WO2002034958A1 - Alliages a memoire a base de silicone-manganese-fer contenant du chrome et de l'azote - Google Patents

Alliages a memoire a base de silicone-manganese-fer contenant du chrome et de l'azote Download PDF

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Publication number
WO2002034958A1
WO2002034958A1 PCT/IB2001/002009 IB0102009W WO0234958A1 WO 2002034958 A1 WO2002034958 A1 WO 2002034958A1 IB 0102009 W IB0102009 W IB 0102009W WO 0234958 A1 WO0234958 A1 WO 0234958A1
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WO
WIPO (PCT)
Prior art keywords
shape memory
alloy
memory alloy
iron
manganese
Prior art date
Application number
PCT/IB2001/002009
Other languages
English (en)
Inventor
Xu Zuyao
Chen Shipu
Wan Jainfeng
Guo Zhenghong
Zhang Jihua
Rong Yonghua
Original Assignee
Emerson Electric (China) Holdings Co. Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Emerson Electric (China) Holdings Co. Ltd. filed Critical Emerson Electric (China) Holdings Co. Ltd.
Priority to AU2002212572A priority Critical patent/AU2002212572A1/en
Publication of WO2002034958A1 publication Critical patent/WO2002034958A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/01—Shape memory effect

Definitions

  • the present invention relates to a shape memory alloys.
  • it relates to iron-manganese-silicon-based shape memory alloys containing Cr and N, and training method therefor.
  • Shape memory alloys are metallic materials that, when deformed, have the ability to recover their previous shape or size when exposed to a thermal procedure.
  • shape memory alloys There are generally two types of shape memory alloys: those that demonstrate shape memory from deformed martensite to austenite only upon heating (“one-way” shape memory alloys); and those that demonstrate a first shape memory when heated and a second memory in an opposite way to deformed martensite when cooled (“two-way” shape memory alloys).
  • shape memory alloy article when the shape memory alloy article is cold (or below its transformation temperature), it can be readily bent from its original first shape to a new second shape. However, when heated to a point above its transformation temperature, the article will return to its first shape as a result of a change in crystal structure.
  • shape memory alloys are known in the art. Since the discovery of memory effects in iron-based single-crystal Fe (30) - Mn (1) - Si alloys, a variety of iron-based shape memory alloys have been developed.
  • Chinese Patent Publication CN1064507A discloses a Fe-Mn-Si shape memory alloy having Cr, C, Ni, and, optionally, Al or N.
  • many such alloys require in excess of three training cycles in order to achieve satisfactory shape memory effect. This requirement causes significant energy consumption and makes difficult the dimensional control of the resulting product.
  • shape memory alloys comprising:
  • the alloys comprise from about 20% to about 30% Mn, from about 5.5% to about 6% of Si, from about 2% to about 5% of Cr, from about 0.1% to about 0.5% N, and from about 61% to about 70% Fe.
  • Preferred embodiments demonstrate about 100% shape recovery with one cycle of thermo- mechanical training with a prestrain of about 3%. Methods for training the alloys are provided, comprising the steps of
  • alloys of this invention afford benefits over alloys among those known in the art. Such benefits include good resistance to corrosion, 100 percent shape recovery after as few as one cycle of training, and economical production.
  • the present invention provides iron-manganese-silicon- based shape memory alloy containing Cr (chromium) and N (nitrogen).
  • the present invention provides an improved iron-manganese- silicon-based shape memory alloy, the improvement comprising the addition to said alloy of from about 1% to about 8% Cr; and from about 0.08% to about 0.5% N.
  • the iron-manganese-silicon-based shape memory alloy of comprises from about 18% to about 35% Mn (manganese); from about 5% to about 8% Si (silicon); and from about 55% to about 75% Fe (iron).
  • the alloy comprises from about 20% to about 30% Mn; from about 5.5% to about 6% Si; from about 55% to about 75% Fe; from about 2% to about 5% of Cr; and from about 0.1 % to about 0.4% N.
  • the words "preferred” and “preferably” refer to embodiments of the invention that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.)
  • the shape memory mechanism of iron-based shape memory alloys results from the ⁇ (fcc) -> ⁇ (hcp) stress-induced martensitic phase transformation generated by partial dislocation slipping and its reverse transformation.
  • Fe-Mn-Si based alloys have very low stacking fault energy (about mJ/m 2 order of magnitude). Therefore, on the ⁇ 111 ⁇ f cc planes, ⁇ h ⁇ 110 perfect dislocation dissociates into two 1/6 ⁇ 112> partial dislocations, between which there is a stacking fault.
  • ⁇ (hep) martensite can form every other layer of the ⁇ 111 ⁇ planes through these Shockley partial imperfect dislocation slips and through fault extension and stacking.
  • This phase transformation can occur when the alloy is quenched from austenitic state hardening to temperatures lower than M s (about 0°C, for example), i.e. the so-called thermally-induced martensite (TIM) phase transformation.
  • Phase transformation can also occur when there is deformation at temperatures higher than M s , but lower than M d , i.e. so-called stress-induced martensite (SIM) phase transformation.
  • SIM stress-induced martensite
  • the straining (or deformation) in austenitic state at room temperature generates SIM. Then it is heated to a temperature (about 600°C, for example) above Af. Reverse transformation to an austenitic state results from the reverse movement (or slipping) of Shockley partial dislocations or the contraction of previously formed stacking faults. At the same time, the sample shape returns to its pre-deformation (austenite) state.
  • the deformation process can be divided into three stages. The first stage is elastic deformation, the second stage is that in which ⁇ martensitic phase transformation occurs, and the third stage will produce plastic deformation.
  • Training can raise the strength of parent austenite phase and increase the amount of reversible strain during the martensitic formation stage and thus improve the shape memory effect of the alloys. Alloying likewise can increase matrix strength and thereby magnify the effect of the martensite phase transformation stage.
  • a preferred alloy of the present invention comprises an effective amount, preferably at least about 18%, of Mn.
  • An effective amount of Mn is that which allows formation of a shape memory alloy, preferably functioning as an austentite formation and stabilizing element.
  • a preferred alloy comprises from about 20% to about 35%, more preferably from about 20% to about 30%, of Mn.
  • a preferred alloy also comprises an effective amount, preferably at least about 5%, of Si.
  • An effective amount of Si is that allows formation of a shape memory alloy, preferably functioning to improve the shape-memorizing characteristics of the alloy by acting on the austenite to raise its yield strength.
  • a preferred alloy comprises from about 5.2% to about 8%, more preferably from about 5.5% to about 6%, of Si.
  • a preferred alloy also comprises from about 1% to about 8% Cr, preferably from about 2% to about 5% of Cr.
  • a preferred alloy also comprises an effective amount, preferably greater than about 0.08%, of N.
  • An effective amount of N is that which allows formation of a shape memory alloy, preferably functioning to aid formation of austenite or improving corrosion resistance.
  • a preferred alloy comprises from about 0.08% to about 5%, preferably from about 0.1% to about 0.4%, more preferably from about 0.1 % to about 0.3%, of N.
  • the balance of the alloy preferably comprises iron, preferably from about 55% to about 75%, more preferably from about 61% to about 70%, of iron.
  • a preferred embodiment consists essentially of: (a) from about 18% to about 35% of Mn; (b) from about 5% to about 8% of Si; (c) from about 1% to about 8% of Cr; (d) from about 0.08 % to about 0.5% N; and (e) the balance of Fe, wherein the alloy does not contain significant amounts of materials that degrade performance.
  • the alloys do not contain significant amounts of C (carbon) or Ni (nickel).
  • the following alloy compositions are among those particularly preferred. 20% Mn, 5.5% Si, 5% Cr, 0.16% N, and the remainder Fe.
  • Effectiveness 3% prestrain, one training cycle, 100% shape recovery rate.
  • the present invention only requires a minimum number of training cycles to strengthen the parent austenitic matrix so as to increase the reversible strain and thereby improve the shape memory effect. Alloying with appropriate matrix-strengthening elements fundamentally improves the shape memory effect of the resulting alloy.
  • the resulting alloy possesses superior shape memory features. In embodiments among those that are preferred, a 100% shape recovery rate is achieved after only one (or perhaps two, if the composition varies) thermomechanical training cycle in which a prestrain of from about 3.0% to about 3.5% is applied. In a preferred embodiment, the shape memory alloys of this invention demonstrate about 100% shape recovery with one cycle of thermo-mechanical training with a prestrain of about 3%.
  • a new iron-based shape memory alloy is made in which the proportions are, preferably, from about 20% to about 30% Mn, from about 5% to about 6% Si, from about 2% to about 5% Cr, from about 0.10% to about 0.5% N, and the remainder Fe. This both improves the anti- corrosion properties of the alloy and makes possible a 100% shape recovery rate after just one or two training cycles.
  • training consists of tensile deforming an alloy by applying from about 3.0% to about 3.5% prestrain at room temperature, heating the alloy to approximately 600°C, and then cooling the alloy after keeping it at this temperature for about 10 minutes. If necessary, the aforesaid process can be repeated.
  • the present invention also provides methods of training an iron-manganese-silicon-based shape memory alloy containing Cr and N, comprising the steps of:
  • the tensile deforming step comprises applying from about 3.0% to about 3.5% prestrain at ambient temperature.
  • the heating step is for from about 5 minutes to about 15 minutes, at a temperature of from about 550°C to about 650°C. In a preferred embodiment, the heating step is conducted for about 10 minutes at about 600°C.
  • the method additionally comprising repeating the training steps (a), (b), and (c), so that the training is performed two or three times.
  • the present invention possesses substantive characteristics and is a significant improvement over alloys among those in the art. Preferred embodiments of the alloys are inexpensive, highly strengthened, have good working qualities, and are highly corrosion resistant. Preferred embodiments can also achieve a 100% shape recovery rate after just one or two training cycles.
  • Such alloys are suitable, for example, for manufacturing water and oil pipe couplings, fasteners, connectors, and other such parts, and have broad industrial and civil engineering applications.
  • water pipe couplings made from preferred alloys can withstand hydrostatic water pressure of up to 5 Mpa without leakage. With an improved design, they can withstand 50 Mpa and bear cyclic water pressures of 0-30 Mpa up to more than 500,000 times without leakage.
  • the corrosion resistance and intergranular corrosion resistance in acidic and alkaline media of preferred alloys are superior to stainless steel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

La présente invention concerne des alliages à mémoire de forme à base de silicone-manganèse-fer comprenant: (a) une quantité effective de Mn supérieure à environ 18 %; (b) une quantité effective de SI supérieure à environ 5 %; (c) d'environ 1 % à environ 8 % de Cr; (d) une quantité effective de N; et (e) le complément de Fe. De préférence, les alliages comprennent environ 20 % à environ 30 % de Mn, environ 5,5 % à environ 6 % de SI, environ 2 % à environ 5 % de Cr, environ 0,1 % à environ 0,5 % de N, et environ 61 % à environ 70 % de Fe. Des modes de réalisation préférés mettent en évidence un rétablissement de forme de près de 100 % avec un cycle de formation thermo-mécanique avec une prétension d'environ 3 %. Des procédés pour la formation des alliages sont décrits, comprenant les étapes de déformation par traction des échantillons par application d'une prétension de 3,0 % ou 3,5 % à température ambiante, chauffage de chaque échantillon à approximativement 600 °C, et puis refroidissement desdits échantillons après les avoir maintenus à cette température pendant 10 minutes.
PCT/IB2001/002009 2000-10-26 2001-10-26 Alliages a memoire a base de silicone-manganese-fer contenant du chrome et de l'azote WO2002034958A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002212572A AU2002212572A1 (en) 2000-10-26 2001-10-26 Iron-manganese-silicon-based shape memory alloys containing chromium and nitrogen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN00125769.2 2000-10-26
CN00125769A CN1128244C (zh) 2000-10-26 2000-10-26 含Cr和N铁锰硅基形状记忆合金及其训练方法

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WO2002034958A1 true WO2002034958A1 (fr) 2002-05-02

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US (2) US20020119069A1 (fr)
CN (1) CN1128244C (fr)
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100535148C (zh) * 2006-03-10 2009-09-02 江阴职业技术学院 高强度高塑性高阻尼锰基记忆合金及其制备方法
CN101215678B (zh) * 2008-01-17 2010-06-09 四川大学 含高温铁素体的免训练铸造铁基形状记忆合金
US8409372B1 (en) 2010-09-02 2013-04-02 The United States of America as Represented by the Administraton of National Aeronautics and Space Administration Thermomechanical methodology for stabilizing shape memory alloy (SMA) response
CN104561918B (zh) * 2014-12-22 2017-01-11 上海交通大学 一种MnFeCu三元反铁磁形状记忆合金薄膜的制备方法
CN114836654B (zh) * 2022-04-08 2023-05-23 华南理工大学 一种等原子比镍钛合金单程形状记忆效应的高效训练方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0176272A1 (fr) * 1984-09-07 1986-04-02 Nippon Steel Corporation Alliage à mémoire de forme et procédé pour sa fabrication
JPS63183154A (ja) * 1987-01-22 1988-07-28 Nippon Steel Corp 鉄基の形状記憶合金を用いた温度検出端
EP0336157A1 (fr) * 1988-04-05 1989-10-11 Nkk Corporation Alliage à mémoire de forme, à base de fer et présentant d'excellentes caractéristiques de mémoire de forme et de résistance à la corrosion
CN1070006A (zh) * 1992-08-11 1993-03-17 北京科技大学 优良冷加工性能的铁基形状记忆合金
WO1997003215A1 (fr) * 1995-07-11 1997-01-30 Kari Martti Ullakko Alliages ferreux a memoire de forme et amortissement de vibrations, contenant de l'azote
CN1249356A (zh) * 1999-09-30 2000-04-05 上海交通大学 稀土铁基高温形状记忆合金

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Publication number Priority date Publication date Assignee Title
US4533411A (en) * 1983-11-15 1985-08-06 Raychem Corporation Method of processing nickel-titanium-base shape-memory alloys and structure
US5032195A (en) * 1989-03-02 1991-07-16 Korea Institute Of Science And Technology FE-base shape memory alloy
FR2654748B1 (fr) * 1989-11-22 1992-03-20 Ugine Aciers Alliage inoxydable a memoire de forme et procede d'elaboration d'un tel alliage.
US5244513A (en) * 1991-03-29 1993-09-14 Mitsubishi Jukogyo Kabushiki Kaisha Fe-cr-ni-si shape memory alloys with excellent stress corrosion cracking resistance

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0176272A1 (fr) * 1984-09-07 1986-04-02 Nippon Steel Corporation Alliage à mémoire de forme et procédé pour sa fabrication
JPS63183154A (ja) * 1987-01-22 1988-07-28 Nippon Steel Corp 鉄基の形状記憶合金を用いた温度検出端
EP0336157A1 (fr) * 1988-04-05 1989-10-11 Nkk Corporation Alliage à mémoire de forme, à base de fer et présentant d'excellentes caractéristiques de mémoire de forme et de résistance à la corrosion
CN1070006A (zh) * 1992-08-11 1993-03-17 北京科技大学 优良冷加工性能的铁基形状记忆合金
WO1997003215A1 (fr) * 1995-07-11 1997-01-30 Kari Martti Ullakko Alliages ferreux a memoire de forme et amortissement de vibrations, contenant de l'azote
CN1249356A (zh) * 1999-09-30 2000-04-05 上海交通大学 稀土铁基高温形状记忆合金

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US20020119069A1 (en) 2002-08-29
AU2002212572A1 (en) 2002-05-06
US20040231761A1 (en) 2004-11-25
CN1288974A (zh) 2001-03-28
CN1128244C (zh) 2003-11-19

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