EP3276016B1 - Alpha-beta titanium alloy - Google Patents

Alpha-beta titanium alloy Download PDF

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Publication number
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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titanium alloy
content
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cutting
machinability
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German (de)
English (en)
French (fr)
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EP3276016A1 (en
EP3276016A4 (en
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Keitaro Tamura
Koichi Akazawa
Yoshio Itsumi
Hideto Oyama
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority claimed from PCT/JP2016/058247 external-priority patent/WO2016152663A1/ja
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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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JP2015064275 2015-03-26
JP2016009417A JP6719216B2 (ja) 2015-03-26 2016-01-21 α−β型チタン合金
PCT/JP2016/058247 WO2016152663A1 (ja) 2015-03-26 2016-03-16 α－β型チタン合金

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CN107858558B (zh) * 2017-11-23 2019-09-03 北京有色金属研究总院 一种超塑性钛合金板材及其制备方法
JP6927418B2 (ja) * 2018-04-10 2021-08-25 日本製鉄株式会社 チタン合金およびその製造方法
CN108559872B (zh) * 2018-06-05 2020-06-30 中国航发北京航空材料研究院 一种TiAl合金及其制备方法
JP6901049B2 (ja) * 2019-04-17 2021-07-14 日本製鉄株式会社 チタン合金板、チタン合金板の製造方法、銅箔製造ドラム及び銅箔製造ドラムの製造方法
JP7387139B2 (ja) * 2019-08-22 2023-11-28 国立研究開発法人物質・材料研究機構 チタン合金、その製造方法およびそれを用いたエンジン部品
EP4340961A1 (en) * 2021-05-19 2024-03-27 Karsten Manufacturing Corporation Beta enhanced titanium alloys and methods of manufacturing beta enhanced titanium alloys
KR102544467B1 (ko) * 2022-10-05 2023-06-20 한밭대학교 산학협력단 응력부식저항성을 갖는 크롬 첨가 타이타늄 합금 및 이의 제조방법

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RU2017134565A (ru) 2019-04-09
EP3276016A1 (en) 2018-01-31
JP2016183407A (ja) 2016-10-20
CN107406918A (zh) 2017-11-28
KR102027100B1 (ko) 2019-10-01
US20180044763A1 (en) 2018-02-15
KR20170125981A (ko) 2017-11-15
RU2695852C2 (ru) 2019-07-29
JP6719216B2 (ja) 2020-07-08
EP3276016A4 (en) 2018-08-22

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