EP3276016B1 - Alpha-beta titanium alloy - Google Patents
Alpha-beta titanium alloy Download PDFInfo
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- EP3276016B1 EP3276016B1 EP16768566.8A EP16768566A EP3276016B1 EP 3276016 B1 EP3276016 B1 EP 3276016B1 EP 16768566 A EP16768566 A EP 16768566A EP 3276016 B1 EP3276016 B1 EP 3276016B1
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- 239000000956 alloy Substances 0.000 title claims description 41
- 229910045601 alloy Inorganic materials 0.000 title claims description 40
- 229910021535 alpha-beta titanium Inorganic materials 0.000 title claims description 36
- 239000012535 impurity Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 description 55
- 238000012360 testing method Methods 0.000 description 46
- 239000000463 material Substances 0.000 description 39
- 229910001069 Ti alloy Inorganic materials 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005242 forging Methods 0.000 description 19
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
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- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- 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
-
- 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
Definitions
- the present invention relates to an ⁇ - ⁇ titanium alloy. More particularly, the present invention relates to an ⁇ - ⁇ titanium alloy with excellent machinability.
- a high-strength ⁇ - ⁇ titanium alloy typified by Ti-6Al-4V, can have its strength level changed easily by a heat treatment, in addition to being lightweight and having high strength and high corrosion resistance. For this reason, this type of ⁇ - ⁇ titanium alloy has been hitherto used very often, especially in the aircraft industry. To further make use of these characteristics, in recent years, applications of the ⁇ - ⁇ titanium alloy have been increasingly expanded into the fields of consumer products, including vehicle parts, such as engine members of automobiles or motorcycles, sporting goods such as golf goods, materials for civil engineering and construction, various working tools, and spectacle frames, the development fields of deep sea and energy, and the like.
- Patent Document 1 mentions an ⁇ - ⁇ titanium alloy extruded material with excellent fatigue strength and a manufacturing method for the ⁇ - ⁇ titanium alloy extruded material.
- the ⁇ - ⁇ titanium alloy extruded material includes specified contents of C and Al, and also includes 2.0 to 10.0% in total of one or more of V, Cr, Fe, Mo, Ni, Nb, and Ta, in which an area ratio of a primary ⁇ -phase is within a certain range, a direction of a major axis of each of 80% or more of primary ⁇ grains in the primary ⁇ -phase is positioned within a specified angle range, and an average minor axis of ⁇ grains in a secondary ⁇ -phase is 0.1 pm or more.
- Patent Document 2 mentions an ⁇ - ⁇ titanium alloy for casting that has higher strength and more excellent castability than a Ti-6Al-4V alloy. Specifically, this ⁇ - ⁇ titanium alloy mentioned includes specified contents of Al, Fe + Cr + Ni, and C + N + O, and further a specified content of V if needed, with the balance being Ti and inevitable impurities.
- the ⁇ - ⁇ titanium alloy has extremely high manufacturing cost, and in addition, especially bad machinability, which interferes with the expansion of the applications of the ⁇ - ⁇ titanium alloy.
- the usage range is limited in practice.
- various titanium alloys with improved machinability have been recently proposed.
- Patent Document 3 mentions a titanium alloy for a connecting rod that has improved the machinability while suppressing the reduction in toughness and ductility by containing rare earth elements (REM) and Ca, S, Se, Te, Pb, and Bi as appropriate to form granular compounds.
- Patent Document 4 mentioned a free-cutting titanium alloy that has improved the machinability by containing a rare earth element and improved the hot workability by containing B.
- Patent Document 5 mentions a free-cutting titanium alloy that achieves the reduction in ductility of a matrix and the refinement of inclusions to improve the free cutting properties, while suppressing the reduction in the fatigue strength and ensuring hot workability, by adding P and S, P and Ni, or P, S and Ni, or further REM in addition to these elements as free-cutting component.
- Patent Document 6 mentions an ⁇ - ⁇ titanium alloy with excellent machinability and hot working.
- the ⁇ - ⁇ titanium alloy includes specified contents of C and Al and 2.0 to 10% in total of one or more elements selected from the group of ⁇ -stabilizing elements consisting of respective specified contents of V, Cr, Fe, Mo, Ni, Nb, and Ta, with the balance being Ti and impurities.
- an average area ratio of TiC precipitates in a microstructure is 1% or less, and an average value of the average circle equivalent diameter of the TiC precipitates is 5 ⁇ m or less.
- the present invention has been made in view of the foregoing circumstance, and it is an object of the present invention to achieve an ⁇ - ⁇ titanium alloy that has high strength and excellent hot workability of the level of the ⁇ - ⁇ titanium alloy, typified by the Ti-6Al-4V, while exhibiting more excellent machinability than the Ti-6Al-4V, without the necessity for the strict control or the like of the manufacturing process.
- An ⁇ - ⁇ titanium alloy according to the present invention which can solve the above-mentioned problem, is defined in claim 1.
- the present invention can provide the ⁇ - ⁇ titanium alloy that has high strength and excellent hot workability, such as forgeability, of the level of an ⁇ - ⁇ titanium alloy, typified by the Ti-6Al-4V, and also exhibits more excellent machinability than the Ti-6Al-4V, making it possible to ensure satisfactory lifetime of working tools.
- Fig. 1 is a photomicrograph of a titanium alloy according to the present invention.
- the inventors have intensively studied to solve the foregoing problems. As a result, it has been found that especially, a specified content of at least one of Cu and Ni is contained in a titanium alloy, thereby significantly improving the ductility of the titanium alloy at high temperatures. In particular, thin chips are formed on the titanium alloy during a cutting process due to the reduction in deformation resistance, leading to a reduced cutting resistance, i.e., improving the machinability thereof.
- the composition of the ⁇ - ⁇ titanium alloy according to the present invention will be described in sequence below, starting from Cu and Ni, which are the features of the present invention.
- Cu is solid-soluted into the ⁇ -phase and the ⁇ -phase in the alloy, thereby increasing its ductility at a high temperature and improving the hot workability. Thus, especially, the cutting resistance of the titanium alloy becomes lower, and the machinability thereof is improved.
- the content of Cu is set at 0.1% or more.
- the content of Cu is preferably 0.3% or more, and more preferably 0.5% or more.
- the content of Cu exceeds 2.0% by mass, the hardness of the titanium alloy is increased, thereby making it more likely to reduce the machinability and the hot workability, such as forgeability.
- the content of Cu is set at 2.0% or less.
- the content of Cu is preferably 1.5% or less, and more preferably 1.0% or less.
- Al is an ⁇ -stabilizing element and thus is contained in the titanium alloy to form the ⁇ -phase. If the Al content is less than 2.0%, the formation of the ⁇ -phase is lessened, failing to obtain sufficient strength. Thus, the Al content is set at 2.0% or more.
- the Al content is preferably 2.2% or more, and more preferably 3.0% or more. Meanwhile, if the Al content exceeds 8.5% to become excessive, the ductility of the titanium alloy is degraded. Thus, the Al content is set at 8.5% or less.
- the Al content is preferably 8.0% or less, more preferably 7.0% or less, and still more preferably 6.0% or less.
- the C is an element that exhibits the effect of improving the strength of the titanium alloy. To exhibit such an effect, the C content needs to be 0.08% or more.
- the C content is preferably 0.10% or more. Meanwhile, if the C content exceeds 0.25%, coarse TiC particles not solid-soluted in the ⁇ -phase will remain, thus degrading the mechanical properties of the titanium alloy. Therefore, the C content is set at 0.25% or less.
- the C content is preferably 0.20% or less.
- These elements are ⁇ -stabilizing elements. These elements may be used alone or in combination. To exhibit the above-mentioned effects, the total content of these elements needs to be 2.0% or more. The total content of these elements is preferably 3.0% or more. The lower limit of the total content of these elements only needs to be 2.0% or more as mentioned above, and the lower limit of the content of each of these elements is not limited specifically. Regarding the lower limit of the content of the individual element, for example, when Cr is contained in the titanium alloy, the lower limit of Cr content can be set at 0.5% or more, and further 1.0% or more. When Fe is contained in the titanium alloy, the lower limit of Fe content can be set at 0.5% or more, and further 1.0% or more.
- the total content of these elements is set at 7.0% or less.
- the total content of these elements is preferably 5.0% or less, and more preferably 4.0% or less. Even when the total content of these elements is within the above-mentioned total content range, if the Fe content is excessive, the degradation in the ductility becomes significant. Thus, the Fe content should be restrained to 2.5% or less.
- the Fe content is preferably 2.0% or less.
- the Cr content is set at 4.5% or less.
- the Cr content is preferably 4.0% or less, and more preferably 3.0% or less.
- the ⁇ - ⁇ titanium alloy according to the present invention contains the above-mentioned components, with the balance being Ti and inevitable impurities.
- the inevitable impurities may include P, N, S, O, and the like.
- the P content is restrained to 0.005% or less; the N content is restrained to 0.05% or less; the S content is restrained to 0.05% or less; and the 0 content is restrained to 0.25% or less.
- the ⁇ - ⁇ titanium alloy according to the present invention may further contain the following elements.
- V more than 0% and 5.0% or less
- Mo more than 0% and 5.0% or less
- Nb more than 0% and 5.0% or less
- Ta more than 0% and 5.0% or less
- the total content of these elements is preferably 2.0% or more and more preferably 3.0% or more.
- the lower limit of the content of the individual element is not limited specifically.
- the lower limit of the content of the individual element for example, when V is contained in the titanium alloy, the lower limit of V content can be set at 0.5% or more, and further 2.0% or more.
- Mo is contained in the titanium alloy
- the lower limit of Mo content can be set at 0.1% or more, and further 1.0% or more.
- Nb is contained in the titanium alloy
- the lower limit of Nb content can be set at 0.1% or more, and further 1.0% or more.
- Ta is contained in the titanium alloy
- the lower limit of Ta content can be set at 0.1% or more, and further 1.0% or more.
- the total content of these elements is 10% or less and preferably 5.0% or less. Even when the total content of these elements is within the above-mentioned range, if the content of at least one element of them is excessive, the ductility of the titanium alloy is degraded.
- the upper limit of the content of any of these elements is preferably 5.0% or less. The content of any of these elements is more preferably 4.0% or less.
- Si more than 0% and 0.8% or less
- the Si acts to precipitate Ti 5 Si 3 in the titanium alloy. During cutting, stress is concentrated on the Ti 5 Si 3 , causing voids from Ti 5 Si 3 as a starting point, which makes it easy to separate chips. Consequently, the cutting resistance is supposed to be reduced. To efficiently exhibit this effect, the Si content is preferably 0.1% or more, and more preferably 0.3% or more.
- the Si content is set at 0.8% or less.
- the Si content is more preferably 0.7% or less, and still more preferably 0.6% or less.
- the titanium alloy according to the present invention has the microstructure at room temperature that is composed of the ⁇ -phase and the ⁇ -phase, or the ⁇ -phase, the ⁇ -phase, and a third-phase, such as Ti 2 Cu or Ti 2 Ni.
- a third-phase such as Ti 2 Cu or Ti 2 Ni.
- a manufacturing method for the ⁇ - ⁇ titanium alloy is not limited specifically.
- the ⁇ - ⁇ titanium alloy can be manufactured, for example, by the following method. That is, the ⁇ - ⁇ titanium alloy is manufactured by smelting titanium alloy material with the above-mentioned components, casting to produce an ingot, and then performing hot working, i.e., hot forging or hot-rolling on the ingot, followed by annealing as needed.
- the above-mentioned hot working involves: heating the ingot in a temperature range of a ⁇ -transformation temperature T ⁇ to approximately (T ⁇ + 250)°C, followed by rough forging or rough rolling at a processing ratio of approximately 1.2 to 4.0, which is represented by "original cross-sectional area/cross-sectional area after the hot working"; and then performing finish processing at a processing ratio of 1.7 or more in a temperature range of approximately (T ⁇ - 50) to 800°C.
- finish processing annealing may be performed at a temperature of 700 to 800°C as needed. The annealing is performed, for example, for two to 24 hours. Then, an aging treatment may be performed as needed.
- T ⁇ is determined from the formula (1) below.
- the formula (1) below corresponds to formulas (1) to (3) mentioned in Morinaga et al., "Titanium alloy design using d electron theory", Light metal, Vol. 42, No. 11 (1992), p. 614-621 .
- Boave 0.326 ⁇ Mdave ⁇ 1.95 ⁇ 10 ⁇ 4 T ⁇ + 2.217
- Boave is an average value of a bond order Bo of the element i
- Xi is an atomic ratio of the element i
- (Bo)i is a value of the bond order Bo of the element i.
- Mdave is an average value of a d-orbital energy parameter Md of the element i
- Xi is an atomic ratio of the element i
- (Md) i is a value of the d-orbital energy parameter Md of the element i.
- Test materials were fabricated in the following way.
- the titanium alloy with each composition shown in Table 1 below was processed by button arc melting to manufacture an ingot with a size of about 40 mm in diameter ⁇ 20 mm in height.
- the P content was restrained to 0.005% or less;
- the N content was restrained to 0.05% or less;
- the S content was restrained to 0.05% or less; and
- the O content was restrained to 0.25% or less.
- the mark "-" means that the corresponding element was not contained.
- the ingot was heated to 1,200°C and subjected to the rough forging at a processing ratio of 2.4, represented by the "original cross-sectional area/cross-sectional area after the hot working", followed by forging at a processing ratio of 4.4 at 870 °C to perform finish processing. Thereafter, annealing was performed on the forged material by holding it at 750°C for 12 hours, thereby producing a test material. Note that as shown in Comparative Example 7 of Table 1 below, a test material in which a crack occurred by the rough forging was not subjected to the finish forging.
- the hot workability was evaluated by the hot forgeability.
- the presence or absence of a crack in each of forging steps namely, the rough forging and the finish forging mentioned above, was evaluated. That is, the surface of the above-mentioned test material after each forging step was visually observed.
- the test materials having any crack were rated as NG, while the test materials having no cracks were rated as OK. Then, the test materials rated as OK in terms of both the rough forging and the finish forging were evaluated to have excellent forgeability.
- the test materials having good forgeability were evaluated for the machinability as follows. That is, a test specimen with the size below was taken out of the above-mentioned test material, and a cutting test was performed on the test specimen on the cutting conditions below.
- the machinability was evaluated as an average cutting resistance by measuring a cutting resistance in the cutting direction with a Kessler's cutting dynamometer, Model: 9257 B, from the start to the end of cutting and then determining an average value of the cutting resistance from the start to the end of the cutting.
- an average cutting resistance was 180 N. Because of this, in the first example, the test materials having an average cutting resistance of lower than 180 N were evaluated to be superior in the machinability, while the test materials having an average cutting resistance of 180 N or higher were evaluated to be inferior in the machinability.
- Test Specimen 10 mm in height ⁇ 10 mm in width ⁇ 150 mm in length Tool: Carbide tip S30T (nose 0.4 mm) manufactured by Sandvik Corporation
- the tensile strength of the ⁇ - ⁇ titanium alloy according to the present invention was also measured for reference.
- the titanium alloys of Examples 1 and 3, and Comparative Example 1 were used and subjected to the tensile test on the following conditions of the shape and testing speed of the test specimen.
- the test materials had a strength of 948 MPa in Example 1, 1, 125 MPa in Example 3, and 948 MPa in Comparative Example 1, all of these strengths being relatively high.
- the strengths of these test materials exhibited higher strength than the strength of 896 MPa of an annealed material of Ti-6Al-4V as a general ⁇ - ⁇ titanium alloy.
- Shape of Test Specimen ASTM E8/E8M Fig. 8 Specimen 3 Test Speed: 4.5 mm/min
- Table 1 shows the following. Examples 1-8, none of which fall within the scope of protection as defined in claim 1, were found to enable good forging and to have excellent forgeability. Furthermore, these examples were found to have a lower average cutting resistance than that of Ti-6Al-4V as a general ⁇ - ⁇ titanium alloy and also to have good machinability.
- Comparative Examples 1 to 7 did not satisfy the composition specified by the present invention and thereby were consequently inferior in forgeability or machinability.
- Comparative Example 1 neither Cu nor Ni was contained, resulting in a high average cutting resistance.
- Comparative Example 1 had the same composition as that mentioned in Patent Document 6.
- the comparison of the above-mentioned Examples 1 to 3 with Comparative Example 1 in which the constituent elements, other than Cu and Ni, and their contents are the same as those in Examples 1 to 3 shows that in order to surely obtain good machinability by sufficiently decreasing the average cutting resistance, it is necessary to contain a specified content of at least one of Cu and Ni, as mentioned in the present invention.
- Comparative Example 2 which contained Ni, the Ni content was excessive.
- Comparative Example 5 which contained Cu, the Cu content was excessive.
- the average cutting resistance was higher than 180 N, resulting in bad machinability.
- Comparative Examples 3 and 6 the respective contents of Cu and Ni were excessive. In both comparative examples, the average cutting resistance was higher than 180 N, resulting in bad machinability.
- Comparative Example 4 since the Cu content was excessive, the forgeabililty was degraded. In Comparative Example 7, since the respective contents of Cu and Ni were drastically excessive, cracking occurred at the stage of the rough forging, resulting in degradation in the forgeability.
- the influence of the Si content, especially, on the machinability were studied.
- Table 2 various ingots with different Si contents were manufactured to produce test materials in the same way as that in the first example.
- the P content was restrained to 0.005% or less; the N content was restrained to 0.05% or less; the S content was restrained to 0.05% or less; and the O content was restrained to 0.25% or less.
- the mark "-" means that the corresponding element was not contained.
- test material No. 3 in Table 2 was measured in the same way as that in the first example.
- This test material No. 3 had a tensile strength of 968 MPa, which was higher than a strength, i.e., 896 MPa of an annealed material of Ti-6Al-4V as the general ⁇ - ⁇ titanium alloy.
- test material was polished to a mirror-smooth state, followed by acid treatment using hydrofluoric acid to an extent that crystal grain boundaries could be seen, and then visually observed at ten field of views, each field of view having a size of 40 pm ⁇ 40 ⁇ m, with a field emission-scanning electron microscope (FE-SEM) at a magnification of 4,000 times.
- FE-SEM field emission-scanning electron microscope
- the test materials in which the precipitation phase was recognized at four or less of the above-mentioned ten field of views in total were evaluated to be in the "absence" of the precipitation phase.
- the above-mentioned precipitation phase was separately recognized as Ti 5 Si 3 by an X-ray diffraction (XRD).
- Fig. 1 shows one example of a photomicrograph observed with the above-mentioned microscope.
- Fig. 1 is one obtained by measurement of the test material No. 3 shown in Table 2, with an arrow indicating one precipitation phase.
- a Vickers hardness HV was measured at five sites of each test material on the condition of a load 10 kgf, and the measured values were averaged. In this way, an average value of the Vickers hardness was determined.
- the test materials evaluated to have good forgeability in the same way as that in the first example, that is, all examples shown in Table 2 were evaluated for the machinability as follows. That is, a test specimen with the size mentioned below was taken out of the above-mentioned test material, and a cutting test was performed on the test specimen on the cutting conditions below.
- the machinability was evaluated as an average cutting resistance by measuring a cutting resistance in the cutting direction by the Kessler's cutting dynamometer, Model: 9257 B, from the start to the end of cutting and then determining an average value of the cutting resistance from the start to the end of the cutting.
- an average cutting resistance was 122 N. Because of this, in the second example, the test materials having an average cutting resistance of lower than 122 N were evaluated to be superior in the machinability, while the test materials having an average cutting resistance of 122 N or higher were evaluated to be inferior in the machinability.
- Test Specimen 10 mm in height ⁇ 10 mm in width ⁇ 60 mm in length Tool: Carbide tip S30T (nose 0.4 mm) manufactured by Sandvik Corporation
- Table 2 shows the following. That is, as clearly shown, the test material No. 1 having the same composition as that in Example 1 of Table 1 were compared with test materials No. 2 to 6, particularly, test materials No. 2 to 4 in which the contents of elements other than Si were the same as those in Example 1 of Table 1. Based on the comparison, the arrangement that contains Si in the titanium alloy made it possible to further reduce the average cutting resistance and to ensure the sufficiently high machinability, compared to a case in which Si was not contained. In contrast, when the Si content was excessive, like the test materials No. 7 and No. 8, the hardness of the titanium alloy becomes extremely high, increasing the average cutting resistance and also causing inconveniences, such as a damage of a working tool.
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Description
- The present invention relates to an α-β titanium alloy. More particularly, the present invention relates to an α-β titanium alloy with excellent machinability.
- A high-strength α-β titanium alloy, typified by Ti-6Al-4V, can have its strength level changed easily by a heat treatment, in addition to being lightweight and having high strength and high corrosion resistance. For this reason, this type of α-β titanium alloy has been hitherto used very often, especially in the aircraft industry. To further make use of these characteristics, in recent years, applications of the α-β titanium alloy have been increasingly expanded into the fields of consumer products, including vehicle parts, such as engine members of automobiles or motorcycles, sporting goods such as golf goods, materials for civil engineering and construction, various working tools, and spectacle frames, the development fields of deep sea and energy, and the like.
- For example, as such an α-β titanium alloy, Patent Document 1 mentions an α-β titanium alloy extruded material with excellent fatigue strength and a manufacturing method for the α-β titanium alloy extruded material. Specifically, the α-β titanium alloy extruded material includes specified contents of C and Al, and also includes 2.0 to 10.0% in total of one or more of V, Cr, Fe, Mo, Ni, Nb, and Ta, in which an area ratio of a primary α-phase is within a certain range, a direction of a major axis of each of 80% or more of primary α grains in the primary α-phase is positioned within a specified angle range, and an average minor axis of α grains in a secondary α-phase is 0.1 pm or more.
- As the α-β titanium alloy with enhanced forgeability, Patent Document 2 mentions an α-β titanium alloy for casting that has higher strength and more excellent castability than a Ti-6Al-4V alloy. Specifically, this α-β titanium alloy mentioned includes specified contents of Al, Fe + Cr + Ni, and C + N + O, and further a specified content of V if needed, with the balance being Ti and inevitable impurities.
- However, the α-β titanium alloy has extremely high manufacturing cost, and in addition, especially bad machinability, which interferes with the expansion of the applications of the α-β titanium alloy. The usage range is limited in practice. In view of such circumstances, various titanium alloys with improved machinability have been recently proposed.
- For example, Patent Document 3 mentions a titanium alloy for a connecting rod that has improved the machinability while suppressing the reduction in toughness and ductility by containing rare earth elements (REM) and Ca, S, Se, Te, Pb, and Bi as appropriate to form granular compounds. Patent Document 4 mentioned a free-cutting titanium alloy that has improved the machinability by containing a rare earth element and improved the hot workability by containing B.
- Patent Document 5 mentions a free-cutting titanium alloy that achieves the reduction in ductility of a matrix and the refinement of inclusions to improve the free cutting properties, while suppressing the reduction in the fatigue strength and ensuring hot workability, by adding P and S, P and Ni, or P, S and Ni, or further REM in addition to these elements as free-cutting component.
- Further, Patent Document 6 mentions an α-β titanium alloy with excellent machinability and hot working. The α-β titanium alloy includes specified contents of C and Al and 2.0 to 10% in total of one or more elements selected from the group of β-stabilizing elements consisting of respective specified contents of V, Cr, Fe, Mo, Ni, Nb, and Ta, with the balance being Ti and impurities. In the titanium alloy, an average area ratio of TiC precipitates in a microstructure is 1% or less, and an average value of the average circle equivalent diameter of the TiC precipitates is 5 µm or less.
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- Patent Document 1:
JP 2012-52219 A - Patent Document 2:
JP 2010-7166 A - Patent Document 3:
JP 06-99764 B - Patent Document 4:
JP 06-53902 B - Patent Document 5:
JP 2626344 B1 - Patent Document 6:
JP 2007-84865 B JP2009299110 - In the methods like Patent Documents 3 and 4 mentioned above, metallic inclusions are precipitated by using REM. In the method like Patent Document 5 mentioned above, P is positively contained to form a P inclusion. In the method like Patent Document 6, the size of a TiC precipitate is controlled. However, in these methods, it is considered that precipitation of these precipitates and inclusions are more likely to be affected by the temperatures and cooling rates of melting to forging steps, thus making it difficult to control the size of the precipitate or the like. Furthermore, the shape or size of a raw material tends to cause variations in the size or the like of the precipitate or inclusion. Thus, to achieve the excellent machinability by precipitating inclusions of interest, there is a problem that strict control of a manufacturing process is necessary.
- The present invention has been made in view of the foregoing circumstance, and it is an object of the present invention to achieve an α-β titanium alloy that has high strength and excellent hot workability of the level of the α-β titanium alloy, typified by the Ti-6Al-4V, while exhibiting more excellent machinability than the Ti-6Al-4V, without the necessity for the strict control or the like of the manufacturing process.
- An α-β titanium alloy according to the present invention, which can solve the above-mentioned problem, is defined in claim 1.
- Accordingly, the present invention can provide the α-β titanium alloy that has high strength and excellent hot workability, such as forgeability, of the level of an α-β titanium alloy, typified by the Ti-6Al-4V, and also exhibits more excellent machinability than the Ti-6Al-4V, making it possible to ensure satisfactory lifetime of working tools.
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Fig. 1 is a photomicrograph of a titanium alloy according to the present invention. - The inventors have intensively studied to solve the foregoing problems. As a result, it has been found that especially, a specified content of at least one of Cu and Ni is contained in a titanium alloy, thereby significantly improving the ductility of the titanium alloy at high temperatures. In particular, thin chips are formed on the titanium alloy during a cutting process due to the reduction in deformation resistance, leading to a reduced cutting resistance, i.e., improving the machinability thereof. The composition of the α-β titanium alloy according to the present invention will be described in sequence below, starting from Cu and Ni, which are the features of the present invention.
- Cu is solid-soluted into the α-phase and the β-phase in the alloy, thereby increasing its ductility at a high temperature and improving the hot workability. Thus, especially, the cutting resistance of the titanium alloy becomes lower, and the machinability thereof is improved. If the content of Cu is less than 0.1%, the effect of improving the ductility is lessened. Thus, the content of Cu is set at 0.1% or more. The content of Cu is preferably 0.3% or more, and more preferably 0.5% or more. In contrast, if the content of Cu exceeds 2.0% by mass, the hardness of the titanium alloy is increased, thereby making it more likely to reduce the machinability and the hot workability, such as forgeability. Thus, the content of Cu is set at 2.0% or less. The content of Cu is preferably 1.5% or less, and more preferably 1.0% or less.
- Al is an α-stabilizing element and thus is contained in the titanium alloy to form the α-phase. If the Al content is less than 2.0%, the formation of the α-phase is lessened, failing to obtain sufficient strength. Thus, the Al content is set at 2.0% or more. The Al content is preferably 2.2% or more, and more preferably 3.0% or more. Meanwhile, if the Al content exceeds 8.5% to become excessive, the ductility of the titanium alloy is degraded. Thus, the Al content is set at 8.5% or less. The Al content is preferably 8.0% or less, more preferably 7.0% or less, and still more preferably 6.0% or less.
- C is an element that exhibits the effect of improving the strength of the titanium alloy. To exhibit such an effect, the C content needs to be 0.08% or more. The C content is preferably 0.10% or more. Meanwhile, if the C content exceeds 0.25%, coarse TiC particles not solid-soluted in the α-phase will remain, thus degrading the mechanical properties of the titanium alloy. Therefore, the C content is set at 0.25% or less. The C content is preferably 0.20% or less.
- These elements are β-stabilizing elements. These elements may be used alone or in combination. To exhibit the above-mentioned effects, the total content of these elements needs to be 2.0% or more. The total content of these elements is preferably 3.0% or more. The lower limit of the total content of these elements only needs to be 2.0% or more as mentioned above, and the lower limit of the content of each of these elements is not limited specifically. Regarding the lower limit of the content of the individual element, for example, when Cr is contained in the titanium alloy, the lower limit of Cr content can be set at 0.5% or more, and further 1.0% or more. When Fe is contained in the titanium alloy, the lower limit of Fe content can be set at 0.5% or more, and further 1.0% or more.
- In contrast, when the total content of these elements is excessive, the ductility of the titanium alloy is degraded. Thus, the total content of these elements is set at 7.0% or less. The total content of these elements is preferably 5.0% or less, and more preferably 4.0% or less. Even when the total content of these elements is within the above-mentioned total content range, if the Fe content is excessive, the degradation in the ductility becomes significant. Thus, the Fe content should be restrained to 2.5% or less. The Fe content is preferably 2.0% or less. Meanwhile, if the Cr content is excessive, the machinability of the titanium alloy is degraded. Thus, the Cr content is set at 4.5% or less. The Cr content is preferably 4.0% or less, and more preferably 3.0% or less.
- The α-β titanium alloy according to the present invention contains the above-mentioned components, with the balance being Ti and inevitable impurities. The inevitable impurities may include P, N, S, O, and the like. In the α-β titanium alloy according to the present invention, the P content is restrained to 0.005% or less; the N content is restrained to 0.05% or less; the S content is restrained to 0.05% or less; and the 0 content is restrained to 0.25% or less. The α-β titanium alloy according to the present invention may further contain the following elements.
- More than 0% and 10% or less in total of one or more elements selected from the group consisting of V: more than 0% and 5.0% or less, Mo: more than 0% and 5.0% or less, Nb: more than 0% and 5.0% or less, and Ta: more than 0% and 5.0% or less
- These elements are β-stabilizing elements. These elements may be used alone or in combination. To form a β-phase, the total content of these elements is preferably 2.0% or more and more preferably 3.0% or more. As long as the total content of these elements is more than 0%, the lower limit of the content of the individual element is not limited specifically. Regarding the lower limit of the content of the individual element, for example, when V is contained in the titanium alloy, the lower limit of V content can be set at 0.5% or more, and further 2.0% or more. When Mo is contained in the titanium alloy, the lower limit of Mo content can be set at 0.1% or more, and further 1.0% or more. When Nb is contained in the titanium alloy, the lower limit of Nb content can be set at 0.1% or more, and further 1.0% or more. When Ta is contained in the titanium alloy, the lower limit of Ta content can be set at 0.1% or more, and further 1.0% or more.
- In contrast, if the total content of these elements is excessive, the ductility of the titanium alloy is degraded. Thus, the total content of these elements is 10% or less and preferably 5.0% or less. Even when the total content of these elements is within the above-mentioned range, if the content of at least one element of them is excessive, the ductility of the titanium alloy is degraded. Thus, the upper limit of the content of any of these elements is preferably 5.0% or less. The content of any of these elements is more preferably 4.0% or less.
- Si acts to precipitate Ti5Si3 in the titanium alloy. During cutting, stress is concentrated on the Ti5Si3, causing voids from Ti5Si3 as a starting point, which makes it easy to separate chips. Consequently, the cutting resistance is supposed to be reduced. To efficiently exhibit this effect, the Si content is preferably 0.1% or more, and more preferably 0.3% or more.
- Meanwhile, if the Si content is excessive, the strength of the titanium alloy becomes extremely high, whereby a working tool might be worn significantly or broken, which makes it difficult to cut the titanium alloy. Accordingly, the Si content is set at 0.8% or less. The Si content is more preferably 0.7% or less, and still more preferably 0.6% or less.
- The titanium alloy according to the present invention has the microstructure at room temperature that is composed of the α-phase and the β-phase, or the α-phase, the β-phase, and a third-phase, such as Ti2Cu or Ti2Ni. When Si is contained in the titanium alloy, Ti5Si3 is precipitated in the titanium alloy as mentioned above.
- A manufacturing method for the α-β titanium alloy is not limited specifically. However, the α-β titanium alloy can be manufactured, for example, by the following method. That is, the α-β titanium alloy is manufactured by smelting titanium alloy material with the above-mentioned components, casting to produce an ingot, and then performing hot working, i.e., hot forging or hot-rolling on the ingot, followed by annealing as needed. The above-mentioned hot working involves: heating the ingot in a temperature range of a β-transformation temperature Tβ to approximately (Tβ + 250)°C, followed by rough forging or rough rolling at a processing ratio of approximately 1.2 to 4.0, which is represented by "original cross-sectional area/cross-sectional area after the hot working"; and then performing finish processing at a processing ratio of 1.7 or more in a temperature range of approximately (Tβ - 50) to 800°C. After the above-mentioned finish processing, annealing may be performed at a temperature of 700 to 800°C as needed. The annealing is performed, for example, for two to 24 hours. Then, an aging treatment may be performed as needed.
- Note that the above-mentioned Tβ is determined from the formula (1) below. The formula (1) below corresponds to formulas (1) to (3) mentioned in Morinaga et al., "Titanium alloy design using d electron theory", Light metal, Vol. 42, No. 11 (1992), p. 614-621.
- When each element is represented as an element i in the formula (2), Boave is an average value of a bond order Bo of the element i, Xi is an atomic ratio of the element i, and (Bo)i is a value of the bond order Bo of the element i.
- When each element is represented as an element i in the formula (3), Mdave is an average value of a d-orbital energy parameter Md of the element i, Xi is an atomic ratio of the element i, and (Md) i is a value of the d-orbital energy parameter Md of the element i.
- The bond order Bo and the d-orbital energy parameter Md of each element are mentioned in Table 1 at p.616 of the above-mentioned reference. Xi is determined from the composition. From these data, Boave and Mdave of each element including Ti are determined and substituted into the above-mentioned formula (1), thereby making it possible to calculate a Tβ. Note that this reference does not have data on Bo and Md of C. However, since the C content in the present invention is small, C is neglected to calculate the Tβ.
- The present invention will be more specifically described below by way of Examples, but is not limited to the following Examples. It is obvious that various modifications can be made to these examples as long as they are adaptable to the above-mentioned and below-mentioned concepts and are included within the scope of the present invention as defined by claim 1.
- Test materials were fabricated in the following way. The titanium alloy with each composition shown in Table 1 below was processed by button arc melting to manufacture an ingot with a size of about 40 mm in diameter × 20 mm in height. In any example, the P content was restrained to 0.005% or less; the N content was restrained to 0.05% or less; the S content was restrained to 0.05% or less; and the O content was restrained to 0.25% or less. In Table 1, the mark "-" means that the corresponding element was not contained. The ingot was heated to 1,200°C and subjected to the rough forging at a processing ratio of 2.4, represented by the "original cross-sectional area/cross-sectional area after the hot working", followed by forging at a processing ratio of 4.4 at 870 °C to perform finish processing. Thereafter, annealing was performed on the forged material by holding it at 750°C for 12 hours, thereby producing a test material. Note that as shown in Comparative Example 7 of Table 1 below, a test material in which a crack occurred by the rough forging was not subjected to the finish forging.
- In this example, the hot workability was evaluated by the hot forgeability. In detail, the presence or absence of a crack in each of forging steps, namely, the rough forging and the finish forging mentioned above, was evaluated. That is, the surface of the above-mentioned test material after each forging step was visually observed. The test materials having any crack were rated as NG, while the test materials having no cracks were rated as OK. Then, the test materials rated as OK in terms of both the rough forging and the finish forging were evaluated to have excellent forgeability.
- The test materials having good forgeability were evaluated for the machinability as follows. That is, a test specimen with the size below was taken out of the above-mentioned test material, and a cutting test was performed on the test specimen on the cutting conditions below. The machinability was evaluated as an average cutting resistance by measuring a cutting resistance in the cutting direction with a Kessler's cutting dynamometer, Model: 9257 B, from the start to the end of cutting and then determining an average value of the cutting resistance from the start to the end of the cutting. When performing the cutting test on Ti-6Al-4V as a general α-β titanium alloy on the same conditions, an average cutting resistance was 180 N. Because of this, in the first example, the test materials having an average cutting resistance of lower than 180 N were evaluated to be superior in the machinability, while the test materials having an average cutting resistance of 180 N or higher were evaluated to be inferior in the machinability.
- Test Specimen: 10 mm in height × 10 mm in width × 150 mm in length
Tool: Carbide tip S30T (nose 0.4 mm) manufactured by Sandvik Corporation - End mill R390 manufactured by Sandvik Corporation (20 mm in diameter, one blade)
Cutting speed Vc: 100 m/min
Cutting amount in the axial direction: 1.2 mm
Cutting amount in the radial direction: 1 mm
Feeding speed: 0.08 mm/blade
Cutting length: 150 mm
Cutting oil: None - The tensile strength of the α-β titanium alloy according to the present invention was also measured for reference. In detail, the titanium alloys of Examples 1 and 3, and Comparative Example 1 were used and subjected to the tensile test on the following conditions of the shape and testing speed of the test specimen. As a result, the test materials had a strength of 948 MPa in Example 1, 1, 125 MPa in Example 3, and 948 MPa in Comparative Example 1, all of these strengths being relatively high. Specifically, the strengths of these test materials exhibited higher strength than the strength of 896 MPa of an annealed material of Ti-6Al-4V as a general α-β titanium alloy.
Shape of Test Specimen: ASTM E8/E8M Fig. 8 Specimen 3
Test Speed: 4.5 mm/min - The evaluation result of the above-mentioned forgeability and an average cutting resistance are also shown in Table 1.
[Table 1] Composition (% by mass) Balance being Ti and inevitable impurities Tβ Forgeability Average cutting resistance Cu Ni Si Al C Cr Fe (°C) Rough forging Finish forging (N) Example 1 0.5 0.5 - 4.5 0.10 2.5 1.2 976 OK OK 148 Example 2 1.0 1.0 - 4.5 0.10 2.5 1.2 974 OK OK 170 Example 3 2.0 2.0 - 4.5 0.10 2.5 1.2 969 OK OK 167 Example 4 - 0.5 - 4.5 0.10 - 1.2 1,010 OK OK 129 Example 5 0.5 0.5 - 4.5 0.10 - 1.2 1,011 OK OK 148 Example 6 - 1.0 - 4.5 0.10 - 1.2 1,006 OK OK 140 Example 7 1.0 1.0 - 4.5 0.10 - 1.2 1,009 OK OK 146 Example 8 2.0 2.0 - 4.5 0.10 - 1.2 1,004 OK OK 155 Comparative Example 1 - - - 4.5 0.10 2.5 1.2 979 OK OK 199 Comparative Example 2 - 3.0 - 4.5 0.10 2.5 1.2 957 OK OK 229 Comparative Example 3 3.0 3.0 - 4.5 0.10 2.5 1.2 965 OK OK 241 Comparative Example 4 4.0 - - 4.5 0.10 2.5 1.2 989 OK NG - Comparative Example 5 6.0 - - 4.5 0.10 2.5 1.2 994 OK OK 234 Comparative Example 6 4.0 4.0 - 4.5 0.10 2.5 1.2 960 OK OK 261 Comparative Example 7 6.0 6.0 - 4.5 0.10 2.5 1.2 950 NG - - - Table 1 shows the following. Examples 1-8, none of which fall within the scope of protection as defined in claim 1, were found to enable good forging and to have excellent forgeability. Furthermore, these examples were found to have a lower average cutting resistance than that of Ti-6Al-4V as a general α-β titanium alloy and also to have good machinability.
- In contrast, all Comparative Examples 1 to 7 did not satisfy the composition specified by the present invention and thereby were consequently inferior in forgeability or machinability. In detail, in Comparative Example 1, neither Cu nor Ni was contained, resulting in a high average cutting resistance. Comparative Example 1 had the same composition as that mentioned in Patent Document 6. The comparison of the above-mentioned Examples 1 to 3 with Comparative Example 1 in which the constituent elements, other than Cu and Ni, and their contents are the same as those in Examples 1 to 3 shows that in order to surely obtain good machinability by sufficiently decreasing the average cutting resistance, it is necessary to contain a specified content of at least one of Cu and Ni, as mentioned in the present invention.
- In Comparative Example 2, which contained Ni, the Ni content was excessive. In Comparative Example 5, which contained Cu, the Cu content was excessive. In both examples, the average cutting resistance was higher than 180 N, resulting in bad machinability. In Comparative Examples 3 and 6, the respective contents of Cu and Ni were excessive. In both comparative examples, the average cutting resistance was higher than 180 N, resulting in bad machinability.
- In Comparative Example 4, since the Cu content was excessive, the forgeabililty was degraded. In Comparative Example 7, since the respective contents of Cu and Ni were drastically excessive, cracking occurred at the stage of the rough forging, resulting in degradation in the forgeability.
- In the second example, the influence of the Si content, especially, on the machinability were studied. As shown in Table 2, various ingots with different Si contents were manufactured to produce test materials in the same way as that in the first example. In any example, the P content was restrained to 0.005% or less; the N content was restrained to 0.05% or less; the S content was restrained to 0.05% or less; and the O content was restrained to 0.25% or less. In Table 2, the mark "-" means that the corresponding element was not contained.
- Each of the above-mentioned test materials was used to confirm the presence or absence of a precipitation phase, as mentioned below, and the Vickers hardness of the test material was measured as an index of strength in the second example. Furthermore, the forgeability of the test material was evaluated in the same way as that in the first example, and the machinability thereof was evaluated as mentioned below. For reference, the tensile strength of test material No. 3 in Table 2 was measured in the same way as that in the first example. This test material No. 3 had a tensile strength of 968 MPa, which was higher than a strength, i.e., 896 MPa of an annealed material of Ti-6Al-4V as the general α-β titanium alloy.
- The cross section of the test material was polished to a mirror-smooth state, followed by acid treatment using hydrofluoric acid to an extent that crystal grain boundaries could be seen, and then visually observed at ten field of views, each field of view having a size of 40 pm × 40 µm, with a field emission-scanning electron microscope (FE-SEM) at a magnification of 4,000 times. The test materials in which the precipitation phase with a circle equivalent diameter of 2 µm or more was recognized at five or more of the above-mentioned ten field of views in total were evaluated to be in the "presence" of the precipitation phase. The test materials in which the precipitation phase was recognized at four or less of the above-mentioned ten field of views in total were evaluated to be in the "absence" of the precipitation phase. Note that the above-mentioned precipitation phase was separately recognized as Ti5Si3 by an X-ray diffraction (XRD).
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Fig. 1 shows one example of a photomicrograph observed with the above-mentioned microscope.Fig. 1 is one obtained by measurement of the test material No. 3 shown in Table 2, with an arrow indicating one precipitation phase. - A Vickers hardness HV was measured at five sites of each test material on the condition of a load 10 kgf, and the measured values were averaged. In this way, an average value of the Vickers hardness was determined.
- The test materials evaluated to have good forgeability in the same way as that in the first example, that is, all examples shown in Table 2 were evaluated for the machinability as follows. That is, a test specimen with the size mentioned below was taken out of the above-mentioned test material, and a cutting test was performed on the test specimen on the cutting conditions below. The machinability was evaluated as an average cutting resistance by measuring a cutting resistance in the cutting direction by the Kessler's cutting dynamometer, Model: 9257 B, from the start to the end of cutting and then determining an average value of the cutting resistance from the start to the end of the cutting. When performing the cutting test on Ti-6Al-4V as the general α-β titanium alloy on the same conditions, an average cutting resistance was 122 N. Because of this, in the second example, the test materials having an average cutting resistance of lower than 122 N were evaluated to be superior in the machinability, while the test materials having an average cutting resistance of 122 N or higher were evaluated to be inferior in the machinability.
- Test Specimen: 10 mm in height × 10 mm in width × 60 mm in length
Tool: Carbide tip S30T (nose 0.4 mm) manufactured by Sandvik Corporation - End mill R390 manufactured by Sandvik Corporation (20 mm in diameter, one blade)
Cutting speed Vc: 100 m/min
Cutting amount in the axial direction: 1.2 mm
Cutting amount in the radial direction: 1 mm
Feeding speed: 0.08 mm/blade
Cutting length: 15 mm
Cutting oil: None - These results are also shown in Table 2.
[Table 2] No. Composition (% by mass) Balance being Ti and inevitable impurities Tβ Precipitation phase HV Forgeability Average cutting resistance Cu Ni Si Al C Cr Fe (°C) Rough forging Finish forging (N) 1 0.5 0.5 - 4.5 0.10 2.5 1.2 976 Absent 298 OK OK 111 2 0.5 0.5 0.1 4.5 0.10 2.5 1.2 993 Present 316 OK OK 99 3 0.5 0.5 0.3 4.5 0.10 2.5 1.2 1,027 Present 320 OK OK 105 4 0.5 0.5 0.8 4.5 0.10 2.5 1.2 1,110 Present 335 OK OK 112 5 0.3 0.3 0.3 4.5 0.10 2.5 1.2 1,028 Present 316 OK OK 106 6 2.0 2.0 0.5 4.5 0.10 2.5 1.2 1,054 Present 365 OK OK 120 7 2.0 2.0 1.0 4.5 0.10 2.5 1.2 1,137 Present 380 OK OK 134 8 2.0 2.0 2.0 4.5 0.10 2.5 1.2 1,303 Present 397 OK OK Measurement was impossible due to damage to a working tool - None of the example alloys 1-7 in table 2 fall within the scope of protection as defined by claim 1. Table 2 shows the following. That is, as clearly shown, the test material No. 1 having the same composition as that in Example 1 of Table 1 were compared with test materials No. 2 to 6, particularly, test materials No. 2 to 4 in which the contents of elements other than Si were the same as those in Example 1 of Table 1. Based on the comparison, the arrangement that contains Si in the titanium alloy made it possible to further reduce the average cutting resistance and to ensure the sufficiently high machinability, compared to a case in which Si was not contained. In contrast, when the Si content was excessive, like the test materials No. 7 and No. 8, the hardness of the titanium alloy becomes extremely high, increasing the average cutting resistance and also causing inconveniences, such as a damage of a working tool.
Claims (1)
- An α-β titanium alloy consisting of, in percent by mass:0.1 to 2.0% of Cu;2.0 to 8.5% of Al;0.08 to 0.25% of C;2.0 to 7.0% in total of at least one element of 0 to 4.5% of Cr and 0 to 2.5% of Fe,0.005% or less of P;0.05% or less of N;0.05% or less of S;0.25% or less of O;optionally more than 0% and 10% or less in total of one or more elements selected from the group consisting of more than 0% and 5.0% or less of V; more than 0% and 5.0% or less of Mo; more than 0% and 5.0% or less of Nb; and more than 0% and 5.0% or less of Ta; andoptionally more than 0% and 0.8% or less of Si, with the balance being Ti and inevitable impurities.
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JP2626344B2 (en) | 1990-10-01 | 1997-07-02 | 住友金属工業株式会社 | Method for improving free-cutting ability of Ti alloy and free-cutting Ti alloy |
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JP4493028B2 (en) * | 2005-09-21 | 2010-06-30 | 株式会社神戸製鋼所 | Α-β type titanium alloy with excellent machinability and hot workability |
JP4493029B2 (en) * | 2005-09-21 | 2010-06-30 | 株式会社神戸製鋼所 | Α-β type titanium alloy with excellent machinability and hot workability |
JP2009299110A (en) * | 2008-06-11 | 2009-12-24 | Kobe Steel Ltd | HIGH-STRENGTH alpha-beta TYPE TITANIUM ALLOY SUPERIOR IN INTERMITTENT MACHINABILITY |
JP2010007166A (en) | 2008-06-30 | 2010-01-14 | Daido Steel Co Ltd | alpha+beta TYPE TITANIUM ALLOY FOR CASTING, AND GOLF CLUB HEAD USING THE SAME |
JP5435333B2 (en) * | 2009-04-22 | 2014-03-05 | 新日鐵住金株式会社 | Manufacturing method of α + β type titanium alloy thin plate and manufacturing method of α + β type titanium alloy thin plate coil |
RU2436858C2 (en) * | 2010-02-24 | 2011-12-20 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Secondary titanium alloy and procedure for its production |
JP5592818B2 (en) | 2010-08-03 | 2014-09-17 | 株式会社神戸製鋼所 | Α-β type titanium alloy extruded material excellent in fatigue strength and method for producing the α-β type titanium alloy extruded material |
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JP5796810B2 (en) * | 2012-06-18 | 2015-10-21 | 株式会社神戸製鋼所 | Titanium alloy material with high strength and excellent cold rolling properties |
RU2583556C2 (en) * | 2014-09-16 | 2016-05-10 | Публичное Акционерное Общество "Корпорация Всмпо-Ависма" | Sparingly alloyed titanium alloy |
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2016
- 2016-01-21 JP JP2016009417A patent/JP6719216B2/en not_active Expired - Fee Related
- 2016-03-16 US US15/560,533 patent/US20180044763A1/en not_active Abandoned
- 2016-03-16 RU RU2017134565A patent/RU2695852C2/en active
- 2016-03-16 KR KR1020177029948A patent/KR102027100B1/en active IP Right Grant
- 2016-03-16 EP EP16768566.8A patent/EP3276016B1/en active Active
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KR102027100B1 (en) | 2019-10-01 |
JP6719216B2 (en) | 2020-07-08 |
KR20170125981A (en) | 2017-11-15 |
EP3276016A1 (en) | 2018-01-31 |
EP3276016A4 (en) | 2018-08-22 |
CN107406918A (en) | 2017-11-28 |
JP2016183407A (en) | 2016-10-20 |
US20180044763A1 (en) | 2018-02-15 |
RU2695852C2 (en) | 2019-07-29 |
RU2017134565A3 (en) | 2019-04-09 |
RU2017134565A (en) | 2019-04-09 |
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