EP1778885A1 - Hochfeste, oxidationsbeständige und verschleissfeste legierung auf titan-silicium-basis - Google Patents

Hochfeste, oxidationsbeständige und verschleissfeste legierung auf titan-silicium-basis

Info

Publication number
EP1778885A1
EP1778885A1 EP05767947A EP05767947A EP1778885A1 EP 1778885 A1 EP1778885 A1 EP 1778885A1 EP 05767947 A EP05767947 A EP 05767947A EP 05767947 A EP05767947 A EP 05767947A EP 1778885 A1 EP1778885 A1 EP 1778885A1
Authority
EP
European Patent Office
Prior art keywords
alloy
mpa
oxidation
rare earth
high strength
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.)
Granted
Application number
EP05767947A
Other languages
English (en)
French (fr)
Other versions
EP1778885B1 (de
EP1778885A4 (de
Inventor
Karl Forwald
Georg Frommeyer
Gunnar Halvorsen
Kai Johansen
Øyvind MIKKELSEN
Gunnar Schüssler
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.)
Elkem ASA
Original Assignee
Elkem ASA
Elkem Materials AS
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
Priority claimed from NO20042959A external-priority patent/NO20042959D0/no
Application filed by Elkem ASA, Elkem Materials AS filed Critical Elkem ASA
Publication of EP1778885A1 publication Critical patent/EP1778885A1/de
Publication of EP1778885A4 publication Critical patent/EP1778885A4/de
Application granted granted Critical
Publication of EP1778885B1 publication Critical patent/EP1778885B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof

Definitions

  • the present invention concerns high strength silicon-containing titanium-based alloys with optionally additives of aluminium, boron, chromium, scandium and rare earth metals (Y, Er, and Ce and La containing misch metal).
  • T ⁇ -6AI-4V A variety of two phase ⁇ / ⁇ -titanium and near ⁇ -titanium alloys, such as T ⁇ -6AI-4V, IMI 834 (Ti- ⁇ .8-AMSn-3Zr-0JNb-0. ⁇ Mo-0.3 ⁇ Si-0.06C) and TIMET 1100 (Ti-6AI- 2.7Sn-4Zr-0.4Mo-0.45Si) show great potential application in the air plane and space industry.
  • Ti-6AI-4V exhibits the broadest application due to an optimum combination of high strength and fracture toughness and excellent fatigue properties at room and elevated temperature.
  • These alloys have, however, some disadvantages such as a poor oxidation resistance above 475°C ( ⁇ -case formation), insufficient creep strength at 600°C and higher temperatures and a poor wear resistance at room and elevated temperatures.
  • the ⁇ -case causes crevice formation on the oxidised surface and has a detrimental effect on the fatigue properties.
  • the arc melting process of these relatively high melting point alloy of about 1660 0 C) and the necessary melt overheating to about 1750 to 1770 0 C is a very energy consuming procedure for the manufacture of investment castings for the air plane and automotive industry, and engineering purposes in general.
  • JP 2002060871 A describes a titanium alloy containing 0.2 - 2.3 wt % Si, 0.1 - 0.7 wt
  • % O total content oxygen
  • These are e.g. golf club heads, fishing tackles and medical components such as tooth root, implants, bone plates, joints and crowns.
  • the low silicon-containing titanium-based alloy does, however, suffer from a disadvantage, by forming small needle like Ti 3 Si precipates along grain boundaries, which decrease the fracture toughness and ductility of this material.
  • the alloys described by Frommeyer et. al. have excellent hardness and flow strength.
  • the warm strength of the Ti-Si-Al alloys is, however, moderate and there is no indication of the oxidation resistance at high temperature.
  • Ti-Si alloys with relatively high silicon contents which exhibit a relatively low melting point due to their eutectic constitution, good casting properties and high strength at higher temperatures as well as a very high resistance to oxidation and creep deformation at high temperatures.
  • the present invention thus relates to a Ti-Si alloy comprising 2.5 - 12 wt % Si, 0 - 5 wt % Al, 0 -5 wt % Cr, 0 - 0.5 wt % B, 0 - 1 wt % rare earth metals and/or yttrium and/or Sc, the remaining except for impurities being Ti.
  • the alloy contains 0.3 - 3 wt % Al.
  • the Ti-Si alloy contains 3 - 6 wt % Si and 1.2 - 2.5 wt % Al.
  • the alloy contains 0.001 to 0.15 wt % rare earth metals and/or scandium.
  • the rare earths yttriym and scandium additions form a fine dispersion of thermo- dynamically stable oxides, such as Er 2 ⁇ 3 , Y 2 O 3 etc. in the Ti-Si alloy.
  • the alloy preferably contains 0.1 to 1.5 wt % Cr.
  • the addition of Cr enhances solid solution hardening and therefore increases the strength and increase the oxidation resistance of the alloy.
  • the Ti-Si alloy In the as cast state, the Ti-Si alloy possesses fine-grained hypoeutectic, eutectic or slightly hypereutectic microstructures depending upon the silicon content.
  • the microstructure of the eutectic Ti-Si alloy consists of finely dispersed Ti 5 Si 3 suicide particles of discontinuous rod like shape within the hexagonal close-packed ⁇ - Ti(Si) solid solution matrix.
  • the hypoeutectic microstructure consists of primary solidified ⁇ -Ti(Si) crystals and the surrounding eutectic.
  • the Ti-Si alloy according to the invention has with a yield stress of at least 800 MPa, a Brinell hardness of 350-400 HB and sufficient ductility and fracture toughness -stress intensity factor Kic . of more than 23 MPa Vm at room temperature and up to 500 0 C.
  • the Ti-Si alloy according to the invention further exhibits excellent oxidation resistance up to 65O 0 C and above depending upon the Si content and improved wear resistance both at room and elevated temperature.
  • the hypereutectic microstructures consist of primary solidified TJsSi 3 crystals of hexagonal shape within the fine-grained eutectic microstructure.
  • hypoeutectic Ti-Si alloys exhibit at room temperature fractures toughness -K
  • the eutectic alloy shows a fracture toughness of K
  • C of 15 - 18 MPa Vm and the yield stress exceeds 850 MPa at room temperature. At 600 0 C and above the fracture toughness is increased to 30 MPa Vm and the strength is of the order of at least Rm 450 MPa.
  • Oxidation tests with exposure to air at 600 0 C have resulted in an increase in mass of less than 5 mg/cm 2 after 500 hours.
  • the conventional Ti-AI6- V4 alloy exhibits alpha case formation at 475 0 C during long term exposure on air.
  • the Ti-AI6-V4 alloy with potential application in the air plane and space industry exhibits a creep stress of about 150 MPa at 450 0 C.
  • the Ti-Si alloy according to the invention has a low melting point of between about 1330 and about 138O 0 C.
  • the alloy according to the invention has further excellent casting properties making it possible to cast virtually any size and shape.
  • the Ti-Si alloy according to this invention are advantageously suitable for the manufacture of diverse components, subjected to high temperature, such as:
  • the Ti-Si alloy according to the invention is particularly suitable for as cast components because of their relatively low melting temperatures of about 1330 to 138O 0 C and excellent castability.
  • the Ti-Si alloy according to the invention can be produced in conventional way, such as by arc melting in a water cooled copper hearth. Detailed description of invention
  • a hypoeutectic Ti-6Si-2AI alloy according to the invention was produced by arc melting using a non consumable tungsten electrode. Titanium sponge with a purity of more than 99.8 wt %, metallurgical grade silicon and aluminium granules with a purity of more than 99.8 wt % were used as starting materials. The alloy was kept during arc melting in a water cooled copper hearth by forming a thin solid skull on the copper hearth and was then cast into a copper mould in order to achieve rod like ingots. These were machined by turning and grinding to cylindrical compression and tensile test samples exhibiting a smooth surface finish.
  • the Brinell hardness was determined to be about 336 + 3 HB 187.5/2.5 applying a testing load of 187.5 kp.
  • the flow stress was determined at room temperature in compression test to be about Rp 0 2 « 725 to 750 MPa and the plastic strain exceeds - ⁇ p ⁇ 10 %.
  • the fracture toughness was measured in a four point bend test.
  • the stress intensity factor Kic varies between 19 ⁇ Kic ⁇ 21 MPa Vm. At higher temperature of 65O 0 C the flow stress is still 260 Rp 0 2 275 MPa and the fracture toughness is about 32 ⁇ K
  • the weight gain in an oxidation test on air at 600 0 C was 4.5 mg/cm 2 after 525 hrs.
  • a hypereutectic Ti-IOSi alloy containing 0.2 wt % Al was also produced by arc melting technique as described above in Example 1.
  • the macrohardness -Brinell- of this alloy was determined to be about 365 HB 187.5/2.5 and the yield stress at room temperature ranges between 930 ⁇ Rp ⁇ 965 MPa depending upon the grain size of the alloy.
  • the plastic strain in compression is about 6 to 8 % and the fracture toughness is in between K
  • C 16 and 19 MPa Vm.
  • the yield stress is about 330 to 360 MPa.
  • the fracture toughness is in between 25 and 28 MPa Vm.
  • the creep strength was determined at 600 0 C and exhibits values of 215 to 230 MPa in the coarse-grained state.
  • the oxidation on air at 65O 0 C leads to a weight gain of about 3.8 mg/cm 3 at 500 hrs exposure time.
  • a hypoeutectic (near eutectic) oxide dispersion strengthened Ti-7Si-2Al alloy with addition of 0.07 mass-% Y was also produced by the arc melting technique described in example 1.
  • Metallic Yttrium was added to the melt and formed Y 2 O 3 with the dissolved oxygen of about 1200 ppm.
  • the Brinell hardness was determined to be 347 ⁇ 2 HB 187.5/2.5.
  • the measured yield strength was about 960 to 990 MPa.
  • First creep experiments at 600°C with the creep rate of ⁇ 10 " V 1 showed a creep strength in between 235 and 255 MPa.
  • Example 4 A hypoeutectic oxide dispersion strengthened Ti-5.5Si-3.5AI.-1.5Cr-0.1 Y alloy was produced by the melting method technique described in Example 1. Metallic yttrium was added to the melt and formed Y 2 O 3 with oxygen dissolved in the melt.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
EP05767947.4A 2004-07-13 2005-07-01 Hochfeste, oxidationsbeständige und verschleissfeste legierung auf titan-silicium-basis Active EP1778885B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO20042959A NO20042959D0 (no) 2004-07-13 2004-07-13 High strength, oxidation and wear resistant titanium-silicon base alloys and the use thereof
NO20045664A NO322348B1 (no) 2004-07-13 2004-12-27 Titan-silisiumlegeringer med hoy styrke, oksidasjon- og slitasjemotstandsdyktighet
PCT/NO2005/000246 WO2006006869A1 (en) 2004-07-13 2005-07-01 High strength, oxidation and wear resistant titanium-silicon based alloy

Publications (3)

Publication Number Publication Date
EP1778885A1 true EP1778885A1 (de) 2007-05-02
EP1778885A4 EP1778885A4 (de) 2012-12-26
EP1778885B1 EP1778885B1 (de) 2014-12-10

Family

ID=35209717

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05767947.4A Active EP1778885B1 (de) 2004-07-13 2005-07-01 Hochfeste, oxidationsbeständige und verschleissfeste legierung auf titan-silicium-basis

Country Status (12)

Country Link
EP (1) EP1778885B1 (de)
JP (1) JP4599402B2 (de)
KR (1) KR20070049157A (de)
AU (1) AU2005263030B2 (de)
BR (1) BRPI0513282B1 (de)
CA (1) CA2571761C (de)
DK (1) DK1778885T3 (de)
EA (1) EA010770B1 (de)
ES (1) ES2530635T3 (de)
NO (1) NO322348B1 (de)
UA (1) UA82165C2 (de)
WO (1) WO2006006869A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103555999A (zh) * 2013-11-06 2014-02-05 北京科技大学 一种高强度铸造Ti-Si-Al-B-Zr基合金
CN103556000A (zh) * 2013-11-11 2014-02-05 北京科技大学 含稀土和金属间化合物增强相的Ti-Si-Al基合金

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995009932A1 (en) * 1993-10-06 1995-04-13 The University Of Birmingham Titanium alloy products and methods for their production

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH043459A (ja) * 1990-04-19 1992-01-08 Mitsubishi Electric Corp 積層型半導体装置の製造方法
JPH04105659A (ja) * 1990-08-27 1992-04-07 Shinya Iwamoto 生体用チタン合金およびその製造方法
US5366570A (en) * 1993-03-02 1994-11-22 Cermics Venture International Titanium matrix composites
JP2001089821A (ja) * 1999-09-22 2001-04-03 Sumitomo Metal Ind Ltd 耐高温大気酸化性に優れた高強度、高延性チタン合金
JP2002088407A (ja) * 2000-09-12 2002-03-27 Matsumoto Shika Univ 金属を主原料とする粒子、電極部材及び電極部材の製造方法
JP3765475B2 (ja) * 2000-11-16 2006-04-12 日立金属株式会社 Ｔｉ−Ｓｉ合金系ターゲット材およびその製造方法ならびに皮膜コーティング方法
JP3793813B2 (ja) * 2002-09-13 2006-07-05 独立行政法人産業技術総合研究所 高強度チタン合金及びその製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995009932A1 (en) * 1993-10-06 1995-04-13 The University Of Birmingham Titanium alloy products and methods for their production

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of WO2006006869A1 *
YU PORYADCHENKO N ET AL: "High-Temperature Strength of Titanium Alloys Alloyed with Silicon, Aluminum, and Zirconium in Air", MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS-CONSULTANTS BUREAU, NE, vol. 41, no. 2, 1 March 2005 (2005-03-01), pages 230-236, XP019222284, ISSN: 1573-885X, DOI: 10.1007/S11003-005-0155-1 *

Also Published As

Publication number Publication date
WO2006006869A1 (en) 2006-01-19
KR20070049157A (ko) 2007-05-10
BRPI0513282B1 (pt) 2014-09-16
EA200700126A1 (ru) 2007-04-27
NO20045664L (no) 2006-01-16
NO20045664D0 (no) 2004-12-27
JP2008506838A (ja) 2008-03-06
CA2571761C (en) 2010-06-01
JP4599402B2 (ja) 2010-12-15
BRPI0513282A (pt) 2008-05-06
EP1778885B1 (de) 2014-12-10
UA82165C2 (uk) 2008-03-11
CA2571761A1 (en) 2006-01-19
AU2005263030A1 (en) 2006-01-19
EP1778885A4 (de) 2012-12-26
ES2530635T3 (es) 2015-03-04
NO322348B1 (no) 2006-09-18
DK1778885T3 (en) 2015-02-23
AU2005263030B2 (en) 2009-07-02
EA010770B1 (ru) 2008-10-30

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