WO2019198147A1 - チタン合金およびその製造方法 - Google Patents

チタン合金およびその製造方法 Download PDF

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Publication number
WO2019198147A1
WO2019198147A1 PCT/JP2018/015065 JP2018015065W WO2019198147A1 WO 2019198147 A1 WO2019198147 A1 WO 2019198147A1 JP 2018015065 W JP2018015065 W JP 2018015065W WO 2019198147 A1 WO2019198147 A1 WO 2019198147A1
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WIPO (PCT)
Prior art keywords
content
titanium alloy
phase
corrosion resistance
titanium
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PCT/JP2018/015065
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English (en)
French (fr)
Japanese (ja)
Inventor
浩史 神尾
一浩 ▲高▼橋
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日本製鉄株式会社
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Application filed by 日本製鉄株式会社 filed Critical 日本製鉄株式会社
Priority to CN201880091738.XA priority Critical patent/CN111902550B/zh
Priority to PCT/JP2018/015065 priority patent/WO2019198147A1/ja
Priority to RU2020128914A priority patent/RU2752094C1/ru
Priority to KR1020207026577A priority patent/KR102340036B1/ko
Priority to JP2020512970A priority patent/JP6927418B2/ja
Publication of WO2019198147A1 publication Critical patent/WO2019198147A1/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
    • 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

Definitions

  • the present invention relates to a titanium alloy and a manufacturing method thereof.
  • Industrial pure titanium exhibits excellent corrosion resistance even in seawater that is corroded by general-purpose stainless steel such as SUS304. Utilizing this high corrosion resistance, it is used in seawater desalination plants.
  • materials for chemical plants may be used in environments that are more corrosive than seawater such as hydrochloric acid. Under such circumstances, industrial pure titanium also corrodes significantly.
  • Patent Document 1 discloses an alloy to which a platinum group element such as Pd is added.
  • Patent Document 2 and Non-Patent Document 1 disclose alloys in which intermetallic compounds are precipitated in addition to the addition of platinum group elements.
  • titanium alloys use rare elements such as Pd, the material cost is improved. Therefore, there is a problem of improving the corrosion resistance of titanium without using an expensive rare element. Accordingly, various proposals have been made regarding titanium alloys that use general-purpose elements without using rare elements.
  • Patent Document 3 discloses an invention in which Ti is used to improve the corrosion resistance and strength of Ti.
  • the titanium alloy described in Patent Document 3 has a problem in workability because TiC is precipitated, which causes a problem when actually applied to a heat exchanger or a plant member.
  • An object of the present invention is to provide a titanium alloy having improved corrosion resistance while maintaining high workability by adding C instead of a rare element.
  • a titanium alloy added with 0.10 to 0.30% C is heat-treated at 750 to 820 ° C. and cooled at a rate of 0.001 ° C./sec or more.
  • the present inventors have found that the surface texture can be made into an ⁇ single phase, and the corrosion resistance can be improved while maintaining excellent workability.
  • the gist of the present invention is as follows. (1) By mass%, C: 0.10 to 0.30%, N: 0.001 to 0.03%, S: 0.001 to 0.03%, P: 0.001 to 0.03% , Si: 0.001 to 0.10%, Fe: 0.01 to 0.3%, H: 0.015% or less, O: 0.25% or less, the balance being Ti and inevitable impurities , Titanium alloy whose surface structure is ⁇ single phase.
  • a method for producing a titanium alloy comprising subjecting a titanium alloy to a finish heat treatment at 750 to 820 ° C. and cooling at a rate of 0.001 ° C./sec or more.
  • the present invention it is possible to provide a titanium alloy having good corrosion resistance while maintaining high workability. Specifically, when a titanium alloy having the composition range of the present invention is produced by the production method of the present invention, the surface structure becomes an ⁇ single phase, and both workability and corrosion resistance are improved.
  • the titanium alloy of the present invention has C: 0.10 to 0.30%, N: 0.001 to 0.03%, S: 0.001 to 0.03%, P: 0.001 to 0.03% , Si: 0.001 to 0.10%, Fe: 0.01 to 0.3%, H: 0.015% or less (including 0%), O: 0.25% or less (including 0%)
  • the balance is Ti and inevitable impurities. In the following description, all contents indicated by “%” indicate “% by mass”.
  • ⁇ C 0.10 to 0.30%> C plays an important role in improving the corrosion resistance in the present invention.
  • the corrosion rate decreases and the corrosion resistance improves (FIG. 1).
  • the effect of improving corrosion resistance due to the C content is remarkably exhibited when the content is 0.10% or more.
  • the effect of improving corrosion resistance by adding C is most remarkable when an ⁇ single-phase structure is formed and C exists as an interstitial solid solution element in the ⁇ phase.
  • the addition of a large amount of C is not preferable because it promotes the precipitation of TiC which adversely affects workability. Addition of a large amount of C not only adversely affects the workability but also does not sufficiently exhibit the effect of improving corrosion resistance.
  • the C content is 0.10 to 0.30%.
  • a more preferable lower limit of the content of solid solution C is 0.12%, and a more preferable upper limit of the content of solid solution C is 0.28%.
  • the ⁇ phase in which C dissolves as an interstitial solid solution element is the ⁇ phase of the surface texture described later.
  • N is an essential element effective for improving the strength, but as its content increases, ductility and toughness deteriorate.
  • N is an interstitial solid solution element, like C, which plays an important role in improving corrosion resistance in the present invention. Therefore, there is a possibility that the solid solution content of C is lowered due to the increase of the N content. Therefore, the N content is set to 0.001 to 0.03%. A more preferable upper limit of the N content is 0.025%.
  • S is an essential element effective for improving the strength, but as its content increases, ductility and toughness deteriorate. Further, S is an interstitial solid solution element as C plays an important role in improving the corrosion resistance in the present invention. Therefore, there is a possibility that the solid solution content of C is lowered due to the increase of the S content. Therefore, the S content is set to 0.001 to 0.03%. A more preferable upper limit of the S content is 0.025%.
  • P is an essential element effective for improving the strength, but the ductility and toughness deteriorate as the content increases. Further, P is an interstitial solid solution element like C that plays an important role in improving the corrosion resistance in the present invention. Therefore, there exists a possibility that the solid solution content of C may fall by the increase in P content. Therefore, the P content is 0.001 to 0.03%. A more preferable upper limit of the P content is 0.025%.
  • Si 0.001 to 0.10%>
  • Si is a relatively inexpensive element and is an effective element for improving heat resistance (oxidation resistance, high temperature strength).
  • heat resistance oxidation resistance, high temperature strength
  • the Si content is 0.001 to 0.10%.
  • a more preferable lower limit of the Si content is 0.003%, and a more preferable upper limit of the Si content is 0.08%.
  • Fe is an element effective for improving the strength, but the ductility and toughness deteriorate as the content increases. Moreover, Fe is a strong ⁇ -stabilizing element among the elements contained in the titanium alloy of the present invention, and when added in a large amount, it becomes difficult to obtain an ⁇ single-phase structure described later. Therefore, the Fe content is set to 0.01 to 0.30%. A more preferable lower limit of the Fe content is 0.03%, and a more preferable upper limit of the Fe content is 0.25%.
  • H is an element that forms titanium hydride and degrades the ductility and toughness of the material. Therefore, it is better that the content is small, but an increase in H is inevitable in the manufacturing process.
  • H is an interstitial solid solution element as well as C which plays an important role in improving the corrosion resistance in the present invention. Therefore, there is a possibility that the solid solution content of C is lowered due to the increase of the H content. Therefore, the H content is limited to 0.015% or less.
  • high-purity sponge titanium may be used, but if too much high-purity sponge titanium is used, the cost increases.
  • H is an impurity element and may be 0%, but H is preferably 0.001% or more from the viewpoint of cost. A more preferable upper limit of the H content is 0.005%.
  • O is an essential element effective for improving the strength, but the ductility and toughness deteriorate as the content increases.
  • O is an interstitial solid solution element as C plays an important role in improving the corrosion resistance in the present invention. Therefore, there is a possibility that the solid solution content of C decreases due to an increase in the O content. Therefore, the O content is 0.25% or less.
  • high-purity sponge titanium may be used, but if too much high-purity sponge titanium is used, the cost increases.
  • O is an impurity element and may be 0%. From the viewpoint of cost, O is preferably 0.01% or more. A more preferable upper limit of the O content is 0.20%.
  • ⁇ Surface is ⁇ single phase>
  • the surface layer is ⁇ single phase means that the surface layer structure is ⁇ phase and the intensity of the X-ray diffraction peak of TiC is 10% or less compared to the background intensity.
  • the surface layer is a range from the surface to a depth of 5 ⁇ m.
  • the ⁇ phase does not include the ⁇ ′ phase or the acicular ⁇ phase.
  • FIG. 3 shows the state of the surface of the titanium alloy manufactured by the manufacturing method of the present invention.
  • the ⁇ phase is composed of a hexagonal close packed structure, and has a different crystal structure and grain boundary distribution from the ⁇ ′ phase and the acicular ⁇ phase formed by transformation from the ⁇ phase.
  • C atoms dissolved in the ⁇ phase are likely to exist as interstitial solid solution elements between Ti atoms, and the corrosion resistance can be improved by acting on the electronic state existing around the Ti nucleus to suppress the anode reaction.
  • An anode reaction refers to a reaction in which a metal corrodes and becomes ionized. When the metal is ionized, it is necessary to dissociate the electrons from the Ti nucleus, and by dissolving C in the ⁇ phase, it is difficult for the electrons to dissociate and the corrosion resistance is improved.
  • the ⁇ ′ phase is not a close-packed structure, and the acicular ⁇ phase is largely affected by segregation at the grain boundaries, so that a sufficient corrosion resistance improvement effect cannot be obtained compared to the ⁇ phase.
  • TiC is a hard compound and significantly deteriorates the workability of the material.
  • the carbon of the titanium alloy of the present invention is almost solid-solved and TiC hardly precipitates, the workability is not deteriorated.
  • the heat treatment temperature is 750 to 820 ° C.
  • the holding time is no particular limitation on the holding time in this temperature range, and holding for 1 sec or longer, preferably 30 sec or longer is sufficient.
  • FIG. 4 shows a surface layer of a titanium alloy manufactured by a conventional method in which heat treatment is performed outside this temperature range. In the surface layer, island-like TiC precipitates are generated (FIG. 4). TiC is a hard compound and significantly deteriorates the workability of the material. Therefore, the workability of the titanium alloy manufactured by the conventional method is deteriorated.
  • the cooling rate of the present invention is 0.001 ° C./sec or more, preferably 1 ° C./sec or more. A higher cooling rate can suppress the precipitation of TiC. However, an excessively high cooling rate adversely affects the shape maintenance of the titanium plate, so the upper limit is set to 2000 ° C./sec.
  • the manufacturing method of the titanium alloy of this invention is demonstrated.
  • the titanium alloy of the present invention as with normal industrial pure titanium, may be used at any time between each process such as casting ⁇ bullet rolling (or hot forging) ⁇ hot rolling ⁇ annealing ( ⁇ cold rolling ⁇ final annealing). By using blasting, pickling treatment, etc., it can be produced without using any special method.
  • the step of parentheses ⁇ cold rolling ⁇ final annealing
  • Titanium ingots having respective component compositions shown in Table 1 were cast in a vacuum arc melting furnace using a melting raw material containing sponge titanium and a predetermined additive element.
  • the additive elements Fe was added with electrolytic iron, and C was added with TiC powder.
  • Al, V, Cr, Ru, Pd, Ni, and Co are not intentionally added elements, and the values in the table indicate that the content of each of the above elements is at an impurity level. Is.
  • test piece for corrosion resistance evaluation is produced by pickling and machining. did. Then, vacuum annealing was implemented at each temperature shown in Table 2, and corrosion resistance was evaluated.
  • the surface texture was identified by XRD (X-ray diffraction) and microstructure observation.
  • the X-ray diffraction conditions were CoK ⁇ rays as characteristic X-rays, a voltage of 30 kV, and a current of 100 mA.
  • the range of X-ray diffraction was 10 ° ⁇ 2 ⁇ ⁇ 110 °, the step was 0.04 °, the integration time was 2 s, and the X-ray incident angle was 0.3 °.
  • the corrosion resistance was evaluated based on the calculated corrosion rate by immersing the test piece at 90 ° C. in a 3 mass% hydrochloric acid aqueous solution for 168 hours and comparing the weight before and after the immersion. The case where the corrosion rate was 2 mm / year or less was regarded as acceptable. Table 2 shows the results of the corrosion resistance evaluation test.
  • the workability was evaluated by the tensile test by the method described in JIS Z 2241 and the elongation. The measurement of elongation was performed by an extensometer, and the case where the total elongation was 40% or more was regarded as acceptable.
  • No. 10 to 16 are material components such as carbon within the scope of the present invention, but the heat treatment temperature or cooling rate is outside the scope of the present invention, so the surface texture does not become ⁇ single phase and the corrosion rate is greatly satisfied.
  • No elongation was shown. No. Since 14, 16, 18, and 20 had a slow cooling rate, TiC precipitated during the cooling process. No. In elements 17 to 24, elements such as S, P, Si and the like that lower the solid solubility limit of C are added beyond the range of the present invention. Further, the corrosion resistance was not improved, and TiC was precipitated, so that the elongation was low. Nos. 1 and 5 showed almost no discoloration or the like in the outdoor environment, whereas Nos. 23 and 24 had a brown surface in the outdoor environment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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PCT/JP2018/015065 2018-04-10 2018-04-10 チタン合金およびその製造方法 WO2019198147A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201880091738.XA CN111902550B (zh) 2018-04-10 2018-04-10 钛合金及其制造方法
PCT/JP2018/015065 WO2019198147A1 (ja) 2018-04-10 2018-04-10 チタン合金およびその製造方法
RU2020128914A RU2752094C1 (ru) 2018-04-10 2018-04-10 Титановый сплав и способ его получения
KR1020207026577A KR102340036B1 (ko) 2018-04-10 2018-04-10 티타늄 합금 및 그의 제조 방법
JP2020512970A JP6927418B2 (ja) 2018-04-10 2018-04-10 チタン合金およびその製造方法

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WO2024100802A1 (ja) * 2022-11-09 2024-05-16 日本製鉄株式会社 チタン材、化学装置部品、及び化学装置

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KR102678251B1 (ko) * 2021-11-19 2024-06-26 한국생산기술연구원 급랭으로 미세 석출물을 가지는 고내식성 타이타늄 합금 제조방법 및 이를 통해 제조된 고내식성 타이타늄 합금

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011144413A (ja) * 2010-01-13 2011-07-28 Kobe Steel Ltd 超音波探傷試験における欠陥検出能力に優れたチタン合金ビレット
JP2013095964A (ja) * 2011-10-31 2013-05-20 Kobe Steel Ltd チタン板、チタン板の製造方法、およびプレート式熱交換器の熱交換プレートの製造方法
JP2014205904A (ja) * 2013-03-19 2014-10-30 株式会社神戸製鋼所 チタン板
WO2017018522A1 (ja) * 2015-07-29 2017-02-02 新日鐵住金株式会社 チタン複合材および熱間加工用チタン材

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5727821Y2 (ru) * 1976-02-27 1982-06-17
JPH0625779A (ja) 1992-07-08 1994-02-01 Nkk Corp 硫酸及び塩酸に対する耐食性に優れたチタン合金
JP3426605B2 (ja) * 1995-04-21 2003-07-14 新日本製鐵株式会社 高強度・高延性チタン合金およびその製造方法
US20070062614A1 (en) 2005-09-19 2007-03-22 Grauman James S Titanium alloy having improved corrosion resistance and strength
JP3916088B2 (ja) 2005-12-28 2007-05-16 住友金属工業株式会社 耐食材用チタン合金
JP5491882B2 (ja) * 2010-01-27 2014-05-14 株式会社神戸製鋼所 冷間圧延性に優れた高強度チタン板
RU2643736C2 (ru) * 2014-01-22 2018-02-05 Ниппон Стил Энд Сумитомо Метал Корпорейшн Титановый материал или материал из титанового сплава, имеющий поверхностную электропроводность, а также использующие его сепаратор топливной ячейки и топливная ячейка
CN104099531B (zh) * 2014-07-31 2016-08-24 宁国市宁武耐磨材料有限公司 一种高硬度耐磨球及其制备方法
JP6719216B2 (ja) * 2015-03-26 2020-07-08 株式会社神戸製鋼所 α−β型チタン合金

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011144413A (ja) * 2010-01-13 2011-07-28 Kobe Steel Ltd 超音波探傷試験における欠陥検出能力に優れたチタン合金ビレット
JP2013095964A (ja) * 2011-10-31 2013-05-20 Kobe Steel Ltd チタン板、チタン板の製造方法、およびプレート式熱交換器の熱交換プレートの製造方法
JP2014205904A (ja) * 2013-03-19 2014-10-30 株式会社神戸製鋼所 チタン板
WO2017018522A1 (ja) * 2015-07-29 2017-02-02 新日鐵住金株式会社 チタン複合材および熱間加工用チタン材

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SIMBI D. J. ET AL.: "The effect of residual interstitial elements and iron on mechanical properties of commercially pure titanium", MATERIALS LETTERS, vol. 26, no. 1 / 2, January 1996 (1996-01-01), pages 35 - 39, XP022268755, DOI: 10.1016/0167-577X(95)00204-9 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024100802A1 (ja) * 2022-11-09 2024-05-16 日本製鉄株式会社 チタン材、化学装置部品、及び化学装置

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KR20200118878A (ko) 2020-10-16
KR102340036B1 (ko) 2021-12-16
JPWO2019198147A1 (ja) 2021-01-14
CN111902550B (zh) 2022-03-08
RU2752094C1 (ru) 2021-07-22
CN111902550A (zh) 2020-11-06
JP6927418B2 (ja) 2021-08-25

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