EP1392876B1 - Titanium-base alloy - Google Patents

Titanium-base alloy Download PDF

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Publication number
EP1392876B1
EP1392876B1 EP02739008.7A EP02739008A EP1392876B1 EP 1392876 B1 EP1392876 B1 EP 1392876B1 EP 02739008 A EP02739008 A EP 02739008A EP 1392876 B1 EP1392876 B1 EP 1392876B1
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EP
European Patent Office
Prior art keywords
alloy
titanium
max
carbon
ductility
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.)
Expired - Lifetime
Application number
EP02739008.7A
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German (de)
French (fr)
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EP1392876A1 (en
Inventor
Vladislav Valentinovich Tetyukhin
Vladimir Grigoryevich Smirnov
Igor Vasilyevich Levin
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.)
VERKHNAYA SALDA METALLURG PRODUCTION ASS
Verkhnaya Salda Metallurgical Production Association
Boeing Co
Original Assignee
VERKHNAYA SALDA METALLURG PRODUCTION ASS
Verkhnaya Salda Metallurgical Production Association
Boeing Co
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Publication of EP1392876A1 publication Critical patent/EP1392876A1/en
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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 the non-ferrous metallurgy, especially to the development of new titanium-base alloys offering high formability when seamless cold-worked tubes are manufactured for use in hydraulic systems of aerospace applications and sea vessels.
  • titanium alloys Due to their high strength, light weight and corrosion resistance titanium alloys are used in hydraulic systems of aerospace applications where pipe fittings are produced by welding or highly elastic pressing.
  • alloy Ti-3Al-2.5V One of known industrial titanium alloys, used in the hydraulic systems, is the alloy Ti-3Al-2.5V. This alloy features high formability during cold rolling and allows to produce fittings by elastic pressing at minimum values of yield point 515 MPa and ultimate strength 620 MPa (AMS 4943D, Seamless Annealed Pipes for Hydraulic Systems, Made of Alloy Ti-3Al-2.5V, UNSR56320).
  • Titanium alloy of the following composition in mass % is also known: Aluminum 2.5 - 4.5 Vanadium 2.0 - 3.0 Molybdenum 0.5 - 2.0 Zirconium 0.5 - 2.0 Iron 0.20 max Nitrogen 0.03 max Oxygen 0.15 max
  • This alloy is applicable for hot working, may be used for manufacture of hot-worked and seamless cold-worked pipes, possesses a favorable combination of high strength, formability and corrosion resistance but its ductility is insufficient to flare the pipe or to produce fittings by elastic pressing.
  • JP 07 054081 A discloses titanium alloy compositions with improved properties in regard of corrosion resistance, cold-working and welding, to be used as piping material in chemical, energy of aircraft industry.
  • the titanium alloy comprises (in wt. %): A1 (1.5-4.5%); V (1.5-4.5%); Mo (0.1-2.5%); Zr (0.1-10%); and impurities of C, H, O, N, Fe, Y can be present in the alloy.
  • the object of the invention is to propose titanium alloy possessing a combination of high strength, formability and corrosion resistance, suitable for manufacture of seamless cold-worked pipes for hydraulic systems of aerospace applications and sea vessels as well as for manufacture of pipe fittings by the elastic pressing method.
  • titanium-base alloy containing aluminum, vanadium, molybdenum, zirconium, iron, nitrogen and additional carbon at the following content of components, mass %: Aluminum 2.5 - 4.0 Vanadium 2.5 - 4.0 Molybdenum 2.0 - 3.5 Zirconium 0.4 - 1.5 Iron 0.25 max Nitrogen 0.03 max Oxygen 0.15 max Carbon 0.01 - 0,1 Other impurities, total 0.3 max Titanium balance
  • This titanium-base alloy may also additionally contain palladium or ruthenium in the following quantities, mass %: Palladium 0.03 - 0.1 Ruthenium 0.03 - 0.3
  • the high ductility during cold rolling and expansion of the pipes is achieved due to higher content of the ⁇ -phase which increases the plasticity as a result of large number of sliding planes in the crystal lattice and of the deformation of the ⁇ -phase within the ⁇ -phase under the isostatic compression.
  • zirconium and interstitial impurities content causes the increase in the ⁇ -phase quantity and strength but reduces the ductility.
  • Increase in the ⁇ -stabilizer content reduces the alloy stability, causes grain growth during the heat treatment which also reduces the alloy ductility.
  • the carbon content is below 0.01%, the yield point of the alloy is insufficient to ensure the performance capability of the piping in hydraulic systems.
  • the carbon content exceeds 0.1% the ductility of the alloy decreases at pipe expansion so that the pipe to fitting connection cannot be made by elastic pressing.
  • Additional alloying with palladium and ruthenium in the claimed limits increases the corrosion resistance of the alloy in the marine environment when the alloy is used in sea vessel piping.
  • ingots with the composition shown in Table 1 have been melted in a vacuum arc furnace and pipes with the outside diameter of 1" and wall thickness of 0.051" were made from these ingots.
  • the alloy with the claimed composition possesses high strength and ductility values in combination with high expansion and corrosion resistance and complies with the requirements for pipes used in hydraulic systems of aerospace applications and sea vessels.
  • Table 1 Example Al V Mo Zr Fe N C O Ti Ru Pd 1 2.5 2.5 2.0 0.5 0.05 0.009 0.01 0.06 base - - 2 2.5 4.0 3.5 0.4 0.07 0.008 0.05 0.09 base 0.03 - 3 3.4 3.6 2.8 1.1 0.12 0.006 0.06 0.1 base - - 4 3.1 3.0 2.7 1.1 0.19 0.006 0.07 0.1 base - 0.03 5 4.0 4.0 3.5 1.5 0.08 0.01 0.1 0.15 base - -
  • the outside diameter expansion was determined as the ratio of the outside diameter of the specimen after flaring to the initial outside diameter.

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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)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Description

  • The invention relates to the non-ferrous metallurgy, especially to the development of new titanium-base alloys offering high formability when seamless cold-worked tubes are manufactured for use in hydraulic systems of aerospace applications and sea vessels.
  • Due to their high strength, light weight and corrosion resistance titanium alloys are used in hydraulic systems of aerospace applications where pipe fittings are produced by welding or highly elastic pressing.
  • However, known titanium alloys have insufficient ductility to produce the fittings by elastic pressing.
  • One of known industrial titanium alloys, used in the hydraulic systems, is the alloy Ti-3Al-2.5V. This alloy features high formability during cold rolling and allows to produce fittings by elastic pressing at minimum values of yield point 515 MPa and ultimate strength 620 MPa (AMS 4943D, Seamless Annealed Pipes for Hydraulic Systems, Made of Alloy Ti-3Al-2.5V, UNSR56320).
  • Titanium alloy of the following composition in mass % is also known:
    Aluminum 2.5 - 4.5
    Vanadium 2.0 - 3.0
    Molybdenum 0.5 - 2.0
    Zirconium 0.5 - 2.0
    Iron 0.20 max
    Nitrogen 0.03 max
    Oxygen 0.15 max
  • Ref. German patent application DE 19533743 Al , Int. Cl. C22C 14/00, published 13.03.97, as prior knowledge.
  • This alloy is applicable for hot working, may be used for manufacture of hot-worked and seamless cold-worked pipes, possesses a favorable combination of high strength, formability and corrosion resistance but its ductility is insufficient to flare the pipe or to produce fittings by elastic pressing.
  • JP 07 054081 A discloses titanium alloy compositions with improved properties in regard of corrosion resistance, cold-working and welding, to be used as piping material in chemical, energy of aircraft industry. The titanium alloy comprises (in wt. %): A1 (1.5-4.5%); V (1.5-4.5%); Mo (0.1-2.5%); Zr (0.1-10%); and impurities of C, H, O, N, Fe, Y can be present in the alloy.
  • The object of the invention is to propose titanium alloy possessing a combination of high strength, formability and corrosion resistance, suitable for manufacture of seamless cold-worked pipes for hydraulic systems of aerospace applications and sea vessels as well as for manufacture of pipe fittings by the elastic pressing method.
  • In accordance with the invention this is achieved by creation of titanium-base alloy containing aluminum, vanadium, molybdenum, zirconium, iron, nitrogen and additional carbon at the following content of components, mass %:
    Aluminum 2.5 - 4.0
    Vanadium 2.5 - 4.0
    Molybdenum 2.0 - 3.5
    Zirconium 0.4 - 1.5
    Iron 0.25 max
    Nitrogen 0.03 max
    Oxygen 0.15 max
    Carbon 0.01 - 0,1
    Other impurities, total 0.3 max
    Titanium balance
  • This titanium-base alloy may also additionally contain palladium or ruthenium in the following quantities, mass %:
    Palladium 0.03 - 0.1
    Ruthenium 0.03 - 0.3
  • The lower limit of the alloying element content in mass %, i.e. Al(2.5), V(2.5), Mo(2.0), Zr(0.4), of interstitial impurities Fe(0.05), N(0.005), 0(0.05) and of carbon (0.01) is the minimum at which the high strength (σB = 690 MPa, σ0.2 = 530 MPa) and ductility (δ = 18.4%) are ensured when the pipe diameter is expanded by the factor of 1.43 in comparison with the initial outside diameter. The high ductility during cold rolling and expansion of the pipes is achieved due to higher content of the β-phase which increases the plasticity as a result of large number of sliding planes in the crystal lattice and of the deformation of the α-phase within the β-phase under the isostatic compression.
  • The upper limit of the alloying element content in mass %, i.e. Al(4.0) and Zr(1.5), in combination with the maximum content of β-stabilizers V(4.0), Mo(3.5), interstitial impurities Fe(0.25), N(0.03), O(0.15), and carbon C(0.1) allows to maintain sufficient ductility (δ>17.7%) when the pipe diameter is expanded by the factor of 1.4 at high strength of the material (σB = 932 MPa, σ0.2 = 738 MPa).
  • Further increase in aluminum, zirconium and interstitial impurities content causes the increase in the α-phase quantity and strength but reduces the ductility. Increase in the β-stabilizer content reduces the alloy stability, causes grain growth during the heat treatment which also reduces the alloy ductility.
  • Addition of 0.01-0.1% of carbon increases the strength and ductility of the alloy and allows to use the same for manufacture of hydraulic system piping operating under severe conditions.
  • If the carbon content is below 0.01%, the yield point of the alloy is insufficient to ensure the performance capability of the piping in hydraulic systems. When the carbon content exceeds 0.1% the ductility of the alloy decreases at pipe expansion so that the pipe to fitting connection cannot be made by elastic pressing.
  • Additional alloying with palladium and ruthenium in the claimed limits increases the corrosion resistance of the alloy in the marine environment when the alloy is used in sea vessel piping.
  • Overalloying with the additional elements Pd and Ru in excess of the claimed limits will increase the alloy cost without any significant increase in the corrosion resistance, and underalloying below these limits cannot ensure the required corrosion resistance for long-term operation in marine environment.
  • Examples of the embodiment of the invention are given below.
  • To study the properties of the alloy, ingots with the composition shown in Table 1 have been melted in a vacuum arc furnace and pipes with the outside diameter of 1" and wall thickness of 0.051" were made from these ingots.
  • The mechanical and corrosion properties of the pipes are shown in Table 2.
  • As can be seen, the alloy with the claimed composition possesses high strength and ductility values in combination with high expansion and corrosion resistance and complies with the requirements for pipes used in hydraulic systems of aerospace applications and sea vessels. Table 1
    Example Al V Mo Zr Fe N C O Ti Ru Pd
    1 2.5 2.5 2.0 0.5 0.05 0.009 0.01 0.06 base - -
    2 2.5 4.0 3.5 0.4 0.07 0.008 0.05 0.09 base 0.03 -
    3 3.4 3.6 2.8 1.1 0.12 0.006 0.06 0.1 base - -
    4 3.1 3.0 2.7 1.1 0.19 0.006 0.07 0.1 base - 0.03
    5 4.0 4.0 3.5 1.5 0.08 0.01 0.1 0.15 base - -
    Figure imgb0001
  • The outside diameter expansion was determined as the ratio of the outside diameter of the specimen after flaring to the initial outside diameter.
  • All specimens have sustained the test; the test was interrupted only because the support faces of the specimens lost the stability or the entire specimen lost the longitudinal stability.

Claims (1)

  1. Titanium-base alloy containing aluminum, vanadium, molybdenum, zirconium, iron, nitrogen, wherein it additionally contains carbon, at the following content of components, mass %: Aluminum 2.5 - 4.0 Vanadium 2.5 - 4.0 Molybdenum 2.0 - 3.5 Zirconium 0.4 - 1.5 Iron 0.25 max Nitrogen 0.03 max Oxygen 0.15 max Carbon 0.01 - 0,1 Other impurities, total 0.3 max
    wherein it additionally optionally contains palladium or ruthenium in the following quantities, mass %: Palladium 0.03 - 0.1 Ruthenium 0.03 - 0.3 Titanium Balance
EP02739008.7A 2001-05-07 2002-05-07 Titanium-base alloy Expired - Lifetime EP1392876B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
RU2001112580 2001-05-07
RU2001112580/02A RU2203974C2 (en) 2001-05-07 2001-05-07 Titanium-based alloy
PCT/RU2002/000227 WO2002090607A1 (en) 2001-05-07 2002-05-07 Titanium-base alloy

Publications (2)

Publication Number Publication Date
EP1392876A1 EP1392876A1 (en) 2004-03-03
EP1392876B1 true EP1392876B1 (en) 2014-10-08

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RU (1) RU2203974C2 (en)
WO (1) WO2002090607A1 (en)

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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
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
US8499605B2 (en) 2010-07-28 2013-08-06 Ati Properties, Inc. Hot stretch straightening of high strength α/β processed titanium
US8613818B2 (en) 2010-09-15 2013-12-24 Ati Properties, Inc. Processing routes for titanium and titanium alloys
US9206497B2 (en) 2010-09-15 2015-12-08 Ati Properties, Inc. Methods for processing titanium alloys
US10513755B2 (en) 2010-09-23 2019-12-24 Ati Properties Llc High strength alpha/beta titanium alloy fasteners and fastener stock
US8652400B2 (en) 2011-06-01 2014-02-18 Ati Properties, Inc. Thermo-mechanical processing of nickel-base alloys
RU2502819C1 (en) * 2012-04-19 2013-12-27 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") Titanium-base alloy
US9050647B2 (en) 2013-03-15 2015-06-09 Ati Properties, Inc. Split-pass open-die forging for hard-to-forge, strain-path sensitive titanium-base and 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
JP6750157B2 (en) * 2014-04-28 2020-09-02 ナショナル・カプリング・カンパニー，インコーポレーテッド Titanium alloys, parts made therefrom and methods of use
RU2583566C1 (en) * 2014-12-24 2016-05-10 Открытое Акционерное Общество "Корпорация Всмпо-Ависма" METHOD FOR PRODUCING COLD-DEFORMED SEAMLESS PIPES MADE OF TITANIUM ALLOY Ti-3Al-2,5V
US10094003B2 (en) 2015-01-12 2018-10-09 Ati Properties Llc Titanium alloy
RU2582171C1 (en) * 2015-04-27 2016-04-20 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") Titanium-based alloy
US10502252B2 (en) 2015-11-23 2019-12-10 Ati Properties Llc Processing of alpha-beta titanium alloys
RU2614229C1 (en) * 2016-03-01 2017-03-23 Федеральное Государственное Унитарное Предприятие "Центральный Научно-Исследовательский Институт Конструкционных Материалов "Прометей" (Фгуп "Цнии Км "Прометей") Titanium-based alloy
CN108893632B (en) * 2018-08-03 2020-11-17 燕山大学 Tough corrosion-resistant titanium alloy and preparation method thereof
CN110592425B (en) * 2019-09-02 2022-03-11 中国船舶重工集团公司第七二五研究所 High-impact-toughness titanium alloy and method for preparing seamless pipe by using titanium alloy

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JP2797913B2 (en) * 1993-08-11 1998-09-17 住友金属工業株式会社 High corrosion resistance titanium alloy with excellent cold workability and weldability
DE19533743A1 (en) * 1995-09-12 1997-03-13 Vladislav Prof Tetjuchine Titanium alloy with high resistance to corrosion
EP0969109B1 (en) * 1998-05-26 2006-10-11 Kabushiki Kaisha Kobe Seiko Sho Titanium alloy and process for production
WO2001011095A1 (en) * 1999-08-09 2001-02-15 Otkrytoe Aktsionernoe Obschestvo Verkhnesaldinskoe Metallurgicheskoe Proizvodstvennoe Obiedinenie (Oao Vsmpo) Titanium alloy

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WO2002090607A8 (en) 2003-08-07
RU2203974C2 (en) 2003-05-10
EP1392876A1 (en) 2004-03-03
WO2002090607A1 (en) 2002-11-14

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