WO2017164602A1 - Alliage à entropie élevée à base de cr-fe-mn-ni-v - Google Patents

Alliage à entropie élevée à base de cr-fe-mn-ni-v Download PDF

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Publication number
WO2017164602A1
WO2017164602A1 PCT/KR2017/002989 KR2017002989W WO2017164602A1 WO 2017164602 A1 WO2017164602 A1 WO 2017164602A1 KR 2017002989 W KR2017002989 W KR 2017002989W WO 2017164602 A1 WO2017164602 A1 WO 2017164602A1
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atomic
alloy
phase
entropy alloy
high entropy
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PCT/KR2017/002989
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English (en)
Korean (ko)
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이병주
이성학
김형섭
나영상
홍순익
최원미
전창우
정승문
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포항공과대학교 산학협력단
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Priority claimed from KR1020170032630A external-priority patent/KR101888300B1/ko
Application filed by 포항공과대학교 산학협력단 filed Critical 포항공과대학교 산학협력단
Priority to US16/084,610 priority Critical patent/US10988834B2/en
Publication of WO2017164602A1 publication Critical patent/WO2017164602A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent

Definitions

  • the present invention relates to a high entropy alloy designed using a thermodynamic calculation of a computer simulation technique. Through the thermodynamic calculation, an alloy composition region having a microstructure of a face centered cubic (FCC) single phase is set up to 700 ° C. or more.
  • the present invention relates to a Cr-Fe-Mn-Ni-V-based high entropy alloy having excellent low-temperature tensile strength and elongation by allowing FCC single-phase microstructure at room temperature and cryogenic temperature after rapid heat treatment at 700 ° C or higher. .
  • High Entropy Alloy (HEA) alloy is a five-element or more multi-element alloy system. Despite being a high alloy system, the high entropy alloy has a high mixed entropy, so that no intermetallic compound is formed and the ductility is excellent.
  • Body Centered Cubic (BCC) is a new concept of new material consisting of a single phase.
  • High entropy alloys having a face-centered cubic lattice (FCC) structure not only have excellent fracture toughness at cryogenic temperatures, but also have excellent corrosion resistance, high mechanical strength, and high mechanical properties.
  • Republic of Korea Patent Publication No. 2016-0014130 is a high entropy alloy that can be used as a heat-resistant material Ti 16 . 6 Zr 16 . 6 Hf 16 . 6 Ni 16 . 6 Cu 16 .
  • High entropy alloys such as 6 Co 17 , Ti 16.6 Zr 16.6 Hf 16.6 Ni 16.6 Cu 16.6 Nb 17 have been proposed, and Japanese Laid-Open Patent Publication No. 2002-173732 discloses Cu-Ti-V-Fe-Ni-Zr as the main element. High entropy alloys with high hardness and corrosion resistance are proposed.
  • the present invention is to solve the problem to provide a Cr-Fe-Mn-Ni-V-based high entropy alloy having a FCC single-phase structure at room temperature and cryogenic temperature and having low temperature tensile strength and low temperature stretching characteristics can be used for cryogenic applications It is a task.
  • the present invention Cr: 3 to 18 atomic%, Fe: 3 to 60 atomic%, Mn: 3 to 40 atomic%, Ni: 20 to 80 atomic%, V: 3 to 12 atomic% It is to provide a high entropy alloy, containing unavoidable impurities, the ratio of the V content to the Ni content (V / Ni) is 0.5 or less.
  • the alloy having such a composition consists of a single phase of the FCC structure without formation of an intermediate phase, and exhibits better tensile strength and elongation at cryogenic temperature (77K) than at room temperature (298K).
  • the new high entropy alloys provided by the present invention have high tensile strength and elongation at cryogenic temperatures rather than at room temperature, and thus have high utility as structural materials used in extreme environments such as cryogenic environments.
  • 1 is a phase at 700 ° C. according to the molar fractions of iron (Fe), manganese (Mn) and nickel (Ni) of an alloy comprising 15 atomic% chromium (Cr) and 10 atomic% vanadium (V). Equilibrium information is shown.
  • FIG. 2 shows a change in equilibrium with temperature for an alloy having a composition marked with a star in FIG. 1.
  • FIG. 3 shows the phase at 700 ° C. according to the molar fractions of iron (Fe), manganese (Mn) and nickel (Ni) of an alloy comprising 10 atomic percent chromium (Cr) and 10 atomic percent vanadium (V). Equilibrium information is shown.
  • FIG. 4 illustrates a change in equilibrium with temperature of an alloy having a composition indicated by a star ( ⁇ ) in FIG.
  • FIG. 5 shows the phase at 700 ° C. according to the remaining mole fractions of chromium (Cr), nickel (Ni) and vanadium (V) of an alloy comprising 30 atomic% iron (Fe) and 20 atomic% manganese (Mn). Equilibrium information is shown.
  • FIG. 6 illustrates a change in equilibrium with temperature of an alloy having a composition indicated by a star ( ⁇ ) in FIG. 5.
  • FIG. 7 shows a binary alloy based state diagram composed of two elements of five elements of chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), and vanadium (V).
  • FIG. 10 is an EBSD phase map photograph of a high entropy alloy sheet prepared according to Examples 1 and 3 of the present invention.
  • FIG. 10 is an EBSD phase map photograph of a high entropy alloy sheet prepared according to Examples 1 and 3 of the present invention.
  • Figure 11 shows the results of room temperature (298K) tensile test of the high entropy alloy prepared according to Examples 1 and 3 of the present invention.
  • Figure 13 shows the cryogenic (77K) tensile test results of the high entropy alloy prepared according to Example 2 of the present invention.
  • Regions 1 and 2 in FIG. 1 represent regions for maintaining the FCC single phase at 700 ° C. or lower, and regions for maintaining two-phase or three-phase equilibrium are indicated in the remaining regions. Alloys having a composition belonging to region 2 of FIG. 1 maintain the FCC single phase from melting temperature up to 700 ° C. to 500 ° C. FIG. The composition at the two-phase equilibrium region and the boundary maintains the FCC single phase up to 700 ° C.
  • the line between the zone 1 and zone 2 is a line representing the boundary between the FCC single-phase zone and the two-phase equilibrium zone calculated at 500 ° C. Alloys having a composition belonging to zone 1 of FIG. Maintain FCC single phase. The composition located at the boundaries of zones 1 and 2 computationally maintains the FCC single phase up to 500 ° C.
  • FIG. 2 illustrates a change in equilibrium with temperature for an alloy having a composition indicated by a star ( ⁇ ) in FIG. 1.
  • An alloy having a composition indicated by a star ( ⁇ ) has a boundary between regions 2 and a two-phase equilibrium region in FIG. 1. Because of the composition located at, it forms the FCC single phase region from the melting temperature to 700 ° C.
  • 5 is an alloy containing 30 atomic% iron (Fe) and 20 atomic% manganese (Mn), according to the mole fractions of chromium (Cr), nickel (Ni) and vanadium (V), which are the remaining alloy components, Phase equilibrium information at 700 ° C is shown.
  • FIG. 6 shows a change in equilibrium with temperature of an alloy having a composition indicated by a star ( ⁇ ) in FIG.
  • FIG. 7 shows a binary alloy-based state diagram composed of two elements of five elements of chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), and vanadium (V).
  • the FCC single phase region and the sigma phase region which degrades mechanical properties are shown in dark color.
  • Six binary alloy systems containing no vanadium (V) have a small sigma phase region and a wide FCC single phase region.
  • the sigma phase is relatively widely distributed in four binary alloy systems including vanadium (V).
  • the sigma phase is distributed up to a high temperature at which the liquid phase is stable.
  • the sigma phase in the nickel (Ni) -vanadium (V) alloy-based state diagram mainly appears in the section where the ratio (V / Ni) of the vanadium (V) content to the nickel (Ni) content is high.
  • the section where the ratio of vanadium (V) to V content is low a wide FCC single phase section appears.
  • the present inventors are high-entropy alloys composed of FCC single phase and excellent low temperature characteristics, Cr: 3-18 atomic%, Fe: 3-60 atomic %, Mn: 3 to 40 atomic%, Ni: 20 to 80 atomic%, V: 3 to 12 atomic%, and inevitable impurities, and the ratio of V content to Ni content (V / Ni) is 0.5 or less High entropy alloys were derived.
  • the content of Mn is less than 3 atomic%, it is disadvantageous in terms of manufacturing cost, and if it is more than 40 atomic%, the phase becomes unstable, and it is disadvantageous due to oxide formation during the manufacturing process.
  • the Mn content is more preferably 10 to 25 atomic percent in terms of phase stability and mechanical properties.
  • Ni content When the content of Ni is less than 20 atomic%, the phase becomes unstable, and if it is more than 80 atomic%, it becomes disadvantageous in terms of manufacturing cost, so 20 to 80 atomic% is preferable, and the stability of the phase In terms of mechanical properties, more preferable Ni content is 25 to 45 atomic%.
  • V When the content of V is less than 3 atomic%, it is difficult to obtain a reinforcing effect, and when the content of V is higher than 12 atomic%, the possibility of forming an intermediate phase is increased, and 3 to 12 atomic% is preferable, and the phase stability, mechanical properties and In view of the production cost, a more preferable content of V is 5 to 12 atomic%.
  • the ratio of the V content to the content of Ni is preferably 0.5 or less.
  • composition range of the alloy it is difficult to obtain a solid solution having an FCC single phase when it is out of each composition constituting the alloy.
  • the sum of the Fe and Mn contents is preferably 50 atomic% or less.
  • the composition of each component constituting the high entropy alloy is 7-18 atomic% Cr, 18-35 atomic% Fe, 10-25 atomic% Mn. , Ni: 25 to 45 atomic%, V: 5 to 12 atomic%, more preferably the ratio (V / Ni) of the V content to the content of Ni is 0.5 or less.
  • the high entropy alloy may have a tensile strength of 1000 MPa or more and an elongation of 30% or more at cryogenic temperatures (77 K).
  • the high entropy alloy may have a tensile strength of 1000 MPa or more and an elongation of 60% or more at cryogenic temperatures (77 K).
  • the high entropy alloy may have a tensile strength of 800 MPa or more and an elongation of 30% or more at room temperature (298 K).
  • Table 1 below shows three compositions selected for the alloy preparation of the regions calculated through the above-mentioned thermodynamic review.
  • the ingot was prepared by a known method by dissolving the alloy at 1500 ° C or more using an induction furnace.
  • the alloy ingot was kept in the FCC single phase region for 2 hours at 1000 ° C. to homogenize the tissue, and then the homogenized ingot was pickled to remove surface impurities and oxide layer.
  • the pickled ingot was cold rolled at a reduction ratio of 75% to prepare a cold rolled sheet.
  • the cold rolled sheet was heat-treated (800 ° C., 2 hours) in the FCC single phase region to remove residual stress, completely recrystallized the crystal grains, and then cooled with water to prepare a high entropy alloy sheet.
  • the ingot of the alloy 1 was homogenized by maintaining the ingot in the FCC single-phase region at 1100 ° C. for 6 hours, and then the homogenized ingot was pickled to remove impurities and oxide layers from the surface.
  • the pickled ingot was cold rolled at a reduction ratio of 75% to prepare a cold rolled sheet.
  • the high entropy alloy sheet manufactured according to Example 2 is different from the heat treatment conditions in the same composition as in Example 1.
  • the microstructure of the high entropy alloy sheet prepared as described above was analyzed using a scanning electron microscope, an X-ray diffractometer and an EBSD.
  • FIG. 8 is an EBSD inverse pole figure (IPF) map photograph of a high entropy alloy sheet prepared according to Examples 1 and 2 of the present invention.
  • FIG. 8 is an EBSD inverse pole figure (IPF) map photograph of a high entropy alloy sheet prepared according to Examples 1 and 2 of the present invention.
  • the grain size can be measured, and the two alloys (Examples 1 and 3) subjected to cold rolling and recrystallization heat treatment with a 75% reduction ratio have an average grain size of 5.4-7.4 ⁇ m.
  • the crystalline phases were in polycrystalline form and their sizes were relatively uniform regardless of the alloy composition.
  • FIG. 10 is an EBSD phase map photograph of a high entropy alloy sheet prepared according to Examples 1 and 3 of the present invention.
  • FIG. The EBSD phase map displays each phase in a different color when two or more different phases are in the microstructure.
  • the alloys according to Example 1 and Example 3 are all the same. Shown in color, this means that the microstructure of these alloys consists of the FCC single phase and no second phase, such as a sigma phase, that degrades mechanical properties has been produced.
  • the yield strength at room temperature (298K) of the high entropy alloy sheet according to Examples 1 and 3 of the present invention is 460 to 503 MPa
  • tensile strength is 815 to 842 MPa
  • elongation is about 35 to 45% shows excellent tensile properties.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

La présente invention concerne un alliage à entropie élevée, ayant en particulier une excellente résistance à la traction à basse température et un excellent allongement grâce à la configuration, à l'aide de calculs thermodynamiques, d'une région de composition d'alliage ayant une microstructure monophasique FCC à 700 °C ou plus, et permettant la création de la microstructure monophasique FCC à température ambiante et à ultra-basse température. L'alliage à entropie élevée selon la présente invention comprend : Cr : 3-18 % atomique ; Fe : 3-60 % atomique ; Mn : 3-40 % atomique ; Ni: 20-80 % atomique ; V : 3-12 % atomique ; et des impuretés inévitables, le rapport entre la teneur en V et la teneur en Ni (V/Ni) étant inférieur ou égal à 0,5.
PCT/KR2017/002989 2016-03-21 2017-03-21 Alliage à entropie élevée à base de cr-fe-mn-ni-v WO2017164602A1 (fr)

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Application Number Priority Date Filing Date Title
US16/084,610 US10988834B2 (en) 2016-03-21 2017-03-21 Cr—Fe—Mn—Ni—V-based high-entropy alloy

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160033419 2016-03-21
KR10-2016-0033419 2016-03-21
KR1020170032630A KR101888300B1 (ko) 2016-03-21 2017-03-15 Cr-Fe-Mn-Ni-V계 고 엔트로피 합금
KR10-2017-0032630 2017-03-15

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108660354A (zh) * 2018-08-20 2018-10-16 太原理工大学 一种Fe-Mn-Cr-Ni系高熵不锈钢及其制备方法
US10640854B2 (en) 2016-08-04 2020-05-05 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11318566B2 (en) 2016-08-04 2022-05-03 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11339817B2 (en) 2016-08-04 2022-05-24 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11511375B2 (en) 2020-02-24 2022-11-29 Honda Motor Co., Ltd. Multi component solid solution high-entropy alloys

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002173732A (ja) * 2000-11-29 2002-06-21 Univ Qinghua ハイエントロピー多元合金
KR20090030198A (ko) * 2007-09-19 2009-03-24 인더스트리얼 테크놀로지 리써치 인스티튜트 초고경도 복합 물질 및 그 제조 방법
US20160025386A1 (en) * 2014-07-28 2016-01-28 Ut-Battelle, Llc High Entropy NiMn-based Magnetic Refrigerant Materials
JP2016023352A (ja) * 2014-07-23 2016-02-08 株式会社日立製作所 合金構造体
KR20160014130A (ko) * 2014-07-28 2016-02-11 세종대학교산학협력단 우수한 강도 및 연성을 갖는 하이엔트로피 합금

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002173732A (ja) * 2000-11-29 2002-06-21 Univ Qinghua ハイエントロピー多元合金
KR20090030198A (ko) * 2007-09-19 2009-03-24 인더스트리얼 테크놀로지 리써치 인스티튜트 초고경도 복합 물질 및 그 제조 방법
JP2016023352A (ja) * 2014-07-23 2016-02-08 株式会社日立製作所 合金構造体
US20160025386A1 (en) * 2014-07-28 2016-01-28 Ut-Battelle, Llc High Entropy NiMn-based Magnetic Refrigerant Materials
KR20160014130A (ko) * 2014-07-28 2016-02-11 세종대학교산학협력단 우수한 강도 및 연성을 갖는 하이엔트로피 합금

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10640854B2 (en) 2016-08-04 2020-05-05 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11318566B2 (en) 2016-08-04 2022-05-03 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11339817B2 (en) 2016-08-04 2022-05-24 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11535913B2 (en) 2016-08-04 2022-12-27 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
CN108660354A (zh) * 2018-08-20 2018-10-16 太原理工大学 一种Fe-Mn-Cr-Ni系高熵不锈钢及其制备方法
US11511375B2 (en) 2020-02-24 2022-11-29 Honda Motor Co., Ltd. Multi component solid solution high-entropy alloys

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