EP2682485A1 - Procédé et dispositif de fabrication de tubes en acier ayant des propriétés particulières - Google Patents

Procédé et dispositif de fabrication de tubes en acier ayant des propriétés particulières Download PDF

Info

Publication number: EP2682485A1
Authority: EP; European Patent Office
Prior art keywords: max; cooling; pipe; tube; temperature
Prior art date: 2008-11-20
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

EP13187253.3A

Other languages

German (de)

English (en)

Other versions

EP2682485B1 (fr

Inventor

Jürgen KLARNER

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.)

Voestalpine Tubulars GmbH and Co KG

Original Assignee

Voestalpine Tubulars GmbH and Co KG

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.)

2008-11-20

Filing date

2009-11-16

Publication date

2014-01-08

2009-11-16 Application filed by Voestalpine Tubulars GmbH and Co KG filed Critical Voestalpine Tubulars GmbH and Co KG

2014-01-08 Publication of EP2682485A1 publication Critical patent/EP2682485A1/fr

2017-03-15 Application granted granted Critical

2017-03-15 Publication of EP2682485B1 publication Critical patent/EP2682485B1/fr

2017-06-01 Priority to HRP20170838TT priority Critical patent/HRP20170838T1/hr

Status Active legal-status Critical Current

2029-11-16 Anticipated expiration legal-status Critical

Links

229910000831 Steel Inorganic materials 0.000 title claims abstract description 14
239000010959 steel Substances 0.000 title claims abstract description 14
238000000034 method Methods 0.000 title claims description 19
238000001816 cooling Methods 0.000 claims abstract description 39
239000002826 coolant Substances 0.000 claims abstract description 25
238000004519 manufacturing process Methods 0.000 claims abstract description 11
239000000463 material Substances 0.000 claims description 29
239000010936 titanium Substances 0.000 claims description 8
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
229910052799 carbon Inorganic materials 0.000 claims description 6
238000005096 rolling process Methods 0.000 claims description 6
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
239000011572 manganese Substances 0.000 claims description 5
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
239000010949 copper Substances 0.000 claims description 4
239000010955 niobium Substances 0.000 claims description 4
229910052698 phosphorus Inorganic materials 0.000 claims description 4
239000011574 phosphorus Substances 0.000 claims description 4
229910052717 sulfur Inorganic materials 0.000 claims description 4
239000011593 sulfur Substances 0.000 claims description 4
229910052719 titanium Inorganic materials 0.000 claims description 4
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
229910052782 aluminium Inorganic materials 0.000 claims description 3
238000009826 distribution Methods 0.000 claims description 3
239000012535 impurity Substances 0.000 claims description 3
239000007921 spray Substances 0.000 claims description 3
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
238000005275 alloying Methods 0.000 claims description 2
229910052802 copper Inorganic materials 0.000 claims description 2
229910052748 manganese Inorganic materials 0.000 claims description 2
229910052750 molybdenum Inorganic materials 0.000 claims description 2
239000011733 molybdenum Substances 0.000 claims description 2
229910052759 nickel Inorganic materials 0.000 claims description 2
229910052758 niobium Inorganic materials 0.000 claims description 2
GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
229910052757 nitrogen Inorganic materials 0.000 claims description 2
238000003303 reheating Methods 0.000 claims description 2
229910052710 silicon Inorganic materials 0.000 claims description 2
239000010703 silicon Substances 0.000 claims description 2
LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
239000011575 calcium Substances 0.000 claims 2
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
229910052791 calcium Inorganic materials 0.000 claims 1
238000007493 shaping process Methods 0.000 claims 1
239000000523 sample Substances 0.000 description 6
239000000203 mixture Substances 0.000 description 4
229910000859 α-Fe Inorganic materials 0.000 description 4
238000006243 chemical reaction Methods 0.000 description 3
230000002349 favourable effect Effects 0.000 description 3
238000010438 heat treatment Methods 0.000 description 3
235000019362 perlite Nutrition 0.000 description 3
239000010451 perlite Substances 0.000 description 3
230000009466 transformation Effects 0.000 description 3
229910001563 bainite Inorganic materials 0.000 description 2
238000005452 bending Methods 0.000 description 2
238000011835 investigation Methods 0.000 description 2
238000005259 measurement Methods 0.000 description 2
238000001953 recrystallisation Methods 0.000 description 2
238000012360 testing method Methods 0.000 description 2
229910045601 alloy Inorganic materials 0.000 description 1
239000000956 alloy Substances 0.000 description 1
238000000137 annealing Methods 0.000 description 1
229910001566 austenite Inorganic materials 0.000 description 1
230000001580 bacterial effect Effects 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
230000003247 decreasing effect Effects 0.000 description 1
230000001419 dependent effect Effects 0.000 description 1
238000011161 development Methods 0.000 description 1
238000005516 engineering process Methods 0.000 description 1
239000007789 gas Substances 0.000 description 1
239000002245 particle Substances 0.000 description 1
230000035515 penetration Effects 0.000 description 1
238000005507 spraying Methods 0.000 description 1
239000000126 substance Substances 0.000 description 1
238000004781 supercooling Methods 0.000 description 1
238000005496 tempering Methods 0.000 description 1
238000003856 thermoforming Methods 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1

Images

Classifications

- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/085—Cooling or quenching
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
- C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese

Definitions

the invention relates to a method for the production of tubes made of steel with increased strength and improved toughness of the material.
the invention relates to a device for producing pipes with a special property profile consisting of a device for coolant treatment of a pipe surface.
the properties of the material of the tube wall can have significant differences locally and los related. These property differences are usually based on an uneven microstructure and on an unfavorable steel composition or an increased proportion of accompanying and impurity elements.
Tubes with a length of 7m and larger and an outer diameter of less than 200mm with a wall thickness of less than 25mm can be subjected to a heat treatment only with great effort, which provides a uniformly fine structure with the desired structure over the entire tube volume and minimizes bending perpendicular to the longitudinal direction ,
the invention is now based on the object of specifying a method with which during the production of a tube by hot forming, in particular by drawdown, downstream of a treatment thereof takes place, which causes an increase in strength and an improvement in the toughness of the pipe material.
the object is achieved by a generic method, in which by immediate rapid cooling after hot forming, in particular after deformation by means of stretch reducing, in each case within a period of at most 20 seconds after the final deformation at a temperature of higher 700 ° C, but below 1050 ° C. in the passage on the outer surface of the tube circumferentially in a length of greater than 400 times the pipe wall thickness, a cooling medium with increased pressure in an amount is applied, which in the rapid cooling an equal cooling rate of greater than 1 ° C / sec of the pipe wall over the pipe length to a temperature in the range of 500 ° C to 250 ° C, after which a further cooling of the Fbhres takes place in air to room temperature.
For an integrated tempering treatment may also be advantageous if, after the rapid cooling in a further cooling of the tube in air, a targeted reheating of the pipe wall surface area.
the method is used for producing seamless pipes with a length greater than 7 m, in particular up to 200 m, an outer diameter of greater than 20 mm, but less than 200 mm, a wall thickness of greater than 2.0 mm, but less than 25 mm, the increased quality of the pipe can be a considerable advantage reduce inventory and minimize damage due to breakage with significant repair costs.
At least one element of the steel may advantageously contain, in terms of a homogeneous high grade of pipe, contents in% by weight of: Carbon (C) 12:05 to 12:35 Phosphorus (P) Max 0015 Sulfur (S) Max 0005 Chrome (Cr) Max 1.0 Titanium (Ti) Max 12:02 exhibit.
the further object of the invention to provide a device for producing tubes made of steel with increased strength and improved toughness of the material by rapid cooling after deformation consisting of a means for coolant loading a pipe surface is achieved in that in the rolling direction after the last deformation stand a switchable passage cooling section with a plurality of arranged concentrically around the rolling stock, longitudinally differently positionable distributor rings for the cooling medium is formed in each case with at least 3, each directed substantially to the axis of nozzles, each distribution ring or each group of the same throughput controlled with the cooling medium is anspeisbar ,
a device according to the invention it is advantageously possible with a device according to the invention to subject tubes having a different longitudinal extent and with different diameters and wall thicknesses to a targeted heat treatment from the rolling heat, such that a desired microstructure, which is represented uniformly over the tube length, can be obtained.
the coolant stream can be designed in each case as a spray stream of coolant, usually water, and / or as a spray stream of coolant and air and / or as a gas stream.
regulations for tube cooling with position and temperature sensors are used to control the coolant flows.
Example 1 from tube pre-material of the same mother melt with a chemical composition in wt .-% according to Tab. 1
the pipe was introduced into a through-flow cooling section at a temperature of 880 ° C. after a time of 12 seconds.
microstructure revealed that at most there was in each case an advantageously rectified microstructure, essentially without texture, but with a grain size and microstructure distribution dependent on the final cooling temperature.
Fig. 1 shows a structure of sample P1, wherein a particle size of 20 .mu.m - 30 .mu.m at high ferrite content was present.
the further structural component was essentially perlite.
Fig. 5 shows in a bar graph the measured values yield strength (Rp) (0.2) [MPa], tensile strength (Rm) [MPa], constriction (Ac) [%] and toughness (KV450) [J] of the samples P1 to P4, ie depending on the achieved by the different cooling parameters in the annealing technology, mechanical material properties.
Fig. 6 shows the measured hardness values over the pipe length of test tubes P1 and P4.
Fig. 7 the hardness profile of the material in the quadrant is shown over the pipe wall thickness of the test tube P2.
the measurement results of the four quadrants Q1 to Q4 are averages of four spaced measurements per quadrant in the outer, middle and inner regions of the tube wall.

Landscapes

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)
Manufacturing & Machinery (AREA)
Heat Treatment Of Articles (AREA)
Heat Treatment Of Steel (AREA)

EP13187253.3A 2008-11-20 2009-11-16 Procédé et dispositif de fabrication de tubes en acier ayant des propriétés particulières Active EP2682485B1 (fr)

Priority Applications (1)

Application Number	Priority Date	Filing Date	Title
HRP20170838TT HRP20170838T1 (hr)	2008-11-20	2017-06-01	Metoda i uređaj za proizvodnju čeličnih cijevi sa posebnim svojstvima

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
AT0181408A AT507596B1 (de)	2008-11-20	2008-11-20	Verfahren und vorrichtung zur herstellung von stahlrohren mit besonderen eigenschaften
EP09763823.3A EP2356262B1 (fr)	2008-11-20	2009-11-16	Procédé et dispositif pour fabriquer des tubes en acier aux propriétés particulières

Related Parent Applications (3)

Application Number	Title	Priority Date	Filing Date
EP09763823.3A Division EP2356262B1 (fr)	2008-11-20	2009-11-16	Procédé et dispositif pour fabriquer des tubes en acier aux propriétés particulières
EP09763823.3A Division-Into EP2356262B1 (fr)	2008-11-20	2009-11-16	Procédé et dispositif pour fabriquer des tubes en acier aux propriétés particulières
EP09763823.3 Division		2009-11-16

Publications (2)

Publication Number	Publication Date
EP2682485A1 true EP2682485A1 (fr)	2014-01-08
EP2682485B1 EP2682485B1 (fr)	2017-03-15

Family

ID=41785584

Family Applications (2)

Application Number	Title	Priority Date	Filing Date
EP09763823.3A Active EP2356262B1 (fr)	2008-11-20	2009-11-16	Procédé et dispositif pour fabriquer des tubes en acier aux propriétés particulières
EP13187253.3A Active EP2682485B1 (fr)	2008-11-20	2009-11-16	Procédé et dispositif de fabrication de tubes en acier ayant des propriétés particulières

Family Applications Before (1)

Application Number	Title	Priority Date	Filing Date
EP09763823.3A Active EP2356262B1 (fr)	2008-11-20	2009-11-16	Procédé et dispositif pour fabriquer des tubes en acier aux propriétés particulières

Country Status (18)

Country	Link
US (1)	US9394582B2 (fr)
EP (2)	EP2356262B1 (fr)
JP (1)	JP2012509398A (fr)
KR (2)	KR101694679B1 (fr)
CN (1)	CN102224265A (fr)
AR (1)	AR075551A1 (fr)
AT (1)	AT507596B1 (fr)
BR (2)	BRPI0921077B1 (fr)
CA (1)	CA2748046C (fr)
EA (1)	EA021245B1 (fr)
ES (2)	ES2625085T3 (fr)
HR (2)	HRP20160591T1 (fr)
MX (1)	MX2011005110A (fr)
PL (2)	PL2356262T3 (fr)
SG (2)	SG10201500738QA (fr)
UA (1)	UA98088C2 (fr)
WO (1)	WO2010057235A1 (fr)
ZA (1)	ZA201102056B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US11873538B2 (en)	2019-04-18	2024-01-16	Sms Group Gmbh	Cooling device for seamless steel pipes

Families Citing this family (4)

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CN102021488B (zh) *	2010-11-30	2013-05-08	攀钢集团钢铁钒钛股份有限公司	核岛无缝钢管用钢及其生产方法
CN102367560B (zh) *	2011-11-09	2013-06-19	南京钢铁股份有限公司	一种高强度耐腐蚀直缝焊管用钢的制造方法
AR096272A1 (es) *	2013-05-31	2015-12-16	Nippon Steel & Sumitomo Metal Corp	Tubo de acero sin costura para tubería de conducción utilizado en ambientes agrios
DE102020212926A1 (de)	2020-10-14	2022-04-14	Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein	Verfahren zur Umformung eines Halbzeugs und Vorrichtung zur Durchführung des Verfahrens

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US3507712A (en) *	1967-09-08	1970-04-21	United States Steel Corp	Method and apparatus for quenching pipe
JPS5437011A (en) *	1977-08-29	1979-03-19	Mitsubishi Electric Corp	Apparatus for hardening pipes
WO1998038345A1 (fr) *	1997-02-27	1998-09-03	Exxon Production Research Company	Acier a resistance elevee a la rupture et procede de production
US7018488B2 (en) *	2000-06-14	2006-03-28	Jfe Steel Corporation	Steel pipe for use in reinforcement of automobile and method for production thereof
US20070181234A1 (en) *	2006-02-08	2007-08-09	Nallen Michael A	Spray quench systems for heat treated metal products

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2008
- 2008-11-20 AT AT0181408A patent/AT507596B1/de not_active IP Right Cessation
2009
- 2009-10-19 AR ARP090104006A patent/AR075551A1/es not_active Application Discontinuation
- 2009-11-16 EP EP09763823.3A patent/EP2356262B1/fr active Active
- 2009-11-16 SG SG10201500738QA patent/SG10201500738QA/en unknown
- 2009-11-16 ES ES13187253.3T patent/ES2625085T3/es active Active
- 2009-11-16 WO PCT/AT2009/000439 patent/WO2010057235A1/fr active Application Filing
- 2009-11-16 SG SG10202013010SA patent/SG10202013010SA/en unknown
- 2009-11-16 CA CA2748046A patent/CA2748046C/fr active Active
- 2009-11-16 US US13/128,838 patent/US9394582B2/en active Active
- 2009-11-16 BR BRPI0921077-6A patent/BRPI0921077B1/pt active IP Right Grant
- 2009-11-16 MX MX2011005110A patent/MX2011005110A/es active IP Right Grant
- 2009-11-16 EP EP13187253.3A patent/EP2682485B1/fr active Active
- 2009-11-16 PL PL09763823T patent/PL2356262T3/pl unknown
- 2009-11-16 BR BR122017014778A patent/BR122017014778B1/pt active IP Right Grant
- 2009-11-16 UA UAA201107654A patent/UA98088C2/ru unknown
- 2009-11-16 KR KR1020117014023A patent/KR101694679B1/ko active IP Right Grant
- 2009-11-16 CN CN200980146610XA patent/CN102224265A/zh active Pending
- 2009-11-16 ES ES09763823.3T patent/ES2569103T3/es active Active
- 2009-11-16 PL PL13187253T patent/PL2682485T3/pl unknown
- 2009-11-16 KR KR1020167032619A patent/KR101760654B1/ko active IP Right Grant
- 2009-11-16 EA EA201100799A patent/EA021245B1/ru not_active IP Right Cessation
- 2009-11-16 JP JP2011536700A patent/JP2012509398A/ja active Pending
2011
- 2011-03-18 ZA ZA2011/02056A patent/ZA201102056B/en unknown
2016
- 2016-06-01 HR HRP20160591TT patent/HRP20160591T1/hr unknown
2017
- 2017-06-01 HR HRP20170838TT patent/HRP20170838T1/hr unknown

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3507712A (en) *	1967-09-08	1970-04-21	United States Steel Corp	Method and apparatus for quenching pipe
JPS5437011A (en) *	1977-08-29	1979-03-19	Mitsubishi Electric Corp	Apparatus for hardening pipes
WO1998038345A1 (fr) *	1997-02-27	1998-09-03	Exxon Production Research Company	Acier a resistance elevee a la rupture et procede de production
US7018488B2 (en) *	2000-06-14	2006-03-28	Jfe Steel Corporation	Steel pipe for use in reinforcement of automobile and method for production thereof
US20070181234A1 (en) *	2006-02-08	2007-08-09	Nallen Michael A	Spray quench systems for heat treated metal products

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US11873538B2 (en)	2019-04-18	2024-01-16	Sms Group Gmbh	Cooling device for seamless steel pipes

Also Published As

Publication number	Publication date
CA2748046A1 (fr)	2010-05-27
ES2569103T3 (es)	2016-05-06
KR101760654B1 (ko)	2017-08-04
MX2011005110A (es)	2011-05-30
EP2682485B1 (fr)	2017-03-15
US20110272067A1 (en)	2011-11-10
AT507596A1 (de)	2010-06-15
BRPI0921077B1 (pt)	2018-01-16
US9394582B2 (en)	2016-07-19
JP2012509398A (ja)	2012-04-19
AR075551A1 (es)	2011-04-20
CN102224265A (zh)	2011-10-19
PL2682485T3 (pl)	2017-09-29
AT507596B1 (de)	2011-04-15
ES2625085T3 (es)	2017-07-18
WO2010057235A1 (fr)	2010-05-27
EP2356262A1 (fr)	2011-08-17
SG10201500738QA (en)	2015-03-30
ZA201102056B (en)	2011-11-30
CA2748046C (fr)	2018-01-09
UA98088C2 (ru)	2012-04-10
PL2356262T3 (pl)	2016-08-31
KR20160137675A (ko)	2016-11-30
KR101694679B1 (ko)	2017-01-10
BRPI0921077A2 (pt)	2015-12-15
KR20110095376A (ko)	2011-08-24
EP2356262B1 (fr)	2016-03-09
BR122017014778B1 (pt)	2018-10-16
HRP20160591T1 (hr)	2016-07-01
EA021245B1 (ru)	2015-05-29
EA201100799A1 (ru)	2011-12-30
HRP20170838T1 (hr)	2017-08-25
SG10202013010SA (en)	2021-02-25

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