EP1574587A1 - VERFAHREN ZUR THERMOMECHANISCHEN BEHANDLUNG FÜR EINE MIT NbC DOTIERTE Fe-Mn-Si-FORMGEDÄCHTNISLEGIERUNG - Google Patents

VERFAHREN ZUR THERMOMECHANISCHEN BEHANDLUNG FÜR EINE MIT NbC DOTIERTE Fe-Mn-Si-FORMGEDÄCHTNISLEGIERUNG Download PDF

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Publication number
EP1574587A1
EP1574587A1 EP03780855A EP03780855A EP1574587A1 EP 1574587 A1 EP1574587 A1 EP 1574587A1 EP 03780855 A EP03780855 A EP 03780855A EP 03780855 A EP03780855 A EP 03780855A EP 1574587 A1 EP1574587 A1 EP 1574587A1
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European Patent Office
Prior art keywords
shape memory
weight
memory alloy
addition
treatment
Prior art date
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Granted
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EP03780855A
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English (en)
French (fr)
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EP1574587B1 (de
EP1574587A4 (de
Inventor
T. c/o NAT. INSTITUTE FOR MAT. SCIENCE KIKUCHI
S. c/o NAT. INSTITUTE FOR MAT. SCIENCE KAJIWARA
A. c/o NAT. INSTITUTE FOR MAT. SCIENCE BARUJ
K. c/o NAT. INSTITUTE FOR MAT. SCIENCE OGAWA
N. c/o NAT. INSTITUTE FOR MAT. SCIENCE SHINYA
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National Institute for Materials Science
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National Institute for Materials Science
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Publication of EP1574587A4 publication Critical patent/EP1574587A4/de
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C22/00Alloys based on manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/006Resulting in heat recoverable alloys with a memory effect
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2201/00Treatment for obtaining particular effects
    • C21D2201/01Shape 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).
  • 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 excellentshape 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 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.
  • 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; 2)
  • 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
  • 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.
  • 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 310MPa 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)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
EP03780855A 2002-12-18 2003-12-17 VERFAHREN ZUR THERMOMECHANISCHEN BEHANDLUNG FÜR EINE MIT NbC DOTIERTE Fe-Mn-Si-FORMGEDÄCHTNISLEGIERUNG Expired - Fee Related EP1574587B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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
JP2002367062 2002-12-18
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

Publications (3)

Publication Number Publication Date
EP1574587A1 true EP1574587A1 (de) 2005-09-14
EP1574587A4 EP1574587A4 (de) 2006-02-01
EP1574587B1 EP1574587B1 (de) 2008-07-16

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US (1) US20050236077A1 (de)
EP (1) EP1574587B1 (de)
JP (1) JP3950963B2 (de)
KR (1) KR20050083601A (de)
CN (1) CN100342039C (de)
DE (1) DE60322260D1 (de)
WO (1) WO2004055222A1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014135530A1 (de) * 2013-03-08 2014-09-12 Thyssenkrupp Steel Europe Ag Temperaturgesteuertes umlenkmittel
WO2014146733A1 (de) 2013-03-22 2014-09-25 Thyssenkrupp Steel Europe Ag Eisenbasierte formgedächtnislegierung
WO2018219514A1 (de) 2017-06-01 2018-12-06 Thyssenkrupp Steel Europe Ag Fe-mn-si formgedächtnislegierung
WO2020030358A1 (de) 2018-08-08 2020-02-13 Thyssenkrupp Steel Europe Ag Inline vorrecken von formgedächtnislegierungen, insbesondere flachstahl
WO2020108754A1 (de) 2018-11-29 2020-06-04 Thyssenkrupp Steel Europe Ag Flachprodukt aus einem eisenbasierten formgedächtniswerkstoff

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104328323A (zh) * 2014-10-24 2015-02-04 王健英 一种锰铁合金材料及制备方法
CN109477175B (zh) * 2016-09-06 2021-02-12 国立大学法人东北大学 Fe基形状记忆合金材料及其制造方法
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

Citations (4)

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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
EP1123983A1 (de) * 2000-02-09 2001-08-16 Japan as represented by Director General of Formgedächtnislegierung
EP1348772A1 (de) * 2002-03-20 2003-10-01 National Institute for Materials Science Verfahren zur Herstellung und thermischen Behandlung von Formgedächtnis- Fe-Mn-Si-Legierung mit NbC

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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
JPH0382741A (ja) * 1989-08-25 1991-04-08 Nisshin Steel Co Ltd 耐応力腐食割れ性に優れた形状記憶ステンレス鋼およびその形状記憶方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP1123983A1 (de) * 2000-02-09 2001-08-16 Japan as represented by Director General of Formgedächtnislegierung
EP1348772A1 (de) * 2002-03-20 2003-10-01 National Institute for Materials Science Verfahren zur Herstellung und thermischen Behandlung von Formgedächtnis- Fe-Mn-Si-Legierung mit NbC

Non-Patent Citations (4)

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BARUJ A ET AL: "EFFECT OF PRE-DEFORMATION OF AUSTENITE ON SHAPE MEMORY PROPERTIES IN FE-MN-SI-BASED ALLOYS CONTAINING NB AND C" MATERIALS TRANSACTIONS. JIM, SENDAI, JP, vol. 43, no. 3, March 2002 (2002-03), pages 585-588, XP009012787 ISSN: 0916-1821 *
BARUJ A ET AL: "FURTHER IMPROVEMENT IN THE SHAPE-MEMORY PROPERTIES OF FEMNSI-BASED SHAPE-MEMORY ALLOYS CONTAINING NBC PRECIPITATES" MATERIALS SCIENCE FORUM, AEDERMANNSFDORF, CH, vol. 394/395, 2 September 2001 (2001-09-02), pages 403-406, XP009012763 ISSN: 0255-5476 *
DATABASE INSPEC [Online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; 15 December 1999 (1999-12-15), KAJIWARA S: "Characteristic features of shape memory effect and related transformation behavior in Fe-based alloys" XP002357339 Database accession no. 6526328 -& ICOMAT 98. INTERNATIONAL CONFERENCE ON MARTENSITIC TRANSFORMATIONS 7-11 DEC. 1998 SAN CARLOS DE BARILOCHE, ARGENTINA, vol. A273-275, 1999, pages 67-88, XP009058192 Materials Science & Engineering A (Structural Materials: Properties, Microstructure and Processing) Elsevier Switzerland ISSN: 0921-5093 *
See also references of WO2004055222A1 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014135530A1 (de) * 2013-03-08 2014-09-12 Thyssenkrupp Steel Europe Ag Temperaturgesteuertes umlenkmittel
WO2014146733A1 (de) 2013-03-22 2014-09-25 Thyssenkrupp Steel Europe Ag Eisenbasierte formgedächtnislegierung
WO2018219514A1 (de) 2017-06-01 2018-12-06 Thyssenkrupp Steel Europe Ag Fe-mn-si formgedächtnislegierung
WO2018219463A1 (de) 2017-06-01 2018-12-06 Thyssenkrupp Steel Europe Ag Fe-Mn-Si FORMGEDÄCHTNISLEGIERUNG
WO2020030358A1 (de) 2018-08-08 2020-02-13 Thyssenkrupp Steel Europe Ag Inline vorrecken von formgedächtnislegierungen, insbesondere flachstahl
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

Also Published As

Publication number Publication date
KR20050083601A (ko) 2005-08-26
JP3950963B2 (ja) 2007-08-01
EP1574587B1 (de) 2008-07-16
EP1574587A4 (de) 2006-02-01
DE60322260D1 (de) 2008-08-28
CN1692163A (zh) 2005-11-02
CN100342039C (zh) 2007-10-10
JP2004197161A (ja) 2004-07-15
US20050236077A1 (en) 2005-10-27
WO2004055222A1 (ja) 2004-07-01

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