EP1632581A1 - Titane à haute résistance mécanique et à prix réduit et méthode pour sa production - Google Patents

Titane à haute résistance mécanique et à prix réduit et méthode pour sa production Download PDF

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Publication number
EP1632581A1
EP1632581A1 EP05090250A EP05090250A EP1632581A1 EP 1632581 A1 EP1632581 A1 EP 1632581A1 EP 05090250 A EP05090250 A EP 05090250A EP 05090250 A EP05090250 A EP 05090250A EP 1632581 A1 EP1632581 A1 EP 1632581A1
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Prior art keywords
alloy
percent
weight
range
titanium
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EP05090250A
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German (de)
English (en)
Inventor
Rahbar Nasserrafi
Del Antonio Rosario
Michael Wyte
Jose Monterrosa
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Gainsmart Group Ltd a Corp of British Virgin Islands with offices at
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Gainsmart Group Ltd a Corp of British Virgin Islands with offices at
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    • 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
    • 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 present invention relates generally to titanium alloys, and more particularly, to a new titanium alloy and method for making the same which can be manufactured from recycled titanium.
  • Titanium alloys offer attractive combinations of physical and mechanical properties which make them ideal for applications requiring high strength, low weight, and good corrosion properties.
  • titanium alloys are expensive to manufacture, which severely limits their application.
  • a number of processing steps are required to refine titanium from its raw form to a usable form.
  • the refining process must be carefully controlled, further increasing manufacturing costs.
  • the use of titanium is typically limited to military vehicles, airplane engine and air-frame components, chemical processing, and sports hardware.
  • a titanium alloy comprises titanium and one or more elements selected from the group consisting of chromium, manganese, and iron, wherein in an as-cast condition, the alloy has a yield strength of at least about 135,000 psi.
  • the alloy preferably comprises aluminum in a range of about 3.5 to about 6.25 percent by weight of the alloy, with ranges of about 4.5 to about 6.0 percent and about 5.0 to about 6.0 percent being more preferred and especially preferred, respectively.
  • the alloy comprises vanadium in a range of about 3.0 to about 4.5 percent by weight of the alloy, with ranges of about 3.3 to about 4.5 percent and about 3.5 to about 4.5 percent being more preferred and especially preferred, respectively.
  • the amount of chromium is in a range of up to about 3.8 percent by weight of the alloy, with ranges of about 1.0 to about 2.5 percent and about 1.2 to about 2.0 percent being more preferred and especially preferred, respectively.
  • the amount of manganese is in a range of up to about 2.0 percent by weight of the alloy, with ranges of up to about 1.5 percent and about 0.75 to about 1.25 percent being more preferred and especially preferred, respectively.
  • the alloy comprises oxygen in a range of up to about 0.3 percent by weight, with ranges of up to about 0.29 percent and up to about 0.27 percent being more preferred and especially preferred, respectively. It is further preferred that the combined amount of chromium, manganese, and iron is in a range of about 1.0 to about 5.0 percent by weight of the alloy, with ranges of about 1.0 to about 4.5 percent and about 2.0 to about 3.5 percent being more preferred and especially preferred, respectively.
  • a titanium alloy comprises aluminum, in a range of about 3.5 to about 6.25 percent by weight of the alloy; vanadium, in a range of about 3.0 to about 4.5 percent by weight of the alloy; and one or more elements selected from the group consisting of chromium, iron, and manganese, wherein the one or more elements are present in a range of about 1.0 to about 5.0 percent by weight of the alloy.
  • Titanium is present in a remaining amount, and in an as-cast condition, the alloy preferably has a yield strength of at least about 135,000 psi.
  • the amount of aluminum is more preferably in a range of about 4.5 to about 6.0 percent by weight of the alloy, with a range of about 5.0 to about 6.0 percent being especially preferred.
  • the amount of vanadium is more preferably in a range of about 3.3 to about 4.5 percent by weight of the alloy, with a range of about 3.5 to about 4.5 percent being especially preferred.
  • the amount of chromium in the alloy is preferably in a range of up to about 3.8 percent by weight of the alloy, with ranges of about 1.0 to about 2.5 percent and about 1.2 to about 2.0 percent being more preferred and especially preferred, respectively.
  • the amount of manganese is preferably in a range of up to about 2.0 percent by weight of the alloy, with ranges of up to about 1.5 percent and about 0.75 to about 1.25 percent being more preferred and especially preferred, respectively.
  • the amount of iron is preferably in a range of up to about 1.0 percent by weight of the alloy.
  • the amount of oxygen is preferably in a range of up to about 0.3 percent by weight of the alloy, with ranges of up to about 0.29 percent and up to about 0.27 percent being more preferred and especially preferred, respectively.
  • the alloy preferably has a tensile strength of at least about 155,000 psi and a percent elongation of at least about 5.0 percent.
  • a titanium alloy which comprises chromium, in an range of up to about 3.8 percent by weight of the alloy; iron, in a range of up to about 1.0 percent by weight of the alloy; and manganese, in a range of about 0.75 to about 1.25 percent by weight of the alloy, wherein the combined amount of chromium, iron, and manganese is in a range of about 1.0 to about 5.0 percent by weight of the alloy. Titanium is present in a remaining amount.
  • a titanium alloy which comprises aluminum in a range of about 3.5 to about 6.25 percent by weight of the alloy; vanadium, in a range of about 3.0 to about 4.5 percent by weight of the alloy; chromium, in range of up to about 3.8 percent by weight of the alloy; manganese, in a range of up to about 2.0 percent by weight of the alloy; iron, in a range of up to about 1.0 percent by weight of the alloy; oxygen, in a range of more than about 0.2 to about 0.3 percent by weight of the alloy; and titanium in a remaining amount, wherein the combined amount of chromium, manganese, and iron is in a range of about 2.0 to about 3.5 percent by weight of the alloy.
  • a method of making a titanium alloy comprises combining a titanium material with one or more elements selected from the group consisting of chromium, manganese, and iron, wherein in an as-cast condition, the titanium alloy has a yield strength of at least about 135,000 psi.
  • the combined amount of chromium, manganese, and iron in the alloy is in a range of about 1.0 to about 5.0 percent by weight of the alloy.
  • the combined amount of chromium, manganese, and iron in the alloy is in a range of about 2.0 to about 3.5 percent by weight of the alloy.
  • the alloy comprises oxygen in range of up to about 0.3 percent by weight of the alloy. Even more preferably, the amount of oxygen in the alloy is greater than about 0.2 percent by weight of the alloy. In another preferred embodiment, the amount of manganese in the alloy is in a range of about 0.75 to about 1.25 percent of the alloy. In additional preferred embodiments, the amount of chromium in the alloy is in a range of up to about 3.8 percent by weight of the alloy, with a range of about 1.0 to about 2.5 percent being more preferred. In other preferred embodiments, the amount of iron in the alloy is in a range of up to about 1.0 percent by weight of the alloy.
  • the titanium material is a recycled titanium material.
  • the titanium material is a Ti-6Al-4V material.
  • the titanium material is a commercially pure titanium material.
  • the titanium material is a Ti-3Al-2,5Al material.
  • a method of making a titanium alloy comprises providing a titanium material and combining it with manganese, such that the amount of manganese in the alloy is in a range of about 0.75 to about 1.25 percent by weight of the alloy; chromium, such that the amount of chromium in the alloy is in an range of up to about 3.8 percent by weight of the alloy; and iron, such that the amount of iron in the alloy is in an range of up to about 1.0 percent by weight of the alloy, wherein the combined amount of chromium, manganese, and iron in the alloy is in a range of about 1.0 to about 5.0 percent by weight of the alloy.
  • the present invention is directed to titanium alloys that can be produced from recycled commercial titanium alloys. As indicated in Table 1, in order to maintain desirable strength and ductility, commercial titanium alloys are typically limited to an oxygen content of no more than 0.2 percent by weight of the alloy.
  • Table 1--Conventional Titanium alloys Alloy Al V Mo Sn Zr Cr Fe Mn O Ti-6Al-4V 5.5-6.75 3.5-4.5 0.3 max 0.2 max Ti-6Al-2Sn-2Mo-2Zr-2Cr 5.25-6.25 1.75-2.25 1.75-2.25 1.75-2.25 1.75-2.25 0.13 max Ti-6Al-2Sn-4Zr-6Mo 5.5-6.5 5.5-6.5 1.75-2.25 3.5-4.5 0.15 max 0.15 max Ti-15V-3Cr-3Al-3Sn 2.5-3.5 14.0-1about 6.0 2.5-3.5 2.5-3.5 0.25 max 0.13 max Ti-10V-2Fe-3Al 2.6-3.4 9.0-11.0 1.6-2.2 0.13 max
  • titanium alloys of the present invention can tolerate higher levels of oxygen, and therefore, can be manufactured from increased amounts of recycled materials. Alloys of the present invention preferably have yield strengths of at least about 135,000 psi, tensile strengths of at least about 155,000 psi and percent elongation values of at least about 5 percent.
  • the base titanium material used to form alloys of the present invention is preferably a Ti-3Al-2,5V alloy, a Ti-6Al-4V alloy or commercially pure titanium.
  • commercially pure titanium refers to a titanium material in which the amount of titanium is at least about 98 percent by weight of the material.
  • Ti-6Al-4V alloys and commercially pure titanium are abundantly available in various forms, including electrodes, scrap and plate material and are readily available for recycling.
  • the alloy preferably contains no tin or zirconium. It is especially preferred that the aluminum content not exceed about 6.0 percent aluminum, because in the absence of tin and zirconium, such an alloy will satisfy Rosenberg's formula at oxygen levels of up to 0.3 percent by weight of the alloy.
  • the alloy preferably contains vanadium in a range of about 3.0 to about 4.5 percent by weight of the alloy.
  • Vanadium is a beta-isomorphous stabilizer which is used to increase the strength of the alloy.
  • the ratio of vanadium to aluminum may impact the alloy's phase balance and is preferably maintained at a level which allows for optimization of mechanical properties by precipitation hardening alpha-beta and metastable beta titanium alloys.
  • the alloy also preferably contains at least one beta-eutectoid stabilizing element selected from the group consisting of chromium, iron and manganese.
  • the combined amount of chromium, iron, and manganese is preferably in a range of about 1.0 to about 5.0 percent by weight of the alloy. A range of about 1.0 to about 4.5 percent is more preferred, and a range of about 2.0 to about 3.5 percent is especially preferred.
  • Chromium is preferably present in a range of up to about 3.8 percent by weight of the alloy.
  • a chromium range of about 1.0 to about 2.5 percent is more preferred, and a range of about 1.2 to about 2.0 percent is especially preferred.
  • iron is preferably present in a range of up to about 1.0 percent by weight.
  • Manganese is preferably present in a range of up to about 2.0 percent by weight of the alloy.
  • a manganese range of up to about 1.5 percent is more preferred, and a range of about 0.75 to about 1.25 percent by weight is especially preferred. It has been found that adding Manganese in the foregoing levels improves alloy strength.
  • Chromium, iron, and manganese are effective beta-eutectoid stabilizers. They are used to increase strength and control ductility and the alloy's response to thermal treatment. They are easy to melt and can be added in their elemental forms. As a result, they are relatively inexpensive to process. Although all three elements are beta-eutectoid stabilizers, it has been found that combining them is especially preferred for obtaining alloys with excellent strength and ductility from recycled titanium materials.
  • oxygen is present in a range of up to about 0.3 percent by weight of the alloy. Oxygen ranges of up to 0.29 percent are more preferred, and an oxygen range of up to about 0.27 percent is especially preferred.
  • the ability of alloys of this embodiment to tolerate such levels of oxygen allows them to be manufactured from increased amounts of recycled titanium materials. In addition, the increased levels of oxygen improve alloy ductility.
  • nitrogen levels are not more than about 0.05 percent by weight of the alloy. Nitrogen levels of not more than about 0.04 percent are more preferred, and nitrogen levels of not more than about 0.035 percent are especially preferred.
  • the alloy preferably contains carbon levels of not more than about 0.1 percent by weight of the alloy. Carbon levels of not more than about 0.05 percent are more preferred, and carbon levels of not more than about 0.03 are especially preferred.
  • Hydrogen levels are preferably maintained at not more than about 150 ppm of the alloy weight. Hydrogen levels of not more than about 125 ppm are especially preferred. If present, it is preferred that any elements other than the foregoing are present in amounts of not more than about 0.1 percent by weight each, with their combined amounts not exceeding 0.4 percent by weight.
  • Table 2 Ranges of elements as weight percent of alloy Element Preferred Range More Preferred Range Especially Preferred Range aluminum about 3.5-about 6.25 about 4.5-about 6.0 about 5.0-about 6.0 vanadium about 3.0-about 4.5 about 3.3-about 4.5 about 3.5-about 4.5 chromium up to about 3.8 about 1.0 to about 2.5 about 1.2 to about 2.0 manganese up to about 2.0 up to about 1.5 about 0.75-about 1.25 iron up to about 1.0 up to about 1.0 up to about 1.0 oxygen up to about 0.3 up to about 0.29 up to about 0.27 nitrogen not more than about 0.05 not more than about 0.04 not more than about 0.035 hydrogen not more than about 150 ppm not more than about 125 ppm not more than about 125 ppm carbon not more than about 0.1 not more than about 0.05 not more than about 0.03 others, each not more than about 0.1 not more than about 0.05 not more than about 0.03 others, each not more than about 0.1 not more than about 0.05 not more than about 0.03 others, each not more
  • alloys prepared in accordance with this embodiment will preferably have a tensile strength of at least about 135,000 psi. They will also preferably have a yield strength of at least about 155,000 psi and a percent elongation of at least about 5.0 percent.
  • the term "as-cast” refers to the condition of the alloy following casting but prior to any heat treatment, annealing, forming, or any other thermo-mechanical treatment. It is expected that wrought products which have undergone such processes will have even higher yield strengths, tensile strengths and percent elongation values.
  • a pre-existing commercially pure titanium material which is preferably recycled or scrap titanium
  • Grade 1 commercially pure titanium designated as UNS (Unified Numbering System) R50250
  • R50250 comprises 0.20 weight percent iron and 0.18 weight percent oxygen. Because it is recycled, however, the oxygen level will be higher than that of virgin R50250 material.
  • the R50250 material is melted and combined with an aluminum/vanadium master alloy.
  • the amount of aluminum in the Al/V master alloy is such that the aluminum composition in the titanium alloy is in a range of about 3.5 to about 6.25 percent by weight of the alloy.
  • the amount of vanadium in the Al/V master alloy is preferably such that the vanadium composition of the titanium alloy is in a range of about 3.0 to about 4.5 percent by weight of the alloy.
  • At least one beta-eutectoid stabilizer selected from the group consisting of chromium, iron and manganese is added such that their combined amount in the alloy is in a range of about 1.0 to about 5.0 percent by weight of the alloy.
  • the amount of chromium in the alloy is preferably in a range of up to about 3.8 percent by weight of the alloy, and the amount of manganese in the alloy is preferably in a range of up to about 2.0 percent by weight of the alloy.
  • the amount of iron in the alloy is preferably in a range of up to about 1.0 percent by weight of the alloy.
  • the amount of oxygen in the alloy is preferably in a range of up to about 0.3 percent by weight of the alloy. Oxygen levels are preferably controlled by selecting scrap titanium or sponge with suitably low oxygen content. If present, carbon, hydrogen, nitrogen and additional impurities are preferably kept within the ranges specified in the "preferred range" in Table 1. Levels of these elements in the alloy are also preferably controlled by selecting recycled titanium materials with suitably low levels of them.
  • alloys prepared in accordance with this embodiment contain the amounts of the foregoing elements listed in the "especially preferred range” column of Table 2. Alloys prepared according to the method of this embodiment will preferably have a yield strength of at least about 135,000 psi, a tensile strength of at least about 155,000 psi, and a percent elongation of at least about 5.0 percent.
  • a method of preparing a titanium alloy from a pre-existing Ti-6Al-4V material is provided.
  • the Ti-6Al-4V material is preferably a recycled or scrap material.
  • Commercially produced Ti-6Al-4V contains 5.5 to 6.75 percent by weight aluminum, 3.5 percent to 4.5 percent by weight vanadium, up to 0.3 percent by weight iron, and up to 0.2 percent by weight oxygen. However, due to the use of recycled material, the oxygen content will typically exceed 0.2 percent.
  • the aluminum content in the Ti-6Al-4V will preferably not exceed about 6.0 percent by weight of the alloy.
  • At least one beta-eutectoid stabilizer selected from the group consisting of chromium, manganese, and iron is combined with the Ti-6Al-4V material such that the combined amount of chromium, manganese, and iron is within the preferred range specified in Table 2. It is more preferred to use the range specified in the more preferred column of Table 2 and especially preferred to use the range specified in the especially preferred column of Table 2. Oxygen, carbon, hydrogen, nitrogen, and other impurities are also preferably kept within the ranges specified in Table 2.
  • Alloys prepared according to the method of this embodiment will preferably have a yield strength of at least about 135,000 psi, a tensile strength of at least about 155,000 psi, and a percent elongation of at least about 5.0 percent.
  • a method of making a titanium alloy from a pre-existing Ti-3Al-2,5V alloy is provided.
  • the alloy is preferably recycled.
  • aluminum and vanadium are combined with the recycled Ti-3Al-2,5V material such that the resulting alloy contains aluminum in a range of about 3.5 to about 6.25 percent by weight of the alloy and vanadium in a range of about 3.0 to about 4.5 percent by weight of the alloy.
  • At least one beta-eutectoid stabilizer selected from the group consisting of chromium, manganese, and iron is added such that their combined amounts in the alloy are in a range of about 1.0 to about 5.0 percent by weight of the alloy.
  • the alloy has an oxygen content in a range of up to about 0.3 percent by weight of the alloy.
  • the invention may be better understood by referring to the following examples of titanium alloys prepared in accordance with the present invention. All samples were heat treated by hipping (hot isostatically pressing) at 1650°F and 15,000 ⁇ 500 psi for 2 hours followed by aging in a range of from 900°F to 1100°F for periods of from 4 to 12 hours.
  • bal. balance
  • YS yield strength
  • ksi 1000 lb/(.in) 2
  • UTS Ultimate Tensile Strength
  • % elong. percent elongation
  • % RA percent reduction in area.
  • heat treat refers to the material following heat treating.
  • the alloys in Table 3 all had oxygen levels well above the conventional limit of 0.2 weight percent, yet attained as-cast yield strengths of greater than 135,000 psi, tensile strengths of greater than 155,000 psi, and percent elongation values of greater than 5%. In addition, strength and ductility were further improved with heat treating.
  • Table 4 provides a comparison of the yield strength, tensile strength, and percent elongation of certain of the alloys in Table 3 with several commercial alloys: Table 4 Comparison of Commercial Alloys to Embodiments of the Present Invention Alloy and condition YS ksi UTS ksi % elongation Ti-6Al-4V (cast and heat treated) 120 134 8 Ti-6Al-4V (wrought mill annealed) 137 151 14 Ti-6Al-2Sn-2Mo-2Zr-2Cr (cast and heat treated) 131 155 5 BT-22 (cast and heat treated) 151 151 1.5 Sample 1 (cast and heat treated) 144 160 9.5 Sample 3 (cast and heat treated) 150 165 10 Sample 7 (cast and heat treated) 153 165 8 Sample 8 (cast and heat treated) 149 164 7.5
  • the samples prepared in accordance with the foregoing embodiments of the present invention achieved yield and tensile strengths comparable or superior to those found in virgin Ti-6Al-4V and Ti-6Al-2Sn-2Mo-2Zr-2Cr, while tolerating significantly higher oxygen levels (See Tables 1 and 3).
  • alloys of the present invention can be manufactured from greater amounts of recycled materials than alloys with lower oxygen tolerances.

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EP05090250A 2004-09-02 2005-08-29 Titane à haute résistance mécanique et à prix réduit et méthode pour sa production Withdrawn EP1632581A1 (fr)

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US10/933,638 US20060045789A1 (en) 2004-09-02 2004-09-02 High strength low cost titanium and method for making same

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US (1) US20060045789A1 (fr)
EP (1) EP1632581A1 (fr)
JP (1) JP2006070362A (fr)
CN (1) CN1743482A (fr)
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