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WO1999049090A1 - TiAl BASE ALLOY - Google Patents

TiAl BASE ALLOY Download PDF

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Publication number
WO1999049090A1
WO1999049090A1 PCT/EP1999/001868 EP9901868W WO9949090A1 WO 1999049090 A1 WO1999049090 A1 WO 1999049090A1 EP 9901868 W EP9901868 W EP 9901868W WO 9949090 A1 WO9949090 A1 WO 9949090A1
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WO
WIPO (PCT)
Prior art keywords
alloy
tial
tial base
base alloy
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/001868
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German (de)
French (fr)
Inventor
Georg Frommeyer
Jürgen Wesemann
Sven Knippscheer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Max Planck Institut fuer Eisenforschung
Original Assignee
Max Planck Institut fuer Eisenforschung
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Max Planck Institut fuer Eisenforschung filed Critical Max Planck Institut fuer Eisenforschung
Priority to EP99913284A priority Critical patent/EP1070152B1/en
Priority to AU31467/99A priority patent/AU3146799A/en
Priority to AT99913284T priority patent/ATE260996T1/en
Publication of WO1999049090A1 publication Critical patent/WO1999049090A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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

Definitions

  • the invention relates to a TiAl base alloy with a composition of titanium aluminide with 42 to 54 at.% Al, the remainder being titanium, to which further alloying elements can be added up to 12 at.
  • the invention is based on the object of modifying a TiAl base alloy in such a way that it has better properties than conventional alloys based on it in several respects. In particular, improved castability, formability and ductility with higher strength is sought.
  • a TiAl base alloy which contains 0.1 to 5 at.% Cu, preferably 0.2 to 1 at.% Cu.
  • the alloy may contain 0.1 to 2 at.% Si, preferably 0.1 to 0.3 at.% Si, and / or 0.1 to 5 at.% Mo, preferably 0.4 to 1, 2 at.% Mo, and / or 0.1 to 5 at.% Cr, preferably 0.4 to 1.2 at.% Cr, and up to a total of 12 at.% Further alloy elements.
  • one or more of the strength-increasing elements Nb, Mn, V, B, W, Ti, Ta, Zr m of the alloy can be contained as "further alloy elements".
  • the invention has proven to be particularly advantageous for the following alloys: - 2 -
  • the addition of copper to TiAl provided according to the invention results in a greatly reduced grain size or a significantly finer structured casting structure compared to TiAl base alloys without the addition of copper.
  • Lamellar TiAl base alloys with copper addition also have reduced lamella spacing. These effects are reinforced by the addition of silicon.
  • the addition of copper leads to an increased strength of TiAl base alloys with increased ductility compared to comparable alloys. Arm formability is also improved. As a result, the forming of TiAl base alloys with copper addition can be carried out with lower forces or at lower temperatures than with comparable alloys.
  • At least 0.1 at% Cu is required to achieve the desired effects. More than 5 at.-o cause embrittlement and are therefore not useful. Even small amounts of the order of magnitude up to 0.2 at.% Cu improve the castability by reducing the melt viscosity and, compared to comparable alloys without the addition of Cu, result in a significantly finer structured casting structure.
  • Figure 1 shows the solidification structure of a T1AIM0S1 alloy.
  • TiAl base alloys with copper addition represented by the T ⁇ 52 Al 4 6 sCu.Sio 2 ⁇ alloy according to Figure 2
  • Figures 3 and 4 show, the grain-refining influence of the - 3 -
  • Copper additive to TiAl is also pronounced after the alloy has been annealed for 30 mm at 1400 ° C.
  • Figure 5 shows the temperature-dependent fracture upsets of modified TiAl alloys with copper addition compared to a TI 52 A1 P and a TiAlMoSi alloy.
  • the strength of TiAl base alloys is significantly increased by the addition of copper to TiAl provided according to the invention.
  • the comparatively steep drop in strength at temperatures> 800 ° C for the TiAl base alloys with copper addition leads to improved hot formability.
  • R c S ⁇ 2- alloy has, for example with upsetting boundaries between 580 MPa at room temperature and 538 MPa at 800 ° C, a higher compression strength than an already high strength T I 5 Al "M ⁇ S ⁇ 0 -? Alloy.
  • the TiAl base alloy according to the invention is suitable as a construction material for cast female parts, but also for parts which are produced by extrusion, isothermal forging and / or superplastic forming to the desired final shape.
  • Application examples are valves for internal combustion engines, piston crown segments, turbocharger rotors and components for turbines and compressors.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Forging (AREA)
  • Physical Vapour Deposition (AREA)
  • Conductive Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Continuous Casting (AREA)

Abstract

The invention relates to a TiAl base alloy, where the titanium aluminide contains between 42 and 54 atomic % Al, the rest being titanium, and to which as much as 12 atomic %, in relation to the TiAl, of other alloy elements can be added. The invention is characterized in that the alloy contains between 0.1 and 5 atomic % copper.

Description

- 1 - - 1 -

TiAl-Bas1s1egierungTiAl-Bas1s1 alloy

Die Erfindung betrifft eine TiAl-Basislegierung mit einer Zusammensetzung des Titanaluminids mit 42 bis 54 at.-% AI, Rest Titan, der bis zu 12 at.-° bezogen auf TiAl weitere Legierungselemente zugesetzt werden können.The invention relates to a TiAl base alloy with a composition of titanium aluminide with 42 to 54 at.% Al, the remainder being titanium, to which further alloying elements can be added up to 12 at.

Der Erfindung liegt die Aufgabe zugrunde, eine TiAl- Basislegierung derart zu modifizieren, daß sie m mehrfacher Hinsicht bessere Eigenschaften aufweist als herkömmliche Legierungen auf dieser Basis. Insbesondere wird eine verbesserte Vergießbarkeit, armumformbarkeit und Duktilitat bei höherer Festigkeit angestrebt.The invention is based on the object of modifying a TiAl base alloy in such a way that it has better properties than conventional alloys based on it in several respects. In particular, improved castability, formability and ductility with higher strength is sought.

Zur Losung dieser Aufgabe wird erfmdungsgemaß eine TiAl- Basislegierung vorgeschlagen, die 0,1 bis 5 at.-% Cu, vorzugsweise 0,2 bis 1 at.-% Cu, enthalt. Zusätzlich kann die Legierung 0,1 bis 2 at.-% Si, vorzugsweise 0,1 bis 0,3 at.-% Si, und/oder 0,1 bis 5 at.-% Mo, vorzugsweise 0,4 bis 1,2 at.-% Mo, und/oder 0,1 bis 5 at.-% Cr, vorzugsweise 0,4 bis 1,2 at.-% Cr, sowie bis insgesamt 12 at.-% weitere Legierungselemente enthalten. Bis insgesamt 2 at.-% kann ein oder können mehrere der festigkeitssteigernden Elemente Nb, Mn, V, B, W, Ti, Ta, Zr m der Legierung als "weitere Legierungselemente" enthalten sein.To solve this problem, a TiAl base alloy is proposed according to the invention which contains 0.1 to 5 at.% Cu, preferably 0.2 to 1 at.% Cu. In addition, the alloy may contain 0.1 to 2 at.% Si, preferably 0.1 to 0.3 at.% Si, and / or 0.1 to 5 at.% Mo, preferably 0.4 to 1, 2 at.% Mo, and / or 0.1 to 5 at.% Cr, preferably 0.4 to 1.2 at.% Cr, and up to a total of 12 at.% Further alloy elements. Up to a total of 2 at%, one or more of the strength-increasing elements Nb, Mn, V, B, W, Ti, Ta, Zr m of the alloy can be contained as "further alloy elements".

Als besonders vorteilhaft hat sich die Erfindung bei folgenden Legierungen erwiesen: - 2 -The invention has proven to be particularly advantageous for the following alloys: - 2 -

Tι52.3A146.5CulSι0.2 Tι52.0A146.6CrlCu0.2Sι0.2 Tι52.0A146.6MolCu0.2Sι0.2 Tι52.0A146.5Mo0.5Cu0.8Sι0.2Tι52.3A146.5CulSι0.2 Tι52.0A146.6CrlCu0.2Sι0.2 Tι52.0A146.6MolCu0.2Sι0.2 Tι52.0A146.5Mo0.5Cu0.8Sι0.2

Der erfmdungsgemaß vorgesehene Zusatz an Kupfer zu TiAl bewirkt eine stark verringerte Korngroße bzw. ein wesentlich feiner strukturiertes Gußgefuge gegenüber TiAl-Basislegierungen ohne Kupferzusatz. Lamellare TiAl- Basislegierungen mit Kupferzusatz weisen darüber hinaus reduzierte Lamellenabstande auf. Diese Effekte werden durch den Zusatz von Silizium noch verstärkt. Der Zusatz von Kupfer fuhrt zu einer erhöhten Festigkeit von TiAl- Basislegierungen bei gegenüber vergleichbaren Legierungen gesteigerter Duktilitat. Außerdem wird die armumformbarkeit verbessert. Die Umformung von TiAl- Basislegierungen mit Kupferzusatz kann dadurch mit geringeren Kräften bzw. bei niedrigeren Temperaturen als bei vergleichbaren Legierungen durchgeführt werden.The addition of copper to TiAl provided according to the invention results in a greatly reduced grain size or a significantly finer structured casting structure compared to TiAl base alloys without the addition of copper. Lamellar TiAl base alloys with copper addition also have reduced lamella spacing. These effects are reinforced by the addition of silicon. The addition of copper leads to an increased strength of TiAl base alloys with increased ductility compared to comparable alloys. Arm formability is also improved. As a result, the forming of TiAl base alloys with copper addition can be carried out with lower forces or at lower temperatures than with comparable alloys.

Mindestens 0,1 at.-% Cu ist erforderlich, um die angestrebten Wirkungen herbeizufuhren. Mehr als 5 at.-o rufen eine Versprodung hervor und sind daher nicht sinnvoll. Schon geringe Mengen m der Größenordnung bis 0,2 at.-% Cu verbessern die Vergießbarkeit durch eine Verringerung der Schmelzviskositat und bewirken gegenüber vergleichbaren Legierungen ohne Cu-Zusatze ein deutlich feiner strukturiertes Gußgefuge.At least 0.1 at% Cu is required to achieve the desired effects. More than 5 at.-o cause embrittlement and are therefore not useful. Even small amounts of the order of magnitude up to 0.2 at.% Cu improve the castability by reducing the melt viscosity and, compared to comparable alloys without the addition of Cu, result in a significantly finer structured casting structure.

Bild 1 zeigt die Erstarrungsstruktur einer T1AIM0S1- Legierung. Im Vergleich dazu weisen TiAl-Basislegierungen mit Kupferzusatz, repräsentiert durch die Tι52Al46 sCu.Sio 2 ~ Legierung gemäß Bild 2, ein deutlich feiner strukturiertes Erstarrungsgefuge auf. Wie die Bilder 3 und 4 belegen, ist der kornfeinende Einfluß des - 3 -Figure 1 shows the solidification structure of a T1AIM0S1 alloy. In comparison, TiAl base alloys with copper addition, represented by the Tι 52 Al 4 6 sCu.Sio 2 ~ alloy according to Figure 2, have a significantly finer structured solidification structure. As Figures 3 and 4 show, the grain-refining influence of the - 3 -

Kupferzusatzes zu TiAl auch noch nach dem Glühen der Legierung für 30 mm bei 1400 °C ausgeprägt.Copper additive to TiAl is also pronounced after the alloy has been annealed for 30 mm at 1400 ° C.

In Bild 5 sind die temperaturabhangigen Bruchstauchungen modifizierter TiAl-Legierungen mit Kupferzusatz im Vergleich zu einer TI52A1 P- und einer TiAlMoSi-Legierung dargestellt. Die Festigkeit von TiAl-Basislegierungen wird durch den erf dungsgemaß vorgesehenen Zusatz von Kupfer zu TiAl signifikant erhöht. Der vergleichsweise steile Festigkeitsabfall bei Temperaturen > 800 °C bei den TiAl-Basislegierungen mit Kupferzusatz fuhrt zu einer verbesserten Warmu formbarkeit . Die Tι5-Al,b -Mo .Cu. RSιc 2- Legierung weist z.B. mit Stauchgrenzen zwischen 580 MPa bei Raumtemperatur und 538 MPa bei 800 °C eine höhere Stauchgrenze als eine bereits hochfeste Tι5?Al „MθιSι0 -- Legierung auf. Ab 1000 °C zeigt die Tι52Al b DMo .Cut 8Sι0 2- Legierung ηedoch einen deutlich geringeren Verformungswiderstand als die Tι52Al4„ 8MθιSι0 ^-Legierung. Gleichzeitig zeichnet sich die Tι57Al,0 MO0 SCU „SI0 I~ Legierung, wie auch andere Legierungsmodifikationen mit Kupferzusatz, durch eine verbesserte Duktilitat aus. Die Bilder 5 und 6 belegen, daß durch die Variation des Kupfergehaltes bzw. der Legierungszusammensetzung die Einstellung einer optimalen Eigenschaftskombination aus Festigkeit, Duktilitat und Umformbarkeit möglich ist.Figure 5 shows the temperature-dependent fracture upsets of modified TiAl alloys with copper addition compared to a TI 52 A1 P and a TiAlMoSi alloy. The strength of TiAl base alloys is significantly increased by the addition of copper to TiAl provided according to the invention. The comparatively steep drop in strength at temperatures> 800 ° C for the TiAl base alloys with copper addition leads to improved hot formability. The Tι 5 -Al, b -Mo .Cu. R c Sι 2- alloy has, for example with upsetting boundaries between 580 MPa at room temperature and 538 MPa at 800 ° C, a higher compression strength than an already high strength T I 5 Al "MθιSι 0 -? Alloy. From 1000 ° C the Tι 52 Al b D Mo .Cu t 8 Sι 0 2- alloy ηhowever shows a significantly lower resistance to deformation than the Tι 52 Al 4 " 8 MθιSι 0 ^ alloy. At the same time the Tι 57 Al, 0 MO 0 S CU "SI 0 I ~ alloy, like other alloy modifications with copper addition, is characterized by an improved ductility. Figures 5 and 6 show that the variation of the copper content or the alloy composition enables the setting of an optimal combination of properties of strength, ductility and formability.

Aufgrund seiner besonderen verbesserten Eigenschaften eignet sich die erfmdungsgemaße TiAl-Basislegierung als Konstruktionswerkstoff für Femgußteile, aber auch für Teile, die durch Strangpressen, Isothermschmieden und/oder superplastisch.es Umformen an die gewünschte Endform erzeugt werden. Anwendungsbeispiele sind Ventile für Verbrennungsmotoren, Kolbenbodensegmente, Turboladerrotoren und Komponenten für Turbinen und Verdichter. Due to its particularly improved properties, the TiAl base alloy according to the invention is suitable as a construction material for cast female parts, but also for parts which are produced by extrusion, isothermal forging and / or superplastic forming to the desired final shape. Application examples are valves for internal combustion engines, piston crown segments, turbocharger rotors and components for turbines and compressors.

Claims

- 4 -Patentansprüche - 4 patent claims 1. TiAl-Basislegierung mit 42 bis 54 at.-% Aluminium, Rest Titan und unvermeidbare Verunreinigungen, der insgesamt bis 12 at.-%, bezogen auf TiAl weitere Legierungselemente zugesetzt werden können, d a d u r c h g e k e n n z e i c h n e t , d a ß, sie 0,1 bis 5 at.-% Kupfer enthält.1. TiAl base alloy with 42 to 54 at .-% aluminum, balance titanium and unavoidable impurities, to which a total of up to 12 at .-%, based on TiAl further alloying elements can be added, characterized in that ß, they 0.1 to 5 at .-% copper contains. 2. TiAl-Basislegierung nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , d a ß sie 0,2 bis 1 at.-% Cu enthält.2. TiAl base alloy according to claim 1, d a d u r c h g e k e n n z e i c h n e t, that it contains 0.2 to 1 at .-% Cu. 3. TiAl-Basislegierung nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , d a ß sie als weiteres Legierungselement 0,1 bis 2 at.-% Si enthält.3. TiAl base alloy according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t, that it contains 0.1 to 2 at.% Si as a further alloy element. 4. TiAl-Basislegierung nach Anspruch 3, d a d u r c h g e k e n n z e i c h n e t , d a ß sie als weiteres Legierungselement 0, 1 bis 0,3 at.-% Si enthält.4. TiAl base alloy according to claim 3, d a d u r c h g e k e n n z e i c h n e t, that it contains 0.1 to 0.3 at.% Si as a further alloying element. 5. TiAl-Basislegierung nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t , d a ß sie als weitere Legierungselemente 0,1 bis 5 at.-% Mo und/oder 0,1 bis5. TiAl base alloy according to one of claims 1 to 4, d a d u r c h g e k e n n z e i c h n e t, d a ß as further alloy elements 0.1 to 5 at .-% Mo and / or 0.1 to 5 at.-% Cr enthält. - 5 -Contains 5 at .-% Cr. - 5 - 6. TiAl-Basislegierung nach Anspruch 5, d a d u r c h g e k e n n z e i c h n e t , d a ß sie als weitere Legierungselemente 0,4 bis 1,2 at.-% Mo und/oder 0,4 bis 1,2 at.-°o Cr enthalt.6. TiAl base alloy according to claim 5, d a d u r c h g e k e n n z e i c h n e t, d a ß as further alloying elements contains 0.4 to 1.2 at .-% Mo and / or 0.4 to 1.2 at.- ° o Cr. 7. TiAl-Basislegierung nch einem der Ansprüche 1 bis 6, d a d u r c h g e k e n n z e i c h n e t , d a ß sie als weitere Legierungselemente oder als weiteres Legierungselement bis insgesamt7. TiAl base alloy according to one of claims 1 to 6, d a d u r c h g e k e n n z e i c h n e t, d a ß as additional alloying elements or as a further alloying element up to a total 2 at.-% eines oder mehrere der Elemente Nb, Mn, V, B, W, Ti, Ta, Zr enthalt. 2 at .-% contains one or more of the elements Nb, Mn, V, B, W, Ti, Ta, Zr.
PCT/EP1999/001868 1998-03-21 1999-03-20 TiAl BASE ALLOY Ceased WO1999049090A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99913284A EP1070152B1 (en) 1998-03-21 1999-03-20 TiAl BASE ALLOY
AU31467/99A AU3146799A (en) 1998-03-21 1999-03-20 Tial base alloy
AT99913284T ATE260996T1 (en) 1998-03-21 1999-03-20 TIAL BASE ALLOY

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19812444A DE19812444B4 (en) 1998-03-21 1998-03-21 TiAl-based alloy
DE19812444.9 1998-03-21

Publications (1)

Publication Number Publication Date
WO1999049090A1 true WO1999049090A1 (en) 1999-09-30

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PCT/EP1999/001868 Ceased WO1999049090A1 (en) 1998-03-21 1999-03-20 TiAl BASE ALLOY

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EP (1) EP1070152B1 (en)
AT (1) ATE260996T1 (en)
AU (1) AU3146799A (en)
DE (1) DE19812444B4 (en)
WO (1) WO1999049090A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294132B1 (en) * 1996-10-28 2001-09-25 Mitsubishi Heavy Industries Ltd. TiAl intermetallic compound-based alloy

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2006260791B2 (en) * 2005-06-21 2011-12-22 University Of Leeds Electrode
GB0512836D0 (en) * 2005-06-21 2005-08-03 Jha Animesh Inert alloy anodes for aluminium electrolysis cell using molten salt bath confidential
WO2007108178A1 (en) * 2006-03-17 2007-09-27 University Of Tsukuba Titanium-tantalum shape memory alloy, actuator, and engine

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865666A (en) * 1987-10-14 1989-09-12 Martin Marietta Corporation Multicomponent, low density cubic L12 aluminides
JPH03226538A (en) * 1990-01-30 1991-10-07 Nkk Corp Ti-al base heat resistant alloy and its manufacture
JPH04235262A (en) * 1991-01-08 1992-08-24 Mitsubishi Materials Corp Manufacture of ti-al intermetallic compound-series ti alloy excellent in strength and ductility
JPH05230570A (en) * 1992-02-21 1993-09-07 Toyota Motor Corp Tial-base alloy with high ductility

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1179006B (en) * 1952-12-18 1964-10-01 Crucible Steel Internat Titanium alloys
JPH06116692A (en) * 1992-10-05 1994-04-26 Honda Motor Co Ltd TiAl intermetallic compound excellent in high temperature strength and method for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865666A (en) * 1987-10-14 1989-09-12 Martin Marietta Corporation Multicomponent, low density cubic L12 aluminides
JPH03226538A (en) * 1990-01-30 1991-10-07 Nkk Corp Ti-al base heat resistant alloy and its manufacture
JPH04235262A (en) * 1991-01-08 1992-08-24 Mitsubishi Materials Corp Manufacture of ti-al intermetallic compound-series ti alloy excellent in strength and ductility
JPH05230570A (en) * 1992-02-21 1993-09-07 Toyota Motor Corp Tial-base alloy with high ductility

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 015, no. 512 (C - 0898) 26 December 1991 (1991-12-26) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 584 (C - 1013) 24 December 1992 (1992-12-24) *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 693 (C - 1144) 17 December 1993 (1993-12-17) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294132B1 (en) * 1996-10-28 2001-09-25 Mitsubishi Heavy Industries Ltd. TiAl intermetallic compound-based alloy

Also Published As

Publication number Publication date
ATE260996T1 (en) 2004-03-15
EP1070152A1 (en) 2001-01-24
DE19812444A1 (en) 1999-09-30
AU3146799A (en) 1999-10-18
EP1070152B1 (en) 2004-03-03
DE19812444B4 (en) 2004-02-19

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