EP3215648A1 - Ultrahochfeste geschmiedete 6xxx-aluminiumlegierungen - Google Patents

Ultrahochfeste geschmiedete 6xxx-aluminiumlegierungen

Info

Publication number
EP3215648A1
EP3215648A1 EP15790515.9A EP15790515A EP3215648A1 EP 3215648 A1 EP3215648 A1 EP 3215648A1 EP 15790515 A EP15790515 A EP 15790515A EP 3215648 A1 EP3215648 A1 EP 3215648A1
Authority
EP
European Patent Office
Prior art keywords
temperature
aluminium alloy
billet
typically
room temperature
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
EP15790515.9A
Other languages
English (en)
French (fr)
Other versions
EP3215648B1 (de
Inventor
Alexis Skubich
Martin Jarrett
Marc Bertherat
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.)
Constellium Valais AG
Original Assignee
Constellium Valais AG
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 Constellium Valais AG filed Critical Constellium Valais AG
Priority to PL15790515T priority Critical patent/PL3215648T3/pl
Priority to SI201530705T priority patent/SI3215648T1/sl
Publication of EP3215648A1 publication Critical patent/EP3215648A1/de
Application granted granted Critical
Publication of EP3215648B1 publication Critical patent/EP3215648B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/05Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00Extruding metal; Impact extrusion
    • B21C23/001Extruding metal; Impact extrusion to improve the material properties, e.g. lateral extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21JFORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J1/00Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
    • B21J1/06Heating or cooling methods or arrangements specially adapted for performing forging or pressing operations
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08Alloys based on aluminium with magnesium as the next major constituent with silicon
    • 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
    • C22F1/002Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor

Definitions

  • the invention relates to ultra-high strength ⁇ -series aluminium alloy forgings particularly suitable for automotive, rail or transportation structural components, exhibiting an ultimate tensile strength UTS typically higher than 400 MPa in T6 temper, preferably higher than 450 MPa, and excellent corrosion resistance.
  • More particularly such forgings are produced through a manufacturing process which, besides including subsequent extrusion and forging steps, includes multiple solutionising and quench steps in order to achieve, after ultimate age hardening, high strength and excellent corrosion resistance on Cu-doped ⁇ -series alloys.
  • Static tensile mechanical characteristics in other words, the ultimate tensile strength R m (or UTS), the tensile yield strength at 0.2% plastic elongation Rp 0 ,2 (or YTS), and elongation A% (or E%), are determined by a tensile test according to NF EN ISO 6892-1.
  • Aluminium alloy compositions and tempers have been developed for obtaining satisfying strength and corrosion behavior in car components such as chassis-suspension or body structure parts, but also rail or transportation structural components in particular when they are made from forgings obtained from extruded rough products.
  • the invention relates to forgings manufactured through a process including, besides subsequent extrusion and forging steps, multiple solutionising and quench steps, to achieve exceUent solutionising and strong retention of the fibrous structure on 6xxx type aUoys, achieving typically, after last step age hardening (T6 temper), an ultimate tensile strength UTS higher than 400 MPa, and preferably higher than 450 MPa, and an exceUent corrosion resistance.
  • T6 temper typically, after last step age hardening
  • UTS ultimate tensile strength
  • SoUdus Ts is the temperature below which the aUoy exhibits a solid fraction equal to 1.
  • Solvus defines the temperature, which is the Umit of soUd solubility in the equiUbrium phase diagram of the aUoy.
  • eutectic alloying elements such as Si, Mg and Cu should be added to form precipitated hardening phases.
  • alloying elements generaUy results in a decrease in the difference between soUdus and solvus temperatures.
  • soUdus to solvus range of the aUoy becomes a narrow "window", with typically a soUdus to solvus difference lower than 20°C, and consequently the solution heat treatment of the aforementioned elements usually achieved during extrusion cannot be obtained without observing incipient melting. Indeed local temperature gradients achieved during extrusion and forging, generally exceed 20°C implying that, as solvus is reached, parts of the product will display temperatures in excess of soUdus Ts.
  • T6 temper by a one-or multiple-step heat treatment at temperatures ranging from 150 to 200°C for holding times ranging from 2 to 20 hours.
  • a first object of the invention is an aluminium alloy forged product obtained by following steps:
  • a) casting a billet from a 6xxx aluminium alloy comprising: Si: 0.7-1.3 wt. %; Fe : ⁇ 0.5 wt. %; Cu: 0.1-1.5 wt. %; Mn: 0.4-1.0 wt. %; Mg: 0.6-1.2 wt. %; Cr: 0.05-0.25 wt.%; Zr: 0.05-0.2 wt. %; Zn: ⁇ 0.2 wt.%; Ti: ⁇ 0.2 wt.% , the rest being aluminium and inevitable impurities;
  • the aluminium alloy extruded product is obtained by casting a billet from a 6xxx aluminium alloy comprising: Si: 0.7-1.3 wt. %; Fe: ⁇ 0.5 wt. %; Cu: 0.1-1.5 wt. %; Mn: 0.4-1.0 wt. %; Mg: 0.6-1.2 wt. %; Cr: 0.05-0.25 wt.%; Zr: 0.05-0.2 wt. %; Zn: ⁇ 0.2 wt.%; Ti: ⁇ 0.2 wt.%, the rest being aluminium and inevitable impurities.
  • the aluminium alloy according to the invention is of the AlMgSi type, which, compared with other such as e.g. AlZnMg alloys, provides an excellent combination of high tensile strength and resistance to corrosion.
  • the process according to the invention consists in particular in replacing conventional homogenising followed by slow cooling, heating and extruding followed again by slow cooling of ⁇ alloy billets, by high temperature homogenising and quenching followed by heating, extruding and quenching again, and does not comprise a separate post-extrusion solution heat treatment, because, as a result of steps b) and c), most part of the alloying elements which contribute to the formation of hardening particles are in solid solution in the lattice of the extrudate.
  • the present invention therefore provides a process to manufacture a range of 6xxx alloys with superior mechanical properties, especially if applied to a sufficiently copper-doped AlMgSiCu, with strength levels in excess of 400 MPa and even 450 or 480 MPa, hitherto not achieved through a conventional route.
  • good extrudability and forgeability is maintained because the limitation with extrusion speed due to premature speed cracking resulting from incipient melting is minimised due to a higher level of dissolution of constituent particles while ensuring precipitation and controlled coarsening of dispersoid phases prior to extrusion.
  • a billet is provided resulting from casting a 6xxx aluminium alloy, i.e. an aluminium alloy having magnesium and silicon as major alloying elements.
  • this aluminium alloy is a high-strength 6xxx aluminium alloy, such as AA6082, AA6182, AA6056, AA6110 or any copper-doped alloy derived from the said ⁇ aluminium alloys.
  • This alloy has preferably a high Cu content, typically between 0.1 and 1.5 wt. %, more preferably between 0.4 and 1.2 wt. %, even more preferably between 0.6 and 1.0 wt. %.
  • Dispersoid elements Mn with a content of 0.4-1.0 wt. %, Cr with a content of 0.05-0.25 wt. % and Zr with a content of 0.05-0.2 wt. %, are added to control recrystallization and maximize the retention of fibrous structure of the extrudate and the forged component.
  • Si and Mg content are defined so as to ensure high level of dissolved Mg2Si while minimising presence of undissolved Mg2Si in the forged component after ultimate solutionising step, with a maximum content of 0.5 wt.%.
  • the content of dissolved Mg is 0.623 wt.%
  • dissolved Si is 0.977 wt.%
  • Si is combined with Mg to form Mg2Si. The precipitation of Mg2Si contributes to increasing the strength of the final aluminium alloy forged product.
  • the final product does not have a sufficiently high strength, it means a tensile strength not higher than 400 MPa. If it is lower than 0.9 wt.%, tensile strength will be at most 450 MPa and with less than l.lwt.% it will be lower than 480 MPa.
  • the Si content is more than 1.3 wt.%, the level of undissolved Mg2Si is too high and extrudability is reduced as well as corrosion resistance and toughness of the resultant final forged product.
  • Mg is combined with Si to form Mg2Si. Therefore Mg is indispensable for strengthening the product of the present invention. If the Mg content is lower than 0.7 wt.%, the effect is too weak. On the other hand, if the Mg content is higher than 1.2 wt.%, the billet becomes difficult to be extruded and the extruded bar to be forged. Moreover, a large amount of Mg2Si particles tends to precipitate during quenching process after the solution treatment.
  • the Mg content is preferably between 0.7 wt.% and 1.1 wt.% and more preferably between 0.8 wt.% and 1.0 wt.%.
  • Fe is an impurity and combines with other elements to form intermetallic compounds. These precipitated particles lower fracture toughness and fatigue strength of the final forged product. Especially, if the Fe content is higher than 0.5 wt.% it is difficult to obtain an aluminium alloy forged product with both high strength and high toughness as required for automotive structure and suspension applications. Preferably, its content is lower than or equal to 0.3 wt.% and more preferably, lower than or equal to 0.2 wt.%.
  • Mn also combines with Al to form intermetallic compounds which control recrystallisation. However, if the Mn content is less than 0.4 wt.%, the effect is not sufficient. On the other hand, if the content of Mn is higher than 1.0 wt.%, coarse precipitated particles are formed and both the workability and the toughness of the aluminium alloy are reduced.
  • the Mn content is preferably between 0.5 wt.% and 0.9 wt.% and more preferably between 0.5 wt.% and 0.7 wt.%.
  • the cast billet according to the invention is homogenised for a duration between 2 and 10 hours at a temperature between 5°C and 80°C lower than solidus, and then water quenched.
  • the homogenised and quenched cast billet to be extruded is heated to a soaking temperature Th below the solidus temperature Ts, between Ts-5°C and Ts-125°C.
  • solidus temperature is near 575°C for alloys AA6082 and AA6182.
  • the billets are preferably heated and held at the soaking temperature during ten seconds to several minutes.
  • the billet is then introduced in the extrusion press and extruded through a die to form a solid extruded product or extrudate.
  • the extrusion speed is controlled to have an extrudate surface exit temperature lower than solidus temperature Ts, respectively 530 and 550°C approximately.
  • the exit temperature should be high enough to merely avoid precipitation.
  • the targeted extrudate surface temperature is commonly ranging from 530°C to 550°C, to have an extrusion speed compatible with a satisfying productivity and avoid incipient melting due to non-equilibrium melting of eutectic phases in profile hot-spots but still allowing to dissolve part of the constituent particles.
  • the extrusion ratio (starting cross-sectional area divided by final cross-sectional area) is at least 8 to maximize the fibrous structure of the extrudate.
  • the extruded product is then water quenched at the exit of the extrusion press, i.e. in an area located between 500 mm and 5 m of the exit from the die. It is cooled down to room temperature with an intense cooling device, for example a device projecting sprayed water or a water based cooling liquid on the extrudate.
  • an intense cooling device for example a device projecting sprayed water or a water based cooling liquid on the extrudate.
  • the extrudate is then stretched to obtain a plastic deformation typically between 0.5% and 10%, preferably up to 5%, in order to have stress-relieved straight profiles.
  • the extruded bar is then cut to length, heated to forging temperature, typically between 400 and 520°C, and then forged in a heated mould typically between 150 and 350°C.
  • parts undergo a separate solutionising at a temperature between 530 and 560°C for a duration comprised between 2 min. and 1 hour and then water quenched with an intense cooling device, for example a device projecting sprayed water or a water based cooling liquid, down to room temperature.
  • an intense cooling device for example a device projecting sprayed water or a water based cooling liquid
  • the product is then aged at room temperature for a duration between 6 hours and 30 days , after which artificial ageing is applied to achieve T6 temper by a one-or multiple-step heat treatment at temperatures ranging from 150 to 200°C for holding times ranging from 2 to 20 hours.
  • the process according to the invention allows to obtain forged products made from Cu- doped 6xxx alloys, which were until now very difficult to solutionise because of their very narrow solvus-solidus temperature window and the risk of recrystallization during ultimate separate solutionising prior to final age-hardening treatment.
  • the process and chemical composition of the invention permits to obtain a forged product displaying a near to fully wrought structure by retaining the wrought structure generated during extrusion in parts of the forged component submitted to limited or no deformation during forging and by limiting the extent of recrystallization occurring during the ultimate separate solutionising step.
  • This process is particularly well suited to alloys with Mg2Si content comprised between 1.2 wt. % and 1.6 wt.
  • Si excess up to 0.7% particularly if comprised between 0.2 wt. % and 0.7 wt. %, and especially if copper content lies between 0.4 wt.% and 1.5 wt.%, which gives a solvus to solidus temperature difference approximately equal to or even lower than 10°C, and renders such alloy almost impossible to extrude when processed according to the prior art route.
  • this alloy comprises, further to Mn, additional dispersoid elements zirconium, between 0.05 and 0.2 wt. %, and Cr, between 0.05 and 0.25 wt. %, the microstructures of the extrudates show a strong fibrous retention providing an additional strengthening contribution, considered important in meeting such high mechanical property values.
  • a forged product manufactured according to the invention also displays a limited sensitivity to intergranular corrosion as assessed according to ISO 11846B and opposed to what the copper level would lead a corrosion expert to expect.
  • Such forged products are particularly suitable as automotive body structure or chassis- suspension parts and especially suspension arms.
  • Forged suspension arms were made from two 6xxx aluminium alloys, the first one being of the AA6082 type, the other one according to the invention, starting from extruded round bars with a diameter of 40 mm.
  • Homogenised cast billets having a diameter of 308 mm and a length of 1200 mm were heated, introduced into an extrusion press and pressed to form 40 mm in diameter bars.
  • Forged suspension arms were obtained by following a conventional route for AA6082 alloys: a) homogenising the cast billet at a temperature TH close to 480°C, for a duration of 5 hours; b) cooling said billet down to room temperature;
  • Table 2 [0033] The results of table 2 show that the process route according to the invention enables the manufacture of aluminium alloy forged products having significantly higher strength (UTS and YS) than products obtained by a conventional route, and similar elongation.
  • Corrosion tests were performed using the ISO 11846B test for 24 hours of exposure time on suspension arms as above, the ones obtained from AA6082 alloy following the prior art route, the other ones according to the invention.
  • Figure 1 shows no significant difference for products according to the invention, with a maximum surface attack depth of 310 microns and a maximum end grain attack depth of 380 microns for the product according to the invention compared to respectively 390 and and 320 microns for AA6082 alloys processed through a prior art route.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Forging (AREA)
  • Extrusion Of Metal (AREA)
EP15790515.9A 2014-11-05 2015-11-02 Ultrahochfeste geschmiedete 6xxx-aluminiumlegierungen Active EP3215648B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL15790515T PL3215648T3 (pl) 2014-11-05 2015-11-02 Nadwytrzymały stop aluminium 6xxx kuty
SI201530705T SI3215648T1 (sl) 2014-11-05 2015-11-02 Ultravisokotrdne kovane 6xxx aluminijeve zlitine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14003717.7A EP3018226A1 (de) 2014-11-05 2014-11-05 Aus 6xxx-Aluminiumlegierungen geschmiedete, ultrahochfeste Produkte mit ausgezeichneter Korrosionsbeständigkeit
PCT/EP2015/075401 WO2016071257A1 (en) 2014-11-05 2015-11-02 Ultra high strength 6xxx forged aluminium alloys

Publications (2)

Publication Number Publication Date
EP3215648A1 true EP3215648A1 (de) 2017-09-13
EP3215648B1 EP3215648B1 (de) 2019-01-23

Family

ID=51865969

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14003717.7A Withdrawn EP3018226A1 (de) 2014-11-05 2014-11-05 Aus 6xxx-Aluminiumlegierungen geschmiedete, ultrahochfeste Produkte mit ausgezeichneter Korrosionsbeständigkeit
EP15790515.9A Active EP3215648B1 (de) 2014-11-05 2015-11-02 Ultrahochfeste geschmiedete 6xxx-aluminiumlegierungen

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP14003717.7A Withdrawn EP3018226A1 (de) 2014-11-05 2014-11-05 Aus 6xxx-Aluminiumlegierungen geschmiedete, ultrahochfeste Produkte mit ausgezeichneter Korrosionsbeständigkeit

Country Status (8)

Country Link
US (1) US20170314113A1 (de)
EP (2) EP3018226A1 (de)
CA (1) CA2965738C (de)
HU (1) HUE043253T2 (de)
MX (1) MX2017005153A (de)
PL (1) PL3215648T3 (de)
SI (1) SI3215648T1 (de)
WO (1) WO2016071257A1 (de)

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CN108188192A (zh) * 2018-01-02 2018-06-22 龙口市丛林铝材有限公司 一种大规格大壁厚差多腔铝型材侧弯问题精准控制方法
CN115283593A (zh) * 2022-08-18 2022-11-04 重庆新钰立金属科技有限公司 一种发电机油箱框铝锻件的成型方法

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WO2017142030A1 (ja) * 2016-02-19 2017-08-24 日本発條株式会社 アルミニウム合金および締結部材
MX2019001802A (es) 2016-08-26 2019-07-04 Shape Corp Proceso de modelacion en caliente y aparato para flexion transversal de una viga de aluminio extrudida para modelar en caliente un componente estructural del vehiculo.
EP3299482B1 (de) 2016-09-21 2019-05-29 Aleris Aluminum Duffel BVBA Verfahren zur herstellung von einer hochfesten 6xxx serie schmiedelegierung
EP3529394A4 (de) 2016-10-24 2020-06-24 Shape Corp. Mehrstufiges formen von aluminiumlegierungen und thermisches behandlungsverfahren zur herstellung von fahrzeugkomponenten
CN106938310B (zh) * 2017-03-23 2018-06-05 遵义航天新力精密铸锻有限公司 航空飞行器用连接座的精锻加工方法
MX2020006262A (es) 2017-12-21 2020-09-07 Constellium Extrusions Decin S R O Materia prima de forja extruida de aleacion de aluminio 6xxx y metodo de manufactura de la misma.
AT522376B1 (de) * 2019-04-05 2022-03-15 Hammerer Aluminium Ind Extrusion Gmbh Stranggussbolzen aus einer Aluminiumbasislegierung, extrudiertes Profil und Verfahren zur Herstellung desselben
CN110408805B (zh) * 2019-04-10 2021-06-18 广东坚美铝型材厂(集团)有限公司 一种铝合金棒材及其制备方法
CN110129636A (zh) * 2019-05-29 2019-08-16 安徽生信铝业股份有限公司 一种高铁风挡用铝合金及其制备方法
JP7380127B2 (ja) * 2019-11-20 2023-11-15 株式会社レゾナック 自動車足回り用アルミニウム合金鍛造材の製造方法
JP7380134B2 (ja) * 2019-11-27 2023-11-15 株式会社レゾナック 自動車足回り用アルミニウム合金鍛造材の製造方法
CN110885942B (zh) * 2019-12-17 2021-05-07 中铝材料应用研究院有限公司 一种适用于热冲压成形-淬火一体化工艺的中强7xxx系铝合金板材
CN110938765B (zh) * 2019-12-18 2022-02-22 东北轻合金有限责任公司 一种汽车底盘用高强Al-Mg-Si铝合金棒材的制造方法
EP3981893A1 (de) * 2020-10-07 2022-04-13 AMAG rolling GmbH Platte aus einer gewalzten aluminiumlegierung und herstellung solch einer platte
CN113088773A (zh) * 2021-03-05 2021-07-09 长春市吉通凯撒铝业有限责任公司 一种高强度铝合金及其生产工艺和应用
CN115449652A (zh) * 2022-08-04 2022-12-09 广东伟业铝厂集团有限公司 一种新能源汽车异型多腔体底盘型材及其制备方法
CN115572871B (zh) * 2022-10-31 2023-09-15 山东骏程金属科技有限公司 商用铝合金锻造车轮及其制备方法
CN117265342A (zh) * 2023-09-26 2023-12-22 南京长澄科技制造有限公司 一种铝合金刹车座材料及其制备方法和应用

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108188192A (zh) * 2018-01-02 2018-06-22 龙口市丛林铝材有限公司 一种大规格大壁厚差多腔铝型材侧弯问题精准控制方法
CN108188192B (zh) * 2018-01-02 2019-09-10 龙口市丛林铝材有限公司 一种大规格大壁厚差多腔铝型材侧弯问题精准控制方法
CN115283593A (zh) * 2022-08-18 2022-11-04 重庆新钰立金属科技有限公司 一种发电机油箱框铝锻件的成型方法

Also Published As

Publication number Publication date
WO2016071257A1 (en) 2016-05-12
CA2965738A1 (en) 2016-05-12
SI3215648T1 (sl) 2019-07-31
EP3215648B1 (de) 2019-01-23
PL3215648T3 (pl) 2019-07-31
EP3018226A1 (de) 2016-05-11
US20170314113A1 (en) 2017-11-02
MX2017005153A (es) 2018-01-23
HUE043253T2 (hu) 2019-08-28
CA2965738C (en) 2023-09-12

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