US20050236077A1 - Method of thermo-mechanical-treatment for fe-mn-si shape-memory alloy doped with nbc - Google Patents

Method of thermo-mechanical-treatment for fe-mn-si shape-memory alloy doped with nbc Download PDF

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Publication number
US20050236077A1
US20050236077A1 US10/519,255 US51925504A US2005236077A1 US 20050236077 A1 US20050236077 A1 US 20050236077A1 US 51925504 A US51925504 A US 51925504A US 2005236077 A1 US2005236077 A1 US 2005236077A1
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Prior art keywords
shape memory
weight
memory alloy
addition
treatment
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US10/519,255
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Takehiko Kikuchi
Setsuo Kajiwara
Alberto Baruj
Kazuyuki Ogawa
Norio Shinya
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National Institute for Materials Science
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National Institute for Materials Science
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Assigned to NATIONAL INSTITUTE FOR MATERIALS SCIENCE reassignment NATIONAL INSTITUTE FOR MATERIALS SCIENCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BARUJ, ALBERTO, KAJIWARA, SETSUO, KIKUCHI, TAKEHIKO, OGAWA, KAZUYUKI, SHINYA, NORIO
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    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22F1/006—Resulting in heat recoverable alloys with a memory effect
    • 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 thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition. More particularly, the present invention relates to a thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition which exhibits a satisfactory shape memory effect without undergoing so-called training, providing improved performance.
  • the training means a process sequence of repeating the following treatment several times to improve shape memory effect.
  • the treatment consists of deforming an alloy by 2-3% at room temperature and then heating it to around 600° C. higher than the reverse transformation temperature of the alloy.
  • Patent Document 2 The inventors have studied also about the thermomechanical treatments for the alloy with Nb, C addition, and they found a fact that pre-deformation in a temperature range of from 500° C. to 800° C. and a subsequent aging treatment lead to a further improved shape memory effect and thus also filed patent applications about this (see Patent Document 2, Patent Document 3).
  • Patent Document 1
  • the object of the present invention is to fundamentally solve the aforementioned problems.
  • the inventors of this invention has earnestly studied aiming at developing and ensuring good shape memory properties for a shape memory alloy of specified components even with deformation at low temperatures. As a result, they found that the satisfactory shape memory properties can be sufficiently ensured even with deformation at room temperature so as to achieve the aforementioned object.
  • the excellent shape memory property of alloy can be developed just by applying a basic operation comprising deforming a Fe—Mn—Si-based shape memory alloy with Nb, C addition at room temperature and then subjecting the deformed alloy to aging heating treatment to precipitate NbC carbides.
  • a basic operation comprising deforming a Fe—Mn—Si-based shape memory alloy with Nb, C addition at room temperature and then subjecting the deformed alloy to aging heating treatment to precipitate NbC carbides.
  • the present invention was made on the basis of the aforementioned knowledge and success.
  • the solving means to solve the problems are the followings (1)-(7).
  • thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition comprising: deforming a Fe—Mn—Si-based shape memory alloy with Nb, C addition by a deformation ratio of from 5% to 40% at room temperature, and subjecting the deformed alloy to aging treatment to precipitate NbC carbides.
  • thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition according to the above (1), wherein the Fe—Mn—Si-based shape memory alloy with Nb, C addition comprises, as alloy components, Mn: 15% to 40% by weight, Si: 3% to 15% by weight, Nb: 0.1% to 1.5% by weight, C: 0.01% to 0.2% by weight, and Fe and inevitable impurities: residual amount, wherein the atomic ratio Nb/C between Nb and C is 1 or more.
  • thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition according to the above (1), wherein the Fe—Mn—Si-based shape memory alloy with Nb, C addition comprises, as alloy components, Mn: 15% to 40% by weight, Si: 3% to 15% by weight, Cr: 1% to 20% by weight, Nb: 0.1% to 1.5% by weight, C: 0.01% to 0.2% by weight, and Fe and inevitable impurities: residual amount, wherein the atomic ratio Nb/C between Nb and C is 1 or more.
  • thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition according to the above (1), wherein the Fe—Mn—Si-based shape memory alloy with Nb, C addition comprises, as alloy components, Mn: 15% to 40% by weight, Si: 3% to 15% by weight, Cr: 1% to 20% by weight, Ni: 0.1% to 20% by weight, Nb: 0.1% to 1.5% by weight, C: 0.01% to 0.2% by weight, and Fe and inevitable impurities: residual amount, wherein the atomic ratio Nb/C between Nb and C is 1 or more.
  • thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition according to any one of the above (2) through (5), wherein the Fe—Mn—Si-based shape memory alloy with Nb, C addition contains, as impurities, Cu: 3% by weight or less, Mo: 2% by weight or less, Al: 10% by weight or less, Co: 30% by weight or less, and/or N: 5000 ppm or less.
  • thermomechanical treatment for a Fe—Mn—Si-based shape memory alloy having specified components with Nb, C conventionally, the processing treatment prior to aging is carried out by training. Alternatively, in the inventions of the prior applications, the processing treatment prior to aging is carried out in a temperature range of from 500° C. to 800° C. According to the present invention, however, the processing treatment prior to the aging treatment can be successfully carried out without high temperature, i.e. at room temperature, by setting a processing ratio in a specified range.
  • the technical meaning of the present invention must be clearly understood as compared to the prior art and the inventions of the prior applications on which the present invention is based because there are obvious difference therebetween. That is, according to the present invention, the remarkable improvement in shape memory property is achieved first time by a combination of specified alloy components, specified deformation ratio at room temperature, and setting of aging condition to a certain range. Amazingly by run-of-the-mill thermomechanical treatment comprising a deformation at room temperature and then aging, the shape recovery ratio equivalent to that of the sample subjected to the training can be obtained and, in addition, the shape recovery stress significantly larger than that of the sample subjected to the training can be obtained. With development of the present invention, it is expected that the use of shape memory alloys will be accelerated toward the practical use in a wide variety of fields.
  • FIG. 1 is a diagram showing relations between the amount of initial deformation and the shape recovery ratio depending on the thermomechanical treatment of Fe—Mn—Si-based shape memory alloys with Nb, C addition of the present invention.
  • FIG. 2 is a diagram showing the relation between the recovered shape strain and shape recovery stress depending on the thermomechanical treatment of Fe—Mn—Si-based shape memory alloys with Nb, C addition of the present invention.
  • the reason why the deformation ratio at room temperature is specified to be from 5% to 40% comes from the fact that the deformation ratio lower than 5% does not effectively contribute to improvement in shape memory property while the deformation ratio over 40% makes a sample too hard so that it is extremely difficult to deform the sample after subjected to an aging treatment.
  • An alloy as to be subjected to the thermomechanical treatment method for a Fe—Mn—Si-based shape memory alloy with Nb, C addition of the present invention has the following chemical compositions, just as specified in the prior applications, 1) Mn: 15% to 40% by weight, Si: 3% to 15% by weight, Nb: 0.1% to 1.5% by weight, C: 0.01% to 0.2% by weight, and Fe and inevitable impurities: residual amount, wherein the atomic ratio Nb/C between Nb and C is 1 or more;
  • the Fe—Mn—Si-based shape memory alloy with Nb, C addition has the following compositions Mn: 15% to 40% by weight, Si: 3% to 15% by weight, Cr: 1% to 20% by weight, Nb: 0.1% to 1.5% by weight, C: 0.01% to 0.2% by weight, and Fe and inevitable impurities: residual amount, wherein the atomic ratio Nb/C between Nb and C is 1 or more; has the following compositions Mn: 15% to 40% by weight, Si: 3% to 15% by weight, Cr: 1% to 20% by weight, Ni: 0.1% to 20% by weight, Nb: 0.1% to 1.5% by weight, C: 0.01% to 0.2% by weight, and Fe and inevitable impurities: residual amount, wherein the atomic ratio Nb/C between Nb and C is 1 or more.
  • the atomic ratio Nb/C between Nb and C in the alloy is preferably from 1.0 to 1.2.
  • the alloy as to be subjected to a thermomechanical treatment method for the Fe—Mn—Si-based shape memory alloy of the present invention is permitted to contain, as impurities, one or more of a group consisting of Cu of 3% by weight or less, Mo of 2% by weight or less, Al of 10% by weight or less, Co of 30% by weight or less, and N of 5000 ppm or less.
  • FIG. 1 and FIG. 2 examples shown in the drawings are for the purpose of disclosure for helping the easy understanding of the present invention and are not intended to limit the scope of the present invention.
  • a Fe-28Mn-6Si-5Cr-0.53Nb-0.06C alloy (% by weight) with Nb, C addition of the present invention was prepared by melting. How the shape memory property is improved by rolling at room temperature and then subjecting it to an aging treatment in a temperature range of 400° C. to 1000° C. for a time period from 1 minute to 2 hours, is shown below.
  • FIG. 1 is a graph showing differences in shape recovery ratio among a case in which only aging was conducted (0% rolling) and cases in which aging was conducted after rolling by 10%, 20% and 30% at room temperature. In all of the cases, the aging treatment was conducted at 800° C. for 10 minutes. For comparison, results of samples of the Fe-28Mn-6Si-5Cr alloy with no Nb, C addition prepared only by annealing and samples of the alloy prepared after subjected to the training five times are shown. The abscissa shows the initial strain (%) by tensile deformation at room temperature, and the ordinate shows the recovery ratio of strain when the sample is heated to 600° C. When heated to 400° C., approximately the same shape recovery ratio is also obtained. The samples used in tests were test pieces having a thickness of 0.6 mm, a width of 1 to 4 mm, and a length (gage length) of 15 mm.
  • the sample rolled by 10% has shape memory recovery ratios nearly equivalent to or slightly lower than those of the alloy with no Nb, C addition which was subjected to training five times. Practically the necessary initial strain is believed to be about 4%. A shape memory recovery ratio of about 90% shown at this strain strongly suggests that it is used as a practically applicable alloy. Training of at least five times is necessary for obtaining the same shape recovery ratio as this sample, with a conventional Fe—Mn—Si-based shape memory alloy with no Nb, C addition. As is understood from this, the present invention exhibits shape memory properties with a simple method.
  • the sample with a higher rolling ratio of 20% has shape memory recovery ratios nearly equivalent to or slightly higher than those of the case without rolling (only aged). However, the sample with a further higher rolling ratio of 30% has shape memory recovery ratios lower than those of the case which was only aged in a range with large initial strain.
  • FIG. 2 is a graph showing the degrees of improvement in shape recovery stress of these samples, in comparison with the case in which only aging was conducted (0% rolling) and a case in which the aging was conducted after rolling by 10%.
  • the recovery stress when recovered strain on the abscissa is zero means the stress generated when a sample is tensile-deformed at room temperature, then, heated to the reverse transformation temperature or more in a state that the both ends of the sample are fixed without any recovery, and returned to room temperature again.
  • the recovery stress at recovered strain of 2% for example, means the stress generated in case that the both ends of the sample are fixed after a recovery of strain by 2%. Tests were conducted with the initial strain given at room temperature of from 4% to 6%.
  • the test pieces used were the same as those used for obtaining the results shown in FIG. 1 .
  • the recovered strain on the abscissa in FIG. 2 is explained, taking a case where a shape memory alloy is used as a coupling for examples. It is equivalent to the ratio (%) of clearance between the pipes and the coupling part (shape memory alloy) to the diameter.
  • Remarkable increase in shape recovery stress is observed in a range of high rolling ratio: a shape recovery stress of 310 MPa is obtained at the recovered strain of 0% when the rolling ratio is from 20% to 30% at room temperature and a shape recovery stress of 200 MPa is obtained even at the recovered strain of 2% for the same rolling ratio. It is also found that the same shape recovery stress as the case subjected to training is obtained even in a case that the rolling ratio is 10%.
  • FIG. 2 shows shape recovery stresss of the sample with no Nb, C addition and the sample subjected to the training five times. It is seem from this figure that the recovery stresses of these samples are much smaller than those of the present invention.
  • the present invention was made by finding that the deformation treatment prior to the aging treatment to a Fe—Mn—Si-based shape memory alloy having specified components with Nb, C addition can be successfully carried out at room temperature if the deformation ratio is in a specified range.
  • the technical meaning of the present invention must be clearly understood because there are obvious advantages as compared to a conventional one which requires the training accompanied by troublesome operation and the inventions of the prior applications which still require high-temperature deformation in a range of from 500° C. to 800° C.
  • the remarkable improvement in shape memory property is achieved first time by a combination of specified alloy components, specified deformation ratio at room temperature, and setting of aging condition to a certain range.
  • the shape recovery ratio equivalent to that of the sample subjected to the training can be obtained and, in addition, the shape recovery stress significantly larger than that of the sample subjected to the training can be obtained.
  • the meaning of the present invention is significant.
  • the shape memory alloy according to the present invention can be used as tightening materials for various applications, for example, for tightening water pipes, tightening oil pipes, etc., which will produce great economic effects.
  • the present invention provides a thermomechanical treatment means for a Fe—Mn—Si-based shape memory alloy having specified components with Nb, C addition with simple processing treatment prior to aging.
  • the processing treatment prior to aging is carried out by training.
  • the processing treatment prior to aging is carried out in a temperature range of from 500° C. to 800° C. According to the present invention, however, the processing treatment prior to the aging treatment can be successfully carried out without high temperature, i.e. at room temperature, if using a processing ratio in a specified range.
  • the technical meaning of the present invention must be clearly understood as compared to the prior art and the inventions of the prior applications because there are obvious difference therebetween. That is, according to the present invention, the remarkable improvement in shape memory property is achieved first time by a combination of specified alloy components, specified processing ratio at room temperature, and setting of aging condition into a certain range.
  • the technical meaning of the present invention must be clearly understood as compared to the prior art and the inventions of the prior applications because there are obvious difference therebetween. That is, according to the present invention, the remarkable improvement in shape memory property is achieved first time by a combination of specified alloy components, specified deformation ratio at room temperature, and setting of aging condition to a certain range. Amazingly by run-of-the-mill thermomechanical treatment comprising a deformation at room temperature and then aging, the shape recovery ratio equivalent to that of the sample subjected to the training can be obtained and, in addition, the shape recovery stress significantly larger than that of the sample subjected to the training can be obtained. With development of the present invention, it is expected that the use of shape memory alloys will be accelerated toward the practical use in a wide variety of fields.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
US10/519,255 2002-12-18 2003-12-17 Method of thermo-mechanical-treatment for fe-mn-si shape-memory alloy doped with nbc Abandoned US20050236077A1 (en)

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JP2002-367062 2002-12-18
JP2002367062A JP3950963B2 (ja) 2002-12-18 2002-12-18 ＮｂＣ添加Ｆｅ−Ｍｎ−Ｓｉ系形状記憶合金の加工熱処理法
PCT/JP2003/016189 WO2004055222A1 (ja) 2002-12-18 2003-12-17 ＮｂＣ添加Ｆｅ−Ｍｎ−Ｓｉ系形状記憶合金の加工熱処理方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104328323A (zh) * 2014-10-24 2015-02-04 王健英 一种锰铁合金材料及制备方法
US9273369B1 (en) 2010-09-02 2016-03-01 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Thermomechanical methodology for stabilizing shape memory alloy (SMA) response
US20190153571A1 (en) * 2016-09-06 2019-05-23 Tohoku University Fe-BASED SHAPE MEMORY ALLOY MATERIAL AND METHOD OF PRODUCING THE SAME

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DE102013102353A1 (de) * 2013-03-08 2014-09-11 Thyssenkrupp Steel Europe Ag Temperaturgesteuertes Umlenkmittel
EP2976441B1 (de) 2013-03-22 2019-02-27 ThyssenKrupp Steel Europe AG Eisenbasierte formgedächtnislegierung
CN107012411A (zh) * 2017-03-08 2017-08-04 宁波高新区远创科技有限公司 一种土壤接地网用合金材料的制备方法
WO2018219463A1 (de) 2017-06-01 2018-12-06 Thyssenkrupp Steel Europe Ag Fe-Mn-Si FORMGEDÄCHTNISLEGIERUNG
DE102018119296A1 (de) * 2018-08-08 2020-02-13 Thyssenkrupp Ag Inline Vorrecken von Formgedächtnislegierungen, insbesondere Flachstahl
WO2020108754A1 (de) 2018-11-29 2020-06-04 Thyssenkrupp Steel Europe Ag Flachprodukt aus einem eisenbasierten formgedächtniswerkstoff

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US5032195A (en) * 1989-03-02 1991-07-16 Korea Institute Of Science And Technology FE-base shape memory alloy
US5173131A (en) * 1989-11-22 1992-12-22 Ugine, Aciers De Chatillon Et Gueugnon Shape memory stainless alloy
US5198041A (en) * 1989-08-25 1993-03-30 Nisshin Steel Co., Ltd. Shape memory stainless steel excellent in stress corrosion cracking resistance and method thereof
US6524406B2 (en) * 2000-02-09 2003-02-25 National Research Institute For Metals Shape memory alloy
US6855216B2 (en) * 2002-03-20 2005-02-15 National Institute For Materials Science Method of processing and heat-treating NbC-added Fe-Mn-Si-based shape memory alloy

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JPS62112720A (ja) * 1985-11-09 1987-05-23 Nippon Steel Corp Ｆｅ−Ｍｎ−Ｓｉ系形状記憶合金の特性向上方法

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US5032195A (en) * 1989-03-02 1991-07-16 Korea Institute Of Science And Technology FE-base shape memory alloy
US5198041A (en) * 1989-08-25 1993-03-30 Nisshin Steel Co., Ltd. Shape memory stainless steel excellent in stress corrosion cracking resistance and method thereof
US5173131A (en) * 1989-11-22 1992-12-22 Ugine, Aciers De Chatillon Et Gueugnon Shape memory stainless alloy
US6524406B2 (en) * 2000-02-09 2003-02-25 National Research Institute For Metals Shape memory alloy
US6855216B2 (en) * 2002-03-20 2005-02-15 National Institute For Materials Science Method of processing and heat-treating NbC-added Fe-Mn-Si-based shape memory alloy

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9273369B1 (en) 2010-09-02 2016-03-01 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Thermomechanical methodology for stabilizing shape memory alloy (SMA) response
US9476113B1 (en) 2010-09-02 2016-10-25 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Thermomechanical methodology for stabilizing shape memory alloy (SMA) response
CN104328323A (zh) * 2014-10-24 2015-02-04 王健英 一种锰铁合金材料及制备方法
US20190153571A1 (en) * 2016-09-06 2019-05-23 Tohoku University Fe-BASED SHAPE MEMORY ALLOY MATERIAL AND METHOD OF PRODUCING THE SAME
US10920305B2 (en) * 2016-09-06 2021-02-16 Tohoku University Fe-based shape memory alloy material and method of producing the same

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JP2004197161A (ja) 2004-07-15
JP3950963B2 (ja) 2007-08-01
EP1574587B1 (en) 2008-07-16
CN1692163A (zh) 2005-11-02
EP1574587A1 (en) 2005-09-14
WO2004055222A1 (ja) 2004-07-01
DE60322260D1 (de) 2008-08-28
EP1574587A4 (en) 2006-02-01
CN100342039C (zh) 2007-10-10
KR20050083601A (ko) 2005-08-26

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KIKUCHI, TAKEHIKO;KAJIWARA, SETSUO;BARUJ, ALBERTO;AND OTHERS;REEL/FRAME:016698/0787

Effective date: 20041118

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION