WO2005003399A1 - Beta-titanium alloy, method for producing a hot-rolled product based on said alloy and the uses thereof - Google Patents

Beta-titanium alloy, method for producing a hot-rolled product based on said alloy and the uses thereof Download PDF

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Publication number
WO2005003399A1
WO2005003399A1 PCT/EP2004/007201 EP2004007201W WO2005003399A1 WO 2005003399 A1 WO2005003399 A1 WO 2005003399A1 EP 2004007201 W EP2004007201 W EP 2004007201W WO 2005003399 A1 WO2005003399 A1 WO 2005003399A1
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Prior art keywords
titanium alloy
beta titanium
hot
alloy
beta
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PCT/EP2004/007201
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German (de)
French (fr)
Inventor
Heinz Sibum
Oliver Schauerte
Georg Frommeyer
Sven Knippscheer
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Deutsche Titan Gmbh
Max-Planck-Institut Für Eisenforschung GmbH
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Application filed by Deutsche Titan Gmbh, Max-Planck-Institut Für Eisenforschung GmbH filed Critical Deutsche Titan Gmbh
Priority to JP2006518094A priority Critical patent/JP2007527466A/en
Priority to US10/560,977 priority patent/US20070175552A1/en
Priority to EP04740562A priority patent/EP1641950B1/en
Priority to DE502004007396T priority patent/DE502004007396D1/en
Publication of WO2005003399A1 publication Critical patent/WO2005003399A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • Beta titanium alloy process for producing a hot rolled product from such an alloy and their uses
  • Beta titanium alloys with high vanadium contents are characterized by good strength and good toughness and ductility. They are usually processed in an arm shaping process into semi-finished products, such as sheets, rods, hollow or solid profiles, wires, from which high-quality lightweight components are then manufactured.
  • beta-titanium alloys typically contain V, Nb, Ta, Mo, Fe and Cr as the main alloy elements stabilizing the krz ß mixed crystal, as well as certain contents of Zr, Sn, Al and additives of Si.
  • a beta titanium alloy and a method for producing components from this alloy are also from the
  • the Cr content is less than
  • a melt composed in this way is cast into ingots, which are then thermoformed into a component in a two-stage process.
  • the component obtained is brought into solid solution by a heat treatment in which its temperature is kept at 10 ° C. to 40 ° C. below a value specified in the DD 281 422 A5 "transus ⁇ " real value. After this heat treatment, the part is held between 550 ° C to 650 ° C for four to twelve hours.
  • the parts treated in this way have a proof stress R p o, 2 of at least 1100 MPa and tensile strength R m of at least 1200 MPa.
  • beta titanium alloys are given in AT-PS 272 677, EP 0 408 313 B ⁇ and EP 0 600 579 B1.
  • AT-PS 272 677 Further examples of beta titanium alloys are given in AT-PS 272 677, EP 0 408 313 B ⁇ and EP 0 600 579 B1.
  • Common to the state of the art documented in these publications is the effort to provide a titanium alloy which is as easy to cast as possible, which at the same time has good mechanical properties and can be produced inexpensively.
  • the object of the invention was therefore to create a high-strength beta titanium alloy with good plastic properties before curing for the purpose of good formability and high fatigue strength after curing, which can be produced inexpensively.
  • a procedure should also be specified with which such an alloy can be used to produce high-strength components at low cost.
  • this task is solved by a beta titanium alloy, which (in mass%) V: 10 - 17%, Fe: 2 - 5%, AI: 2 - 5%, Mo: 0.1 - 3 %, and optionally one or more alloy elements from the group Sn, Si, Cr, Nb, Zr according to the following stipulation: Sn: 0.1 - 3%, Si: 0.1 ⁇ 2%, Cr: ⁇ 2%, Nb: ⁇ 2%, Zr: ⁇ 2, where the beta titanium alloy can additionally have contents of C and of elements from the group of the lanthanides, and the balance contains Ti and unavoidable impurities.
  • a beta-titanium alloy composed according to the invention safely achieves an elastic limit R p o, 2 of at least 1400 MPa, a tensile strength R m of at least 1500 MPa and a plastic elongation ⁇ p0 , 2 of more than 4% at room temperature.
  • Their density p does not exceed 4.8 g / cm 3 , so that not only extremely strong but also weight-optimized components can be produced with a beta titanium alloy according to the invention.
  • the alloy according to the invention has vanadium contents which are significantly higher than those which are provided in the prior art in beta titanium alloys.
  • the ß-phase of the structure is stabilized and the heat resistance increased due to the high V-content.
  • the V content in an alloy according to the invention is therefore preferably in the range from 12 to 17% by mass, in particular in the range from 13 to 17% by mass.
  • Levels of 2 - 5% by mass of aluminum stabilize the ⁇ phase of the structure and cause effective mixed crystal hardening.
  • the effect of iron in the titanium alloy composed according to the invention consists in stabilizing the ⁇ phase of the structure, increasing the heat resistance and improving the formation of mixed crystals.
  • a titanium material according to the invention contains molybdenum in amounts of 0.1-3% by mass, preferably at least 0.5% by mass, in order to stabilize the ⁇ -phase of the structure and to increase the heat resistance.
  • a beta titanium alloy according to the invention also contains one or more alloy elements from the group Sn, Si, Cr, Nb, Zr.
  • the presence of tin has a beneficial effect on solid solution hardening and heat resistance.
  • the Sn contents are therefore preferably in the range from 0.5 to 3% by mass.
  • Silicon increases the heat resistance and the oxidation resistance in an alloy according to the invention.
  • Chromium can be added to the alloy to stabilize the ß-phase of the structure and to increase the heat resistance.
  • Additions to niobium also have a favorable influence on the heat resistance and the oxidation resistance of the alloy.
  • the alloy according to the invention can contain further components as long as these do not negatively influence the properties achieved according to the invention.
  • levels of carbon and levels of elements which are assigned to the group of lanthanides are assigned to the group of lanthanides.
  • Optimal properties of the beta titanium alloys according to the invention are obtained if the limit values specified above are adhered to with at least two decimal places.
  • the above-mentioned object is achieved in that the following work steps are carried out when producing a product produced from a beta titanium alloy:
  • the hot forming for the production of strips or sheets can be carried out as hot rolling, which can be followed, if necessary, by coiling.
  • the Ti alloy according to the invention can be produced particularly cost-effectively by alloying the alloy elements V, Fe and Al in a manner known per se, not in the form of a master alloy, but individually.
  • Such master alloys are commercially available.
  • the hot end product obtained by the process according to the invention after the hot final forming consists of single-phase, metastable beta titanium, the transus temperature T B of which is approximately 788 ° C. If the hot end product is produced by hot rolling, it has crystals stretched in the rolling direction and has a partially dynamically recrystallized structure.
  • the block-shaped preliminary product processed in the course of the method according to the invention is obtained by remelting.
  • a vacuum remelting furnace can be used for this in a manner known per se.
  • the preliminary product can be round blocks, for example, which are then hot-formed into billets or blanks in the course of the hot forming.
  • Sticks of this type are typically square-shaped with edge lengths of, for example, 70 mm or round with a diameter of, for example, 60 mm.
  • the hot final forming is typically carried out at forming temperatures which are in the range from 950 ° C. to 1150 ° C. in order to be effective Cross-section reduction and homogenization of the composition and structure.
  • an advantageous embodiment of the method according to the invention provides that the hot final product is solution-annealed after the hot final forming.
  • Cold forming follows the solution annealing.
  • Solution annealing is typically carried out at 875 ° C for 30 minutes.
  • the solution-annealed hot end product is annealed to recrystallize.
  • the temperatures during this annealing treatment with holding times of 20 to 40 minutes are typically in the range from 775 ° C to 875 ° C.
  • the end product obtained after cold working has an elastic limit R po , 2 of at least 870 MPa to 900 MPa, a tensile strength R m which is 890 MPa to 944 MPa, and a plastic elongation of 14-17%.
  • the product obtained has an elastic limit R p o, 2 of at least 1,400 MPa, an elastic limit R m of at least 1,500 MPa and an elongation ⁇ p ⁇ of at least 4%.
  • the typical temperature of the curing treatment is approximately 480 ° C. If these time and temperature specifications are observed, an optimal range of properties of the end products produced according to the invention is established.
  • Semifinished products such as blanks, sheets, rods, profiles or wires, can be produced from a beta titanium alloy according to the invention, which, due to their property profile, are excellently suited to highly resilient components.
  • the semi-finished products can be produced inexpensively, in particular by using the method according to the invention.
  • Beta titanium alloys according to the invention have proven to be particularly suitable as a construction material for the production of components which are used in rail or road-bound vehicles and in the aerospace industry. Examples of this use include axle springs, connecting rods, piston pins, high-strength screws, brake pistons and discs.
  • beta-titanium alloys according to the invention are particularly well suited for the production of components which are used in the field of general mechanical engineering, apparatus construction, plant construction, container construction, cryogenic technology, vehicle construction or in the field of sports.
  • beta titanium alloys obtained according to the invention are particularly suitable for beta titanium alloys obtained according to the invention.
  • Suitable for the production of components that are used in the temperature range from -196 ° C to 300 ° C.
  • Hot rolling temperatures which were in the range from 1100 ° C to 950 ° C, were hot-rolled into wire and then coiled into coils. After hot rolling, the wire had single-phase metastable ß-titanium (transus temperature T ß approx. 788 ° C) with crystallites stretched in the direction of the wire axis and partially dynamically recrystallized structure.
  • the wire was solution annealed at 875 ° C for 30 minutes. After the solution annealing, the wire was cold formed. After the cold forming, the wire was recrystallized at temperatures that were between 775 ° C and 875 ° C, with a holding time that was in the range of 20 minutes to 40 minutes.
  • the annealed wire had a yield strength R p o, 2 / between 870 MPa and 900 MPa, a tensile strength R m between 890 MPa and 944 MPa and an elongation A between 14% and 17%.
  • the recrystallization annealing was followed by a curing treatment in which the wire was kept at 480 ° C. for 5 hours.
  • the wire treated in this way had an elastic limit R po , 2 of more than 1400 MPa, a tensile strength R m of more than 1500 MPa and an elongation A which was at least in the range from 4% to 5% at room temperature.

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Abstract

The invention relates to a high-strength beta titanium alloy which has good plastic properties before hardening for the purpose of a good plasticity as well as excellent fatigue strength. The inventive beta titanium alloy contains (in percent by weight) V: 10 - 17 %, Fe: 2 - 5 %, Al: 2 - 5 %, Mo: 0.1 - 3 %, and optionally one or more alloy elements from the group including Sn, Si, Cr, Nb, Zr under the proviso that Sn: 0.1 - 3 %, Si: 0.1 ≤ 2 %, Cr: ≤ 2 %, Nb: ≤ 2 %, Zr: ≤ 2, wherein additional contents in C and in elements of the group of lanthanides may be present, and as a remainder Ti and unavoidable impurities. The invention also relates to a method by means of which high-strength structural components can be produced at low cost.

Description

Beta-Titanlegierung, Verfahren zur Herstellung eines Warmwalzproduktes aus einer solchen Legierung und deren Verwendungen Beta titanium alloy, process for producing a hot rolled product from such an alloy and their uses
Beta-Titanlegierungen mit hohen Vanadiumgehalten zeichnen sich durch gute Festigkeiten bei gleichzeitig guter Zähigkeit bzw. Duktilität aus. Sie werden üblicherweise in einem armformgebungsverfahren zu Halbzeugen, wie Blechen, Stäben, Hohl- oder Vollprofilen, Drähten, verarbeitet, aus denen dann hochwertige Leichtbaukomponenten hergestellt werden.Beta titanium alloys with high vanadium contents are characterized by good strength and good toughness and ductility. They are usually processed in an arm shaping process into semi-finished products, such as sheets, rods, hollow or solid profiles, wires, from which high-quality lightweight components are then manufactured.
Die Grundlagen der Herstellung und Eigenschaften von Beta- Titanlegierungen sind in U. Zwicker "Titan- und Titanlegierungen", Springer-Verlag Berlin, Heidelberg, New York, 1974 erläutert. Neben Titan als Matrixmetall enthalten demnach Beta-Titanlegierungen als den krz ß- Mischkristall stabilisierende Hauptlegierungselemente üblicherweise V, Nb, Ta, Mo, Fe und Cr sowie gewisse Gehalte an Zr, Sn, AI und Zusätze an Si .The basics of the production and properties of beta titanium alloys are explained in U. Zwicker "Titanium and Titanium Alloys", Springer-Verlag Berlin, Heidelberg, New York, 1974. In addition to titanium as the matrix metal, beta-titanium alloys typically contain V, Nb, Ta, Mo, Fe and Cr as the main alloy elements stabilizing the krz ß mixed crystal, as well as certain contents of Zr, Sn, Al and additives of Si.
Eine Beta-Titanlegierung und ein Verfahren zur Herstellung von Bauteilen aus dieser Legierung sind auch aus derA beta titanium alloy and a method for producing components from this alloy are also from the
DD 281 422 A5 bekannt. Bei der bekannten Legierung betragen die Gehalte an Cr und V in Summe 1,5 - 4,5 Masse-% .DD 281 422 A5 known. In the known alloy, the Cr and V contents total 1.5 - 4.5 mass%.
Gleichzeitig ist der Gehalt an Cr auf weniger alsAt the same time, the Cr content is less than
2,5 Masse-% beschränkt. Zusätzlich enthält die bekannte2.5 mass% limited. In addition, the known one
Legierung weniger als 2,0 Masse-% Fe, 3,8 - 4,8 Masse-% AI,Alloy less than 2.0 mass% Fe, 3.8 - 4.8 mass% AI,
1,5 - 4,5 Masse-% Mo sowie 1,5 - 2,5 Masse-% Sn,1.5 - 4.5 mass% Mo and 1.5 - 2.5 mass% Sn,
2,8 - 4,8 Masse-% Zr und weniger als 0,3 Masse-% Si. Gemäß dem bekannten Verfahren wird eine derart zusammengesetzte Schmelze zu Barren vergossen, die anschließend in einem zweistufig durchgeführten Vorgang zu einem Bauteil warmverformt werden. Das erhaltene Bauteil wird durch eine Wärmebehandlung, bei der seine Temperatur 10 °C bis 40 °C unter einem in der DD 281 422 A5 "transus ß"-Echtwert bezeichneten Wert gehalten wird, in feste Lösung gebracht. Nach dieser Wärmebehandlung wird das Teil für vier bis zwölf Stunden zwischen 550 °C bis 650 °C gehalten. Die so behandelten Teile weisen eine Dehngrenze Rpo,2 von mindestens 1100 MPa und Zugfestigkeit Rm von mindestens 1200 MPa auf.2.8 - 4.8 mass% Zr and less than 0.3 mass% Si. According to In the known method, a melt composed in this way is cast into ingots, which are then thermoformed into a component in a two-stage process. The component obtained is brought into solid solution by a heat treatment in which its temperature is kept at 10 ° C. to 40 ° C. below a value specified in the DD 281 422 A5 "transus β" real value. After this heat treatment, the part is held between 550 ° C to 650 ° C for four to twelve hours. The parts treated in this way have a proof stress R p o, 2 of at least 1100 MPa and tensile strength R m of at least 1200 MPa.
Weitere Beispiele für Beta-Titanlegierungen sind in der AT-PS 272 677, der EP 0 408 313 Bϊ und der EP 0 600 579 Bl gegeben. Dem in diesen Druckschriften dokumentierten Stand der Technik gemeinsam ist das Bestreben, eine möglichst gut vergießbare Titanlegierüng zur Verfügung zu stellen, die gleichzeitig gute mechanische Eigenschaften besitzt und sich kostengünstig erzeugen lässt.Further examples of beta titanium alloys are given in AT-PS 272 677, EP 0 408 313 Bϊ and EP 0 600 579 B1. Common to the state of the art documented in these publications is the effort to provide a titanium alloy which is as easy to cast as possible, which at the same time has good mechanical properties and can be produced inexpensively.
Die Praxis zeigt jedoch, dass die bekannten Legierungen einerseits hinsichtlich ihrer Festigkeiten und andererseits hinsichtlich ihres Dehnungsverhaltens die von den Verarbeitern und Verwendern gestellten Anforderungen nicht ausreichend erfüllen.Practice shows, however, that the known alloys, on the one hand with regard to their strengths and on the other hand with regard to their elongation behavior, do not adequately meet the requirements set by processors and users.
Der Erfindung lag daher die Aufgabe zugrunde, eine hochfeste Beta-Titanlegierung mit guten plastischen Eigenschaften vor der Aushärtung zum Zwecke einer guten Umformbarkeit sowie hoher Dauerfestigkeit nach der Aushärtung zu schaffen, die sich kostengünstig erzeugen lässt. Darüber hinaus sollte ein Verfahren angegeben werden, mit dem sich aus einer solchen Legierung hochbelastbare Bauteile kostengünstig herstellen lassen.The object of the invention was therefore to create a high-strength beta titanium alloy with good plastic properties before curing for the purpose of good formability and high fatigue strength after curing, which can be produced inexpensively. A procedure should also be specified with which such an alloy can be used to produce high-strength components at low cost.
In Bezug auf den Werkstoff wird diese Aufgabe durch eine Beta-Titanlegierung gelöst, die (in Masse-%) V: 10 - 17 %, Fe: 2 - 5 %, AI: 2 - 5 %, Mo: 0,1 - 3 %, sowie optional eines oder mehrere Legierungselemente aus der Gruppe Sn, Si, Cr, Nb, Zr gemäß folgender Maßgabe: Sn: 0,1 - 3 %, Si: 0,1 < 2 %, Cr: < 2 %, Nb: < 2 %, Zr: < 2, wobei die Beta-Titanlegierung zusätzlich Gehalte an C und an Elementen der Gruppe der Lanthanide aufweisen kann, und als Rest Ti und unvermeidbare Verunreinigungen enthält.With regard to the material, this task is solved by a beta titanium alloy, which (in mass%) V: 10 - 17%, Fe: 2 - 5%, AI: 2 - 5%, Mo: 0.1 - 3 %, and optionally one or more alloy elements from the group Sn, Si, Cr, Nb, Zr according to the following stipulation: Sn: 0.1 - 3%, Si: 0.1 <2%, Cr: <2%, Nb: <2%, Zr: <2, where the beta titanium alloy can additionally have contents of C and of elements from the group of the lanthanides, and the balance contains Ti and unavoidable impurities.
Eine erfindungsgemäß zusammengesetzte Beta-Titanlegierung erreicht bei Raumtemperatur sicher eine Dehngrenze Rpo,2 von mindestens 1400 MPa, eine Zugfestigkeit Rm von mindestens 1500 MPa und eine plastische Dehnung εp0,2 von mehr als 4 %. Dabei übersteigt ihre Dichte p 4,8 g/cm3 nicht, so dass sich mit einer erfindungsgemäßen Beta-Titanlegierung nicht nur extrem feste, sondern auch gewichtsoptimierte Bauteile erzeugen lassen.A beta-titanium alloy composed according to the invention safely achieves an elastic limit R p o, 2 of at least 1400 MPa, a tensile strength R m of at least 1500 MPa and a plastic elongation ε p0 , 2 of more than 4% at room temperature. Their density p does not exceed 4.8 g / cm 3 , so that not only extremely strong but also weight-optimized components can be produced with a beta titanium alloy according to the invention.
Dies wird zum einen dadurch erreicht, dass die erfindungsgemäße Legierung Vanadium-Gehalte aufweist, die deutlich über denen liegen, die beim Stand der Technik in Beta-Titanlegierungen vorgesehen sind. Durch die hohen V- Gehalte wird die ß-Phase des Gefüges stabilisiert und die Warmfestigkeit erhöht. Daher liegt der V-Gehalt in einer erfindungsgemäßen Legierung bevorzugt im Bereich von 12 - 17 Masse-%, insbesondere im Bereich von 13 - 17 Masse- Gehalte von 2 - 5 Masse-% Aluminium stabilisieren die α- Phase des Gefüges und bewirken eine effektive Mischkristallhärtung .On the one hand, this is achieved in that the alloy according to the invention has vanadium contents which are significantly higher than those which are provided in the prior art in beta titanium alloys. The ß-phase of the structure is stabilized and the heat resistance increased due to the high V-content. The V content in an alloy according to the invention is therefore preferably in the range from 12 to 17% by mass, in particular in the range from 13 to 17% by mass. Levels of 2 - 5% by mass of aluminum stabilize the α phase of the structure and cause effective mixed crystal hardening.
Die Wirkung des Eisens in der erfindungsgemäß zusammengesetzten Titanlegierung besteht in einer Stabilisierung der ß-Phase des Gefüges, einer Erhöhung der Warmfestigkeit und einer Verbesserung der Mischkristallbildung .The effect of iron in the titanium alloy composed according to the invention consists in stabilizing the β phase of the structure, increasing the heat resistance and improving the formation of mixed crystals.
Molybdän in Gehalten von 0,1 - 3 Masse-%, bevorzugt mindestens 0,5 Masse-%, ist in einem erfindungsgemäßen Titanwerkstoff enthalten, um die ß-Phase des Gefüges zu stabilisieren und die Warmfestigkeit zu erhöhen.A titanium material according to the invention contains molybdenum in amounts of 0.1-3% by mass, preferably at least 0.5% by mass, in order to stabilize the β-phase of the structure and to increase the heat resistance.
Optional enthält eine erfindungsgemäße Beta-Titanlegierung darüber hinaus eines oder mehrere Legierungselemente aus der Gruppe Sn, Si, Cr, Nb, Zr.Optionally, a beta titanium alloy according to the invention also contains one or more alloy elements from the group Sn, Si, Cr, Nb, Zr.
Die Anwesenheit von Zinn wirkt sich dabei günstig auf die Mischkristallhärtung und die Warmfestigkeit aus. Daher liegen die Sn-Gehalte bevorzugt im Bereich von 0,5 - 3 Masse-% .The presence of tin has a beneficial effect on solid solution hardening and heat resistance. The Sn contents are therefore preferably in the range from 0.5 to 3% by mass.
Silizium erhöht in einer erfindungsgemäßen Legierung die Warmfestigkeit und die Oxidationsresistenz.Silicon increases the heat resistance and the oxidation resistance in an alloy according to the invention.
Chrom kann der Legierung zugegeben werden, um die ß-Phase des Gefüges zu stabilisieren und die Warmfestigkeit zu erhöhen.Chromium can be added to the alloy to stabilize the ß-phase of the structure and to increase the heat resistance.
Zugaben an Niob haben darüber hinaus einen günstigen Einfluss auf die Warmfestigkeit und die Oxidationsresistenz der Legierung. Schließlich kann es zur Verbesserung der Mischkristallbildung und der Oxidationsresistenz auch vorteilhaft sein, der erfindungsgemäßen Legierung Zirconium zuzugeben.Additions to niobium also have a favorable influence on the heat resistance and the oxidation resistance of the alloy. Finally, in order to improve mixed crystal formation and oxidation resistance, it may also be advantageous to add zirconium to the alloy according to the invention.
Neben den voranstehend hinsichtlich ihrer Wirkung im Einzelnen erläuterten Bestandteilen kann die erfindungsgemäße Legierung weitere Bestandteile enthalten, solange diese die erfindungsgemäß erzielten Eigenschaften nicht negativ beeinflussen. In diesem Zusammenhang zu nennen sind insbesondere Gehalte an Kohlenstoff und Gehalte an Elementen, die der Gruppe der Lanthaniden zugeordnet sind.In addition to the components explained in detail above with regard to their action, the alloy according to the invention can contain further components as long as these do not negatively influence the properties achieved according to the invention. In this context, particular mention should be made of levels of carbon and levels of elements which are assigned to the group of lanthanides.
Optimale Eigenschaften der erfindungsgemäßen Beta- Titanlegierungen stellen sich dann ein, wenn die voranstehend angegebenen Grenzwerte auf mindestens zwei Dezimalstellen genau eingehalten werden.Optimal properties of the beta titanium alloys according to the invention are obtained if the limit values specified above are adhered to with at least two decimal places.
In Bezug auf das Verfahren wird die oben angegebene Aufgabe dadurch gelöst, dass bei der Herstellung eines aus einer Beta-Titanlegierung erzeugten Produktes folgende Arbeitsschritte durchlaufen werden:With regard to the method, the above-mentioned object is achieved in that the following work steps are carried out when producing a product produced from a beta titanium alloy:
- Erschmelzen einer erfindungsgemäß beschaffenen Beta- Titan-Schmelze zu einem blockförmigen Vorprodukt,Melting a beta-titanium melt obtained according to the invention into a block-shaped preliminary product,
- Warmumformen des Vorprodukts,- hot forming of the preliminary product,
- Warmendumformen des warmumgeformten Vorprodukts zu einem Warmendprodukt,- hot final forming of the hot formed preliminary product into a hot final product,
- Lösungsglühen des Warmendproduktes,- solution annealing of the hot end product,
- Kaltumformen des Warmendproduktes zu einem Endprodukt,Cold forming of the hot end product into an end product,
- Aushärtungsbehandlung des Endproduktes . Dabei kann die Warmumformung für die Herstellung von Bändern oder Blechen als Warmwalzen ausgeführt werden, an das sich erforderlichenfalls ein Haspeln anschließen kann.- Curing treatment of the end product. The hot forming for the production of strips or sheets can be carried out as hot rolling, which can be followed, if necessary, by coiling.
Besonders kostengünstig lässt sich die erfindungsgemäße Ti-Legierung dadurch erzeugen, dass die Legierungselemente V, Fe und AI in an sich bekannter Weise nicht einzeln, sondern in Form einer Vorlegierung zulegiert werden. Derartige Vorlegierungen sind im Handel erhältlich.The Ti alloy according to the invention can be produced particularly cost-effectively by alloying the alloy elements V, Fe and Al in a manner known per se, not in the form of a master alloy, but individually. Such master alloys are commercially available.
Das durch das erfindungsgemäße Verfahren nach der Warmendumformung erhaltene Warmendprodukt besteht aus einphasigem, metastabilen Beta-Titan, dessen Transustemperatur TB bei ca. 788 °C liegt. Wird das Warmendprodukt durch Warmwalzen erzeugt, so weist es in Walzrichtung gestreckte Kristalle auf und besitzt ein teilweise dynamisch rekristallisiertes Gefüge.The hot end product obtained by the process according to the invention after the hot final forming consists of single-phase, metastable beta titanium, the transus temperature T B of which is approximately 788 ° C. If the hot end product is produced by hot rolling, it has crystals stretched in the rolling direction and has a partially dynamically recrystallized structure.
Das im Zuge des erfindungsgemäßen Verfahrens verarbeitete blockförmige Vorprodukt wird durch ein Umschmelzen gewonnen. Dazu kann in an sich bekannter Weise ein Vakuumumschmelzofen ("Vacuum Are Remelt - Ofen") eingesetzt werden.The block-shaped preliminary product processed in the course of the method according to the invention is obtained by remelting. A vacuum remelting furnace can be used for this in a manner known per se.
Bei dem Vorprodukt kann es sich beispielsweise um Rundblöcke handeln, die dann im Zuge der Warmumformung zu Knüppeln oder Platinen warmumgeformt werden. Knüppel dieser Art sind typischerweise vierkantförmig mit Kantenlängen von beispielsweise 70 mm oder rund mit einem Durchmesser von beispielsweise 60 mm ausgebildet.The preliminary product can be round blocks, for example, which are then hot-formed into billets or blanks in the course of the hot forming. Sticks of this type are typically square-shaped with edge lengths of, for example, 70 mm or round with a diameter of, for example, 60 mm.
Die Warmendumformung wird typischerweise bei Umformtemperaturen durchgeführt, die im Bereich von 950 °C bis 1150 °C liegen, um eine effektive Querschnittsreduzierung und eine Homogenisierung der Zusammensetzung und des Gefüges zu erreichen.The hot final forming is typically carried out at forming temperatures which are in the range from 950 ° C. to 1150 ° C. in order to be effective Cross-section reduction and homogenization of the composition and structure.
Für den Fall, dass die Warmendumformung als Warmwalzen durchgeführt wird, sieht eine vorteilhafte Ausgestaltung des erfindungsgemäßen Verfahrens vor, dass das Warmendprodukt nach der Warmendumformung lösungsgeglüht wird. An die Lösungsglühung schließt sich die Kaltumformung an. Die Lösungsglühung erfolgt typischerweise für 30 Minuten bei 875 °C.In the event that the hot final forming is carried out as hot rolling, an advantageous embodiment of the method according to the invention provides that the hot final product is solution-annealed after the hot final forming. Cold forming follows the solution annealing. Solution annealing is typically carried out at 875 ° C for 30 minutes.
Zur weiteren Steigerung der Werte der mechanischen Eigenschaften wird das ggf. lösungsgeglühte Warmendprodukt rekristallisierend geglüht. Die Temperaturen während dieser Glühbehandlung liegen bei Haltezeiten von 20 bis 40 Minuten typischerweise im Bereich von 775 °C bis 875 °C.To further increase the values of the mechanical properties, the solution-annealed hot end product is annealed to recrystallize. The temperatures during this annealing treatment with holding times of 20 to 40 minutes are typically in the range from 775 ° C to 875 ° C.
Anschließend erfolgt die Kaltumformung, beispielsweise durch Kaltwalzen. Das nach der Kaltumformung erhaltene Endprodukt besitzt eine Dehngrenze Rpo,2 von mindestens 870 MPa bis 900 MPa, eine Zugfestigkeit Rm, die 890 MPa bis 944 MPa beträgt, sowie eine plastische Dehnung von 14 - 17 %.Cold forming then takes place, for example by cold rolling. The end product obtained after cold working has an elastic limit R po , 2 of at least 870 MPa to 900 MPa, a tensile strength R m which is 890 MPa to 944 MPa, and a plastic elongation of 14-17%.
Nachdem das rekristallisierend geglühte Walzprodukt dann einer Aushärtungsbehandlung unterzogen worden ist, weist das erhaltene Produkt eine Dehngrenze Rpo,2 von mindestens 1.400 MPa, eine Streckgrenze Rm von mindestens 1.500 MPa und eine Dehnung εpι von mindestens 4 % auf. Bei einer Behandlungsdauer von typischerweise 5 Stunden liegt die typische Temperatur der Aushärtungsbehandlung bei ca. 480 °C. Bei Einhaltung dieser Zeit- und Temperaturvorgaben stellt sich ein optimales Eigenschaftsspektrum der erfindungsgemäß erzeugten Endprodukte ein. Aus einer erfindungsgemäß beschaffenen Beta-Titanlegierung lassen sich Halbzeuge, wie Platinen, Bleche, Stäbe, Profile oder Drähte herstellen, die sich aufgrund ihres Eigenschaftsprofils hervorragend zu hoch belastbaren Bauelementen eignen. Dabei lassen sich die Halbzeuge insbesondere durch Anwendung des erfindungsgemäßen Verfahrens kostengünstig erzeugen.After the recrystallized annealed rolled product has then been subjected to a curing treatment, the product obtained has an elastic limit R p o, 2 of at least 1,400 MPa, an elastic limit R m of at least 1,500 MPa and an elongation ε p ι of at least 4%. With a treatment duration of typically 5 hours, the typical temperature of the curing treatment is approximately 480 ° C. If these time and temperature specifications are observed, an optimal range of properties of the end products produced according to the invention is established. Semifinished products, such as blanks, sheets, rods, profiles or wires, can be produced from a beta titanium alloy according to the invention, which, due to their property profile, are excellently suited to highly resilient components. The semi-finished products can be produced inexpensively, in particular by using the method according to the invention.
Als besonders geeignet erweisen sich erfindungsgemäße Beta- Titanlegierungen als Konstruktionswerkstoff für die Fertigung von Komponenten, die bei schienen- oder straßengebundenen Fahrzeugen sowie in der Luft- und Raumfahrt eingesetzt werden. Als Beispiele für diese Verwendung sind Achsfedern, Pleuel, Kolbenbolzen, hochfeste Schrauben, Bremskolben und -Scheiben zu nennen.Beta titanium alloys according to the invention have proven to be particularly suitable as a construction material for the production of components which are used in rail or road-bound vehicles and in the aerospace industry. Examples of this use include axle springs, connecting rods, piston pins, high-strength screws, brake pistons and discs.
Ebenso eignen sich erfindungsgemäße Beta-Titanlegierungen aufgrund ihrer besonderen Eigenschaften besonders gut zur Herstellung von Komponenten, die im Bereich des allgemeinen •Maschinenbaus, des Apparatebaus, des Anlagenbaus, des Behälterbaus, der Kryogentechnik, des Fahrzeugbaus oder im Bereich des Sports eingesetzt werden.Likewise, due to their special properties, beta-titanium alloys according to the invention are particularly well suited for the production of components which are used in the field of general mechanical engineering, apparatus construction, plant construction, container construction, cryogenic technology, vehicle construction or in the field of sports.
Dabei hat sich gezeigt, dass sich erfindungsgemäß beschaffene Beta-Titanlegierungen insbesondere für dieIt has been shown that beta titanium alloys obtained according to the invention are particularly suitable for
Herstellung von Bauteilen eignen, die im Temperaturbereich von -196 °C bis 300 °C eingesetzt werden.Suitable for the production of components that are used in the temperature range from -196 ° C to 300 ° C.
Nachfolgend wird die Erfindung anhand eines Ausführungsbeispieles näher erläutert.The invention is explained in more detail below using an exemplary embodiment.
In einem VAR-Ofen sind Rundblöcke, die (Angaben in Masse-%) 15 % V, 4 % Fe, 3 % AI, 1 % Mo, 1 % Sn und 0,3 % Si, Rest Ti und unvermeidbare Verunreinigungen enthielten, erschmolzen worden, die anschließend in einer Schmiedeoperation zu vierkantförmigen Knüppeln warmverformt worden sind. Beim Legieren der Schmelze sind die Legierungsbestandteile V, Fe und AI in Form einer kostengünstig erhältlichen Vorlegierung gemeinsam dem Matrixwerkstoff Ti zugegeben worden.In a VAR furnace, round blocks containing (% by mass) 15% V, 4% Fe, 3% Al, 1% Mo, 1% Sn and 0.3% Si, balance Ti and unavoidable impurities, were melted, which were then hot-formed into square-shaped billets in a forging operation. When alloying the melt, the alloy constituents V, Fe and Al were added to the matrix material Ti in the form of an inexpensive master alloy.
Nach dem Schmieden sind die Knüppel beiAfter forging, the billets are on
Warmwalztemperaturen, die im Bereich von 1100 °C bis 950 °C lagen, zu Draht warmgewalzt und anschließend zu Coils gehaspelt worden. Nach dem Warmwalzen wies der Draht einphasiges metastabiles ß-Titan (Transustemperatur Tß ca. 788 °C) mit in Richtung der Drahtachse gestreckten Kristalliten und teilweise dynamisch rekristallisiertem Gefüge auf.Hot rolling temperatures, which were in the range from 1100 ° C to 950 ° C, were hot-rolled into wire and then coiled into coils. After hot rolling, the wire had single-phase metastable ß-titanium (transus temperature T ß approx. 788 ° C) with crystallites stretched in the direction of the wire axis and partially dynamically recrystallized structure.
Im Anschluss an das Haspeln ist der Draht bei 875 °C für 30 Minuten lösungsgeglüht worden. Im Anschluss an die Lösungsglühung erfolgte die Kaltumformung des Drahtes. Nach der Kaltumformung ist der Draht bei Temperaturen, die zwischen 775 °C und 875 °C lagen, bei einer Haltedauer, die im Bereich von 20 Minuten bis 40 Minuten lag, rekristallisierend geglüht worden. Der derart geglühte Draht wies eine zwischen 870 MPa und 900 MPa liegende Dehngrenze Rpo,2/ eine zwischen 890 MPa - 944 MPa liegende Zugfestigkeit Rm und eine zwischen 14 % - 17 % liegende Dehnung A auf. An die Rekristallisationsglühung schloss sich eine Aushärtungsbehandlung an, bei der der Draht für 5 Stunden bei 480 °C gehalten worden ist.Following the coiling, the wire was solution annealed at 875 ° C for 30 minutes. After the solution annealing, the wire was cold formed. After the cold forming, the wire was recrystallized at temperatures that were between 775 ° C and 875 ° C, with a holding time that was in the range of 20 minutes to 40 minutes. The annealed wire had a yield strength R p o, 2 / between 870 MPa and 900 MPa, a tensile strength R m between 890 MPa and 944 MPa and an elongation A between 14% and 17%. The recrystallization annealing was followed by a curing treatment in which the wire was kept at 480 ° C. for 5 hours.
Der derart fertig behandelte Draht wies bei Raumtemperatur eine Dehngrenze Rpo,2 von mehr als 1400 MPa, eine Zugfestigkeit Rm von mehr als 1500 MPa und eine Dehnung A auf, die mindestens im Bereich von 4 % bis 5 % lag. The wire treated in this way had an elastic limit R po , 2 of more than 1400 MPa, a tensile strength R m of more than 1500 MPa and an elongation A which was at least in the range from 4% to 5% at room temperature.

Claims

P A T E N T A N S P R Ü C H E P A T E N T A N S P R Ü C H E
1. Beta-Titanlegierung enthaltend (in Masse-%)1. Containing beta titanium alloy (in mass%)
V: 10 - 17 %, Fe: 2 - 5 %, AI: 2 - 5 %, Mo: 0,1 - 3 %, sowie optional eines oder mehrere Legierungselemente aus der Gruppe Sn, Si, Cr, Nb, Zr gemäß folgender Maßgabe:V: 10-17%, Fe: 2-5%, AI: 2-5%, Mo: 0.1-3%, and optionally one or more alloy elements from the group Sn, Si, Cr, Nb, Zr according to the following provided that:
Sn: 0,1 - 3 %, Si: 0,1 < 2 %, Cr: < 2 %, Nb: < 2 %, Zr: < 2, wobei die Beta-Titanlegierung zusätzlich Gehalte an C und an Elementen der Gruppe der Lanthanide aufweisen kann, und als Rest Ti und unvermeidbare Verunreinigungen. Beta-Titanlegierung enthaltend (in Masse-%)Sn: 0.1-3%, Si: 0.1 <2%, Cr: <2%, Nb: <2%, Zr: <2, the beta titanium alloy additionally containing C and elements of the group of May contain lanthanides, and the balance Ti and unavoidable impurities. Containing beta titanium alloy (in mass%)
V: 10,00 - 17,00 o. ° fV: 10.00 - 17.00 o. ° f
Fe: 2,00 - 5,00 o ,Fe: 2.00 - 5.00 o,
AI: 2,00 - 5,00 ° rAI: 2.00 - 5.00 ° r
Mo: 0,10 - 3,00 ° /Mo: 0.10 - 3.00 ° /
sowie optional eines oder mehrere Legierungselemente aus der Gruppe Sn, Si, Cr, Nb, Zr gemäß folgender Maßgabe:and optionally one or more alloy elements from the group Sn, Si, Cr, Nb, Zr in accordance with the following stipulation:
Sn: 0,10 - 3 00 %, Si: 0,10 - 2, 00 %, Cr: < 2 00 %, Nb: < 2 00 %, Zr : < 2 ,00,Sn: 0.10-300%, Si: 0.10-2.00%, Cr: <2.00%, Nb: <2.00%, Zr: <2.00,
und als Rest Ti und unvermeidbare Verunreinigungen,and the balance Ti and unavoidable impurities,
Beta-Titanlegierung nach einem der voranstehenden Ansprüche, enthaltend 12 - 17 Masse-% V.Beta titanium alloy according to one of the preceding claims, containing 12-17% by mass V.
Beta-Titanlegierung nach einem der voranstehenden Ansprüche, enthaltend 0,5 - 3 Masse-% Mo.Beta titanium alloy according to one of the preceding claims, containing 0.5-3% by mass of Mo.
Beta-Titanlegierung nach einem der voranstehenden Ansprüche, enthaltend 0,5 - 3 Masse-% Sn.Beta titanium alloy according to one of the preceding claims, containing 0.5-3% by mass of Sn.
Beta-Titanlegierung nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s sie bei Raumtemperatur eine Dehngrenze Rpo,2 von mindestens 1400 MPa aufweist.Beta titanium alloy according to one of the preceding claims, characterized in that it Room temperature has a proof stress R p o, 2 of at least 1400 MPa.
7. Beta-Titanlegierung nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s sie bei Raumtemperatur eine Zugfestigkeit Rm von mindestens 1500 MPa aufweist.7. Beta titanium alloy according to one of the preceding claims, characterized in that it has a tensile strength R m of at least 1500 MPa at room temperature.
8. Beta-Titanlegierung nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s sie bei Raumtemperatur eine plastische Dehnung εpo,2 von mehr als 4 % besitzt.8. Beta titanium alloy according to one of the preceding claims, characterized in that it has a plastic elongation ε p o, 2 of more than 4% at room temperature.
9. Beta-Titanlegierung nach einem der voranstehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t, d a s s ihre Dichte p 4,8 g/cm3 nicht übersteigt.9. Beta titanium alloy according to one of the preceding claims, characterized in that its density p does not exceed 4.8 g / cm 3 .
10. Verfahren zum Herstellen eines aus einer Beta-Titanlegierung erzeugten Produktes umfassend folgende Arbeitsschritte: - Erschmelzen einer gemäß einem der Ansprüche 1 bis 9 beschaffenen Beta-Titan-Schmelze zu einem blockförmigen Vorprodukt, - Warmumformen des Vorprodukts, - Warmendumf ormen des warmumgeformten Vorprodukts zu einem Warmendprodukt, - Lösungsglühen des Warmendproduktes, - Kaltumformen des Warmendproduktes zu einem Endprodukt, - Aushärtungsbehandlung des Endproduktes.10. A method for producing a product produced from a beta titanium alloy comprising the following working steps: melting a beta titanium melt procured according to one of claims 1 to 9 into a block-shaped preliminary product, hot forming of the preliminary product, hot final forming of the hot formed preliminary product a hot end product, solution annealing of the hot end product, - cold forming of the hot end product into an end product, - curing treatment of the end product.
11. Verfahren nach Anspruch 10, d a d u r c h g e k e n n z e i c h n e t, d a s s die Warmendumformung als Warmwalzen ausgeführt wird.11. The method of claim 10, d a d u r c h g e k e n n z e i c h n e t, that the hot final forming is carried out as hot rolling.
12. Verfahren nach Anspruch 11, d a d u r c h g e k e n n z e i c h n e t, d a s s sich an das Warmwalzen ein Haspeln anschließt.12. The method according to claim 11, d a d u r c h g e k e n n z e i c h n e t that a coiling is followed by hot rolling.
13. Verfahren na~ch -Anspruch 10 bis 12, d a d u r c h g e k e n n z e i c h n e t, d a s s die Legierungselemente V, Fe und AI in Form einer Vorlegierung zulegiert werden.13. The method na ~ ch art` claim 10 to 12, characterized in that the alloy elements V, Fe and Al are added by alloying in the form of a master alloy.
14. Verfahren nach einem der Ansprüche 10 bis 13, d a d u r c h g e k e n n z e i c h n e t, d a s s das Vorprodukt Rundblöcke sind, die im Zuge der Warmumformung zu Knüppeln oder Platinen warmumgeformt werden.14. The method according to any one of claims 10 to 13, d a d u r c h g e k e n z e i c h n e t, d a s s are the preliminary product round blocks, which are hot formed into billets or blanks in the course of hot forming.
15. Verfahren nach einem der Ansprüche 10 bis 14, d a d u r c h g e k e n n z e i c h n e t, d a s s das Warmendprodukt ein Draht oder ein Blech ist. 15. The method according to any one of claims 10 to 14, characterized in that the hot end product is a wire or a sheet.
16. Verfahren nach einem der Ansprüche 11 bis 15, d a d u r c h g e k e n n z e i c h n e t, d a s s das Warmendprodukt nach dem Haspeln lösungsgeglüht wird.16. The method according to any one of claims 11 to 15, d a d u r c h g e k e n n z e i c h n e t, that the hot end product is solution annealed after coiling.
17. Verfahren nach Anspruch 16, d a d u r c h g e k e n n z e i c h n e, t, d a s s das lösungsgeglühte Warmendprodukt kaltverformt wird.17. The method according to claim 16, d a d u r c h g e k e n n z e i c h n e, t a s s the solution-annealed hot end product is cold worked.
18. Halbzeug hergestellt aus einer gemäß einem der Ansprüche 1 bis 9 beschaffenen Beta-Titanlegierung.18. Semi-finished product made from a beta titanium alloy procured according to one of claims 1 to 9.
19. Verwendung einer gemäß einem der Ansprüche 1 bis 9 beschaffenen Beta-Titanlegierung für die Herstellung von Bauteilen, die im Temperaturbereich von -196 °C bis 300 °C eingesetzt werden.19. Use of a beta titanium alloy obtained according to one of claims 1 to 9 for the production of components which are used in the temperature range from -196 ° C to 300 ° C.
20. Verwendung einer gemäß einem der Ansprüche 1 bis 9 beschaffenen Beta-Titanlegierung für die Herstellung von Fahrzeugkomponenten.20. Use of a beta titanium alloy procured according to one of claims 1 to 9 for the production of vehicle components.
21. Verwendung einer gemäß einem der Ansprüche 1 bis 9 beschaffenen Beta-Titanlegierung für die Herstellung von im Anlagen- oder Apparatebau eingesetzten Komponenten .21. Use of a beta-titanium alloy procured according to one of claims 1 to 9 for the production of components used in plant or apparatus construction.
22. Verwendung einer gemäß einem der Ansprüche 1 bis 9 beschaffenen Beta-Titanlegierung für die Herstellung von Sportgeräten. 22. Use of a beta titanium alloy procured according to one of claims 1 to 9 for the production of sports equipment.
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CN110846535A (en) * 2019-11-25 2020-02-28 江苏威拉里新材料科技有限公司 Titanium alloy powder

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US20070175552A1 (en) 2007-08-02
ATE398686T1 (en) 2008-07-15
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