US20110318220A1 - Titanium alloys and method for manufacturing titanium alloy materials - Google Patents

Titanium alloys and method for manufacturing titanium alloy materials Download PDF

Info

Publication number
US20110318220A1
US20110318220A1 US13/179,754 US201113179754A US2011318220A1 US 20110318220 A1 US20110318220 A1 US 20110318220A1 US 201113179754 A US201113179754 A US 201113179754A US 2011318220 A1 US2011318220 A1 US 2011318220A1
Authority
US
United States
Prior art keywords
titanium alloy
plate
phase
cold
less
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.)
Abandoned
Application number
US13/179,754
Inventor
Atsuhiko Kuroda
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.)
Nippon Steel Corp
Original Assignee
Sumitomo Metal Industries Ltd
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 PCT/JP2004/007614 external-priority patent/WO2005118898A1/en
Application filed by Sumitomo Metal Industries Ltd filed Critical Sumitomo Metal Industries Ltd
Priority to US13/179,754 priority Critical patent/US20110318220A1/en
Publication of US20110318220A1 publication Critical patent/US20110318220A1/en
Assigned to NIPPON STEEL & SUMITOMO METAL CORPORATION reassignment NIPPON STEEL & SUMITOMO METAL CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). Assignors: SUMITOMO METAL INDUSTRIES, LTD.
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/183High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • the present invention relates to titanium alloys in use in chemical industry members such as machine structure members and heat exchanger members and consumer goods members such as golf clubs, and a method for manufacturing titanium alloy materials.
  • the present invention particularly relates to titanium alloys with an excellent cold workability and superplasticity characteristics, and a method for manufacturing the titanium alloy materials.
  • Heat exchangers are instruments capable of transmitting thermal energy between different fluids.
  • the heat exchangers are used in, for example, air conditioners, refrigerators, air preheating equipment of burners, radiators in automobiles, parts for the chemical industry, parts for seawater and the like.
  • heat exchangers made of titanium are used in fields requiring excellent corrosion resistance such as in the chemical industry or in salt water.
  • titanium alloy which are light and strong are used as a material for such heat exchangers.
  • a Ti-6Al-4V alloy has been widely used as the heat exchanger material due to its excellent superplasticity characteristics as described in, for example, Non-patent document 1.
  • this alloy has poor cold workability. For example, when thin plates are manufactured by cold rolling the Ti-6Al-4V alloy plate which is wrapped around a coil, there is a drawback that the number of intermediate annealing needs to be increased.
  • Non-patent document 2 shows that a Ti-9V-2Mo-3Al alloy is a titanium alloy which has an excellent cold workability and also an excellent superplasticity workability.
  • this alloy contains Mo as an essential element, which results in a high cost of raw materials. Also, because of a high melting point of Mo, there is a higher incidence of unmelted portions or solidification segregation in melting.
  • Patent document 1 describes a titanium alloy with excellent superplasticity workability containing, by mass %, Al of 5.5 to 6.5%, V of 3.5 to 4.5%, O of 0.2% or less, Fe of 0.15 to 3.0%, Cr of 0.15 to 3.0% and Mo of 0.85 to 3.15%, in which Fe, Cr and Mo are within a range represented by a specific equation and an average grain diameter of an a crystal is 6 ⁇ m or less.
  • This alloy can be said to be superior to the Ti-6Al-4V alloy in the superplasticity workability, but the cold workability is not considered.
  • this alloy has a high content of Al which is 5.5% or more, which results in high distortion resistance in the cold rolling and a high possibility of edge cracks occurring in the edges of a plate if this alloy is subjected to cold rolling at a cross-section reduction rate of 50%.
  • Patent document 2 describes a titanium alloy with excellent workability which contains, by mass %, Al of 3.0 to 5.0%, V of 2.1 to 3.7%, Mo of 0.85 to 3.15%, 0 of 0.15% or less, and further one or more elements of Fe, Cr, Ni and Co, in which the content of these elements is in a range represented by a specific equation. There is also described a manufacturing method of a titanium alloy material in a specific hot rolling condition, and a superplastic processing method of the titanium alloy material in the specific heat treatment condition. However, since this alloy contains Mo, there will be the same problem with the alloy described in Non-patent document 2.
  • An object of the present invention is to provide titanium alloys with the excellent cold workability and the superplasticity characteristics and a method for manufacturing the titanium alloy materials.
  • the present invention was accomplished as a result of repeated research made by the present inventors based on a Ti-3Al-2.5V alloy which is said to have the excellent cold workability.
  • the present invention is characterized by titanium alloys as shown in (1) and (2) below, and a method for manufacturing a titanium alloy materials as shown in (3) below.
  • a cold rolled titanium alloy plate consisting of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0% and the balance being Ti and impurities, wherein a ratio of ⁇ / ⁇ is not less than 0.3 and not more than 0.6; where “a” is an area of a phase in the plate and “ ⁇ ” is an area of ⁇ phase in the plate, and wherein the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%.
  • a cold rolled titanium alloy plate consisting of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0%, further one or more elements selected from Fe of not less than 0.20% and not more than 0.95%, Cr of not less than 0.01% and not more than 0.95%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0%, and the balance being Ti and impurities, wherein a ratio of ⁇ / ⁇ is not less than 0.3 and not more than 0.6; where “ ⁇ ” is an area of a phase in the plate and “ ⁇ ” is an area of ⁇ phase in the plate, wherein the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%, and wherein Veq obtained by the following equation (1) is in a range of 4.0 to 9.5:
  • a method for manufacturing titanium alloy materials is characterized in that the titanium alloy described in the above (1) or (2) is subjected to the cold working at a cross-section reduction rate of 40% or more.
  • a titanium alloy of the present invention has a sufficient cold workability as well as the excellent superplasticity characteristics. Therefore, it is possible to easily produce a coil by the cold rolling, and a material for superplastic molding with a uniform distribution of a plate thickness can be manufactured. Therefore, it is possible to easily produce thin plates made of titanium alloy at a low cost, allowing for the expansion of an application field for the titanium alloy thin plates.
  • Al is an element that plays a very important role in increasing the strength of the titanium alloy. Al is also an effective element for stabilizing the ⁇ phase of the titanium alloy.
  • the superplasticity characteristics are exhibited in a temperature range in which the ratio of the ⁇ phase and the ⁇ phase is approximately 50/50. If the content of Al is low, this temperature range is narrowed, which results in difficulties obtaining stable superplasticity characteristics.
  • the content of Al needs to be 2.0% or more so as to obtain the superplasticity characteristics in a wider temperature range.
  • the cold workability reduces as the content of Al increases. In particular, if a titanium alloy in which the content of Al exceeds 4.0% is subjected to the cold working at a cross-section reduction rate of about 50%, the edge cracks occur in the edges of the plate. Therefore, the content of Al is limited to 2.0 to 4.0%.
  • V is an effective element for stabilizing the ⁇ phase of titanium alloys, and has an effect of increasing the ratio of the ⁇ phase in a temperature range of about 800 to 850° C.
  • the content of V is 4.0% or more
  • the temperature range in which the ratio of the a phase and the 13 phase is approximately 50/50 can be increased.
  • the content of V exceeds 9.0%, oxidation resistance characteristics of the titanium alloy material are lowered. This is because an oxide of V has a sublimation property, so that a scale generated on the surface of the alloy is not dense but has a high permeability of oxygen if the titanium alloy in which the content of V exceeds 9.0% is exposed to a high temperature. Therefore, cracks occur more easily on the surface of the alloy, and a high temperature ductility is decreased. Accordingly, the content of V is limited to 4.0 to 9.0%.
  • Zr is an element that may not be necessarily added. If Zr is added, it contributes to strengthen the titanium alloy due to a solid solution strengthening effect thereof. If a titanium alloy containing Zr is exposed to the high temperature, a strong Zr oxide is formed on the surface thereof to suppress oxidation inside the alloy, so that a generation of the cracks can be prevented in a deformation of the titanium alloy at the high temperature. Therefore, elongation of the titanium alloy is increased at the high temperature, and the superplasticity characteristics are improved. These effects are largely exhibited in 0.5% or more. However, Zr is an expensive element, and the oxidation suppression effect described above is saturated if the content of Zr exceeds 2.0%, leading to a cost increase. Therefore, if Zr is contained, the content is preferably limited to 2.0% or less.
  • Sn is also an element that may not be necessarily added. Although Sn does not contributes to stabilize the a phase or the 13 phase, it is an element that contributes to strengthen the titanium alloy. To obtain such effect of Sn, the content is preferably 0.2% or more. However, if the content of Sn exceeds 3.0%, a low melting point region is formed in a coagulation process, and the cracks occur from this region as a starting point. Therefore, if Sn is contained, the content is preferably 3.0% or less.
  • the titanium alloy of the present invention has the chemical compositions described above, and the balance being Ti and impurities.
  • the alloy may contain one or more elements selected from Fe of 0.20 to 1.0%, Cr of 0.01 to 1.0%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0% as substitute for a part of Ti. This is based on the following reasons.
  • Fe and Cr are elements contained, as impurities, in a titanium sponge which is a titanium raw material, or in an aluminum-vanadium alloy which is an additional material. Therefore, Fe of less than 0.20% and Cr of less than 0.01% are contained in the titanium alloy even if these elements are not positively added. These elements are a ⁇ -phase stabilizing element having the same effect as V, but they are cheaper than V. Accordingly, cost reduction can be realized by positively adding these elements, so that it is desirable to contain Fe of 0.20% or more and Cr of 0.01% or more. However, Fe and Cr are a eutectoid type element forming an intermetallic compound in the titanium alloy. If Fe and Cr of exceeding 1.0% are respectively contained, there will be embrittlement caused by excessive precipitations of the intermetallic compound.
  • Cu and Ni are a ⁇ stabilizing element in the same manner with V, and an effective element to increase the ratio of the ⁇ phase in a temperature range of 800 to 850° C. These elements are cheaper than V, and can be added as an alternative element of V. It is desirable to contain Cu of 0.01% or more and Ni of 0.01% or more in order to obtain this effect. However, the intermetallic compound is formed and the cold workability is lowered if Cu and Ni of exceeding 1.0% are respectively added, because Cu and Ni are the eutectoid type element for titanium.
  • the content is limited to Fe of 0.20 to 1.0%, Cr of 0.01 to 1.0%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0%.
  • the ratio of the ⁇ phase is lowered in a temperature range of 800 to 850° C., and the superplasticity characteristics are hardly exhibited in this temperature range.
  • the Veq exceeds 9.5, the ratio of the a phase is lowed, the superplasticity characteristics deteriorate in a temperature range of 800 to 850° C. and the specific gravity of the alloy itself increases. Accordingly, if Fe and/or Cr are contained to the titanium alloy of the present invention, it is necessary to limit Veq in a range of 4.0 to 9.5.
  • O (oxygen), C (carbon), N (nitrogen) and H (hydrogen) are major impurities contained in the titanium alloy of the present invention.
  • O is an impurity contained in the titanium sponge and a raw material of V, while C and N are impurities contained in the titanium sponge.
  • H is an impurity which is absorbed from an atmosphere in heating or absorbed in an acid washing process. Impurities are preferably as low as possible in a range where O is 0.2% or less, C is 0.01% or less, N is 0.01% or less, and H is 0.01% or less.
  • is an area of ⁇ phase in the plate and “ ⁇ ” is an area of ⁇ phase in the plate. Crystal grain becomes coarse when an alloy is subjected to a deformation at high temperature; thereby the elongation property of the alloy deteriorates. But it is possible to prevent grain coarsening if ⁇ phase exists sufficiently in the alloy. Therefore, the ratio of ⁇ / ⁇ must set 0.6 or less. In contrast, excessive existence of ⁇ phase causes damages to the alloy surface. Because ⁇ phase absorbs gases at high temperature and encourages oxidizing of the alloy surface. A fracture progresses from the damage, and the elongation property of the alloy also deteriorates in this case. Therefore, the ratio of ⁇ / ⁇ must set 0.3 or more.
  • An ingot is prepared by an ordinary melting method such as VAR and is subjected to hot blooming forging or hot rolling so as to form a slab, after which hot rolling is conducted to prepare a hot coil, followed by the cold rolling to a target plate thickness and annealing to provide the titanium alloy material.
  • the cold rolling is a step that largely influences product characteristics, and a titanium alloy material with the excellent superplasticity characteristics at the high temperature can be obtained particularly by the cold working (cold rolling) at the cross-section reduction rate of 40% or more. This is based on the following reasons.
  • a crystal grain diameter in the titanium alloy particularly a grain diameter of a pro-eutectoid a phase is decreased. Then, if the crystal grain diameter in the titanium alloy is decreased, elongation is increased upon superplastic deformation at the high temperature, thereby the titanium alloy material with the excellent superplasticity characteristics at the high temperature is exhibited.
  • the cross-section reduction rate is increased in the cold rolling, the elongation upon superplastic deformation at the high temperature is sharply increased up to the cross-section reduction rate of about 40%, and less change is observed in a region of 40% or more.
  • the cold working is performed at the cross-section reduction rate of 40% or more.
  • the cross-section reduction rate there is no particular upper limit in the cross-section reduction rate, when the cold rolling is performed at a cross-section reduction rate of exceeding 80%, the edge cracks occur in the edges of the plate. Accordingly, it is desirable in the cold working to limit the cross-section reduction rate in 80% or less.
  • the cold working may be performed in a condition that the cross-section reduction rate exceeds 80%.
  • Cross-section reduction rate (%) ⁇ (cross-section area before working ⁇ cross-section area after working)/cross-section area before working ⁇ 100 (a)
  • a button ingot with a width of 50 mm, a thickness of 15 mm and a longitude of 80 mm was prepared.
  • the button ingot was heated at 850° C., it was subjected to hot rolling to prepare a hot-rolled plate with a thickness of 5 mm.
  • this hot-rolled plate was annealed at 750° C. for ten minutes, an oxide scale was removed by shot blast and acid washing, and the surface was further cut to a thickness of 4 mm by machine working so as to prepare a material for the cold rolling.
  • This material was subjected to the cold rolling to prepare a cold-rolled plate with a thickness of 2 mm.
  • an evaluation of cold-rolling property presence of cracks in the edges on the surface of the cold-rolled plate was performed a visual observation.
  • a plate with no cracks in the cold rolling was subjected to a heat treatment in an argon atmosphere at 700° C. for 30 minutes, followed by cold rolling to a thickness of 1.5 mm, and again subjected to the heat treatment in the argon atmosphere at 700° C. for 30 minutes to provide a test specimen.
  • a platy test piece with a thickness of 1.5 mm and a width of 12.5 mm in a parallel part was obtained so that the longitudinal direction of the test piece was in parallel with the rolling direction.
  • the distance between gauge marks of this tensile test piece was set to be 20 mm, and a tensile test was conducted at a test temperature of 800° C. and a tensile speed of 9 mm/min., so as to measure elongation at break.
  • Table 1 shows chemical compositions of the cold-rolled plate, evaluations of cold rolling property and elongation at break.
  • a plate with no cracks is indicated as [ ⁇ ] and a plate with cracks is indicated as [x] when a cold-rolled plate with a thickness of 2 mm was prepared.
  • a plate of exceeding 200% in elongation at break is indicated as [ ⁇ ]
  • a plate of 200% or less in elongation at break is indicated as [x] when a tensile test was conducted at 800° C.
  • alloys satisfying the chemical compositions specified in the present invention are capable of being cold rolled to obtain an excellent superplastic elongation.
  • a material for cold rolling containing Al of 3.0%, V of 5.0% and the balance being Ti and impurities was prepared with a thickness of 4 mm in the same manner with Example 1.
  • the material for cold rolling was subjected to a cold rolling in different cross-section reduction rates to prepare cold-rolled plates with thicknesses of 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm and 1.5 mm. After these cold-rolled plates were subjected to the heat treatment in the argon atmosphere at 700° C. for 30 minutes, a platy test piece with a thickness of 1.0 mm and a width of 12.5 mm in a parallel part was obtained so that the longitudinal direction of the test piece was in parallel with the rolling direction. The distance between the gauge marks in this tensile test piece was set to 20 mm, and the tensile test was conducted at the test temperature of 800° C. and a tensile speed of 9 mm/min., so as to measure the elongation at break.
  • the cold-rolled plate with a thickness of 2.0 mm was subjected to the heat treatment in the argon atmosphere at 700° C. for 30 minutes, followed by the cold rolling to a thickness of 1.5 mm or 1.0 mm, and again subjected to the hot treatment in the argon atmosphere at 700° C. for 30 minutes so as to prepare a test specimen. From this test specimen, the platy test piece with the thickness of 1.0 mm and the width of 12.5 mm in the parallel part was obtained, and the same tensile test as described above was conducted to measure the elongation at break. Table 2 shows the cross-section reduction rate and the elongations at break.
  • the elongation at break exceeds 200% and the excellent superplasticity characteristics have been obtained.
  • the elongation at break is increased in accordance with the increase of the cross-section reduction rate, and there is almost no change in the elongation at break under a condition that the cross-section reduction rate is 40% or more.
  • the results of No. 39 and No. 40 it is understood that an excellent elongation at break is observed if the cross-section reduction rate before the intermediate annealing is 40% or more, even though the cold rolling rate after the intermediate annealing is low.
  • the titanium alloy of the present invention has the sufficient cold workability as well as the excellent superplasticity characteristics. Accordingly, it is possible to easily prepare the coil by the cold rolling, and also to manufacture a material for a superplasticity molding having a uniform distribution in a plate thickness. Therefore, the titanium alloy thin plates can be easily manufactured at a low cost, allowing the expansion of the application field for the titanium alloy thin plates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metal Rolling (AREA)

Abstract

A cold rolled titanium alloy plate with a sufficient cold workability and excellent superplasticity characteristics is provided. The cold rolled titanium alloy plate consists of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0% and the balance being Ti and impurities, a ratio of α/β is not less than 0.3 and not more than 0.6; where “α” is an area of a phase in the plate and “β” is an area of β phase in the plate, and the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%.

Description

    TECHNICAL FIELD OF THE INVENTION
  • The present invention relates to titanium alloys in use in chemical industry members such as machine structure members and heat exchanger members and consumer goods members such as golf clubs, and a method for manufacturing titanium alloy materials. The present invention particularly relates to titanium alloys with an excellent cold workability and superplasticity characteristics, and a method for manufacturing the titanium alloy materials.
  • BACKGROUND ART
  • Heat exchangers are instruments capable of transmitting thermal energy between different fluids. The heat exchangers are used in, for example, air conditioners, refrigerators, air preheating equipment of burners, radiators in automobiles, parts for the chemical industry, parts for seawater and the like. In particular, heat exchangers made of titanium are used in fields requiring excellent corrosion resistance such as in the chemical industry or in salt water. In order to reduce the size of heat exchangers, it is necessary to increase the strength of the parts being used and that is why titanium alloy which are light and strong are used as a material for such heat exchangers.
  • A Ti-6Al-4V alloy has been widely used as the heat exchanger material due to its excellent superplasticity characteristics as described in, for example, Non-patent document 1. However, this alloy has poor cold workability. For example, when thin plates are manufactured by cold rolling the Ti-6Al-4V alloy plate which is wrapped around a coil, there is a drawback that the number of intermediate annealing needs to be increased.
  • Non-patent document 2 shows that a Ti-9V-2Mo-3Al alloy is a titanium alloy which has an excellent cold workability and also an excellent superplasticity workability. However, this alloy contains Mo as an essential element, which results in a high cost of raw materials. Also, because of a high melting point of Mo, there is a higher incidence of unmelted portions or solidification segregation in melting.
  • Patent document 1 describes a titanium alloy with excellent superplasticity workability containing, by mass %, Al of 5.5 to 6.5%, V of 3.5 to 4.5%, O of 0.2% or less, Fe of 0.15 to 3.0%, Cr of 0.15 to 3.0% and Mo of 0.85 to 3.15%, in which Fe, Cr and Mo are within a range represented by a specific equation and an average grain diameter of an a crystal is 6 μm or less. This alloy can be said to be superior to the Ti-6Al-4V alloy in the superplasticity workability, but the cold workability is not considered. Namely, this alloy has a high content of Al which is 5.5% or more, which results in high distortion resistance in the cold rolling and a high possibility of edge cracks occurring in the edges of a plate if this alloy is subjected to cold rolling at a cross-section reduction rate of 50%.
  • Patent document 2 describes a titanium alloy with excellent workability which contains, by mass %, Al of 3.0 to 5.0%, V of 2.1 to 3.7%, Mo of 0.85 to 3.15%, 0 of 0.15% or less, and further one or more elements of Fe, Cr, Ni and Co, in which the content of these elements is in a range represented by a specific equation. There is also described a manufacturing method of a titanium alloy material in a specific hot rolling condition, and a superplastic processing method of the titanium alloy material in the specific heat treatment condition. However, since this alloy contains Mo, there will be the same problem with the alloy described in Non-patent document 2.
    • Patent document 1: Japanese Examined Patent Publication No. 1996-195026
    • Patent document 2: Japanese Examined Patent Publication No. 1996-23053B
    • Non-patent document 1: N. Furushiro and three other persons, Titanium' 80, 1980, pp. 993-998, published by Metallurgical Society of AIME
    • Non-patent document 2: T. Oka and 2 other persons, “What is being studied about titanium materials in Japan?”, pp. 58-60, edited on Dec. 1, 1989 by The Iron and Steel Institute of Japan
    DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
  • An object of the present invention is to provide titanium alloys with the excellent cold workability and the superplasticity characteristics and a method for manufacturing the titanium alloy materials.
  • Means Adapted to Solve the Problem
  • The present invention was accomplished as a result of repeated research made by the present inventors based on a Ti-3Al-2.5V alloy which is said to have the excellent cold workability.
  • The present invention is characterized by titanium alloys as shown in (1) and (2) below, and a method for manufacturing a titanium alloy materials as shown in (3) below.
  • (1) A cold rolled titanium alloy plate consisting of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0% and the balance being Ti and impurities, wherein a ratio of α/β is not less than 0.3 and not more than 0.6; where “a” is an area of a phase in the plate and “β” is an area of β phase in the plate, and wherein the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%.
  • (2) A cold rolled titanium alloy plate consisting of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0%, further one or more elements selected from Fe of not less than 0.20% and not more than 0.95%, Cr of not less than 0.01% and not more than 0.95%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0%, and the balance being Ti and impurities, wherein a ratio of α/β is not less than 0.3 and not more than 0.6; where “α” is an area of a phase in the plate and “β” is an area of β phase in the plate, wherein the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%, and wherein Veq obtained by the following equation (1) is in a range of 4.0 to 9.5:

  • Veq=V+1.9Cr+3.75Fe  (1)
  • where a symbol of element on a right side of the equation (1) means a content of the element by mass %.
  • (3) A method for manufacturing titanium alloy materials is characterized in that the titanium alloy described in the above (1) or (2) is subjected to the cold working at a cross-section reduction rate of 40% or more.
  • Effect of the Invention
  • A titanium alloy of the present invention has a sufficient cold workability as well as the excellent superplasticity characteristics. Therefore, it is possible to easily produce a coil by the cold rolling, and a material for superplastic molding with a uniform distribution of a plate thickness can be manufactured. Therefore, it is possible to easily produce thin plates made of titanium alloy at a low cost, allowing for the expansion of an application field for the titanium alloy thin plates.
  • BEST MODE FOR CARRYING OUT THE INVENTION
  • First, chemical compositions in the titanium alloy of the present invention and the reasons for the limitation will be described. “%” in each component means “mass %” in the following explanation.
  • Al: 2.0 to 4.0%
  • Al is an element that plays a very important role in increasing the strength of the titanium alloy. Al is also an effective element for stabilizing the α phase of the titanium alloy. The superplasticity characteristics are exhibited in a temperature range in which the ratio of the α phase and the β phase is approximately 50/50. If the content of Al is low, this temperature range is narrowed, which results in difficulties obtaining stable superplasticity characteristics. The content of Al needs to be 2.0% or more so as to obtain the superplasticity characteristics in a wider temperature range. However, the cold workability reduces as the content of Al increases. In particular, if a titanium alloy in which the content of Al exceeds 4.0% is subjected to the cold working at a cross-section reduction rate of about 50%, the edge cracks occur in the edges of the plate. Therefore, the content of Al is limited to 2.0 to 4.0%.
  • V: 4.0 to 9.0%
  • V is an effective element for stabilizing the β phase of titanium alloys, and has an effect of increasing the ratio of the β phase in a temperature range of about 800 to 850° C. In particular, if the content of V is 4.0% or more, the temperature range in which the ratio of the a phase and the 13 phase is approximately 50/50 can be increased. However, if the content of V exceeds 9.0%, oxidation resistance characteristics of the titanium alloy material are lowered. This is because an oxide of V has a sublimation property, so that a scale generated on the surface of the alloy is not dense but has a high permeability of oxygen if the titanium alloy in which the content of V exceeds 9.0% is exposed to a high temperature. Therefore, cracks occur more easily on the surface of the alloy, and a high temperature ductility is decreased. Accordingly, the content of V is limited to 4.0 to 9.0%.
  • Zr: 0 to 2.0%
  • Zr is an element that may not be necessarily added. If Zr is added, it contributes to strengthen the titanium alloy due to a solid solution strengthening effect thereof. If a titanium alloy containing Zr is exposed to the high temperature, a strong Zr oxide is formed on the surface thereof to suppress oxidation inside the alloy, so that a generation of the cracks can be prevented in a deformation of the titanium alloy at the high temperature. Therefore, elongation of the titanium alloy is increased at the high temperature, and the superplasticity characteristics are improved. These effects are largely exhibited in 0.5% or more. However, Zr is an expensive element, and the oxidation suppression effect described above is saturated if the content of Zr exceeds 2.0%, leading to a cost increase. Therefore, if Zr is contained, the content is preferably limited to 2.0% or less.
  • Sn: 0 to 3.0%
  • Sn is also an element that may not be necessarily added. Although Sn does not contributes to stabilize the a phase or the 13 phase, it is an element that contributes to strengthen the titanium alloy. To obtain such effect of Sn, the content is preferably 0.2% or more. However, if the content of Sn exceeds 3.0%, a low melting point region is formed in a coagulation process, and the cracks occur from this region as a starting point. Therefore, if Sn is contained, the content is preferably 3.0% or less.
  • The titanium alloy of the present invention has the chemical compositions described above, and the balance being Ti and impurities. The alloy may contain one or more elements selected from Fe of 0.20 to 1.0%, Cr of 0.01 to 1.0%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0% as substitute for a part of Ti. This is based on the following reasons.
  • Fe and Cr are elements contained, as impurities, in a titanium sponge which is a titanium raw material, or in an aluminum-vanadium alloy which is an additional material. Therefore, Fe of less than 0.20% and Cr of less than 0.01% are contained in the titanium alloy even if these elements are not positively added. These elements are a β-phase stabilizing element having the same effect as V, but they are cheaper than V. Accordingly, cost reduction can be realized by positively adding these elements, so that it is desirable to contain Fe of 0.20% or more and Cr of 0.01% or more. However, Fe and Cr are a eutectoid type element forming an intermetallic compound in the titanium alloy. If Fe and Cr of exceeding 1.0% are respectively contained, there will be embrittlement caused by excessive precipitations of the intermetallic compound.
  • Cu and Ni are a β stabilizing element in the same manner with V, and an effective element to increase the ratio of the β phase in a temperature range of 800 to 850° C. These elements are cheaper than V, and can be added as an alternative element of V. It is desirable to contain Cu of 0.01% or more and Ni of 0.01% or more in order to obtain this effect. However, the intermetallic compound is formed and the cold workability is lowered if Cu and Ni of exceeding 1.0% are respectively added, because Cu and Ni are the eutectoid type element for titanium.
  • Accordingly, if one or more elements of these are contained in the titanium alloy of the present invention, the content is limited to Fe of 0.20 to 1.0%, Cr of 0.01 to 1.0%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0%.

  • Veq(=V+1.9Cr+3.75Fe):4.0 to 9.5
  • As an index to exhibit the stability of the 13 phase in the titanium alloy, there is a Veq represented by the following equation (1):

  • Veq=V+1.9Cr+3.75Fe  (1)
  • where a symbol on the right side of the equation (1) means a content of each element.
  • If the Veq is less than 4.0, the ratio of the β phase is lowered in a temperature range of 800 to 850° C., and the superplasticity characteristics are hardly exhibited in this temperature range. However, if the Veq exceeds 9.5, the ratio of the a phase is lowed, the superplasticity characteristics deteriorate in a temperature range of 800 to 850° C. and the specific gravity of the alloy itself increases. Accordingly, if Fe and/or Cr are contained to the titanium alloy of the present invention, it is necessary to limit Veq in a range of 4.0 to 9.5.
  • O (oxygen), C (carbon), N (nitrogen) and H (hydrogen) are major impurities contained in the titanium alloy of the present invention. O is an impurity contained in the titanium sponge and a raw material of V, while C and N are impurities contained in the titanium sponge. Also, H is an impurity which is absorbed from an atmosphere in heating or absorbed in an acid washing process. Impurities are preferably as low as possible in a range where O is 0.2% or less, C is 0.01% or less, N is 0.01% or less, and H is 0.01% or less.
  • A ratio of α/β: not less than 0.3 and not more than 0.6
  • “α” is an area of α phase in the plate and “β” is an area of β phase in the plate. Crystal grain becomes coarse when an alloy is subjected to a deformation at high temperature; thereby the elongation property of the alloy deteriorates. But it is possible to prevent grain coarsening if β phase exists sufficiently in the alloy. Therefore, the ratio of α/β must set 0.6 or less. In contrast, excessive existence of β phase causes damages to the alloy surface. Because β phase absorbs gases at high temperature and encourages oxidizing of the alloy surface. A fracture progresses from the damage, and the elongation property of the alloy also deteriorates in this case. Therefore, the ratio of α/β must set 0.3 or more.
  • Next, a method for manufacturing titanium alloy materials of the present invention will be explained referring to a case of manufacturing a thin plate. An ingot is prepared by an ordinary melting method such as VAR and is subjected to hot blooming forging or hot rolling so as to form a slab, after which hot rolling is conducted to prepare a hot coil, followed by the cold rolling to a target plate thickness and annealing to provide the titanium alloy material. The cold rolling is a step that largely influences product characteristics, and a titanium alloy material with the excellent superplasticity characteristics at the high temperature can be obtained particularly by the cold working (cold rolling) at the cross-section reduction rate of 40% or more. This is based on the following reasons.
  • When the cross-section reduction rate is increased in the cold rolling, a crystal grain diameter in the titanium alloy, particularly a grain diameter of a pro-eutectoid a phase is decreased. Then, if the crystal grain diameter in the titanium alloy is decreased, elongation is increased upon superplastic deformation at the high temperature, thereby the titanium alloy material with the excellent superplasticity characteristics at the high temperature is exhibited. As described above, when the cross-section reduction rate is increased in the cold rolling, the elongation upon superplastic deformation at the high temperature is sharply increased up to the cross-section reduction rate of about 40%, and less change is observed in a region of 40% or more.
  • Therefore, in the method for manufacturing the titanium alloy materials of the preset invention, the cold working is performed at the cross-section reduction rate of 40% or more. Although there is no particular upper limit in the cross-section reduction rate, when the cold rolling is performed at a cross-section reduction rate of exceeding 80%, the edge cracks occur in the edges of the plate. Accordingly, it is desirable in the cold working to limit the cross-section reduction rate in 80% or less. However, if the intermediate annealing is conducted for the purpose of recovering the ductility of materials, the cold working may be performed in a condition that the cross-section reduction rate exceeds 80%.
  • The cross-section reduction rate is obtained by the following equation (a).

  • Cross-section reduction rate (%)={(cross-section area before working−cross-section area after working)/cross-section area before working}×100  (a)
  • Embodiment 1
  • Using an arc melting furnace of plasma, a button ingot with a width of 50 mm, a thickness of 15 mm and a longitude of 80 mm was prepared. After the button ingot was heated at 850° C., it was subjected to hot rolling to prepare a hot-rolled plate with a thickness of 5 mm. After this hot-rolled plate was annealed at 750° C. for ten minutes, an oxide scale was removed by shot blast and acid washing, and the surface was further cut to a thickness of 4 mm by machine working so as to prepare a material for the cold rolling. This material was subjected to the cold rolling to prepare a cold-rolled plate with a thickness of 2 mm. At this time, as an evaluation of cold-rolling property, presence of cracks in the edges on the surface of the cold-rolled plate was performed a visual observation.
  • A plate with no cracks in the cold rolling was subjected to a heat treatment in an argon atmosphere at 700° C. for 30 minutes, followed by cold rolling to a thickness of 1.5 mm, and again subjected to the heat treatment in the argon atmosphere at 700° C. for 30 minutes to provide a test specimen. From this test specimen, a platy test piece with a thickness of 1.5 mm and a width of 12.5 mm in a parallel part was obtained so that the longitudinal direction of the test piece was in parallel with the rolling direction. The distance between gauge marks of this tensile test piece was set to be 20 mm, and a tensile test was conducted at a test temperature of 800° C. and a tensile speed of 9 mm/min., so as to measure elongation at break.
  • Table 1 shows chemical compositions of the cold-rolled plate, evaluations of cold rolling property and elongation at break.
  • TABLE 1
    Cold Elongation
    Chemical composition rolling at break
    (mass %, the balance being Ti and impurities) property Ratio of Elongation
    No. Al V Zr Sn Fe Cr Cu Ni Veq evaluation α/β (%) Evaluation Remarks
    1 1.58* 5.08 0.11 5.5 0.61* 180 x Comparative example
    2 2.05 4.96 0.12 5.4 0.48 320 Example of
    the present invention
    3 3.00 4.98 0.16 5.6 0.40 440 Example of
    the present invention
    4 3.96 4.90 0.15 5.5 0.31 470 Example of
    the present invention
    5 4.20* 4.94 0.24 5.8 x Comparative example
    6 3.01 3.50* 0.15 4.1 0.25* 160 x Comparative example
    7 3.05 4.12 0.17 4.8 0.39 295 Example of
    the present invention
    8 3.00 7.02 0.17 7.7 0.48 400 Example of
    the present invention
    9 2.98 8.88 0.15 9.4 0.53 320 Example of
    the present invention
    10 3.01 5.05 0.50 6.9 0.48 355 Example of
    the present invention
    11 3.03 4.98 0.98 8.7 0.55 275 Example of
    the present invention
    12 3.02 5.11 1.20* 9.6* 0.65* 150 x Comparative example
    13 2.99 4.97 0.12 0.49 6.3 0.45 335 Example of
    the present invention
    14 2.97 4.96 0.11 0.95 7.2 0.50 300 Example of
    the present invention
    15 2.99 5.00 0.11 2.21* 9.6* x Comparative example
    16 3.02 5.01 0.50 1.15* 9.1 x Comparative example
    17 3.04 4.90 0.88 1.01* 10.2* 0.65* 125 x Comparative example
    18 3.03 4.98 0.51 0.13 5.5 0.41 310 Example of
    the present invention
    19 3.00 5.03 0.95 0.14 5.6 0.45 335 Example of
    the present invention
    20 3.05 4.98 1.88 0.12 5.4 0.43 340 Example of
    the present invention
    21 3.00 5.01 0.98 8.7 0.55 275 Example of
    the present invention
    22 3.03 5.05 0.14 0.05 5.6 0.43 420 Example of
    the present invention
    23 3.01 5.02 0.15 0.98 5.6 0.42 435 Example of
    the present invention
    24 3.02 4.98 0.16 1.13* 5.6 x Comparative example
    25 2.99 5.01 0.18 0.08 5.7 0.44 410 Example of
    the present invention
    26 3.00 5.03 0.17 0.75 5.7 0.41 405 Example of
    the present invention
    27 2.99 5.05 0.15 1.28* 5.6 x Comparative example
    28 3.02 4.97 0.15 0.16 5.6 0.42 425 Example of
    the present invention
    29 3.03 5.02 0.88 0.17 5.7 0.42 430 Example of
    the present invention
    30 3.00 5.04 1.55 0.17 5.7 0.41 440 Example of
    the present invention
    31 2.99 4.99 2.85 0.17 5.6 0.42 400 Example of
    the present invention
    32 3.02 5.01 3.10* 0.17 5.6 x Comparative example
    33 3.01 6.51 0.90 9.9* 0.67* 170 x Comparative example
    34 3.21 7.02 0.51 0.45 9.8* 0.70* 165 x Comparative example
    35 3.11 7.55 0.16 0.95 10.0* 0.82* 135 x Comparative example
    (1) [*] means outside of the range specified in the present invention
    (2) [—] in the chemical composition means an impurity level, in which Fe is less than 0.20% and other than Fe is less than 0.01%.
    (3) Examples with [x] in the cold rolling property had no tensile test conducted.
  • In the cold rolling property evaluation, a plate with no cracks is indicated as [∘] and a plate with cracks is indicated as [x] when a cold-rolled plate with a thickness of 2 mm was prepared. Also, in the elongation at break, a plate of exceeding 200% in elongation at break is indicated as [∘], and a plate of 200% or less in elongation at break is indicated as [x] when a tensile test was conducted at 800° C.
  • As shown in Table 1, alloys satisfying the chemical compositions specified in the present invention are capable of being cold rolled to obtain an excellent superplastic elongation.
  • Embodiment 2
  • A material for cold rolling containing Al of 3.0%, V of 5.0% and the balance being Ti and impurities was prepared with a thickness of 4 mm in the same manner with Example 1.
  • The material for cold rolling was subjected to a cold rolling in different cross-section reduction rates to prepare cold-rolled plates with thicknesses of 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm and 1.5 mm. After these cold-rolled plates were subjected to the heat treatment in the argon atmosphere at 700° C. for 30 minutes, a platy test piece with a thickness of 1.0 mm and a width of 12.5 mm in a parallel part was obtained so that the longitudinal direction of the test piece was in parallel with the rolling direction. The distance between the gauge marks in this tensile test piece was set to 20 mm, and the tensile test was conducted at the test temperature of 800° C. and a tensile speed of 9 mm/min., so as to measure the elongation at break.
  • Further, in order to examine the influence of a cross-section reduction rate to the superplasticity characteristics in the cold rolling after the intermediate annealing, the cold-rolled plate with a thickness of 2.0 mm was subjected to the heat treatment in the argon atmosphere at 700° C. for 30 minutes, followed by the cold rolling to a thickness of 1.5 mm or 1.0 mm, and again subjected to the hot treatment in the argon atmosphere at 700° C. for 30 minutes so as to prepare a test specimen. From this test specimen, the platy test piece with the thickness of 1.0 mm and the width of 12.5 mm in the parallel part was obtained, and the same tensile test as described above was conducted to measure the elongation at break. Table 2 shows the cross-section reduction rate and the elongations at break.
  • TABLE 2
    Before intermediate After intermediate
    annealing annealing
    Plate Cross- Plate Cross-
    thickness section thickness section Elongation
    after cold reduction after cold reduction rate
    rolling rate rolling rate at break
    No. (mm) (%) (mm) (%) (%)
    36 3.50 12.5 210
    37 3.02 24.5 240
    38 2.47 38.3 360
    39 1.99 50.3 470
    40 1.51 62.3 485
    41 2.02 49.5 1.52 24.8 440
    42 2.03 49.3 1.05 48.3 425
  • As shown in Table 2, since all the examples are within a range of the chemical compositions specified in the present invention, the elongation at break exceeds 200% and the excellent superplasticity characteristics have been obtained. In particular, the elongation at break is increased in accordance with the increase of the cross-section reduction rate, and there is almost no change in the elongation at break under a condition that the cross-section reduction rate is 40% or more. Also, from the results of No. 39 and No. 40, it is understood that an excellent elongation at break is observed if the cross-section reduction rate before the intermediate annealing is 40% or more, even though the cold rolling rate after the intermediate annealing is low.
  • Although only some exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciated that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention.
  • INDUSTRIAL APPLICABILITY
  • The titanium alloy of the present invention has the sufficient cold workability as well as the excellent superplasticity characteristics. Accordingly, it is possible to easily prepare the coil by the cold rolling, and also to manufacture a material for a superplasticity molding having a uniform distribution in a plate thickness. Therefore, the titanium alloy thin plates can be easily manufactured at a low cost, allowing the expansion of the application field for the titanium alloy thin plates.

Claims (3)

1. A cold rolled titanium alloy plate consisting of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0% and the balance being Ti and impurities,
wherein a ratio of α/β is not less than 0.3 and not more than 0.6; where “α” is an area of a phase in the plate and “β” is an area of β phase in the plate, and
wherein the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%.
2. A cold rolled titanium alloy plate consisting of, by mass %, Al of 2.0 to 4.0% and V of 4.0 to 9.0%, one element selected from Zr of not more than 2.0% and Sn of not more than 3.0%, further one or more elements selected from Fe of not less than 0.20% and not more than 0.95%, Cr of not less than 0.01% and not more than 0.95%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0%, and the balance being Ti and impurities,
wherein a ratio of α/β is not less than 0.3 and not more than 0.6; where “α” is an area of a phase in the plate and “β” is an area of 13 phase in the plate,
wherein the plate has an elongation at break in a tensile test conducted at 800° C. exceeds 200%, and
wherein Veq obtained by the following equation (1) is in a range of 4.0 to 9.5:

Veq=V+1.9Cr+3.75Fe  (1)
where a symbol of element on a right side of the equation (1) means a content of the element by mass %.
3. A method for manufacturing the titanium alloy material consisting of, by mass %, Al of 2.0 to 4.0%, V of 4.0 to 9.0%, Zr of 0 to 2.0%, Sn of 0 to 3.0%, further one or more elements selected from Fe of 0.20 to 1.0%, Cr of 0.01 to 1.0%, Cu of 0.01 to 1.0% and Ni of 0.01 to 1.0%, and the balance being Ti and impurities, wherein the titanium alloy with the Veq obtained by the following equation (1) being in the range of 4.0 to 9.5 is subjected to the cold working at the cross-section reduction rate of 40% or more:

Veq=V+1.9Cr+3.75Fe  (1)
where a symbol of element on the right side of the equation (1) means a content of the element by mass %.
US13/179,754 2004-06-02 2011-07-11 Titanium alloys and method for manufacturing titanium alloy materials Abandoned US20110318220A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/179,754 US20110318220A1 (en) 2004-06-02 2011-07-11 Titanium alloys and method for manufacturing titanium alloy materials

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/JP2004/007614 WO2005118898A1 (en) 2004-06-02 2004-06-02 Titanium alloy and method of manufacturing titanium alloy material
US11/604,840 US20070131314A1 (en) 2004-06-02 2006-11-28 Titanium alloys and method for manufacturing titanium alloy materials
US13/179,754 US20110318220A1 (en) 2004-06-02 2011-07-11 Titanium alloys and method for manufacturing titanium alloy materials

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11/604,840 Continuation-In-Part US20070131314A1 (en) 2004-06-02 2006-11-28 Titanium alloys and method for manufacturing titanium alloy materials

Publications (1)

Publication Number Publication Date
US20110318220A1 true US20110318220A1 (en) 2011-12-29

Family

ID=45352750

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/179,754 Abandoned US20110318220A1 (en) 2004-06-02 2011-07-11 Titanium alloys and method for manufacturing titanium alloy materials

Country Status (1)

Country Link
US (1) US20110318220A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779818A (en) * 2014-12-25 2016-07-20 北京有色金属研究总院 High-strength high-toughness beta type titanium alloy and preparation method thereof
CN117144275A (en) * 2023-11-01 2023-12-01 中铝科学技术研究院有限公司 Pressure-resistant titanium alloy, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3986868A (en) * 1969-09-02 1976-10-19 Lockheed Missiles Space Titanium base alloy
JP2010255026A (en) * 2009-04-22 2010-11-11 Sumitomo Metal Ind Ltd METHOD FOR MANUFACTURING THIN SHEET OF alpha+beta TYPE TITANIUM ALLOY AND METHOD FOR MANUFACTURING THIN SHEET COIL OF alpha+beta TYPE TITANIUM ALLOY

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3986868A (en) * 1969-09-02 1976-10-19 Lockheed Missiles Space Titanium base alloy
JP2010255026A (en) * 2009-04-22 2010-11-11 Sumitomo Metal Ind Ltd METHOD FOR MANUFACTURING THIN SHEET OF alpha+beta TYPE TITANIUM ALLOY AND METHOD FOR MANUFACTURING THIN SHEET COIL OF alpha+beta TYPE TITANIUM ALLOY

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779818A (en) * 2014-12-25 2016-07-20 北京有色金属研究总院 High-strength high-toughness beta type titanium alloy and preparation method thereof
CN117144275A (en) * 2023-11-01 2023-12-01 中铝科学技术研究院有限公司 Pressure-resistant titanium alloy, preparation method and application thereof

Similar Documents

Publication Publication Date Title
US20070131314A1 (en) Titanium alloys and method for manufacturing titanium alloy materials
US9797029B2 (en) Heat resistant titanium alloy sheet excellent in cold workability and a method of production of the same
WO2021100687A1 (en) Ferritic stainless steel sheet
JP2004323937A (en) Austenitic stainless steel
JP5907320B1 (en) Material for stainless cold-rolled steel sheet and manufacturing method thereof
WO2022123812A1 (en) Method for manufacturing austenitic stainless steel strip
JP6093210B2 (en) Heat-resistant ferritic stainless steel sheet with excellent low-temperature toughness and method for producing the same
JP2536673B2 (en) Heat treatment method for titanium alloy material for cold working
KR101536402B1 (en) Titanium alloy product having high strength and excellent cold rolling property
US20180305797A1 (en) Ferritic stainless steel
EP3587610A1 (en) Hot-rolled and annealed ferritic stainless steel sheet, and method for manufacturing same
JP7341016B2 (en) Ferritic stainless cold rolled steel sheet
US20110318220A1 (en) Titanium alloys and method for manufacturing titanium alloy materials
JP4304425B2 (en) Cold rolled titanium alloy sheet and method for producing cold rolled titanium alloy sheet
JPH0551633A (en) Production of high si-containing austenitic stainless steel
JPH0717946B2 (en) Method for producing duplex stainless steel with excellent resistance to concentrated sulfuric acid corrosion
JP3172848B2 (en) High Cr ferritic steel with excellent creep strength
JP3297011B2 (en) High strength titanium alloy with excellent cold rollability
US20170275722A1 (en) Ferritic stainless steel sheet
JP2009007679A (en) Titanium alloy, and method for producing titanium alloy material
JP3004784B2 (en) High toughness ferritic stainless steel for high temperatures
JP3756795B2 (en) High-tensile steel with excellent toughness of weld heat-affected zone subjected to multiple thermal cycles
JP3297012B2 (en) High strength titanium alloy with excellent cold rollability
EP4372116A1 (en) Ferritic heat-resistant steel

Legal Events

Date Code Title Description
AS Assignment

Owner name: NIPPON STEEL & SUMITOMO METAL CORPORATION, JAPAN

Free format text: MERGER;ASSIGNOR:SUMITOMO METAL INDUSTRIES, LTD.;REEL/FRAME:030018/0455

Effective date: 20130104

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION