramic buffer layers and ceramic superconductor layers (US Pat. No. 5,741,377). The suitability of such metal strips as a substrate material largely depends on the achievable degree of texturing and the stability of the texture in the range of temperatures at which the coating processes work. There are already known textured semi-finished products for the production of high-temperature superconductors, which consist of Ni-Cr, Ni-Cr-V, Ni-Cu and similar alloys (US 5,964,966, US 6,106,615).
Bekannt sind für diese Zwecke auch Ni-Legierungen mit Mo und W (DE 100 05 861 C1 ). Es wurde auch bereits vorgeschlagen, derartigen Ni-Legierungen bis zu maximal 0,3 Atom-% Ag zuzufügen (DE 103 42 965.4).Also known for these purposes, Ni alloys with Mo and W (DE 100 05 861 C1). It has also been proposed to add such Ni alloys up to a maximum of 0.3 atom% Ag (DE 103 42 965.4).
Sämtliche derartigen bekannten Metallbänder mit einer Würfeltextur, die durchAll such known metal bands with a cube texture, by
Rekristallisation entstanden ist, haben ein Gefüge mit äquiaxialen Körnern, das heißt, bezogen auf die Bandebene sind sie etwa gleich lang und breit. Aus theoretischen Überlegungen heraus sollte jedoch eine Kornstreckung in Längsrichtung für den Stromtransport bei der Supraleitung vorteilhaft sein und zu höheren übertragbaren Strömen führen (Hammerl, H. u.a., Eur. Phys. Journ. B (2002) 299-301 ). Allerdings ist es bisher noch nicht gelungen, Substratbänder mit Würfeltextur bei gleichzeitig stark gestreckter Kornstruktur herzustellen.Recrystallization is formed, have a structure with equiaxed grains, that is, based on the band level, they are about the same length and width. However, theoretically, grain extension in the longitudinal direction should be advantageous for current transport in superconductivity and result in higher transmittable currents (Hammerl, H. et al., Eur. Phys. Journal B (2002) 299-301). However, it has not yet been possible to produce substrate tapes with cube texture with simultaneously greatly extended grain structure.
Die bekannten Halbzeuge haben folgende Nachteile:The known semi-finished products have the following disadvantages:
- Rekristallisiertes Nickel oder dessen Legierungen mit Würfeltextur weisen Körner auf, die in Längsrichtung etwa die gleiche Ausdehnung haben wie in Querrichtung,Recrystallized nickel or its cubic texture alloys have grains which are approximately the same lengthwise in the longitudinal direction as in the transverse direction,
- Nickel neigt nach Kaltumformung und Rekristallisationsglühung stark zur Ausbildung einer groben Kornstruktur, die zur Erzielung der hochgradigen Würfeltextur nachteilig ist,Nickel, after cold working and recrystallization annealing, tends strongly to form a coarse grain structure, which is detrimental to obtaining the high grade cube texture.
- kaltumgeformte Ni-Bänder neigen bei der Rekristallisations-Wärmebehandlung, insbesondere bei höheren Temperaturen (800 bis 115O0C) stark zur Bildung von Korngrenzengräben,- cold-formed Ni-tapes tend in the recrystallization heat treatment, especially at higher temperatures (800 to 115o C 0) strongly to the formation of grain boundaries trenches,
- Substratmaterial mit Korngrenzengräben ist wenig geeignet als Unterlage für epitaktische Schichtabscheidungen, zum Beispiel für Pufferschichten undGrain boundary trench substrate material is poorly suited as a substrate for epitaxial layer depositions, for example for buffer layers and
Supraleiterschichten. Offenbarung der ErfindungSuperconductor layers. Disclosure of the invention
Der Erfindung liegt die Aufgabe zu Grunde, ein Verfahren zur Herstellung von Halbzeug auf Nickelbasis zu entwickeln, das verbesserte Gebrauchseigenschaften für die Verwendung als Unterlage für physikalisch-chemische Beschichtungen mit hochgradiger mikrostruktureller Ausrichtung besitzt. Insbesondere soll das Halbzeug eine gestreckte Kornform bei stabiler Würfeltextur aufweisen und das Streckkorn soll auch nach weiterer thermischer Behandlung bei hohen Temperaturen zum Zwecke eines Oxidschichtwachstums erhalten bleiben.It is an object of the present invention to provide a process for producing nickel-based semifinished product which has improved performance for use as a substrate for high chemical microstructural alignment physical-chemical coatings. In particular, the semi-finished product should have an elongated grain shape with stable cube texture, and the expanded grain should remain intact even after further thermal treatment at high temperatures for the purpose of oxide layer growth.
Diese Aufgabe wird mit dem in den Patenansprüchen gekennzeichneten Merkmalen gelöst.This object is achieved with the features characterized in the claims.
Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, dass zunächst auf schmelzmetallurgischem oder pulvermetallurgischem Wege unter Einbeziehung des mechanischen Legierens ein Ausgangshalbzeug hergestellt wird, das aus technisch reinem Ni oder einer Ni-Legierung besteht, worin ein Ag-Zusatz im Mikrolegierungsbereich von mindestens 10 Atom-ppm und maximal 1000 Atom-ppm enthalten ist. Dieses Ausgangshalbzeug wird mittels einer Warmumformung mit nachfolgender Kaltumformung von >50% Dickenreduktion zu Band oder Flachdraht mit einer Zwischenabmessung verarbeitet. In dieser Zwischenabmessung wird das Halbzeug entfestigend im Temperaturbereich zwischen 5000C und 85O0C geglüht, wobei die höheren Temperaturen für die höheren Ag-Gehalte angewandt werden, und daraufhin abgeschreckt. Anschließend wird dieses Zwischenprodukt hochgradig >80% kalt umgeformt. Abschließend wird eine rekristallisierende Glühbehandlung zur Erzielung einer vollständigen Würfeltextur durchgeführt.The method according to the invention is characterized in that initially a starting semi-finished product is produced by fusion metallurgy or powder metallurgy involving mechanical alloying, which consists of technically pure Ni or a Ni alloy, wherein an Ag addition in the microalloying range of at least 10 atomic ppm and a maximum of 1000 atomic ppm is contained. This starting semifinished product is processed by means of a hot forming with subsequent cold working of> 50% thickness reduction to tape or flat wire with an intermediate dimension. In this intermediate dimension, the semifinished product is annealed in the temperature range between 500 0 C and 85O 0 C annealed, the higher temperatures are used for the higher Ag contents, and then quenched. Subsequently, this intermediate is highly> 80% cold formed. Finally, a recrystallizing annealing treatment to achieve a complete cube texture is performed.
Die abschließende Rekristallisationsglühbehandlung wird in Abhängigkeit vom Legierungsgehalt im Nickel bei Temperaturen von 5000C bis 12000C durchgeführt, und zwar vorzugsweise bei 85O0C. Das Halbzeug kann vorteilhaft nach oder während der rekristallisierenden Glühung zum Zwecke des Aufwachsens einer würfeltexturierten NiO-Schicht mit einem Texturgehalt von >90% in einer oxidierenden Atmosphäre wärmebehandelt werden.The final recrystallization annealing treatment is carried out depending on the alloy content in the nickel at temperatures of 500 0 C to 1200 0 C, preferably at 85O 0 C. The semifinished product may advantageously be heat treated after or during the recrystallizing annealing for the purpose of growing a cube-textured NiO layer having a texture content of> 90% in an oxidizing atmosphere.
Vorteilhaft ist es auch, wenn für das Ausgangshalbzeug eine Ni-Legierung verwendet wird, die neben dem Ag-Zusatz noch Mo und/oder W als Legierungselemente enthält.It is also advantageous if a Ni alloy is used for the starting semi-finished product, which still contains Mo and / or W as alloying elements in addition to the Ag addition.
Mit dem erfindungsgemäßen Ag-Zusatz wird die Formierung einer hochgradigen Würfeltextur begünstigt. Außerdem ermöglicht das Metallband mit Streckkorn das Aufwachsen einer hochgradig mit einer Würfeltextur versehenen NiO-Schicht, die ebenfalls gestreckte Körner aufweist.With the Ag addition according to the invention, the formation of a high-grade cube texture is favored. In addition, the expanded metal strip allows the growth of a highly cube textured NiO layer, which also has elongated grains.
Das Halbzeug kann erfindungsgemäß als Unterlage für physikalisch-chemische Beschichtungen mit hochgradiger mikrostruktureller Ausrichtung, insbesondere zur Herstellung draht- oder bandförmiger Hochtemperatur-Supraleiter, verwendet werden.According to the invention, the semifinished product can be used as a substrate for physico-chemical coatings with a high degree of microstructural orientation, in particular for producing wire-shaped or ribbon-shaped high-temperature superconductors.
Die Erfindung ist nachstehend an Hand von Ausführungsbeispielen näher erläutert, mit denen die erfolgreiche Erprobung der Erfindung nachgewiesen wird.The invention is explained below with reference to exemplary embodiments, with which the successful testing of the invention is demonstrated.
Kurze Beschreibung der AbbildungenBrief description of the illustrations
Die nachstehenden Erläuterungen zu den Abbildungen zeigen die positiven Ergebnisse der Anwendung der Erfindung im Rahmen der beschriebenen Ausführungsbeispiele.The following explanations to the figures show the positive results of the application of the invention in the context of the described embodiments.
Abb. 1 zeigt das gestrecktes Gefüge von Nickel mit 0,01 Atom-% Silber nach dem Warmwalzen bei 85O0C und anschließendem Kaltwalzen mit einer Dickenreduktion von 85% und einer Anlassbehandlung mit Teilrekristallisation bei 55O0C über 30 min (Längsschliff, geätzt).Fig. 1 shows the stretched structure of nickel with 0.01 atom% of silver after hot rolling at 85O 0 C and then cold rolling with a thickness reduction of 85% and a tempering treatment with partial recrystallization at 55O 0 C for 30 min (longitudinal grinding, etched) ,
Abb. 2 zeigt gestreckte Körner auf der Oberfläche eines 80 μm dicken Bandes von Nickel mit 0,025 Atom-% Silber, das bei 3 mm Dicke einer Zwischenglühung bei 65O0C über 30 min unterzogen wurde, anschließend an 80 μm Dicke stark kalt umgeformt wurde und abschließend bei 55O0C über 30 min geglüht wurde (Rasterelektronenaufnahme).Fig. 2 shows elongated grains on the surface of a 80 micron thick band of nickel with 0.025 atom% of silver, which was subjected to an intermediate annealing at 65O 0 C for 30 minutes at 3 mm thickness, then was strongly cold formed at 80 microns thick and was finally annealed at 55O 0 C for 30 min (scanning electron micrograph).
Abb. 3 zeigt gestreckte Körner mit Würfellage auf der Oberfläche eines 80 μm dicken Bandes von Nickel mit 0,025 Atom-% Silber nach einerFig. 3 shows elongated grains with dice layer on the surface of an 80 micron thick band of nickel with 0.025 atom% of silver after a
Zwischenglühung bei 65O0C über 30 min bei 3mm Dicke, anschließender starker Kaltumformung an 80 μm Dicke und der abschließenden Glühung bei 55O0C über 30 min (Orientierungsmapping mit dem Rasterelektronenmikroskop).Intermediate annealing at 65O 0 C over 30 min at 3mm thickness, followed by strong cold forming at 80 microns thickness and the final annealing at 55O 0 C for 30 min (orientation mapping with the scanning electron microscope).
Abb. 4 zeigt gestreckte Körner mit Würfellage des Nickeloxids auf der Oberfläche eines 80 μm dicken Bandes von Nickel mit 0,025 Atom-% Silber nach einer Zwischenglühung bei 65O0C über 30 min bei 3 mm Dicke, anschließender starker Kaltumformung an 80 μm Dicke, der Texturglühung bei 55O0C über 30 min und der Oxidation in Sauerstoff beiFig. 4 shows elongated grains with cube layer of nickel oxide on the surface of a 80 micron thick strip of nickel with 0.025 atom% of silver after an intermediate annealing at 65O 0 C over 30 min at 3 mm thickness, followed by strong cold forming at 80 microns thickness, the Texture annealing at 55O 0 C over 30 min and the oxidation in oxygen at
115O0C über 2 min (Orientierungsmapping mit dem Rasterelektronenmikroskop).115O 0 C over 2 min (orientation mapping with the scanning electron microscope).
Beispiel 1 Technisch reines Nickel, beispielsweise mit einem Reinheitsgrad von 99,9 Atomprozent Nickel, wird unter Zulegieren von 0,025 Atomprozent Silber in eine Kokille abgegossen. Der Ingot wird bei 85O0C an die Vierkantabmessung (22 x 22) mm2 gewalzt, homogenisierend geglüht und abgeschreckt. Anschließend wird das Vierkantmaterial spanabhebend überarbeitet, um eine fehlerfreie Oberfläche für die folgende Kaltumformung durch Walzen zu erhalten. Das Kaltwalzen wird zunächst mit einem Abwalzgrad von über 50 Prozent Dickenreduktion von 20 mm an 3 mm Dicke durchgeführt, in diesem Fall 85% Dickenreduktion. Die nachfolgende Anlassbehandlung bei 65O0C über 30 min bewirkt eine Rekristallisation mit einem Anteil von gestreckten Körnern. Abb. 1 zeigt ein typisches Gefügebild (Nickel mit 0,01 Atomprozent Silber). Dieses Gefüge mit gestreckten Körnern dient alsExample 1 Technically pure nickel, for example having a purity of 99.9 atomic percent nickel, is poured into a mold while 0.025 atomic percent silver is added. The ingot is rolled at 85O 0 C to the square dimension (22 x 22) mm 2 , homogenizing annealed and quenched. Subsequently, the square material is machined to obtain a defect-free surface for subsequent cold working by rolling. The cold rolling is first carried out with a rolling degree of over 50 percent thickness reduction of 20 mm to 3 mm thickness, in this case, 85% thickness reduction. The subsequent tempering at 65O 0 C for 30 min causes recrystallization with a proportion of elongated grains. Fig. 1 shows a typical microstructure (nickel with 0.01 atomic percent silver). This structure with elongated grains serves as
Ausgangszustand für die weitere Verarbeitung zum gewünschten Nickelband mit Würfeltextur und mit in Längsrichtung gestreckten Körnern. Es wird im Weiteren durchgängig mit einer Dickenreduktion von 97,3% von 3 mm bis an 80 μm Dicke kalt umgeformt und abschließend in einer nicht oxidierenden Gasatmosphäre bei 55O0C über 30 min geglüht. Das Ergebnis sind Körner an der Oberfläche des Bandes, die um ein Mehrfaches länger als breit sind, wie Abb. 2 zeigt. Zugleich resultiert eine außerordentlich scharfe Rekristallisationswürfeltextur, wie aus Abb. 3 ersichtlich ist. Der Anteil der Kristallite mit Würfellage beträgt 97,5 Prozent, und der Anteil der Kleinwinkelkorngrenzen liegt bei 92 Prozent.Initial state for further processing to the desired nickel ribbon with cube texture and with longitudinally stretched grains. It is further cold formed with a thickness reduction of 97.3% from 3 mm to 80 microns thickness cold and finally annealed in a non-oxidizing gas atmosphere at 55O 0 C for 30 min. The result is grains on the surface of the strip that are several times longer than they are wide, as shown in Figure 2. At the same time results in an exceptionally sharp Rekristallisationswürfeltextur, as shown in Fig. 3 can be seen. The proportion of crystallites with dice position is 97.5 percent, and the proportion of small-angle grain boundaries is 92 percent.
Beispiel 2 Technisch reines Nickel, beispielsweise mit einem Reinheitsgrad von 99,9 Atomprozent Nickel, wird unter Zulegieren von 0,01 Atomprozent Silber in einem Vakuuminduktionsofen geschmolzen und in eine Kokille abgegossen. Der Ingot wird bei 9000C an die Vierkantabmessung (22 x 22) mm2 gewalzt, homogenisierend geglüht und abgeschreckt. Anschließend wird das Vierkantmaterial spanabhebend überarbeitet, um eine fehlerfreie Oberfläche für die folgende Kaltumformung durch Walzen zu erhalten. Das Kaltwalzen wird mit einem Abwalzgrad von über 50 Prozent Dickenreduktion durchgeführt, in diesem Fall 85%. Das resultierende Nickelband hat eine Dicke von 3 mm. Es wird nachfolgend bei 65O0C über 30 min angelassen und in Wasser abgeschreckt. Die Rekristallisation erzeugt einen Anteil von gestreckten Körnern. Es wird im Weiteren durchgängig mit einer Dickenreduktion von 97,3% ausgehend von 3 mm bis an 80 μm Dicke kalt umgeformt und abschließend in einer nicht oxidierenden Gasatmosphäre bei 55O0C über 30 min geglüht. Das Ergebnis ist eine nahezu vollständige Rekristallisationswürfeltextur in einem Streckkomgefüge (vergl. Abb. 3). Anschließend wird das Band in reinem Sauerstoffgas bei 115O0C einer 2-minütigen Oxidation ausgesetzt.Example 2 Technically pure nickel, for example having a purity of 99.9 atomic percent nickel, is melted by adding 0.01 atomic percent silver in a vacuum induction furnace and poured into a mold. The ingot is rolled at 900 ° C. to the square dimension (22 × 22) mm 2 , homogenized and quenched. Subsequently, the square material is machined to obtain a defect-free surface for subsequent cold working by rolling. Cold rolling is carried out with a rolling degree of over 50 percent thickness reduction, in this case 85%. The resulting nickel strip has a thickness of 3 mm. It is subsequently annealed min at 65O 0 C for 30 and quenched in water. The recrystallization produces a proportion of elongated grains. In addition, it is continuously cold formed with a thickness reduction of 97.3% from 3 mm to 80 microns thickness and finally annealed in a non-oxidizing gas atmosphere at 55O 0 C for 30 min. The result is an almost complete recrystallization cube texture in a stretched microstructure (see Fig. 3). Subsequently, the strip is exposed in pure oxygen gas at 115O 0 C a 2-minute oxidation.
Die entstandene Nickeloxidschicht weist ein Gefüge mit gestreckten Körnern auf, deren einen Anteil mit Würfellage 97% beträgt (Abb. 4). Der Anteil der Kleinwinkelkorngrenzen liegt bei 96%. Diese Textur ist um 45° gegenüber der Textur des Nickelbandes gedreht. Beispiel 3The resulting nickel oxide layer has a structure with elongated grains, with a share of the cube layer of 97% (FIG. 4). The proportion of small-angle grain boundaries is 96%. This texture is rotated 45 ° from the texture of the nickel strip. Example 3
Technisch reines Nickelpulver wird unter Zugabe von 5,0 Atomprozent Wolframpulver und 0,1 Atom-% Silberpulver pulvermetallurgisch prozessiert. Nach dem Verpressen, Tempern und Warmumformen wird ein Stabmaterial von (22 x 22) mm2 erhalten. Die Oberfläche wird spanabhebend überarbeitet, um eine fehlerfreie Oberfläche für die folgende Kaltumformung durch Walzen zu erhalten. Das Kaltwalzen wird ausgehend von ca. (20 X 20) mm2 bis an eine Dicke von 3 mm durchgeführt.Technically pure nickel powder is powder metallurgically processed with the addition of 5.0 atomic percent tungsten powder and 0.1 atom% silver powder. After pressing, annealing and hot forming, a rod material of (22 x 22) mm 2 is obtained. The surface is machined to obtain a defect free surface for subsequent cold working by rolling. The cold rolling is carried out from about (20 X 20) mm 2 to a thickness of 3 mm.
Es wird nachfolgend bei 65O0C über 30 min angelassen und in Wasser abgeschreckt. Darauf wird an die Fertigabmessung von 80 μm Dicke kalt gewalzt. Die Randbereiche des Bandes werden abgetrennt und verworfen. Das erhaltene Nickelband wird anschließend zunächst bei 85O0C einer 30-minütigen Glühbehandlung zum Rekristallisieren in reduzierender Atmosphäre unterzogen. Danach wird das Band in einer zweiten Glühung über 8 Minuten bei 115O0C in reduzierender Atmosphäre behandelt, um eine thermisch hoch belastbare Würfellage einzustellen. It is subsequently annealed min at 65O 0 C for 30 and quenched in water. Then cold rolled to the finished size of 80 microns thickness. The edge areas of the band are separated and discarded. The nickel tape obtained is then subjected initially at 85O 0 C a 30-minute annealing treatment for recrystallization in a reducing atmosphere. Thereafter, the strip is treated in a second annealing for 8 minutes at 115O 0 C in a reducing atmosphere to set a thermally highly resilient cube layer.

Claims

Ansprüche claims
1. Verfahren zur Herstellung eines Halbzeuges auf Nickelbasis mit1. A process for the preparation of a semi-finished nickel-based with
Rekristallisationswürfeltextur, dadurch gekennzeichnet, dass zunächst auf schmelzmetallurgischem oder pulvermetallurgischem Wege unter Einbeziehung des mechanischen Legierens ein Ausgangshalbzeug hergestellt wird, das aus technisch reinem Ni oder einer Ni-Legierung besteht, worin ein Ag-Zusatz im Mikrolegierungsbereich von mindestens 10 Atom-ppm und maximal 1000 Atom- ppm enthalten ist, dass dieses Ausgangshalbzeug mittels einer Warmumformung mit nachfolgender Kaltumformung von >50% Dickenreduktion zu Band oder Flachdraht mit einer Zwischenabmessung verarbeitet wird, diese entfestigend im Temperaturbereich zwischen 5000C und 85O0C geglüht wird, wobei die höheren Temperaturen für die höheren Ag-Gehalte angewandt werden, dass daraufhin abgeschreckt wird, dass anschließend dieses Zwischenprodukt hochgradig >80% kalt umgeformt wird und dass abschließend eine rekristallisierende Glühbehandlung zur Erzielung einer vollständigen Würfeltextur durchgeführt wird.Recrystallization cube texture, characterized in that initially by fusion metallurgy or powder metallurgy involving mechanical alloying a starting semi-finished product is prepared, which consists of technically pure Ni or a Ni alloy, wherein an Ag addition in the microalloying of at least 10 atomic ppm and a maximum of 1000 Atomic ppm is that this starting semi-finished by hot working with subsequent cold forming of> 50% thickness reduction to strip or flat wire is processed with an intermediate dimension, this is annealed in the temperature range between 500 0 C and 85O 0 C annealed, the higher temperatures for the higher Ag contents are used, which is then quenched that then this intermediate product is highly> 80% cold formed and that finally a recrystallizing annealing treatment to achieve a complete cube texture is performed.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die abschließende Rekristallisationsglühbehandlung in Abhängigkeit vom Legierungsgehalt im Nickel bei Temperaturen von 5000C bis 12000C durchgeführt wird.2. The method according to claim 1, characterized in that the final recrystallization annealing is carried out in dependence on the alloy content in the nickel at temperatures of 500 0 C to 1200 0 C.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die abschließende Rekristallisationsglühbehandlung mit einer Temperatur von 85O0C durchgeführt wird.3. The method according to claim 2, characterized in that the final recrystallization annealing is carried out at a temperature of 85O 0 C.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das Halbzeug nach oder während der rekristallisierenden Glühung zum Zwecke des Aufwachsens einer würfeltexturierten NiO-Schicht mit einem Texturgehalt von >90% in einer oxidierenden Atmosphäre wärmebehandelt wird. 4. A method according to claim 1, characterized in that the semifinished product is heat treated after or during the recrystallizing annealing for the purpose of growing a cube-textured NiO layer having a texture content of> 90% in an oxidizing atmosphere.
5. Halbzeug nach Anspruch 1 , dadurch gekennzeichnet, dass für das5. Semi-finished product according to claim 1, characterized in that for the
Ausgangshalbzeug eine Ni-Legierung verwendet wird, die Mo und/oder W und den Ag-Zusatz enthält.Starting semi-finished a Ni alloy is used, which contains Mo and / or W and the Ag addition.
6. Verwendung des gemäß der Ansprüche 1 bis 5 hergestellten Halbzeuges in Bandoder Flachdrahtform mit Rekristallisationswürfeltextur und gestreckter Kornform als Unterlage für physikalisch-chemische Beschichtungen mit hochgradiger mikrostruktureller Ausrichtung.6. Use of the semifinished product produced according to claims 1 to 5 in strip or flat wire form with Rekristallisationswürfeltextur and elongated grain shape as a support for physical-chemical coatings with high-grade microstructural alignment.
7. Verwendung des gemäß der Ansprüche 1 bis 5 hergestellten Halbzeuges in Bandoder Flachdrahtform mit Rekristallisationswürfeltextur und gestreckter Kornform als Unterlage zur Herstellung draht- oder bandförmiger Hochtemperatur- Supraleiter. 7. Use of the semifinished product produced according to claims 1 to 5 in ribbon or flat wire form with Rekristallisationswürfeltextur and elongated grain shape as a base for the production of wire or ribbon-shaped high-temperature superconductor.
EP06725088.6A 2005-03-16 2006-03-15 Method for producing and using a nickel-based semi-finished product having a recrystallisation cube structure Not-in-force EP1922426B1 (en)

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DE102005013368A DE102005013368B3 (en) 2005-03-16 2005-03-16 Making nickel-based blank with cubic recrystallization structure for use as backing for high temperature superconductor, employs silver micro-alloying and specified thermal and mechanical treatments
PCT/EP2006/060774 WO2006097501A1 (en) 2005-03-16 2006-03-15 Method for producing and using a nickel-based semi-finished product having a recrystallisation cube structure

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DE102010031058A1 (en) * 2010-07-07 2012-01-12 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Metallic profile wire with recrystallization cube texture and process for its production
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