EP2402468A1 - Titanium alloy excellent in intergranular corrosion resistance - Google Patents

Titanium alloy excellent in intergranular corrosion resistance Download PDF

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Publication number
EP2402468A1
EP2402468A1 EP11005263A EP11005263A EP2402468A1 EP 2402468 A1 EP2402468 A1 EP 2402468A1 EP 11005263 A EP11005263 A EP 11005263A EP 11005263 A EP11005263 A EP 11005263A EP 2402468 A1 EP2402468 A1 EP 2402468A1
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Prior art keywords
content
nickel
titanium
titanium alloy
corrosion
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP11005263A
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German (de)
English (en)
French (fr)
Inventor
Takashi Yashiki
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Kobe Steel Ltd
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Kobe Steel Ltd
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Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Publication of EP2402468A1 publication Critical patent/EP2402468A1/en
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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/086—Heat exchange elements made from metals or metal alloys from titanium or titanium alloys

Definitions

  • the present invention relates to a titanium alloy which excels in corrosion resistance, particularly in intergranular corrosion resistance, in specific environments.
  • Titanium is known to show satisfactory corrosion resistance in chloride solutions such as seawater and in oxidizing acids such as nitric acid. Titanium, however, may not exhibit its satisfactory corrosion resistance when exposed to a non-oxidizing environment such as hydrochloric acid or sulfuric acid in a high concentration at high temperatures.
  • Ti-Pd alloys containing palladium (Pd) in a content of about 0.12% to 0.25% Japanese Industrial Standards (JIS) H 4650 Types 11 to 13; ASTM Grade 7 and Grade 11 have been employed.
  • Such novel inexpensive corrosion-resistant titanium alloys are known to develop corrosion resistance according to a mechanism different from that of existing inexpensive corrosion-resistant titanium alloys (e.g., " Tetsu-to-Hagane (in Japanese; Iron and Steel)", vol. 80, No. 4 (1994), p.353-358 ).
  • the novel inexpensive corrosion-resistant titanium alloys contain chromium (Cr) unlike the existing inexpensive corrosion-resistant titanium alloys.
  • novel alloys When the novel alloys are exposed to a corrosive environment, chromium selectively dissolves out during early stages of the exposure to allow Pd and Ru to be concentrated on the surface, in which Pd and Ru are platinum-group elements contained in less contents than those of the existing inexpensive corrosion resistant titanium alloys. As a result, the novel alloy exhibits satisfactory corrosion resistance even though they contain platinum-group elements in less contents.
  • the Ti-Ni-Pd-Ru-Cr alloys have been widely used typically in the chemical industry and in heat exchangers using seawater because of their inexpensiveness and satisfactory corrosion resistance. However, even the Ti-Ni-Pd-Ru-Cr alloys undergo corrosion in the form of intergranular corrosion in certain specific environments. Exemplary specific environments include severe use environments such that the Ti-Ni-Pd-Ru-Cr alloys are disable to maintain their passive state and that the Ti-Ni-Pd-Ru-Cr alloys have to be exchanged every several years; and environments typically in parts attached around electrodes of electrolysis tanks such that an anode current also passes through the Ti-Ni-Pd-Ru-Cr alloys.
  • Such corrosion-resistant titanium alloys are originally excellent in intergranular corrosion resistance, and even pure titanium is resistant to intergranular corrosion in regular environments.
  • intergranular corrosion may proceed in the specific use environments.
  • the intergranular corrosion is abominated by users because it may cause rapid fracture of apparatuses, unlike general corrosion which is a regular corrosion form. Accordingly, demands are made to provide a Ti-Ni-Pd-Ru-Cr alloy that can minimize the proceeding of intergranular corrosion even in the specific corrosive environments.
  • the present invention has been made under these circumstances, and an object thereof is to provide a titanium alloy that may minimize the proceeding of intergranular corrosion even in specific environments where the intergranular corrosion may easily proceed.
  • the present invention has achieved the object and provides, in an aspect, a titanium alloy which contains nickel (Ni) in a content of 0.35 to 0.55 percent by mass (hereinafter contents will be simply expressed in"%"); palladium (Pd) in a content of 0.01% to 0.02%; ruthenium (Ru) in a content of 0.02% to 0.04%; and chromium (Cr) in a content of 0.1% to 0.2%, with the remainder including titanium and inevitable impurities, in which the titanium alloy includes nickel-rich phases, each nickel-rich phase being a phase (other than titanium alpha phase) locally containing Ni in a content of 10 times or more the average Ni content of the titanium alloy, the nickel-rich phases are aligned along a rolling direction to form a row, and a multiplicity of the rows are aligned substantially in parallel in a cross direction.
  • the respective titanium alloys according to the present invention may be obtained by performing final annealing at a temperature in the range of 600°C to 725°C after rolling.
  • the conditions for final annealing after rolling of Ti-Ni-Pd-Ru-Cr alloys are suitably controlled, and whereby the titanium alloys are allowed to have (1) a microstructure in which the nickel-rich phases are aligned along a rolling direction to form a row, and a multiplicity of the rows are aligned substantially in parallel in a cross direction; or (2) a microstructure in which the nickel-rich phases mainly contain Ti 2 Ni.
  • the resulting titanium alloys excel in intergranular corrosion resistance in specific environments and are thereby very useful as materials typically for apparatuses to be used in such environments which are believed to cause intergranular corrosion.
  • the present inventors made various investigations to improve intergranular corrosion resistance of Ti-Ni-Pd-Ru-Cr alloys and, as a result, have found that titanium alloys manufactured through final annealing at a temperature in the range of 600°C to 725°C have distinct microstructures.
  • the titanium alloys manufactured through final annealing at a temperature in the above-specified range include nickel-rich phases, each nickel-rich phase being a phase (other than titanium alpha phase) locally containing Ni in a content of 10 times or more the average Ni content of the titanium alloy and have (1) a microstructure in which the nickel-rich phases are aligned along the rolling direction to form a row, and a multiplicity of the rows are aligned substantially in parallel in the cross direction; or (2) a microstructure in which the nickel-rich phases contain Ti 2 Ni.
  • the present inventors have also found that the titanium alloys having these microstructures may exhibit satisfactory intergranular corrosion resistance even in specific corrosive environments where customary titanium alloys suffer from intergranular corrosion. The present invention has been made based on these findings.
  • the "nickel-rich phase” being a phase (other than titanium alpha phase) locally containing Ni in a content of 10 times or more the average Ni content, and the microstructure containing Ti 2 Ni may be verified by observation under a transmission electron microscope (TEM) or electron diffraction analysis of the crystal structure.
  • TEM transmission electron microscope
  • a rolled plate manufactured through final annealing at a temperature of 750°C includes nickel-rich phases which are somewhat aligned in a row, but includes not so many rows of nickel-rich phases as in the cold-rolled plates manufactured at final annealing temperatures of 650°C and 725°C; and that cold-rolled plates manufactured through final annealing at temperatures of 800°C and 830°C include nickel-rich phases, but the nickel-rich phases do not substantially form rows.
  • the time or duration for final annealing (the time for which the article is exposed to the annealing temperature) is about 1 to 10 minutes in the case of continuous annealing (and acid wash) in an air atmosphere. It generally takes about 1 to 8 hours to attain uniform heating of the entire coil (plate) in the case of vacuum annealing.
  • Nickel (Ni) element is relatively inexpensive as compared to Pd and, when contained in a content of 0.35% or more, is effective to impart corrosion resistance (corrosion resistance in a non-oxidizing environment in an atmosphere at high temperature and at a high concentration) to the titanium alloys even when Pd is contained in a lower content.
  • corrosion resistance corrosion resistance in a non-oxidizing environment in an atmosphere at high temperature and at a high concentration
  • Ni if present in a content of more than 0.55%, may cause the titanium alloys to have poor workability.
  • the lower limit of the Ni content is preferably 0.40% or more, and more preferably 0.45% or more, from the viewpoint of corrosion resistance.
  • Ruthenium (Ru) element is, as with Ni, relatively inexpensive as compared to Pd and, when contained in a content of 0.02% or more, is effective to impart corrosion resistance (corrosion resistance in a non-oxidizing environment in an atmosphere at high temperature and at a high concentration) to the titanium alloys even when Pd is contained in a lower content
  • corrosion resistance corrosion resistance in a non-oxidizing environment in an atmosphere at high temperature and at a high concentration
  • Ru if present in a content of more than 0.04%, causes excessively high material cost, thus being undesirable.
  • the lower limit of the Ru content is preferably 0.025% or more, and more preferably 0.03% or more, from the viewpoint of corrosion resistance.
  • Chromium (Cr) element contributes to improvements of corrosion resistance and crevice corrosion resistance of titanium alloys without adversely affecting the workability. By using in combination with the above-mentioned elements, Cr further improves the corrosion resistance of titanium alloys. To exhibit these effects, Cr should be contained in a content of 0.1% or more. However, the Cr content should be 0.2% or less, because Cr, if contained in excess, may adversely affect the workability. The lower limit of the Cr content is preferably 0.12% or more, and more preferably 0.15% or more, from the viewpoint of corrosion resistance.
  • the titanium alloys according to the present invention have improved intergranular corrosion resistance by having the above-mentioned microstructures, probably because the coexistence of Ni and Cr, main added elements of the titanium alloys, affects the intergranular corrosion resistance in some manner or other.
  • the anodic reaction and the cathodic reaction occur simultaneously inside and outside of the crevice at early stages, but dissolved oxygen or hydrogen ion is hardly fed into the crevice from the outside of the crevice, and this causes a difference in concentration of oxidizing agent between inside and outside of the crevice. Accordingly, an oxidizing-agent concentration cell is formed between the inside and outside of the crevice, in which the anodic reaction occurs inside the crevice and the cathodic reaction occurs outside the crevice. Inside the crevice, the H + concentration increases due to the anodic reaction, and the pH decreases.
  • anions such as Cl - migrate from the outside of the crevice to form a high-concentration hydrochloric acid. This impedes the maintenance of passive state to lead to active dissolution, namely, crevice corrosion.
  • Ti-Ni-Pd-Ru-Cr alloy i.e., JIS Type 14 cold-rolled annealed plate (Ti-0.4Ni-0.015Pd-0.025R.u-0.14Cr alloy) was subjected to cold rolling at a rolling reduction of 40% to a plate thickness of 1.1 mm, the resulting plate was divided in small necessary quantities, subjected sequentially to the following air annealing (final annealing), salt immersion, and acid wash treatments simulating continuous annealing and acid wash processes, and thereby yielded corrosion specimens.
  • air annealing final annealing
  • salt immersion salt immersion
  • acid wash treatments simulating continuous annealing and acid wash processes
  • the manufactured corrosion specimens were subjected to corrosion tests under the following conditions, and corrosion resistance of the specimens was determined.
  • the test conditions simulate such a severe use environment that Ti-Ni-Pd-Ru-Cr alloys to which the present invention is applied do not maintain their passive state.
  • FIGS. 2A, 2B, 2C , 3A, 3B, 3C, and 3D depicts one obtained at an annealing temperature of 670°C
  • FIG. 2B depicts one obtained at an annealing temperature of 700°C
  • FIG. 2C depicts one obtained at an annealing temperature of 725°C
  • FIG. 3A depicts one obtained at an annealing temperature of 750°C
  • FIG. 3B depicts one obtained at an annealing temperature of 775°C
  • FIG. 3C depicts one obtained at an annealing temperature of 800°C
  • FIG. 3D depicts one obtained at an annealing temperature of 830°C, respectively.
  • FIG. 4 depicts results of EPMA mapping ofNi and Cr in cross section (L direction cross section) of the specimens used in the corrosion tests (also see FIG. 1 regarding the Ni mapping of specimens prepared at annealing temperatures of 650°C to 830°C).
  • the results demonstrate that the titanium alloys containing both Ni and Cr include Ni and Cr which are distributed in coexistence; and that the specimens prepared through final annealing at temperatures of 750°C or higher include Ni and Cr which are distributed in remarkable coexistence (namely, Ni and Cr are distributed in the same manner). This indicates that the coexistence of Ni and Cr adversely affects intergranular corrosion resistance.
  • FIGS. 6A and 6B exemplary images in 14- ⁇ m square fields of view are shown in FIGS. 6A and 6B (photographs).
  • TEM transmission electron microscope
  • FIGS. 6A and 6B photographs.
  • Precipitates with a size of 0.2 ⁇ m or more are circled in the TEM images, and by spot-spectrometry of these precipitates in TEM, the Ni content may be measured.
  • FIG. 6A depicts an image where the nickel-rich phase is Ti 2 Ni
  • FIG. 6B depicts an image where the nickel-rich phase is the beta phase.
  • the raw-material ingot for the samples had Ni contents of 0.49% and 0.43% at the top and the bottom, respectively. Accordingly, the matrix (base metal) had an average Ni content of 0.46%.
  • nickel-rich phases are phases each having a Ni content of 10 times or more the average Ni content of the matrix. In this connection, the mapping indicated that most of the precipitates are nickel-rich phases.
  • the precipitates are Ti 2 Ni or the beta phase can be determined by applying electron beams to each of the precipitates, and analyzing the crystal structures of the precipitates through electron diffraction analysis. Exemplary results of the analysis of nickel-rich phases are also illustrated in FIGS. 6A and 6B .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP11005263A 2010-06-29 2011-06-28 Titanium alloy excellent in intergranular corrosion resistance Ceased EP2402468A1 (en)

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JP2010148100A JP5379752B2 (ja) 2010-06-29 2010-06-29 耐粒界腐食性に優れたチタン合金

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US (1) US20110315278A1 (ru)
EP (1) EP2402468A1 (ru)
JP (1) JP5379752B2 (ru)
KR (1) KR20120001660A (ru)
CN (1) CN102312126A (ru)
RU (1) RU2464334C1 (ru)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2883972A4 (en) * 2012-08-10 2016-04-06 Nippon Steel & Sumitomo Metal Corp TITANIUM ALLOY MATERIAL
EP3266887A4 (en) * 2015-03-02 2018-07-18 Nippon Steel & Sumitomo Metal Corporation Thin titanium sheet and manufacturing method therefor

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CN103212570B (zh) * 2013-03-22 2015-12-09 西安思维金属材料有限公司 钛镍基形状记忆合金大单重盘条的半连轧加工方法
US10574515B2 (en) * 2014-06-05 2020-02-25 Lg Electronics Inc. Method for configuring transmission opportunity section in wireless access system supporting unlicensed band, and device for supporting same
CN104084712B (zh) * 2014-07-04 2016-08-24 哈焊所华通（常州）焊业股份有限公司 一种耐腐蚀性强的钛合金焊接用低成本钛合金焊丝
WO2016047692A1 (ja) * 2014-09-25 2016-03-31 新日鐵住金株式会社 Ｒｕを含有する耐食チタン合金の製造方法
KR102100946B1 (ko) * 2015-07-29 2020-04-14 닛폰세이테츠 가부시키가이샤 티탄 복합재 및 열간 압연용 티탄재
JP6686744B2 (ja) * 2016-07-04 2020-04-22 日本製鉄株式会社 チタン合金板およびその製造方法。
CN108300899A (zh) * 2018-02-02 2018-07-20 宝鸡巨成钛业股份有限公司 耐腐蚀钛合金及钛合金板材的制备方法
CN108998696A (zh) * 2018-07-20 2018-12-14 中国航发北京航空材料研究院 一种海洋工程装备用中强耐腐蚀钛合金
KR102698892B1 (ko) 2019-10-30 2024-08-27 닛폰세이테츠 가부시키가이샤 티타늄 합금
KR102678251B1 (ko) 2021-11-19 2024-06-26 한국생산기술연구원 급랭으로 미세 석출물을 가지는 고내식성 타이타늄 합금 제조방법 및 이를 통해 제조된 고내식성 타이타늄 합금
KR102544467B1 (ko) 2022-10-05 2023-06-20 한밭대학교 산학협력단 응력부식저항성을 갖는 크롬 첨가 타이타늄 합금 및 이의 제조방법

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JPH0457735A (ja) 1990-06-22 1992-02-25 Mitsui Toatsu Chem Inc 移送保管容器
JPH04308051A (ja) 1991-01-16 1992-10-30 Kobe Steel Ltd 耐蝕性Ｔｉ基合金

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2883972A4 (en) * 2012-08-10 2016-04-06 Nippon Steel & Sumitomo Metal Corp TITANIUM ALLOY MATERIAL
EP3575422A1 (en) * 2012-08-10 2019-12-04 Nippon Steel Corporation Titanium alloy material
EP3266887A4 (en) * 2015-03-02 2018-07-18 Nippon Steel & Sumitomo Metal Corporation Thin titanium sheet and manufacturing method therefor
US10480050B2 (en) 2015-03-02 2019-11-19 Nippon Steel Corporation Titanium sheet and method for producing the same

Also Published As

Publication number Publication date
RU2464334C1 (ru) 2012-10-20
JP5379752B2 (ja) 2013-12-25
JP2012012636A (ja) 2012-01-19
CN102312126A (zh) 2012-01-11
KR20120001660A (ko) 2012-01-04
US20110315278A1 (en) 2011-12-29

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