EP1783235A1 - Titanium-based alloy - Google Patents

Titanium-based alloy Download PDF

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Publication number
EP1783235A1
EP1783235A1 EP05772406A EP05772406A EP1783235A1 EP 1783235 A1 EP1783235 A1 EP 1783235A1 EP 05772406 A EP05772406 A EP 05772406A EP 05772406 A EP05772406 A EP 05772406A EP 1783235 A1 EP1783235 A1 EP 1783235A1
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EP
European Patent Office
Prior art keywords
alloy
titanium
molybdenum
vanadium
aluminum
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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.)
Granted
Application number
EP05772406A
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German (de)
French (fr)
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EP1783235B1 (en
EP1783235A4 (en
Inventor
Vladislav Valentinovich Tetyukhin
Igor Vasilievich Levin
Alexandr Vladimirovich Trubochkin
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VSMPO Avisma Corp PSC
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VSMPO Avisma Corp PSC
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Application filed by VSMPO Avisma Corp PSC filed Critical VSMPO Avisma Corp PSC
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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

  • the invention relates to the field of metallurgy and particularly to the field of development of state-of-the-art titanium alloys used for making high-strength and high-workable articles including large articles, i.e. alloys of high versatility.
  • Titanium alloys are widely used as aerospace materials, e.g. in airplanes and rockets since the alloys possess tough mechanical properties and are comparatively light.
  • Ti6A14V alloy B.A. Kalachyov, I.S. Polkin and V.D. Talalayev. Titanium Alloys of Different countries. Reference Book. Moscow: VILS, 2000, p. 58-59 ) - [1].
  • This alloy was developed in 1950s in the USA. It is characterized by medium strength of 850 up to 1000 MPa and high workability. It is a good material to work by forming: forging, die forging, and extruding. It is widely used in aeronautical and aerospace engineering, shipbuilding, automotive industry, etc., as well as in manufacturing fasteners for various applications. This alloy is good to work by all types of welding including diffusion bonding.
  • Ti6A14V alloy has insufficient versatility. It is difficult to make rolled sheet products, foil, and tubes thereof since the alloy possesses relatively high resistance to deformation, which in case that the deformation temperature becomes below 800°C leads to the generation of defects such as cracks and shortens the life of working tools or necessitates costly tools.
  • a pseudo- ⁇ -titanium alloy Grade 9 (Ti-3Al-2,5V), which is highly capable of cold working (see [1], p. 44, 45).
  • the strength of this alloy is intermediate between that of Ti-6Al-4V alloy and titanium (600-800 MPa).
  • This alloy is used as cold-worked and stress annealed; it is characterized by high corrosion resistance in various media including sea water.
  • This alloy is used in making tubes for hydraulics and fuel systems of airplanes, rockets, and submarines.
  • the most close analogue of the invented alloy is ⁇ + ⁇ -titanium alloy consisting of 3.0-5.0 Al; 2.1-3.7 V; 0.85-3.15 Mo; 0.85-3.15 Fe; 0.06-0.2 O 2 , and inevitable impurities ( Japanese application No. 3007214 B2, filed Feb. 7, 2000 ) - prior art.
  • a titanium base alloy consisting of Aluminum, Vanadium, Molybdenum, Iron, and Oxygen in the following ratio, wt.%: Aluminum 3.5-4.4 Vanadium 2.0-4.0 Molybdenum 0.1-0.8 Iron max 0.4 Oxygen max 0.25 Ti balance
  • Aluminum is a ⁇ -stabilizer for the ⁇ + ⁇ -titanium alloys, which contributes to the increase of mechanical strength.
  • Aluminum content is below 3.5%, sufficient strength aimed in this invention cannot be obtained, whereas in case that Aluminum content exceeds 4.4%, the hot deformation resistance is increased and ductility at lower temperatures is deteriorated, which leads to the lowering of productivity.
  • Vanadium is added to titanium as a ⁇ -stabilizer for the ⁇ + ⁇ -titanitun alloys, which contributes to the increase of mechanical strength without forming brittle intermetallic compounds with titanium. Presence of Vanadium in the alloy impedes formation of ⁇ 2 -superstructure in ⁇ -phase as ⁇ -phase stabilizes, and contributes to the increase of both strength and ductility. In case that Vanadium content is below 2%, sufficient strength aimed in this invention cannot be obtained, whereas in case that Vanadium content exceeds 4.0%, the superplastic elongation is decreased by exceedingly lowering of the beta transus. Vanadium content within the range of 2.0-4.0% in this alloy has the merit in which the scrap of the most used Ti6A14V can be utilized.
  • Molybdenum is added to titanium as a ⁇ -stabilizer for the ⁇ + ⁇ -titanium alloys. In case that Molybdenum is added within the range of 0.1-0.8% this contributes to its full dissolution in ⁇ -phase, which enables to obtain the sufficient strength properties without deteriorating plastic properties. In case that Molybdenum content exceeds 0.8% this contributes to the increase of the specific weight of the alloy due to the fact that Molybdenum is a heavy metal and the plastic properties of the alloy are deteriorated. In case that Molybdenum content is below 0.1%, Molybdenum does not contribute to the alloy properties in full.
  • Iron added to the alloy up to 0.4% contributes to increase of the volume ratio of ⁇ -phase decreasing resistance to deformation in hot working of this alloy which leads to evading of the generation of such defects as cracking. In case that Iron content exceeds 0.4%, this generates a segregation phase with beta-flecks in melting and solidifying of the alloy, which leads to heterogeneity of mechanical properties, especially ductility.
  • Oxygen contributes to the enhancement of mechanical strength by constituting a solid solution mainly in ⁇ -phase. In case that Oxygen content exceeds 0.25%, the alloy ductility may be deteriorated.
  • the alloy may contain up to 0.1% of carbon and up to 0.05% of nitrogen as inevitable impurities; the total quantity of impurities shall not exceed 0.16%.
  • Bars with the diameter of 50 mm were made of each ingot by hot working. Part of the bars was heat treated by annealing at 750°C, soaking for 1 hour and cooling in the air. The mechanical properties at room temperature were evaluated on the bars heat treated and on those not heat treated. The evaluation results are given in Table 2. In addition, the mechanical properties of ⁇ -upset workpieces were evaluated, which were heat treated at 710°C, soaked for 3 hours and cooled in air. The results of mechanical test of workpieces upset in ⁇ + ⁇ and ⁇ -field are given in Table 2.
  • the invented alloy is highly versatile, economically beneficial and has lower cost due to the fact that scrap of widely known alloys, such as Ti6Al4V, can be used for its production.
  • This alloy possesses required and sufficient mechanical properties and can be utilized for making a wide range of products, such as large forgings and die forgings, thin sheets and foil, by working in both ⁇ + ⁇ -field and ⁇ -field.

Abstract

The invention relates to the field of metallurgy and particularly to titanium base alloys used for making high-strength and high-workable articles. The titanium base alloy consists of Aluminum, Vanadium, Molybdenum, Iron, and Oxygen in the following ratio, wt.%: Aluminum 3.5 - 4.4, Vanadium 2.0 - 4.0, Molybdenum 0.1 - 0.8, Iron max 0.4, Oxygen max 0.25, the balance is titanium. The technical objective is to provide a versatile alloy to be used for making of large forgings and die forgings, rolled sheet products and foil having sufficient strength and ductility and structure. 2 tables.

Description

    Field of the Invention
  • The invention relates to the field of metallurgy and particularly to the field of development of state-of-the-art titanium alloys used for making high-strength and high-workable articles including large articles, i.e. alloys of high versatility.
  • Titanium alloys are widely used as aerospace materials, e.g. in airplanes and rockets since the alloys possess tough mechanical properties and are comparatively light.
    • Prior state of Art
  • Known is the most widely used titanium alloy, Ti6A14V alloy (B.A. Kalachyov, I.S. Polkin and V.D. Talalayev. Titanium Alloys of Different Countries. Reference Book. Moscow: VILS, 2000, p. 58-59) - [1]. This alloy was developed in 1950s in the USA. It is characterized by medium strength of 850 up to 1000 MPa and high workability. It is a good material to work by forming: forging, die forging, and extruding. It is widely used in aeronautical and aerospace engineering, shipbuilding, automotive industry, etc., as well as in manufacturing fasteners for various applications. This alloy is good to work by all types of welding including diffusion bonding.
  • The disadvantage of Ti6A14V alloy is its insufficient versatility. It is difficult to make rolled sheet products, foil, and tubes thereof since the alloy possesses relatively high resistance to deformation, which in case that the deformation temperature becomes below 800°C leads to the generation of defects such as cracks and shortens the life of working tools or necessitates costly tools.
  • Known is a pseudo-α-titanium alloy Grade 9 (Ti-3Al-2,5V), which is highly capable of cold working (see [1], p. 44, 45). The strength of this alloy is intermediate between that of Ti-6Al-4V alloy and titanium (600-800 MPa). This alloy is used as cold-worked and stress annealed; it is characterized by high corrosion resistance in various media including sea water. This alloy is used in making tubes for hydraulics and fuel systems of airplanes, rockets, and submarines.
  • The disadvantage of this alloy is also its low versatility since it requires stress relieving in making large structural parts thereof. Therefore, articles have to be annealed which reduces strength of Grade 9 alloy down to 400-500 MPa.
  • The most close analogue of the invented alloy is α+β-titanium alloy consisting of 3.0-5.0 Al; 2.1-3.7 V; 0.85-3.15 Mo; 0.85-3.15 Fe; 0.06-0.2 O2, and inevitable impurities ( Japanese application No. 3007214 B2, filed Feb. 7, 2000 ) - prior art.
  • The disadvantage of this alloy is that it is rich in Fe and Mo and, therefore, is prone to segregation process. In order to reduce possibility of segregational heterogeneity it is required to use a special ingot melting technology, then carry out rolling and forging at a small deformation rate in order to exclude decoration of "beta-flecks", which decreases the productivity.
    • Disclosure of the Invention
  • It is an object of the invention to provide a versatile titanium alloy which requires the least manufacturing costs and is capable of making a wide product mix thereof, such as large forgings and die forgings, as well as rolled sheet products and foil having sufficient strength and plastic properties and structure.
  • According to the invention an optimum mix of α- and β-stabilizing alloying elements in a semi-finished product is provided.
  • According to the invention a titanium base alloy is provided consisting of Aluminum, Vanadium, Molybdenum, Iron, and Oxygen in the following ratio, wt.%:
    Aluminum 3.5-4.4
    Vanadium 2.0-4.0
    Molybdenum 0.1-0.8
    Iron max 0.4
    Oxygen max 0.25
    Ti balance
  • High strength and ductility combined in the invented alloy is achieved through targeted selection and experimental evaluation of the alloying ranges. The content of α- stabilizers (Aluminum, Oxygen) and β-stabilizers (Vanadium, Molybdenum, and Iron) was determined so as to meet a goal objective.
  • Aluminum is a α-stabilizer for the α +β-titanium alloys, which contributes to the increase of mechanical strength. However in case that Aluminum content is below 3.5%, sufficient strength aimed in this invention cannot be obtained, whereas in case that Aluminum content exceeds 4.4%, the hot deformation resistance is increased and ductility at lower temperatures is deteriorated, which leads to the lowering of productivity.
  • Vanadium is added to titanium as a β-stabilizer for the α +β-titanitun alloys, which contributes to the increase of mechanical strength without forming brittle intermetallic compounds with titanium. Presence of Vanadium in the alloy impedes formation of α2-superstructure in α-phase as β-phase stabilizes, and contributes to the increase of both strength and ductility. In case that Vanadium content is below 2%, sufficient strength aimed in this invention cannot be obtained, whereas in case that Vanadium content exceeds 4.0%, the superplastic elongation is decreased by exceedingly lowering of the beta transus. Vanadium content within the range of 2.0-4.0% in this alloy has the merit in which the scrap of the most used Ti6A14V can be utilized.
  • Molybdenum is added to titanium as a β-stabilizer for the α +β-titanium alloys. In case that Molybdenum is added within the range of 0.1-0.8% this contributes to its full dissolution in α-phase, which enables to obtain the sufficient strength properties without deteriorating plastic properties. In case that Molybdenum content exceeds 0.8% this contributes to the increase of the specific weight of the alloy due to the fact that Molybdenum is a heavy metal and the plastic properties of the alloy are deteriorated. In case that Molybdenum content is below 0.1%, Molybdenum does not contribute to the alloy properties in full.
  • Iron added to the alloy up to 0.4% contributes to increase of the volume ratio of β-phase decreasing resistance to deformation in hot working of this alloy which leads to evading of the generation of such defects as cracking. In case that Iron content exceeds 0.4%, this generates a segregation phase with beta-flecks in melting and solidifying of the alloy, which leads to heterogeneity of mechanical properties, especially ductility.
  • Oxygen contributes to the enhancement of mechanical strength by constituting a solid solution mainly in α-phase. In case that Oxygen content exceeds 0.25%, the alloy ductility may be deteriorated.
  • The alloy may contain up to 0.1% of carbon and up to 0.05% of nitrogen as inevitable impurities; the total quantity of impurities shall not exceed 0.16%.
    • Embodiment of the invention
  • To evaluate the properties of the claimed alloy ingots were melted by the method of double vacuum arc remelt, having the following chemical composition (Table 1). Table 1
    Alloy Chemical Composition, wt.%
    Al V Mo Fe O
    1 3.9 2.2 0.2 0.13 0.17
    2 4.3 2.8 0.3 0.24 0.23
    3 4.3 3.3 0.6 0.32 0.20
    Table 2
    Alloy Heat Treatment Mechanical Properties
    σB, MPa σ0.2, MPa δ, % ψ, %
    1 W/o annealing 810 735 15.2 38.2
    750°C 1 hour, air 780 693 13.2 32.0
    2 W/o annealing 960 840 14.2 33.1
    750°C 1 hour, air 920 845 13.6 32.5
    3 α+β 710°C 3 hours, air 900 835 15 33.0
    β 710°C 3 hours, air 870 800 14 28.0
  • Bars with the diameter of 50 mm were made of each ingot by hot working. Part of the bars was heat treated by annealing at 750°C, soaking for 1 hour and cooling in the air. The mechanical properties at room temperature were evaluated on the bars heat treated and on those not heat treated. The evaluation results are given in Table 2. In addition, the mechanical properties of β-upset workpieces were evaluated, which were heat treated at 710°C, soaked for 3 hours and cooled in air. The results of mechanical test of workpieces upset in α+β and β-field are given in Table 2.
    • Commercial practicability
  • In comparison with the known alloys the invented alloy is highly versatile, economically beneficial and has lower cost due to the fact that scrap of widely known alloys, such as Ti6Al4V, can be used for its production. This alloy possesses required and sufficient mechanical properties and can be utilized for making a wide range of products, such as large forgings and die forgings, thin sheets and foil, by working in both α+β-field and β-field.

Claims (1)

  1. A titanium base alloy consisting of Aluminum, Vanadium, Molybdenum, Iron, and Oxygen in the following ratio, wt.%: Aluminum 3.5-4.4 Vanadium 2.0-4.0 Molybdenum 0.1-0.8 Iron max 0.4 Oxygen max 0.25 Titanium balance
EP05772406A 2004-07-30 2005-07-14 Titanium-based alloy Not-in-force EP1783235B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2004123500/02A RU2269584C1 (en) 2004-07-30 2004-07-30 Titanium-base alloy
PCT/RU2005/000381 WO2006014124A1 (en) 2004-07-30 2005-07-14 Titanium-based alloy

Publications (3)

Publication Number Publication Date
EP1783235A1 true EP1783235A1 (en) 2007-05-09
EP1783235A4 EP1783235A4 (en) 2008-02-13
EP1783235B1 EP1783235B1 (en) 2009-01-07

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ID=35787368

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Application Number Title Priority Date Filing Date
EP05772406A Not-in-force EP1783235B1 (en) 2004-07-30 2005-07-14 Titanium-based alloy

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US (1) US20080181809A1 (en)
EP (1) EP1783235B1 (en)
AT (1) ATE420217T1 (en)
DE (1) DE602005012284D1 (en)
DK (1) DK1783235T3 (en)
ES (1) ES2320684T3 (en)
RU (1) RU2269584C1 (en)
WO (1) WO2006014124A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101543948B (en) * 2008-03-28 2011-06-08 北京有色金属研究总院 Processing technology of Ti5Mo5V2Cr3Al alloy
CN102586639A (en) * 2012-03-16 2012-07-18 广州有色金属研究院 Method for preparing titanium alloy through high-speed pressing formation

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RU2211873C2 (en) * 2001-11-22 2003-09-10 ОАО Верхнесалдинское металлургическое производственное объединение METASTABLE β-TITANIUM ALLOY
US20040221929A1 (en) 2003-05-09 2004-11-11 Hebda John J. Processing of titanium-aluminum-vanadium alloys and products made thereby
US7837812B2 (en) 2004-05-21 2010-11-23 Ati Properties, Inc. Metastable beta-titanium alloys and methods of processing the same by direct aging
DE102009050603B3 (en) * 2009-10-24 2011-04-14 Gfe Metalle Und Materialien Gmbh Process for producing a β-γ-TiAl base alloy
RU2425164C1 (en) * 2010-01-20 2011-07-27 Открытое Акционерное Общество "Корпорация Всмпо-Ависма" Secondary titanium alloy and procedure for its fabrication
US10053758B2 (en) 2010-01-22 2018-08-21 Ati Properties Llc Production of high strength titanium
US9255316B2 (en) 2010-07-19 2016-02-09 Ati Properties, Inc. Processing of α+β titanium alloys
US9631261B2 (en) 2010-08-05 2017-04-25 Titanium Metals Corporation Low-cost alpha-beta titanium alloy with good ballistic and mechanical properties
US9206497B2 (en) 2010-09-15 2015-12-08 Ati Properties, Inc. Methods for processing titanium alloys
US8613818B2 (en) 2010-09-15 2013-12-24 Ati Properties, Inc. Processing routes for titanium and titanium alloys
US10513755B2 (en) * 2010-09-23 2019-12-24 Ati Properties Llc High strength alpha/beta titanium alloy fasteners and fastener stock
RU2463365C2 (en) * 2010-09-27 2012-10-10 Открытое Акционерное Общество "Корпорация Всмпо-Ависма" METHOD TO PRODUCE INGOT OF PSEUDO β-TITANIUM ALLOY, CONTAINING (4,0-6,0)%Al, (4,5-6,0)% Mo, (4,5-6,0)% V, (2,0-3,6)%Cr, (0,2-0,5)% Fe, (0,1-2,0)%Zr
US8652400B2 (en) 2011-06-01 2014-02-18 Ati Properties, Inc. Thermo-mechanical processing of nickel-base alloys
US9869003B2 (en) 2013-02-26 2018-01-16 Ati Properties Llc Methods for processing alloys
US9192981B2 (en) 2013-03-11 2015-11-24 Ati Properties, Inc. Thermomechanical processing of high strength non-magnetic corrosion resistant material
US9777361B2 (en) 2013-03-15 2017-10-03 Ati Properties Llc Thermomechanical processing of alpha-beta titanium alloys
US11111552B2 (en) 2013-11-12 2021-09-07 Ati Properties Llc Methods for processing metal alloys
US9956629B2 (en) * 2014-07-10 2018-05-01 The Boeing Company Titanium alloy for fastener applications
JP6392179B2 (en) * 2014-09-04 2018-09-19 株式会社神戸製鋼所 Method for deoxidizing Ti-Al alloy
US10094003B2 (en) 2015-01-12 2018-10-09 Ati Properties Llc Titanium alloy
US10502252B2 (en) 2015-11-23 2019-12-10 Ati Properties Llc Processing of alpha-beta titanium alloys
ES2953496T3 (en) * 2016-04-25 2023-11-13 Howmet Aerospace Inc BCC materials of titanium, aluminum, vanadium, and iron, and products manufactured therefrom

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN101543948B (en) * 2008-03-28 2011-06-08 北京有色金属研究总院 Processing technology of Ti5Mo5V2Cr3Al alloy
CN102586639A (en) * 2012-03-16 2012-07-18 广州有色金属研究院 Method for preparing titanium alloy through high-speed pressing formation

Also Published As

Publication number Publication date
EP1783235B1 (en) 2009-01-07
EP1783235A4 (en) 2008-02-13
DK1783235T3 (en) 2009-03-16
ES2320684T3 (en) 2009-05-27
RU2269584C1 (en) 2006-02-10
ATE420217T1 (en) 2009-01-15
WO2006014124A1 (en) 2006-02-09
US20080181809A1 (en) 2008-07-31
DE602005012284D1 (en) 2009-02-26

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