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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/02—Inorganic materials
  • A61L27/04—Metals or alloys
  • A61L27/06—Titanium or titanium alloys
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
  • B62D—MOTOR VEHICLES; TRAILERS
  • B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
  • B62D—MOTOR VEHICLES; TRAILERS
  • B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
  • B62D29/008—Superstructures, understructures, or sub-units thereof, characterised by the material thereof predominantly of light alloys, e.g. extruded
• • 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
• • 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 present disclosure relates to high strength and ductile alpha/beta titanium alloys. DESCRIPTION OF THE BACKGROUND OF THE TECHNOLOGY
• Titanium alloys typically exhibit a high strength-to-weight ratio, are corrosion resistant, and are resistant to creep at moderately high temperatures. For these reasons, titanium alloys are used in aerospace, aeronautic, defense, marine, and automotive applications including, for example, landing gear members, engine frames, ballistic armor, hulls, and mechanical fasteners.
• Titanium and titanium alloys are attractive materials for achieving weight reduction in aircraft applications because of their high strength-to-weight ratio.
• Most titanium alloy parts used in aerospace applications are made from Ti-6AI-4V alloy (ASTM Grade 5; UNS R56400; AMS 4928, AMS 491 1 ), which is an alpha/beta titanium alloy.
• Ti-6AI-4V alloy is one of the most common titanium-based
• Ti-6AI-4V alloy is used in a number of applications that benefit from the alloy's advantageous combination of light weight, corrosion resistance, and high strength at low to moderate temperatures.
• Ti-6AI-4V alloy is used to produce aircraft engine components, aircraft structural components, fasteners, high- performance automotive components, components for medical devices, sports equipment, components for marine applications, and components for chemical processing equipment.
• Ti-6AI-4V alloy mill products are generally used in either a mill annealed condition or in a solution treated and aged (STA) condition.
• the "mill- annealed condition” refers to the condition of a titanium alloy after a "mill-annealing" heat treatment in which a workpiece is annealed at an elevated temperature (e.g., 1200- 1500°F / 649-816°C) for about 1 -8 hours and cooled in still air.
• a mill-annealing heat treatment is performed after a workpiece is hot worked in the ⁇ + ⁇ phase field.
• Round bar of Ti-6AI-4V alloy having a diameter of about 2 to 4 inches (5.08 to 10.16 cm) in a mill-annealed condition has a minimum specified ultimate tensile strength of 130 ksi (896 MPa) and a minimum specified yield strength of 120 ksi (827 MPa), at room temperature.
• Mill annealed Ti-6AI-4V plate is often produced to specification AMS 491 1
• mill annealed Ti-6AI-4V bar is often produced to specification AMS 4928.
• an alpha/beta titanium alloy that comprises, in weight percentages, from 2.90 to 5.00 aluminum, from 2.00 to 3.00 vanadium, from 0.40 to 2.00 iron, from 0.20 to 0.30 oxygen, incidental impurities, and titanium.
• the alpha/beta titanium alloys disclosed in the '655 patent are referred to herein as "the '655 alloys".
• a commercially available alloy composition within the '655 alloys nominally includes, in weight percentages based on total alloy weight, 4.00 aluminum, 2.50 vanadium, 1 .50 iron, 0.25 oxygen, incidental impurities, and titanium, and may be referred to herein as Ti-4AI-2.5V-1 .5Fe-0.25O alloy.
• the '655 alloys surprisingly may be cold worked to achieve high strength while retaining a workable level of ductility.
• a workable level of ductility is defined herein a condition wherein an alloy exhibits greater than 6% elongation.
• the strength of the '655 alloys is comparable to that which can be achieved with " ⁇ -6 ⁇ - 4V alloy.
• the tensile stress measured for a Ti-6AI-4V alloy is 145.3 ksi ( ,002 MPa), whereas tested samples of '655 alloys exhibited tensile strengths in a range from 138.7 ksi to 142.7 ksi (956.3 MPa to 983.9 MPa).
• Aerospace Material Specification 6946B (AMS 6946B) specifies a more limited chemistry range than is recited in the claims of the '655 patent.
• the alloys specified in AMS 6946B retain the formability of the broader elemental range limits of the '655 patent, but the mechanical strength property minimums allowed by AMS 6946B are lower than those specified for commercially available Ti-6AI-4V alloy.
• the minimum tensile strength for 0.125 inch (3.175 mm) thick Ti-6AI-4V plate is 134 ksi (923.9 MPa) and the minimum yield strength is 126 ksi (868.7 MPa).
• the minimum tensile strength for 0.125 inch (3.175 mm) thick Ti-4AI-2.5V-1 .5Fe-0.25O plate is 130 ksi (896.3 MPa) and the minimum yield strength is 1 15 ksi (792.9 MPa).
• an alpha/beta titanium alloy comprises, in percent by weight based on total alloy weight: 3.9 to 4.5 aluminum; 2.2 to 3.0 vanadium; 1 .2 to 1 .8 iron; 0.24 to 0.30 oxygen; up to 0.08 carbon; up to 0.05 nitrogen; up to 0.015 hydrogen; titanium; and up to a total of 0.30 of other elements.
• an alpha/beta titanium alloy consists essentially of, in percent by weight: 3.9 to 4.5 aluminum; 2.2 to 3.0 vanadium; 1.2 to 1 .8 iron; 0.24 to 0.30 oxygen; up to 0.08 carbon; up to 0.05 nitrogen; up to 0.015 hydrogen; titanium; and up to a total of 0.30 of other elements.
• FIG. 1 is a plot of ultimate tensile strength and yield strength as a function of aluminum equivalent for bar and wire comprised of non-limiting embodiments of alloys according to the present disclosure
• FIG. 2 is a plot of ultimate tensile strength and yield strength as a function of aluminum equivalent for 0.5 inch (1 .27 cm) diameter wire comprised of non- limiting embodiments of alloys according to the present disclosure.
• FIG. 3 is a plot of tensile strength, yield strength, and percent elongation as a function of aluminum equivalent for 1 inch (2.54 cm) thick plate comprised of non- limiting embodiments of alloys according to the present disclosure.
• Non-limiting embodiments of alpha/beta titanium alloys according to the present disclosure comprise, consist of, or consist essentially of, in percent by weight: 3.9 to 4.5 aluminum; 2.2 to 3.0 vanadium; 1 .2 to 1 .8 iron; 0.24 to 0.30 oxygen; up to 0.08 carbon; up to 0.05 nitrogen; up to 0.015 hydrogen; titanium; and up to a total of 0.30 of other elements.
• other elements that may be present in the alpha/beta titanium alloy include one or more of boron, tin, zirconium, molybdenum, chromium, nickel, silicon, copper, niobium, tantalum, manganese, yttrium, and cobalt, and in certain non-limiting embodiments the weight level of each such other element present is 0.10 or less, but with two exceptions. The exceptions are boron and yttrium, which if present at all as part of the other elements are present in individual concentrations less than 0.005 weight percent.
• Non-limiting embodiments of alloys according to the present disclosure comprise titanium, aluminum, vanadium, iron, and oxygen. If only the alloying elements are stated in compositions discussed below, it is to be understood that the balance includes titanium and incidental impurities.
• Aluminum is an alpha phase strengthener in titanium alloys.
• the compositional range of aluminum in non-limiting embodiments of alpha/beta titanium alloys according to the present disclosure is narrower than the aluminum range disclosed in the '655 patent.
• the minimum level of aluminum according to certain non-limiting embodiments of alloys according to the present disclosure is greater than the minimum level set out in AMS 6946B. It has been observed that these
• compositional features allow the alloy to more consistently exhibit mechanical properties comparable to Ti-6AI-4V alloy.
• the minimum concentration of aluminum in alpha/beta titanium alloys according to the present disclosure is 3.9 percent by weight.
• the maximum concentration of aluminum in alpha/beta titanium alloys according to the present disclosure is 4.5 percent by weight.
• Vanadium is a beta phase stabilizer in titanium alloys.
• the minimum concentration of vanadium in alpha/beta titanium alloys according to the present disclosure is greater than minimum concentration disclosed in the '655 patent and set out in AMS 6946B. It has been observed that this compositional feature provides for an optimal, controlled balance of the volume fractions of the alpha and beta phases.
• the balance of alpha and beta phases provides alloys according to the present disclosure with excellent ductility and formability.
• Vanadium is present in alpha/beta titanium alloys according to the present disclosure in a minimum concentration of 2.2 percent by weight.
• the maximum concentration of vanadium in alpha/beta titanium alloys according to the present disclosure is 3.0 percent by weight.
• Iron is a eutectoid beta stabilizer in titanium alloys.
• the alpha/beta titanium alloys according to the present disclosure include a greater minimum
• the balance provides alloys according to the present disclosure with excellent ductility and formability. Iron is present in the alpha/beta alloys according to the present disclosure in a minimum concentration of 1 .2 percent by weight. The maximum concentration of iron in alpha/beta titanium alloys according to the present disclosure is 1 .8 percent by weight.
• Oxygen is an alpha phase strengthener in titanium alloys.
• the compositional range of oxygen in alpha/beta titanium alloys according to the present disclosure is narrower than the ranges disclosed in the '655 patent and in the .
• compositional features allow alloys according to the present disclosure to consistently exhibit mechanical properties comparable to certain Ti-6AI-4V mechanical properties.
• the minimum concentration of oxygen in alpha/beta titanium alloys according to the present disclosure is 0.24 percent by weight.
• the maximum concentration of oxygen in alpha/beta titanium alloys according to the present disclosure is 0.30 percent by weight.
• certain non-limiting embodiments of alpha/beta titanium alloys according to the present disclosure include other elements in a total concentration not exceeding 0.30 percent by weight.
• these other elements include one or more of boron, tin, zirconium, molybdenum, chromium, nickel, silicon, copper, niobium, tantalum, manganese, yttrium, and cobalt, wherein, with two exceptions, the weight percent of each such element is 0.10 or less.
• the exceptions are boron and yttrium. If present in alloys according to the present disclosure, the weight percentage each of boron and yttrium is less than 0.005.
• Incidental impurities may also be present in alpha/beta titanium alloys according to the present disclosure.
• carbon may be present up to about 0.008 percent by weight.
• Nitrogen may be present up to about 0.05 percent by weight.
• Hydrogen may be present up to about 0.015 percent by weight.
• Other possible incidental impurities will be apparent to those having ordinary skill in the metallurgical arts.
• Table 1 provides a summary of the compositions of (i) certain non- limiting embodiments of alpha/beta titanium alloys according to the present disclosure and (ii) certain alloys disclosed in the '655 patent and specified in AMS 6946B.
• the present inventors unexpectedly discovered that providing the present alloy with minimum levels of aluminum, oxygen, and iron greater than minimum levels taught in the '655 patent provides an alpha/beta titanium alloy that consistently exhibits mechanical properties, such as strength, for example, at least comparable to certain mechanical properties of mill annealed Ti-6AI-4V alloy.
• the inventors also unexpectedly discovered that increasing the minimum levels and narrowing the ranges of iron and vanadium relative to those minimums and ranges disclosed in the '655 patent provides alloys that exhibit an optimal and controlled balance of the volume fractions of the alpha and beta phases in a mill annealed form.
• This optimal balance of phases in the alpha/beta titanium alloys according to the present disclosure provides embodiments of the alloys with improved ductility compared to Ti-6AI-4V alloys, while retaining the ductility of alloys disclosed in the '655 patent and specified in AMS 6946B.
• a person skilled in the art understands that strength and ductility of metallic materials generally exhibit an inverse relationship. In other words, in general, as the strength of a metallic material increases, the ductility of the material decreases. The combination of increased mechanical strength and retained ductility of the alpha/beta titanium alloys according to the present disclosure was not expected because an inverse relationship between strength and ductility generally is observed for mill annealed titanium alloys.
• alpha/beta alloys according to the present disclosure having an aluminum equivalent value (Al eq ) of at least 6.3, or more preferably at least 6.4, have been observed to exhibit strength at least comparable to the strength of Ti-6AI-4V alloys. Such alloys also have been observed to exhibit ductility superior to Ti-6AI-4V alloys, which typically has an aluminum equivalent value of about 7.5.
• an alpha/beta titanium alloy comprises an aluminum equivalent value of at least 6.4, or is in certain embodiments within the range of 6.4 to 7.2, and a yield strength of at least 120 ksi (827.4 MPa), or in certain embodiment is at least 130 ksi (896.3 MPa).
• an alpha/beta titanium alloy comprises an aluminum equivalent value of at least 6.4, or in certain embodiments is in a range of 6.4 to 7.2, and a yield strength in the range of 120 ksi (827.4 MPa) to 155 ksi (1 ,069 MPa).
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value of at least 6.4, or in certain embodiments is in a range of 6.4 to 7.2, and an ultimate tensile strength of at least 130 ksi (896.3 MPa), or in certain embodiments is at least 140 ksi (965.3 MPa).
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value of at least 6.4, or in certain embodiments is in a range of 6.4 to 7.2, and an ultimate tensile strength in the range of 130 ksi (896.3MPa) to 165 ksi (1 ,138 MPa).
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value of at least 6.4, or in certain embodiments is in a range of 6.4 to 7.2, and a ductility of at least 12%, or at least 16% (percent elongation).
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value of at least 6.4, or in certain embodiments is in a range of 6.4 to 7.2, and a ductility in the range of 12% to 30% (percent elongation or "%el").
• 6.3 is the absolute minimum value for Al eq
• the inventors have determined that an Al eq value of at least 6.4 is required to achieve the same strength as exhibited by Ti-6AI-4V alloy. It also recognized that in other non-limiting embodiments of an alpha/beta titanium alloy according to this disclosure, the maximum value for Al eq is 7.5 and that the relationship of strength to ductility according to other non-limiting
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value of at least 6.4, a yield strength of at least 120 ksi (827.4 MPa), an ultimate tensile strength of at least 130 ksi (896.3 MPa), and a ductility of at least 12% (percent elongation).
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value of at least 6.4, a yield strength of at least 130 ksi (896.3 MPa), an ultimate tensile strength of at least 140 ksi (965.3 MPa), and a ductility of at least 12%.
• an alpha/beta titanium alloy according to the present disclosure comprises an aluminum equivalent value in the range of 6.4 to 7.2, a yield strength in the range of 120 ksi (827.4 MPa) to 155 ksi (1 ,069 MPa), an ultimate tensile strength in the range of 130 ksi (896.3MPa) to 165 ksi (1 , 138 MPa), and a ductility in the range of 12% to 30% (percent elongation).
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ultimate tensile strength (UTS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average yield strength (YS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ductility of: %el ⁇ 3.3669 (Al eq ) - 1 .9417.
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ultimate tensile strength (UTS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ultimate tensile strength (UTS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average yield strength (YS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ductility of:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ultimate tensile strength (UTS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ultimate tensile strength (UTS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average yield strength (YS) that satisfies the equation:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ductility of:
• an alpha/beta titanium alloy according to the present disclosure exhibits an average ultimate tensile strength (UTS) that satisfies the equation . ⁇
• non-limiting embodiments of alpha/beta titanium alloys according to the present disclosure exhibit comparable or higher mechanical strength, higher ductility, and improved formability compared with Ti-6AI-4V alloy. Therefore, it is possible to use articles formed of alloys according to the present disclosure as substitutes for Ti-6AI-4V alloy articles in aerospace, aeronautic, marine, automotive, and other applications.
• the high strength and ductility of embodiments of alloys according to the present disclosure permits manufacturing of certain mill and finished article shapes with high tolerances and which cannot presently be
• An aspect of the present disclosure is directed to articles of manufacture comprising and/or made from an alloy according to the present disclosure.
• Certain non- limiting embodiments of the articles of manufacture may be selected from an aircraft engine component, an aircraft structural component, an automotive component, a medical device component, a sports equipment component, a marine applications component, and a chemical processing equipment component.
• Other articles of manufacture that may be comprise and/or be made from embodiments of alpha/beta titanium alloys according to the present disclosure that are known now or hereafter to a person of ordinary skill in the art are within the scope of embodiments disclosed herein.
• Articles of manufacture comprising and/or made from alloys according to the present disclosure by forming and other fabrication techniques known now or at a future time buy those having ordinary skill in the art.
• VAR vacuum arc remelting
• PAM plasma arc melting
• EB electron beam cold hearth melting
• the ingot compositions produced in this Example 1 had aluminum equivalent values ranging from about 6.0 to about 7.1 .
• the ingots were processed using various hot rolling practices into hot rolled bars and wire having diameters between 0.25 inch (0.635 cm) and 3.25 inch (8.255 cm). Hot rolling was conducted at starting temperatures between 1550°F (843.3°C) and 1650°F (898.9°C). This temperature range is below the alpha/beta transus temperature of the alloys of this example, which is about 1750°F to about 1850°F (about 954.4°C to about 1010°C), depending upon the actual chemistry. After hot rolling, the hot rolled bars and wire were annealed at 1275°F (690.6°C) for one hour, followed by air cooling. The diameter, aluminum concentration, iron concentration, oxygen concentration, and calculated Al, of each of the bar and wire samples produced in Example 1 are provided in Table 2.
• FIG. 1 graphically displays room temperature ultimate tensile strengths
• FIG. 1 also includes trend lines through the UTS, YS, and %el data points determined by linear regression, !t is seen that both average strength and the average percent elongation increase with increasing Al eq . This relationship is surprising and unexpected as it is counter to the generally observed relationship that increasing strength is accompanied by decreasing ductility.
• Typical Ti-6AI-4V minimums for UTS and YS are 135 ksi (930.8 MPa) and 125 ksi (861 .8 MPa), respectively.
• the YS for the inventive samples listed in Table 2 ranged from about 125 ksi for a sample with Al eq of about 6.0, up to about 141 ksi for a sample with Al eq of about 7.1 .
• a sample having Al eq of about 6.4 exhibited YS of about 130 ksi (896.3 MPa).
• the UTS for the inventive samples listed in Table 2 ranged from about 135 ksi for a sample with Al eq of about 6.0, up to about 153 ksi for a sample with Ale q of about 7. .
• a sample having Al eq of about 6.4 exhibited YS of about 41 ksi (972 MPa).
• Wire sample nos. 9-1 1 from Example 1 having a diameter of 0.5 inch (1 .27 cm) and aluminum equivalent values of about 6.5, about 6.8 and about 7.15, were tensile tested at room temperature. The results of the tensile tests are displayed graphically in FIG. 2. All of these samples exhibited tensile and yield strengths that are comparable to or higher than strengths exhibited by commercial Ti-6AI-4V alloy. As with FIG. 1 , it is seen from FIG. 2 that increasing Al eq results in increased strength, along with an increase in average percent elongation. As discussed above, this trend is surprising and unexpected because it is counter to the generally observed relationship that increasing strength is accompanied by decreasing ductility. There is less scatter in the data of FIG. 2, which is representative of testing done on samples of the same size, as compared with FIG. 1 , which is representative of testing done on samples of various sizes, because mechanical properties are influenced to some degree by the size of the test sample.
• Hot rolled 1 inch (2.54 cm) thick plate samples were fabricated from ingots manufactured according to steps described in Example 1 .
• the alloys ingots had compositions within the ranges listed in the "Non-Limiting Embodiments according to the Present Disclosure" column in Table 1 above, with aluminum and oxygen concentrations and aluminum equivalent values as listed in Table 3.
• All hot rolling temperatures were below the alpha/beta transus temperatures of the alloys.
• the alloys had Al eq values from about 6.5 to about 7.1.

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