EP2157201A1 - Legierung auf mg-basis - Google Patents

Legierung auf mg-basis Download PDF

Info

Publication number
EP2157201A1
EP2157201A1 EP08752560A EP08752560A EP2157201A1 EP 2157201 A1 EP2157201 A1 EP 2157201A1 EP 08752560 A EP08752560 A EP 08752560A EP 08752560 A EP08752560 A EP 08752560A EP 2157201 A1 EP2157201 A1 EP 2157201A1
Authority
EP
European Patent Office
Prior art keywords
alloy
heat treatment
strength
aging
subjected
Prior art date
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.)
Granted
Application number
EP08752560A
Other languages
English (en)
French (fr)
Other versions
EP2157201B1 (de
EP2157201A4 (de
Inventor
Chamini Mendis
Keiichiro Oishi
Kazuhiro Houno
Yoshiaki Kawamura
Shigeharu Kamado
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute for Materials Science
Original Assignee
National Institute for Materials Science
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 National Institute for Materials Science filed Critical National Institute for Materials Science
Publication of EP2157201A1 publication Critical patent/EP2157201A1/de
Publication of EP2157201A4 publication Critical patent/EP2157201A4/de
Application granted granted Critical
Publication of EP2157201B1 publication Critical patent/EP2157201B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent

Definitions

  • This invention relates to an Mg base alloy containing Mg as a main material, realization of which is desired as a lightweight material which is a replacement for Al.
  • Patent Documents 2, 3, 4, 6 and 8 in order to contrive to improve strength, a rare earth element, scandium or lithium is added.
  • a rare earth element is a rare element which is hardly obtainable on the earth, alloys thereof are high in the price and low in the multiplicity of use.
  • Patent Document 1 is concerned with a quinary alloy containing from 0.3 to 3 % by mass of Ca and simultaneously containing Al, Sr and Mn. In such an alloy, a precipitate (crystal) is formed on the grain boundary of Mg.
  • Patent Document 2 is concerned with an Mg alloy which contains 0.3 % or more and not more than 1.0 % of Zr and which in the case of containing Ca, contains 0.2 % or more and not more than 2.0 % of Ca (% means % by mass).
  • Patent Document 8 discloses an Mg alloy developed as a casting material, which contains from 3 to 8 % by weight of Zn and from 0.8 to 5 % by weight of Ca.
  • An alloy of Patent Document 7 is an alloy developed as a casting material. Specifically, it is disclosed that Ca is zero or 0.5 % by weight, and Zn is from 1 % by weight to 7 % by weight; and in combinations of zero, in the case where Ca is zero or 0.5 % by weight, when Zn is zero, then the alloy has a 0.2 % proof stress of less than 75 MPa, whereas when Zn is from 1 % by weight to 7 % by weight, then the alloy has a 0.2 % proof stress of 75 MPa or more and less than 100 MPa. Thus, it is demonstrated that when such an alloy is used as a structural material, its strength is insufficient. Also, according to the foregoing knowledge obtained in the experiments of this Invention made by the present inventors, there is nothing other than estimation that an alloy containing Ca in a high concentration is low in the ductility.
  • Patent Document 5 discloses an Mg base alloy containing Mn and Zn as main components of additive materials, and in order to obtain a high strength, it is described to perform a solution heat treatment. However, there is involved such a problem that the process is complicated because, for example, an additional heat treatment of two-stage aging is required.
  • Patent Document 8 an alloy in which not more than 10 % by weight of Cu is added is developed. However, the addition of Cu encounters a defect that the corrosion resistance of the Mg alloy is remarkably lowered.
  • Mg-Al-Zn AZ based alloy
  • Mg-Zn-Zr ZK based alloy
  • the rare earth element is expensive, its multiplicity of use is low; and furthermore, the addition of large amounts of alloying elements is accompanied with the formation of a coarse compound phase and involves such a defect that though a high strength is obtained, the ductility is impaired. Then, the development of a new wrought Mg alloy which is free from a rare earth element and which is excellent in strength and ductility by the addition of inexpensive alloying elements is being demanded.
  • an object of this invention is to provide an Mg base alloy having not only a practically sufficient strength but good ductility at room temperature to an extent that it has hitherto been unable to be desired and having small anisotropy in strength characteristics.
  • An Mg base alloy of Invention 1 is characterized in that Ag is contained in an amount of not more than 1.98 at% as an additive material other than Zn.
  • Invention 2 is characterized in that In the Mg base alloy as set forth in Invention 1, Ca is further contained in an amount of not more than 0.61 at% as an additive material other than Zn and Ag.
  • Invention 3 is characterized in that in the Mg base alloy as set forth in Invention 2, Zr is further contained in an amount of not more than 0.17 at% as an additive material other than Zn, Ag and Ca.
  • Invention 4 is characterized in that in the Mg base alloy as set forth in any one of Inventions 1 to 3, a crystal grain size thereof is from 0.1 ⁇ m to 25 ⁇ m.
  • the alloy of this invention has an average Schmid factor in the bottom slip direction against the load application direction of 0.2 or more and has uniform distribution of the Schmid factor as compared with extruded materials of the existing AZ91 alloy (Mg-9 mass % Al-1 mass % Zn alloy) which is a practical Mg alloy. Namely, the alloy of this invention is characterized in that a degree of integration of the bottom parallel to the extrusion direction is weak.
  • the alloy of this invention has such excellent mechanical properties that the compression proof stress is 75 % or more of the tensile proof stress and that anisotropy in strength is small.
  • age hardening properties are enhanced by adding trace amounts of Ag, Ca and Zr, each of which is free from a rare earth element and is relatively easily available. Also, it is noted that even by merely hot extruding the alloy, a fine grain structure having a fine precipitate dispersed therein is formed and that the subject alloy is an Mg base alloy which is excellent in not only strength but ductility and which has small anisotropy in strength as compared with the conventional alloys. Also, in view of the Examples and the technical common knowledge, it can be expected that the foregoing effects are displayed within the following ranges.
  • the maximum solubility of Zn in Mg is 2.4 at%.
  • the composition range of Zn is 0.75 at% or more, age hardening is achieved.
  • the Zn content is as high as possible, and the Zn content is preferably 1.52 at% or more.
  • the Zn content is preferably 1.92 at% or more.
  • an upper limit thereof is preferably 0.2 at%.
  • a lower limit value thereof is preferably 0.08 at% or more.
  • the maximum solubility of Ca in Mg is 0.82 at%.
  • an upper limit thereof is preferably 0.2 at%.
  • a lower limit value thereof is preferably 0.08 at% or more.
  • the maximum solubility of Zr in Mg is 1.04 at%.
  • the Zr content exceeds 0.17 at%, a peritectic reaction exists in the vicinity of 650°C, and a coarse precipitate is formed. Therefore, the Zr content was specified to be not more than 0.17 at%.
  • a lower limit of the Zr content is preferably 0.08 at% or more.
  • the quenched material was aged at a temperature of 160°C and 200°C, respectively using an oil bath. Its hardness by aging was measured by a Vickers hardness meter under a condition at a load of 1 kg for a holding time of 15 seconds.
  • Figs. 2 and 3 show hardness changes in aging at 160°C and 200°C, respectively. From these figures, the hardness reaches the maximum at around 100 hours in the aging at 160°C and at around 10 hours in the aging at 200°C, respectively.
  • the age hardening properties become better by adding Ag, (Ag + Ca) or (Ag + Ca + Zr) to the Mg-2.3Zn alloy.
  • the maximum hardness of an alloy obtained by adding (Ag + Ca + Zr) to the Mg-2.3Zn alloy is the highest and reaches 100 Hv.
  • the grain size was measured by linear intercept method (ASTM standards E112).
  • the average grain size was about 100 ⁇ m in the Mg-2.3Zn binary alloy shown in Fig. 4 , about 50 ⁇ m in the Mg-2.3Zn-0.1Ag alloy shown in Fig. 5 , about 50 ⁇ m In the Mg-2.3Zn-0.1Ag-0.1Ca alloy shown in Fig. 6 and about 10 ⁇ m In the Mg-2.3Zn-0.1Ag-0.1Ca-0.17Zr alloy shown in Fig. 8 , respectively.
  • Ag or combined addition of (Ag + Ca)
  • the crystal grain size becomes small and that by the further addition of Zr, the grain size becomes finer.
  • FIG. 4 to 9 shows a TEM micrograph of each of the alloys at the peak aging stage when aged at 160°C.
  • This refinement of the precipitate is considered to cause an increase of the peak aging hardness.
  • Fig. 10 Details of experimental procedures are shown in Fig. 10 . Alloying elements were blended so as to have an alloy composition shown in Table 1 and melted and cast in a (CO 2 + SF 6 ) mixed gas atmosphere. Thereafter, the ingot was subjected to a homogenous heat treatment at 350°C for 48 hours. Thereafter, the ingot was hot extruded at 300°C and 350°C, respectively. With respect to the hot extrusion condition, an extrusion ratio was 20, and a ram rate was 0.1 mm/s. The material after extrusion was subjected to a solution heat treatment at 400°C for from 0.5 to 4 hours and then subjected to an aging treatment at a temperature of 160°C and 200°C, respectively, followed by measurement for a Vickers hardness.
  • a solution heat treatment at 400°C for from 0.5 to 4 hours and then subjected to an aging treatment at a temperature of 160°C and 200°C, respectively, followed by measurement for a Vickers hardness.
  • sample after extrusion was subjected to microstructure observation by an optical microscope and TEM.
  • Figs. 11 and 12 show an aging curve of an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca alloy at 160°C and 200°C, respectively.
  • Figs. 13 and 14 show an aging curve of an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca-0.17 % Zr alloy at 160°C and 200°C, respectively.
  • Fig. 15 shows an optical micrograph structure of an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca alloy when hot extruded at 350°C.
  • the crystal grain size was measured by linear intercept method using this photograph. As a result, the average crystal grain size was 20 ⁇ m.
  • Fig. 16 shows an optical micrograph of an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca-0.17 % Zr alloy when hot extruded at 350°C.
  • Figs. 17 and 18 are each a TEM micrograph of the same alloy.
  • the structure after extrusion is classified into three of (A) a coarse unrecrystallized grain, (B) a fine equi-axed recrystallized grain and (C) an obscure region.
  • the obscure region (C) is considered to be corresponding to the TEM micrograph of Fig. 17 , and it is noted that the obscure region (C) is a fine grained recrystallized grain structure in a submicron order.
  • Fig. 18 shows enlargement of the interior of the fine grain in a submicron order, and fine rod-like precipitates of several tens nm as formed along the c-axis of Mg.
  • the grain size of the hot extruded Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca-0.17 % Zr alloy was measured from Figs. 16 and 17 . Since the obtained structure was not homogenous, the major axis and the minor axis were measured for crystals of the respective regions without employing the linear intercept method, and an average value thereof was defined as the grain size. Also, with respect to the unrecrystallized grain (A) and the equi-axed recrystallized grain (B), the optical micrograph of Fig. 16 was used, and with respect to the fine grain region in a submicron order (C), the TEM micrograph of Fig. 17 was used.
  • the unrecrystallized grain (A) had size distribution of from about 5 to 25 ⁇ m and had an average grain size of 11 ⁇ m; the equl-axed recrystallized grain (B) had size distribution of from about 1 to 5 ⁇ m and had an average grain size of 2.8 ⁇ m; and the fine grain region in a submicron order (C) had size distribution of from about 0.1 to 1 ⁇ m and had an average grain size of 0.75 ⁇ m.
  • a tensile test at room temperature and a compression test at room temperature were executed in parallel to the extrusion direction.
  • a tensile specimen was a JIS 14B specimen and had a gauge length of 20 mm.
  • a compression specimen had a diameter of 9.5 mm and a height of 14.3 mm. The tensile test and the compression test were performed under a condition at an initial strain rate of 10 -3 s -1 .
  • Fig. 19 shows distribution of a Schmid factor in the basal slip direction against the tensile load application direction, namely the extrusion direction. Since the degree of integration of the basal texture parallel to the extrusion direction is weak, the Schmid factors of the alloys of this invention are uniformly distributed as compared with those of extruded materials of the existing AZ91 alloy (Mg-9 mass % Al-1 mass % Zn alloy), and an average value thereof is 0.20 or more.
  • Fig. 20 shows a stress-strain curve obtained by each of a tensile test and a compression test at room temperature of an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca-0.17 % Zr alloy as extruded at 350°C.
  • Tables 3 to 7 show measurement data corresponding to the stress-strain curve in the tensile test shown in Fig. 20 ; and
  • Tables 8 to 11 show measurement data corresponding to the stress-strain curve in the compression test shown in Fig. 20 .
  • Table 12 summarizes results obtained in a tensile test and a compression test regarding an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca alloy and an Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca-0.17 % Zr alloy as extruded at 300°C and 350°C, respectively.
  • the hot extruded Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca alloy and Mg-2.3 % Zn-0.1 % Ag-0.1 % Ca,-0.17 % Zr alloy are a material having both high strength and high ductility and having small anisotropy in proof stress.
  • the material of this invention has high strength and high ductility and can be used for transportation equipment which is expected to realize weight reduction as a replacement for Al alloys, such as automobiles, motorcycles, aircrafts, etc. Furthermore, since the mechanical properties of the material of this Invention can be obtained without necessity of an additional heat treatment after the hot working, the material of this invention is also expected as a replacement for currently used wrought Mg alloys. Also, in view of the fact that the samples after hot extrusion at 350°C display an ultrafine grain structure of about 500 nm in terms of an average grain size, there is a possibility that the material of this Invention is applicable as a superplastic material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Of Metal (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Heat Treatment Of Steel (AREA)
  • Contacts (AREA)
EP08752560.6A 2007-05-09 2008-05-09 Legierung auf mg-basis Not-in-force EP2157201B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007124879A JP2010047777A (ja) 2007-05-09 2007-05-09 Ｍｇ基合金
PCT/JP2008/058677 WO2008140062A1 (ja) 2007-05-09 2008-05-09 Ｍｇ基合金

Publications (3)

Publication Number Publication Date
EP2157201A1 true EP2157201A1 (de) 2010-02-24
EP2157201A4 EP2157201A4 (de) 2014-07-09
EP2157201B1 EP2157201B1 (de) 2015-11-18

Family

ID=40002256

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08752560.6A Not-in-force EP2157201B1 (de) 2007-05-09 2008-05-09 Legierung auf mg-basis

Country Status (5)

Country Link
US (1) US20100202916A1 (de)
EP (1) EP2157201B1 (de)
JP (2) JP2010047777A (de)
KR (1) KR101561147B1 (de)
WO (1) WO2008140062A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2764130A4 (de) * 2011-10-06 2016-03-09 Univ Pittsburgh Biologisch abbaubare metalllegierungen

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899600B (zh) * 2010-08-13 2012-04-25 上海交通大学 骨科用镁合金内植入材料及其制备方法
KR101252784B1 (ko) * 2010-11-09 2013-04-11 도쿠리츠교세이호징 붓시쯔 자이료 겐큐키코 고강도 고성형성 마그네슘 합금 판재 및 그 제조방법
KR101303585B1 (ko) * 2010-11-23 2013-09-11 포항공과대학교 산학협력단 상온성형성이 우수한 마그네슘 합금 판재 및 그 제조방법

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB544351A (en) * 1940-10-04 1942-04-09 Dow Chemical Co Improved magnesium base alloys
GB987515A (en) * 1963-04-03 1965-03-31 Magnesium Elektron Ltd Improvements in or relating to magnesium base alloys
US4765954A (en) * 1985-09-30 1988-08-23 Allied Corporation Rapidly solidified high strength, corrosion resistant magnesium base metal alloys
JP2725112B2 (ja) 1992-03-25 1998-03-09 三井金属鉱業株式会社 高強度マグネシウム合金
JPH08134581A (ja) * 1994-11-14 1996-05-28 Mitsui Mining & Smelting Co Ltd マグネシウム合金の製造方法
JP2001239326A (ja) 2000-02-28 2001-09-04 Mitsui Mining & Smelting Co Ltd マグネシウム材製品の製造方法
JP2001300643A (ja) * 2000-04-21 2001-10-30 Mitsui Mining & Smelting Co Ltd マグネシウム材製品の製造方法
ATE505567T1 (de) 2000-09-26 2011-04-15 Shin Kwang Seon Hochfeste magnesiumlegierung
JP2002212662A (ja) 2001-01-19 2002-07-31 Aisin Takaoka Ltd マグネシウム合金
JP2003226929A (ja) 2002-02-01 2003-08-15 Kasatani:Kk マグネシウム合金材の冷間プレス成形方法
JP2003328064A (ja) 2002-05-10 2003-11-19 Toyo Kohan Co Ltd 成形性に優れる展伸用マグネシウム薄板およびその製造方法
JP4064720B2 (ja) 2002-05-10 2008-03-19 東洋鋼鈑株式会社 成形性に優れる展伸用マグネシウム薄板およびその製造方法
WO2004085689A1 (ja) * 2003-03-25 2004-10-07 Yoshihito Kawamura 高強度高靭性マグネシウム合金及びその製造方法
JP2005113235A (ja) 2003-10-09 2005-04-28 Toyota Motor Corp 高強度マグネシウム合金およびその製造方法
EP1690954B1 (de) * 2003-11-26 2014-10-08 KAWAMURA, Yoshihito Hochfeste und hochzähe aluminiumlegierung und herstellungsverfahren dafür
JP4840751B2 (ja) 2004-06-30 2011-12-21 独立行政法人物質・材料研究機構 高強度マグネシウム合金及びその製造方法
JP4433916B2 (ja) 2004-07-13 2010-03-17 株式会社豊田中央研究所 塑性加工用マグネシウム合金およびマグネシウム合金部材
JP4803357B2 (ja) 2005-09-06 2011-10-26 独立行政法人産業技術総合研究所 熱間加工により作製される耐熱マグネシウム合金及びその製造方法
DE102006015457A1 (de) * 2006-03-31 2007-10-04 Biotronik Vi Patent Ag Magnesiumlegierung und dazugehöriges Herstellungsverfahren

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2764130A4 (de) * 2011-10-06 2016-03-09 Univ Pittsburgh Biologisch abbaubare metalllegierungen

Also Published As

Publication number Publication date
EP2157201B1 (de) 2015-11-18
US20100202916A1 (en) 2010-08-12
KR101561147B1 (ko) 2015-10-16
JPWO2008140062A1 (ja) 2010-08-05
KR20100021563A (ko) 2010-02-25
JP2010047777A (ja) 2010-03-04
WO2008140062A1 (ja) 2008-11-20
EP2157201A4 (de) 2014-07-09
JP5404391B2 (ja) 2014-01-29

Similar Documents

Publication Publication Date Title
Homma et al. Fabrication of extraordinary high-strength magnesium alloy by hot extrusion
Zhang et al. Effects of rare-earth element, Y, additions on the microstructure and mechanical properties of CoCrFeNi high entropy alloy
EP2295613B1 (de) LEGIERUNG AUF Mg-BASIS
EP2350330B1 (de) Seltenerdmetalle enthaltende magnesiumlegierungen
US5437744A (en) Molybdenum-rhenium alloy
EP2143811B1 (de) Magnesiumlegierungen und herstellungsverfahren dafür
Jing et al. Effect of extrusion on microstructures, and mechanical and creep properties of Mg–Al–Sr and Mg–Al–Sr–Ca alloys
Zhang et al. Microstructure and mechanical properties of high-performance Mg–Y–Er–Zn extruded alloy
EP3656884B1 (de) Knetprodukt aus einer legierung auf magnesiumbasis und verfahren zu seiner herstellung
JP7468931B2 (ja) マグネシウム合金、マグネシウム合金板、マグネシウム合金棒およびこれらの製造方法、マグネシウム合金部材
US9347123B2 (en) Mg-base alloy
EP3653742A1 (de) Knetlegierungsmaterial auf magnesiumbasis und herstellungsverfahren dafür
WO2006004072A1 (ja) 高強度・高延性マグネシウム合金及びその製造方法
EP2692884B1 (de) Magnesiumlegierung
JPH0941065A (ja) 高強度マグネシウム合金及びその製造方法
Cao et al. Microstructure evolution and mechanical properties in an ultralight Mg-2.76 Li–3Al-2.6 Zn-0.39 Y alloy
EP2835437A1 (de) Magnesiumlegierung, magnesiumlegierungselement und verfahren zur herstellung davon sowie verfahren zur verwendung der magnesiumlegierung
US20150047756A1 (en) HIGH STRENGTH Mg ALLOY AND METHOD FOR PRODUCING SAME
EP2157201B1 (de) Legierung auf mg-basis
KR20190120227A (ko) 내식성이 우수한 마그네슘 합금 및 그 제조방법
DE69402406T2 (de) Hitzebeständige Magnesiumlegierung
Wang et al. Effects of samarium on microstructures and tensile properties of Mg–5Al–0.3 Mn alloy
EP2021521B1 (de) Magnesium-basislegierung
Dong et al. Superplasticity in Mg–Li–Zn alloys processed by high ratio extrusion
Bayat Tork et al. Superplasticity of a fine-grained Mg–1.5 wt% Gd alloy after severe plastic deformation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091209

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: OISHI, KEIICHIRO

Inventor name: HOUNO, KAZUHIRO

Inventor name: KAMADO, SHIGEHARU

Inventor name: MENDIS, CHAMINI

Inventor name: KAWAMURA, YOSHIAKI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HOUNO, KAZUHIRO

Inventor name: MENDIS, CHAMINI

Inventor name: KAMADO, SHIGEHARU

Inventor name: KAWAMURA, YOSHIAKI

Inventor name: OISHI, KEIICHIRO

A4 Supplementary search report drawn up and despatched

Effective date: 20140605

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 23/00 20060101ALI20140530BHEP

Ipc: C22C 23/04 20060101AFI20140530BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150722

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 761623

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008041263

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160218

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 761623

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160318

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160318

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160219

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008041263

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20160819

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160509

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20080509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160531

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190521

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20190521

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008041263

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201201