EP2855041B1 - Verfahren zur herstellung von umgeformten blechteilen bei tieftemperatur - Google Patents
Verfahren zur herstellung von umgeformten blechteilen bei tieftemperatur Download PDFInfo
- Publication number
- EP2855041B1 EP2855041B1 EP13726170.7A EP13726170A EP2855041B1 EP 2855041 B1 EP2855041 B1 EP 2855041B1 EP 13726170 A EP13726170 A EP 13726170A EP 2855041 B1 EP2855041 B1 EP 2855041B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- panel
- forming tool
- shaped
- semifinished
- board
- 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.)
- Not-in-force
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
- B21J1/06—Heating or cooling methods or arrangements specially adapted for performing forging or pressing operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/16—Heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21K—MAKING FORGED OR PRESSED METAL PRODUCTS, e.g. HORSE-SHOES, RIVETS, BOLTS OR WHEELS
- B21K7/00—Making railway appurtenances; Making vehicle parts
- B21K7/12—Making railway appurtenances; Making vehicle parts parts for locomotives or vehicles, e.g. frames, underframes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49616—Structural member making
- Y10T29/49622—Vehicular structural member making
Definitions
- the invention relates to a method for producing a formed sheet metal part from a board or a semi-finished product of a material consisting of steel with at least 60 wt .-% Fe and a Austentenitgehalt of at least 5%, wherein the board or the semi-finished product before forming at least partially is cooled to a temperature of less than -20 ° C and is formed at a temperature below -20 ° C in a forming tool.
- the invention relates to a device for carrying out the method and an advantageous use of the sheet metal parts produced.
- the board or the semi-finished product usually has to be heated to a temperature above the AC 1 transformation temperature point, so that there is essentially austenitic structure in the sheet metal part, in order subsequently to be formed at a very high temperature and rapidly cooled.
- Object of the present invention is therefore to propose a method for the production of components designed for load-balanced, which on the one hand enables a large-scale use of low-temperature forming and is particularly simple.
- the above-indicated object is achieved according to the first teaching of the present invention in that a reduction of the material temperature of the board or the semi-finished product to below -20 ° C takes place in a tempered cooling device.
- the board or the semi-finished product is tempered in a tempered cooling device to forming temperature below -20 ° C, preferably to a temperature in the range of -40 ° C to -180 ° C.
- the low temperatures in combination With a transformation effect in the used Austeniteitstahl the board or semi-finished product, a partial conversion of austenite into martensite, so that a significant increase, especially the yield strength is achieved.
- the tempered cooling device also makes it possible to easily reduce the risk by using liquid, frozen cooling media such as liquid oxygen, liquid nitrogen or liquid or solid carbon dioxide (dry ice) considerably, so that the large-scale use of low-temperature forming is possible.
- tempered cooling devices are devices in which the blanks or semi-finished products are positioned and brought to cryogenic temperature using appropriately cold cooling media.
- the cooling medium for example with liquid oxygen, nitrogen or carbon dioxide.
- the board or the semi-finished product is removed from the cooling device immediately before the forming process and fed to the forming tool.
- the immediate removal of the board or semifinished product before the forming process is made possible that the board or the semi-finished product can still be kept at forming temperature to the extent possible and thus also at least at the beginning of the forming process has the desired temperature.
- the tempered cooling device In addition to using the tempered cooling device, it is possible to use a temperature-controlled forming tool, so that the board or semi-finished product removed from the cooling device can be kept at low temperature in the forming tool for as long as possible.
- a cooling device to use the forming tool itself, in which the board or the semi-finished product is cooled and reshaped.
- the forming tool has means for cooling the board or for tempering the areas in contact with the blank or semifinished product, so that an optimum cooling process is achieved.
- the board or the semi-finished product only has to be introduced into a forming tool and can be formed in this without further removal or transport. As a result, a maximum process control is achieved because the forming temperatures can be easily controlled by the forming tool.
- the forming tool tempers the board to be reshaped or the semi-finished product to be formed only in the areas in which a high yield strength and tensile strength is required. This makes it possible that only by the configuration of the forming tool, the areas of the formed sheet metal part are determined, which should have an increased strength, ie an increased tensile strength and / or yield strength due to the low-temperature deformation.
- the process reliability can be further increased by preventing the icing of the forming tool, the blank and / or the semifinished product using de-icing means before and during the forming operations.
- any existing icing can be easily removed on the forming tool.
- a protective gas can be generated at the cooled regions of the forming tool, the blank or the semifinished product so that icing is prevented.
- the cooling of the forming tool, the circuit board and / or the semifinished product by a protective gas wherein preferably the protective gas flows through provided in the forming flow channels in the corresponding areas to be cooled of the forming tool, the circuit board and / or semifinished product flows.
- particularly small wall thicknesses of the board or of the semifinished product can be used. These are preferably 0.5 mm to 1.80 mm, more preferably 0.7 mm to 1.20 mm.
- a corresponding deformation of the board or semi-finished with these small thicknesses are particularly advantageous, since they can be brought to cryogenic particularly quickly in forming and thus with a relatively low cycle time load-adapted, formed sheet metal parts can be produced which the higher-load areas have significant increases in strength.
- a board or a semi-finished product is formed, which or which has a surface coating, wherein as a surface coating optionally a zinc-containing surface coating is used.
- a surface coating optionally a zinc-containing surface coating is used.
- the surface coating is not damaged, so that cathodic corrosion protection can be easily used by using a zinc-containing surface coating without adversely affecting the forming.
- the sheet metal part produced in this way has strength values which are commensurate with stress and, moreover, is particularly well protected from corrosion owing to the surface coating.
- an organic coating can be used, which is deformable at the correspondingly low temperatures.
- the above-described object is achieved by a device for carrying out the method in that a forming tool is provided, which has a receptacle for inserting a circuit board or a semifinished product and means for at least partially cooling the circuit board or the semifinished product to a temperature are provided below -20 ° C in the recording.
- the device makes it possible to cool the board or the semi-finished product in the forming tool to forming temperature and transform without further transport step. As a result, maximum efficiency is achieved in that a removal of the board or the semi-finished product between the tempering and forming step from the forming tool no longer needs to be done.
- the forming tool preferably has means for de-icing the cooled areas of the forming tool, the blank and / or the semifinished product, in order to ensure a permanent, process-reliable operation.
- the means may comprise, for example, mechanical means, such as brushes or scrapers, which can also remove existing glaciations.
- the forming tool at least in the areas in contact with the board or the semifinished product in flow channels, through which a cooling medium for local cooling of the board or semifinished product flows.
- the cooling medium used is preferably an anhydrous cooling medium, for example dry ice or liquid nitrogen.
- the flow channels to the board or be led to the semi-finished product so that they cool the corresponding areas of the inserted in the forming tool board or the inserted semi-finished product to low temperatures and at the same time a protective gas atmosphere is formed, which prevents the icing of the areas.
- the flow channels can also run only in the forming tool, so that no cooling media, such as oxygen, nitrogen or carbon dioxide leak in the region of the forming tool.
- the board or the semifinished product is formed as a structural part of a motor vehicle, wherein the structural part has areas with different strengths, solved.
- the structural part has areas with different strengths, solved.
- a surface coating which protects against corrosion in particular a coating containing zinc, is used in the process according to the invention no damage, it is particularly advantageous to reshape the board or the semi-finished product as a column, carrier, large-area component, floor panel, tunnel, end wall or wheel arch of a motor vehicle.
- All sheet metal parts mentioned are usually exposed to a more or less strong corrosion attack in the motor vehicle and therefore require a corrosion-protective surface coating.
- load-bearing designed, ie areas with different strengths having sheet metal parts offer the opportunity to save costs, because no more expensive tailored blanks, which consist of several sheets, must be used.
- the one-piece sheet metal parts also have no strength-weakening weld.
- a component reduction and thus a cost reduction can be achieved because it can be dispensed with separate reinforcements.
- the board or semifinished product is reshaped as A, B, C pillar of a motor vehicle, wherein at least the area of the roof connection of the A, B, C pillar has a higher strength than the area the pillar base of the A, B, C pillars.
- the board or the semi-finished product is formed as a longitudinal member in the front region of a motor vehicle and the longitudinal member has a front portion which has a lower strength than the rear portion.
- the front area of the longitudinal member in the front area with lesser Strength should deform in the event of an impact and thus absorb the impact energy.
- the rear area of the longitudinal member should, as far as possible, not be subject to deformation and thus protect the passenger compartment.
- Corresponding solutions could hitherto only be realized by using patches, tailored blanks or additional reinforcing components.
- the inventive method also makes it possible in a simple manner to provide a one-piece sheet metal part, which also allows a simplified and economical production of a longitudinal member with areas of different strengths in addition to a very good cathodic protection against corrosion.
- a schematic diagram of the method for producing a formed sheet metal part is shown, in which a circuit board 1 is to be formed in a forming tool 2.
- the forming tool 2 is shown as a simple deep-drawing tool. However, the forming tool 2 stands for any forming tools, as they are used to produce formed sheet metal parts of flat boards or already preformed or cut semi-finished products.
- the board 1 consists of a steel with at least 60 wt .-% Fe and a retained austenite content of at least 5%. Typical representatives of these types of steel are, for example, high-manganese steels but also TRIP steels.
- the board 1 is first in a cooling device 3 to a temperature of cooled below -20 ° C, preferably to a temperature of -40 ° C to -190 ° C.
- cooling media such as liquid nitrogen, dry ice or liquid oxygen can be used without any risk to the safety of operating personnel of the device.
- the temperature-controlled cooling device can have, for example, closed circuits of the correspondingly cool cooling media, which transmit the heat to the board or semifinished product, for example via direct metal contact.
- the forming temperature is removed from the cooling device 3 shortly before the forming process and fed to the forming tool 2 , The deformation then takes place directly, so that the temperature rise is limited due to the removal from the cooling device.
- the forming tool 2 itself still be tempered, so that a significant increase in temperature of the board is prevented in the forming tool.
- the cooling device 3 a discontinuous operation of the cooling of the board 1 is available.
- the in Fig. 2 illustrated cooling device 3 'a continuous passage of the board 1 or the semifinished product 1 through the cooling device 3', so that the board 1 and the semifinished product 1 at the output of the cooling device 3 'was brought to forming temperature.
- the circuit board 1 or the semifinished product 1 is then inserted and formed immediately after leaving the cooling device 3 'in the forming tool 2.
- the forming tool 2 is merely here Represented as a thermoforming tool. Basically, AHU / hydroforming tools and any other forming tools are conceivable, which cause a deformation and thus a solidification in the sheet metal part suitable.
- FIG. 3a An optional embodiment of the forming tool is in the Fig. 3a ), b) shown in a perspective, schematic view.
- This in Fig. 3a ) shown forming tool 4 has an upper Umformtechnikmaschineschnet 4a, in which flow channels 5 are arranged, which produce a cooled portion 6 of the board, which is then formed at low temperature.
- a cooling medium for example liquid nitrogen or liquid oxygen or also cooled carbon dioxide flows through the flow channels and cools the board in this area from strong.
- the upper mold half 4a which has the flow channels and thus is particularly cold, even during the opening of the tool, the cooling medium through the flow channels leads.
- icing of the tool surfaces is prevented by training a protective gas atmosphere 8 in the region of the highly cooled surfaces of the forming tool takes place.
- Fig. 4 now an embodiment of a forming tool is shown, which has a closed circuit with respect to the cooling medium.
- the forming tool 9 shown schematically has coolant channels 10 in the region of the punch or the die, through which flows a correspondingly low-temperature cooling medium.
- the circuit board 1, which is arranged between the two halves of the forming tool 9 and having these surface contact, is very strongly cooled in the area of the contact surfaces with the cooled stamp and brought to forming temperature of less than -20 ° C. Should any areas be present that should not be brought to the appropriate temperature, means are provided in the stamp 11, which allow local heating of the board 1 in addition. These means may be configured, for example, as a heating cartridge or similar heat-emitting means.
- the mechanical deicing means 12 consist of a holder for receiving a scraper 12a, which cleans the surface of the punch 9 ', for example, when the forming tool 9 is opened. It is also conceivable to use brushes instead of the scraper 12a.
- the illustrated forming tool 9 can cool an inserted board 1 in a relatively short time due to the large surface contact on the forming temperature below -20 ° C and thus provide a simple, economical manufacturing process.
- FIGS. 5, 6 and 7 show typical embodiments of advantageous uses of the formed sheet metal part 1.
- the use of the sheet metal part as a B-pillar 13 of a motor vehicle 14 is shown schematically.
- the B-pillar 13 should preferably have a high yield strength and tensile strength roof connection area 13b and a lower strength but with a greater elongation at break equipped column foot 13a.
- this B-pillar can be produced in an economical manner by strongly cooling down the upper region of the B-pillar 13 in the forming tool and subsequently shaping it. This gives the upper region a significantly higher yield strength and tensile strength in comparison to the pedestal 13a.
- Fig. 6 shows two side members of a front portion of a vehicle body, which have two different functions in one component.
- the longitudinal members 17 serve, in the event of an impact, first to absorb the impact energy and to deform at least partially and, on the other hand, to protect the passenger compartment located in the rear region against further deformation.
- the longitudinal members 17 are usually designed such that the front region is easier to reshape and the rear region is formed as stiff as possible.
- a longitudinal member 17 can now be produced such that its front region 17a has a lower strength than the rear region 17b, wherein the rear region of the longitudinal member 17b is strongly cooled in the forming tool.
- FIG. 7 an example of an end wall 18, which is preferably produced by the method according to the invention.
- the end wall 18 is usually a large area and has a relatively small thickness.
- individual attachment regions 19 for example with a higher yield strength and tensile strength, so that no reinforcements in the form of patches, tailored blanks or separate components are more necessary.
- tailored blanks or separate components are more necessary.
- by targeted temperature control of the forming tool not only can be achieved that specific areas of the end wall 18 show a significantly different deformation behavior in the event of an impact, but also local areas are provided with corresponding yield strengths and tensile strengths, which are used to hold aggregates, such as Serve brake booster, air conditioning, etc., so that the end wall 18 can be designed load-appropriate without additional measures.
- Fig. 5 to 7 illustrated typical uses of the sheet metal part formed according to the invention can be provided in particular readily cathodic corrosion protection based on a zinc-containing surface coating and / or an organic surface coating, as can be dispensed with hot forming.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Shaping Metal By Deep-Drawing, Or The Like (AREA)
- Heat Treatment Of Articles (AREA)
- Body Structure For Vehicles (AREA)
- Heat Treatment Of Steel (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI201330995T SI2855041T1 (en) | 2012-05-31 | 2013-05-28 | A process for the manufacture of preformed sheet metal parts at a low temperature |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012104734A DE102012104734A1 (de) | 2012-05-31 | 2012-05-31 | Verfahren und Vorrichtung zur Herstellung von umgeformten Blechteilen bei Tieftemperatur |
| PCT/EP2013/060934 WO2013178615A1 (de) | 2012-05-31 | 2013-05-28 | Verfahren und vorrichtung zur herstellung von umgeformten blechteilen bei tieftemperatur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2855041A1 EP2855041A1 (de) | 2015-04-08 |
| EP2855041B1 true EP2855041B1 (de) | 2018-01-31 |
Family
ID=48539135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP13726170.7A Not-in-force EP2855041B1 (de) | 2012-05-31 | 2013-05-28 | Verfahren zur herstellung von umgeformten blechteilen bei tieftemperatur |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US10532395B2 (enExample) |
| EP (1) | EP2855041B1 (enExample) |
| JP (1) | JP6068627B2 (enExample) |
| KR (1) | KR20150016319A (enExample) |
| CN (1) | CN104379272B (enExample) |
| BR (1) | BR112014030042A2 (enExample) |
| DE (1) | DE102012104734A1 (enExample) |
| ES (1) | ES2666312T3 (enExample) |
| IN (1) | IN2014MN02371A (enExample) |
| MX (1) | MX2014014544A (enExample) |
| SI (1) | SI2855041T1 (enExample) |
| WO (1) | WO2013178615A1 (enExample) |
| ZA (1) | ZA201409111B (enExample) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3020491A1 (de) * | 2014-11-14 | 2016-05-18 | Linde Aktiengesellschaft | Verfahren zum Umformen von Aluminiumblechen |
| DE102015203644A1 (de) * | 2015-03-02 | 2016-09-08 | Bayerische Motoren Werke Aktiengesellschaft | Pressgehärtetes Blechformteil mit unterschiedlichen Blechdicken und Festigkeiten |
| DE102016102344B4 (de) * | 2016-02-10 | 2020-09-24 | Voestalpine Metal Forming Gmbh | Verfahren und Vorrichtung zum Erzeugen gehärteter Stahlbauteile |
| US10619223B2 (en) | 2016-04-28 | 2020-04-14 | GM Global Technology Operations LLC | Zinc-coated hot formed steel component with tailored property |
| US10385415B2 (en) | 2016-04-28 | 2019-08-20 | GM Global Technology Operations LLC | Zinc-coated hot formed high strength steel part with through-thickness gradient microstructure |
| CN106140924A (zh) * | 2016-08-30 | 2016-11-23 | 山西北方机械制造有限责任公司 | 一种高强度厚钢板的引伸方法 |
| US20180221937A1 (en) * | 2017-02-06 | 2018-08-09 | Ross Casting And Innovation, Llc | Method and Apparatus For Producing A Forged Compressor Wheel |
| CN108326159B (zh) * | 2018-02-08 | 2020-03-17 | 苑世剑 | 一种大尺寸铝合金拼焊板类构件冷冻成形方法 |
| US11613789B2 (en) | 2018-05-24 | 2023-03-28 | GM Global Technology Operations LLC | Method for improving both strength and ductility of a press-hardening steel |
| WO2019241902A1 (en) | 2018-06-19 | 2019-12-26 | GM Global Technology Operations LLC | Low density press-hardening steel having enhanced mechanical properties |
| JP2020146747A (ja) * | 2019-03-15 | 2020-09-17 | 本田技研工業株式会社 | 車体フレームの製造方法、及び車体フレーム |
| US11530469B2 (en) | 2019-07-02 | 2022-12-20 | GM Global Technology Operations LLC | Press hardened steel with surface layered homogenous oxide after hot forming |
| DE102020116126A1 (de) * | 2020-06-18 | 2021-12-23 | Bilstein Gmbh & Co. Kg | Verfahren zum Presshärten von warmumformbaren Platinen |
| CN112588931B (zh) * | 2020-11-26 | 2021-12-21 | 大连理工大学 | 一种复杂形状曲面件超低温介质压力成形方法 |
| CN112916700B (zh) * | 2021-02-05 | 2022-06-21 | 大连理工大学 | 一种大尺寸小特征曲面件局部超低温成形方法 |
| KR20240003795A (ko) * | 2022-07-01 | 2024-01-10 | 주식회사 엘지에너지솔루션 | 파우치 포밍 장치 및 이를 이용한 파우치 포밍 방법 |
| CN117548551B (zh) * | 2024-01-11 | 2024-03-26 | 湘潭大学 | 一种铝合金的成形方法 |
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2012
- 2012-05-31 DE DE102012104734A patent/DE102012104734A1/de not_active Withdrawn
-
2013
- 2013-05-28 ES ES13726170.7T patent/ES2666312T3/es active Active
- 2013-05-28 CN CN201380028507.1A patent/CN104379272B/zh not_active Expired - Fee Related
- 2013-05-28 IN IN2371MUN2014 patent/IN2014MN02371A/en unknown
- 2013-05-28 KR KR1020147034450A patent/KR20150016319A/ko not_active Abandoned
- 2013-05-28 JP JP2015514458A patent/JP6068627B2/ja not_active Expired - Fee Related
- 2013-05-28 SI SI201330995T patent/SI2855041T1/en unknown
- 2013-05-28 MX MX2014014544A patent/MX2014014544A/es unknown
- 2013-05-28 EP EP13726170.7A patent/EP2855041B1/de not_active Not-in-force
- 2013-05-28 BR BR112014030042A patent/BR112014030042A2/pt not_active Application Discontinuation
- 2013-05-28 WO PCT/EP2013/060934 patent/WO2013178615A1/de not_active Ceased
-
2014
- 2014-11-26 US US14/554,206 patent/US10532395B2/en active Active
- 2014-12-11 ZA ZA2014/09111A patent/ZA201409111B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US10532395B2 (en) | 2020-01-14 |
| IN2014MN02371A (enExample) | 2015-08-14 |
| SI2855041T1 (en) | 2018-06-29 |
| JP2015519205A (ja) | 2015-07-09 |
| ZA201409111B (en) | 2017-09-27 |
| DE102012104734A1 (de) | 2013-12-05 |
| US20150082636A1 (en) | 2015-03-26 |
| MX2014014544A (es) | 2015-09-04 |
| CN104379272A (zh) | 2015-02-25 |
| KR20150016319A (ko) | 2015-02-11 |
| EP2855041A1 (de) | 2015-04-08 |
| WO2013178615A1 (de) | 2013-12-05 |
| JP6068627B2 (ja) | 2017-01-25 |
| BR112014030042A2 (pt) | 2019-09-03 |
| CN104379272B (zh) | 2017-03-15 |
| ES2666312T3 (es) | 2018-05-03 |
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