WO2011120550A1 - Steel product with improved weathering characteristics in saline environment - Google Patents

Steel product with improved weathering characteristics in saline environment Download PDF

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Publication number
WO2011120550A1
WO2011120550A1 PCT/EP2010/054086 EP2010054086W WO2011120550A1 WO 2011120550 A1 WO2011120550 A1 WO 2011120550A1 EP 2010054086 W EP2010054086 W EP 2010054086W WO 2011120550 A1 WO2011120550 A1 WO 2011120550A1
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WIPO (PCT)
Prior art keywords
steel product
steel
weathering
product
niobium
Prior art date
Application number
PCT/EP2010/054086
Other languages
French (fr)
Inventor
Joachim Antonissen
Eddy De Grave
Julieth Alexandra Mejia Gomez
Original Assignee
Arcelormittal Investigación Y Desarrollo Sl
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
Priority to EP20100712049 priority Critical patent/EP2553132B1/en
Application filed by Arcelormittal Investigación Y Desarrollo Sl filed Critical Arcelormittal Investigación Y Desarrollo Sl
Priority to BR112012024642-9A priority patent/BR112012024642B1/en
Priority to CN201080065812.4A priority patent/CN102884214B/en
Priority to PL10712049T priority patent/PL2553132T3/en
Priority to US13/637,461 priority patent/US20130078135A1/en
Priority to CA2793294A priority patent/CA2793294C/en
Priority to ES10712049.5T priority patent/ES2544576T3/en
Priority to PCT/EP2010/054086 priority patent/WO2011120550A1/en
Priority to PT107120495T priority patent/PT2553132E/en
Priority to DK10712049.5T priority patent/DK2553132T3/en
Publication of WO2011120550A1 publication Critical patent/WO2011120550A1/en
Priority to ZA2012/07137A priority patent/ZA201207137B/en
Priority to HRP20150826TT priority patent/HRP20150826T1/en

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Classifications

    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium

Definitions

  • the present invention is related to steel types and products made thereof, which exhibit an increase in corrosion resistance when exposed to a chlorine-rich environment. These steels are known as weathering steels. State of the art
  • the weathering capability in saline environment is mainly obtained by the presence of Sb and/or Sn, which stabilize the amount of Fe2+ ions when the steel is in a wet and saline environment, by reacting with Fe3+ ions, produced by oxidation of Fe2+.
  • Sn and/or Sb is disadvantageous for various reasons :
  • the present invention aims to provide a weathering steel with a Ni-content in the same order of magnitude as in traditional weathering steels, and with an increased corrosion resistance in marine or seaside conditions, as well as with excellent mechanical properties .
  • the invention is related to a steel product as disclosed in the appended claims.
  • the invention is in particular related to a steel product as disclosed in the main independent claim, suitable for use in outdoor environments, in particular in saline conditions.
  • the steel product of the invention may be any type of construction element such as a steel sheet or beam.
  • the invention is related to a steel composition characterized by the following contents (in wt%) :
  • the balance being Fe and accidental impurities, and wherein the sum of the Al and Si levels is higher than about 0.85wt% .
  • the steel product according to the invention comprises no Sn and no Sb .
  • the present invention is related to a steel product of the weathering steel type, i.e. a product exhibiting increased corrosion resistance after having been exposed to the outside environment for a given time.
  • the steel product is defined by a composition consisting of (in wt%) :
  • the amounts of Cu, Ti, Cr, Ni and Nb are as follows (in wt%) :
  • This embodiment combines good weathering behaviour in saline conditions with excellent mechanical properties, due to the minimum amounts of the abovenamed elements (Cu, Ti, Cr, Ni, Nb) .
  • the present invention reveals that the inventive steel compositions favour the formation of fine grained goethite (a-FeOOH) in the corrosion layer forming on the surface of a steel product having these compositions, due to the specific combined Al and Si content.
  • a-FeOOH fine grained goethite
  • x fine grained goethite' is meant goethite with grain sizes from about 8nm to about 15nm.
  • the formation of such fine grained goethite is beneficial for the stability of the oxide layer in saline conditions.
  • inventive compositions do not necessarily include an addition of significant amounts of the traditional elements regarded as beneficial for weathering resistance in saline conditions, such as Ni .
  • inventive compositions do not comprise Sn and Sb above an accidental impurity level.
  • the steel product of the invention comprises no Sb or Sn.
  • Elements such as Nb, Ti, Cu, Cr may be added for improving the mechanical properties of the steel, but are not required for ensuring the weathering behaviour in saline conditions .
  • the invention is related to any type of steel product having the composition as claimed, e.g. steel sheets or beams, obtained by any standard steel-making process, e.g. hot-rolled or cold-rolled sheets or beams.
  • Table 1 shows the compositions of 3 test samples SI to S3 having Al and Si contents according to the invention, as well as 2 comparative samples CI and C2 having Al and Si contents falling outside the claimed ranges and/or wherein the combined Al and Si content is less than 0.85wt%.
  • test samples have been obtained by standard steel processing methods, involving at least a hot rolling step, possibly followed by a cold rolling step.
  • the samples were subjected to a dip-dry test during 60 days, using a 0.05M NaCl solution, in order to test weatherability behaviour in saline conditions.
  • oxide layers were formed on the samples.
  • the composition of these oxide layers was investigated by Mossbauer spectroscopy, used in particular to measure the relative area of superparamagnetic goethite in the oxide layer.
  • Superparamagnetic goethite has a particle size between 8 and 15nm, as opposed to antiferromagnetic goethite, having particle sizes above 15nm.
  • Table 2 clearly shows that the combined Al and Si contents according to the present invention give rise to a considerable increase in the relative area of fine-grained goethite in the oxide layer.
  • Table 1 example compositions (in wt%)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The present invention is related to a steel product of the weathering steel type, i.e. a product exhibiting increased corrosion resistance after having been exposed to the outside environment for a given time. According to the invention, the steel product is defined by a composition consisting of (in wt%) : - Carbon between 0.03 and 0.2, - Manganese between 0.5 and 2, - Copper between 0 and 0.5, - Ti between 0 and 0.1, - Cr between 0 and 0.5, - Nickel between 0 and 0.2, - Niobium between 0 and 0.1, - Nitrogen between 0 and 0.01, - Sulphur between 0 and 0.01, Phosphor between 0 and 0.01, - Aluminium higher than 0 and maximum 1.5, - Silicon between 0.25 and 1.5, the balance being Fe and accidental impurities, and wherein the sum of the Al and Si levels is higher than about 0.85wt%.

Description

STEEL PRODUCT WITH IMPROVED WEATHERING CHARACTERISTICS IN
SALINE ENVIRONMENT
Field of the Invention
[0001] The present invention is related to steel types and products made thereof, which exhibit an increase in corrosion resistance when exposed to a chlorine-rich environment. These steels are known as weathering steels. State of the art
[0002] Weathering steels have been studied and documented for some time. The corrosion resistance is caused by a layer of rust that forms on the steel surface when it is exposed to the outside environment. Traditional alloying elements which enhance this type of weathering resistance are Cu, P, Cr and Ni . However, traditional weathering steels haven proven to be ineffective in an environment containing CI ions, i.e. marine or seaside environments. It was observed that the CI ions destabilize some of the stable components that form the protective oxide layer. Solutions to this problem have been proposed, mainly in the form of changes in the steel composition. The best results have been achieved so far by applying significantly higher levels of Ni . However, given that a high amount of Ni is needed and taking into account that the price of Ni is a highly critical parameter in the commercial exploitation of steels, this solution is not regarded as ideal, and a need has arisen for an alternative to the Ni-solution. [0003] One solution is described in JP2006118011 , in the form of a steel composition comprising C, Al, Si, P, Ni, Cu, N, with Sn and/or Sb added in an amount between 0.03 and 0.5wt% and one or more of Ti, Nb, Mo, W, V, Ca or Mg, with the mass ratio of Ni/Cu smaller than or equal to 0.5. The weathering capability in saline environment is mainly obtained by the presence of Sb and/or Sn, which stabilize the amount of Fe2+ ions when the steel is in a wet and saline environment, by reacting with Fe3+ ions, produced by oxidation of Fe2+. However, the use of Sn and/or Sb is disadvantageous for various reasons :
• both Sn and Sb have a detrimental effect on hot ductility as they decrease the solubility of Cu in austenite at high temperature
· Sb has a detrimental effect on weld toughness
• Sn can not be removed from the steel during refining
• Sb causes a risk of forming Stibine (SbH3) - a toxic and flammable compound. Aims of the invention
[0004] The present invention aims to provide a weathering steel with a Ni-content in the same order of magnitude as in traditional weathering steels, and with an increased corrosion resistance in marine or seaside conditions, as well as with excellent mechanical properties .
Summary of the invention
[0005] The invention is related to a steel product as disclosed in the appended claims. The invention is in particular related to a steel product as disclosed in the main independent claim, suitable for use in outdoor environments, in particular in saline conditions. The steel product of the invention may be any type of construction element such as a steel sheet or beam. In particular, the invention is related to a steel composition characterized by the following contents (in wt%) :
- Carbon between 0.03 and 0.2,
- Manganese between 0.5 and 2,
- Copper between 0 and 0.5,
- Ti between 0 and 0.1,
- Cr between 0 and 0.5,
- Nickel between 0 and 0.2,
- Niobium between 0 and 0.1,
- Nitrogen between 0 and 0.01,
- Sulphur between 0 and 0.01,
- Phosphor between 0 and 0.01,
- Aluminium higher than 0 and maximum 1.5,
- Silicon between 0.25 and 1.5,
the balance being Fe and accidental impurities, and wherein the sum of the Al and Si levels is higher than about 0.85wt% .
[0006] According to a preferred embodiment, the following narrower ranges are defined for Cu, Ti, Cr, Ni and Nb (in wt%) :
- Copper between 0.2 and 0.4
- Ti between 0.01 and 0.07,
- Cr between 0.2 and 0.5,
- Nickel between 0.1 and 0.2,
- Niobium between 0.02 and 0.1.
[0007] According to the preferred embodiment, the steel product according to the invention comprises no Sn and no Sb . Detailed description of the invention
[0008] The present invention is related to a steel product of the weathering steel type, i.e. a product exhibiting increased corrosion resistance after having been exposed to the outside environment for a given time.
[0009] According to the invention, the steel product is defined by a composition consisting of (in wt%) :
- Carbon between 0.03 and 0.2,
- Manganese between 0.5 and 2,
- Copper between 0 and 0.5,
- Ti between 0 and 0.1,
- Cr between 0 and 0.5,
- Nickel between 0 and 0.2,
- Niobium between 0 and 0.1,
- Nitrogen between 0 and 0.01,
- Sulphur between 0 and 0.01,
- Phosphor between 0 and 0.01,
- Aluminium higher than 0 and maximum 1.5,
- Silicon between 0.25 and 1.5,
the balance being Fe and accidental impurities, and wherein the sum of the Al and Si levels is higher than 0.85wt%. The word ^between' as used above is to be understood as inclusive of the borders of the range in question.
[0010] According to a preferred embodiment, the amounts of Cu, Ti, Cr, Ni and Nb are as follows (in wt%) :
- Copper between 0.2 and 0.4
- Ti between 0.01 and 0.07
- Cr between 0.2 and 0.5 ,
- Nickel between 0.1 and 0.2,
- Niobium between 0.02 and 0.1,
This embodiment combines good weathering behaviour in saline conditions with excellent mechanical properties, due to the minimum amounts of the abovenamed elements (Cu, Ti, Cr, Ni, Nb) .
[0011] The present invention reveals that the inventive steel compositions favour the formation of fine grained goethite (a-FeOOH) in the corrosion layer forming on the surface of a steel product having these compositions, due to the specific combined Al and Si content. With xfine grained goethite' is meant goethite with grain sizes from about 8nm to about 15nm. The formation of such fine grained goethite is beneficial for the stability of the oxide layer in saline conditions.
[0012] It is to be noted that the inventive compositions do not necessarily include an addition of significant amounts of the traditional elements regarded as beneficial for weathering resistance in saline conditions, such as Ni . The inventive compositions do not comprise Sn and Sb above an accidental impurity level. Preferably, the steel product of the invention comprises no Sb or Sn. Elements such as Nb, Ti, Cu, Cr may be added for improving the mechanical properties of the steel, but are not required for ensuring the weathering behaviour in saline conditions .
[0013] The invention is related to any type of steel product having the composition as claimed, e.g. steel sheets or beams, obtained by any standard steel-making process, e.g. hot-rolled or cold-rolled sheets or beams.
Examples
[0014] Table 1 shows the compositions of 3 test samples SI to S3 having Al and Si contents according to the invention, as well as 2 comparative samples CI and C2 having Al and Si contents falling outside the claimed ranges and/or wherein the combined Al and Si content is less than 0.85wt%.
[0015] The test samples have been obtained by standard steel processing methods, involving at least a hot rolling step, possibly followed by a cold rolling step. The samples were subjected to a dip-dry test during 60 days, using a 0.05M NaCl solution, in order to test weatherability behaviour in saline conditions. As a result, oxide layers were formed on the samples. The composition of these oxide layers was investigated by Mossbauer spectroscopy, used in particular to measure the relative area of superparamagnetic goethite in the oxide layer. Superparamagnetic goethite has a particle size between 8 and 15nm, as opposed to antiferromagnetic goethite, having particle sizes above 15nm.
[0016] Table 2 clearly shows that the combined Al and Si contents according to the present invention give rise to a considerable increase in the relative area of fine-grained goethite in the oxide layer.
Samp1e C Si Al P Mn S N Ti Mo Cu Ni Cr si 0.19 0.35 1.2 0.077 1.6 0.006 0.005 0.007 0.025 0.02 0.025 0.025
S2 0.07 1 0.03 0.02 0.5 0.003 0.003 - - 0.3 - -
S3 0.07 0.25 0.8 0.02 0.5 0.003 0.003 - - 0.3 - -
Cl 0.07 0.25 0.4 0.02 0.5 0.003 0.003 - - 0.3 - -
C2 0.03 0 1 0.01 1.8 0.003 0.007 - - 0.4 - -
Table 1 : example compositions (in wt%)
5
Figure imgf000008_0001
Table 2:Relative area of superparamagnetic goethite

Claims

1. A steel product consisting of (in wt%) :
- Carbon between 0.03 and 0.2
- Manganese between 0.5 and 2
- Copper between 0 and 0.5,
- Ti between 0 and 0.1,
- Cr between 0 and 0.5,
- Nickel between 0 and 0.2,
- Niobium between 0 and 0.1,
- Nitrogen between 0 and 0.01,
- Sulphur between 0 and 0.01,
- Phosphor between 0 and 0.01,
- Aluminium higher than 0 and maximum 1.5,
- Silicon between 0.25 and 1.5,
the balance being Fe and accidental impurities, and wherein the sum of the Al and Si levels is higher than about 0.85wt% .
2. The steel product according to claim 1, with (in wt%) :
- Copper between 0.2 and 0.4
- Ti between 0.01 and 0.07,
- Cr between 0.2 and 0.5,
- Nickel between 0.1 and 0.2,
- Niobium between 0.02 and 0.1.
3. The steel product according to claim 1 or
2, comprising no Sn and no Sb .
4. A steel product according to any one of claims 1 to 3, said product being a sheet or beam.
PCT/EP2010/054086 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment WO2011120550A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
CA2793294A CA2793294C (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment
BR112012024642-9A BR112012024642B1 (en) 2010-03-29 2010-03-29 STEEL PRODUCT BETTER RESISTANCE TO ATMOSPHERIC CORROSION IN A SALINE ENVIRONMENT AND USE OF A STEEL PRODUCT
CN201080065812.4A CN102884214B (en) 2010-03-29 2010-03-29 There is the product made from steel of the saline environment weather resistance of improvement
PL10712049T PL2553132T3 (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment
US13/637,461 US20130078135A1 (en) 2010-03-29 2010-03-29 Steel Product with Improved Weathering Characteristics in Saline Environment
EP20100712049 EP2553132B1 (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment
ES10712049.5T ES2544576T3 (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in a saline environment
DK10712049.5T DK2553132T3 (en) 2010-03-29 2010-03-29 The steel product with improved weather-resistant properties in a salt environment
PT107120495T PT2553132E (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment
PCT/EP2010/054086 WO2011120550A1 (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment
ZA2012/07137A ZA201207137B (en) 2010-03-29 2012-09-21 Steel product with improved weathering characteristics in saline environment
HRP20150826TT HRP20150826T1 (en) 2010-03-29 2015-07-30 Steel product with improved weathering characteristics in saline environment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/054086 WO2011120550A1 (en) 2010-03-29 2010-03-29 Steel product with improved weathering characteristics in saline environment

Publications (1)

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WO2011120550A1 true WO2011120550A1 (en) 2011-10-06

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Country Status (12)

Country Link
US (1) US20130078135A1 (en)
EP (1) EP2553132B1 (en)
CN (1) CN102884214B (en)
BR (1) BR112012024642B1 (en)
CA (1) CA2793294C (en)
DK (1) DK2553132T3 (en)
ES (1) ES2544576T3 (en)
HR (1) HRP20150826T1 (en)
PL (1) PL2553132T3 (en)
PT (1) PT2553132E (en)
WO (1) WO2011120550A1 (en)
ZA (1) ZA201207137B (en)

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US20140170015A1 (en) * 2012-12-17 2014-06-19 Grzegorz Jan Kusinski Corrosion resistant steel composition
US20150354041A1 (en) * 2013-01-24 2015-12-10 Baoshan Iron & Steel Co., Ltd. Highly corrosion-resistant, high strength, a1-containing weathering steel plate and process of manufacturing same
WO2020084478A1 (en) * 2018-10-23 2020-04-30 Arcelormittal Hot rolled steel and a method of manufacturing thereof

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CN104878322B (en) * 2015-05-14 2017-01-04 中天钢铁集团有限公司 A kind of production technology of low-carbon (LC) weathering steel
CN111101071B (en) * 2020-02-25 2021-04-13 湖南华菱涟源钢铁有限公司 High-strength weathering steel and production method thereof
CN112593158B (en) * 2020-12-11 2021-11-30 湖南华菱涟源钢铁有限公司 690MPa low-temperature-resistant ultrahigh-strength weather-resistant steel plate and preparation method thereof
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Cited By (6)

* Cited by examiner, † Cited by third party
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CN102650015A (en) * 2012-05-29 2012-08-29 江苏省沙钢钢铁研究院有限公司 Economical fine-grain high-toughness weather-resistant medium-thickness steel plate and production method thereof
US20140170015A1 (en) * 2012-12-17 2014-06-19 Grzegorz Jan Kusinski Corrosion resistant steel composition
US20150354041A1 (en) * 2013-01-24 2015-12-10 Baoshan Iron & Steel Co., Ltd. Highly corrosion-resistant, high strength, a1-containing weathering steel plate and process of manufacturing same
US10760149B2 (en) * 2013-01-24 2020-09-01 Baoshan Iron & Steel Co., Ltd. Highly corrosion-resistant, high strength, A1-containing weathering steel plate and process of manufacturing same
WO2020084478A1 (en) * 2018-10-23 2020-04-30 Arcelormittal Hot rolled steel and a method of manufacturing thereof
WO2020084332A1 (en) * 2018-10-23 2020-04-30 Arcelormittal Hot-rolled steel plate and a method of manufacturing thereof

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US20130078135A1 (en) 2013-03-28
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ZA201207137B (en) 2014-04-30
DK2553132T3 (en) 2015-07-27
CA2793294A1 (en) 2011-10-06
CN102884214A (en) 2013-01-16
BR112012024642A2 (en) 2016-06-07
PL2553132T3 (en) 2015-10-30
CN102884214B (en) 2015-09-09
EP2553132A1 (en) 2013-02-06
HRP20150826T1 (en) 2015-11-20
CA2793294C (en) 2015-09-29
BR112012024642B1 (en) 2018-02-06

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