CA2793294A1 - Steel product with improved weathering characteristics in saline environment - Google Patents
Steel product with improved weathering characteristics in saline environment Download PDFInfo
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- CA2793294A1 CA2793294A1 CA2793294A CA2793294A CA2793294A1 CA 2793294 A1 CA2793294 A1 CA 2793294A1 CA 2793294 A CA2793294 A CA 2793294A CA 2793294 A CA2793294 A CA 2793294A CA 2793294 A1 CA2793294 A1 CA 2793294A1
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- steel product
- steel
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- weathering
- saline
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- 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
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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
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 Cl ions, i.e. marine or seaside environments. It was observed that the Cl 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.
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
= 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
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.
- 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
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.
- 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 5 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 `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.
[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.
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
Examples
[0014] Table 1 shows the compositions of 3 test samples S1 to S3 having Al and Si contents according to the invention, as well as 2 comparative samples Cl and C2 having Al and Si contents falling outside the claimed -Printed: 09/02/2012 DESCPAMD EP.~-1 EP2010054086 0 3. 02, 2012 6 ce DI
ranges and/or wherein the combined Al and Si content is less than 0.85wt%. The samples are outside the subject matter of the appended claims because of the presence of Molybdenum in Si and the lower levels of Ti, Cu, Ni, Cr and Nb. They are however illustrative of the influence of the combined presence of Al and Si on the goethite formation, and hence on the weathering steel behaviour of products of the invention.
ranges and/or wherein the combined Al and Si content is less than 0.85wt%. The samples are outside the subject matter of the appended claims because of the presence of Molybdenum in Si and the lower levels of Ti, Cu, Ni, Cr and Nb. They are however illustrative of the influence of the combined presence of Al and Si on the goethite formation, and hence on the weathering steel behaviour of products of the invention.
[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.
[00161 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.
Sample C Si Al P Mn S N Ti Mo Cu Ni Cr S1 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 - -C1 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%) Sample %
Table 2:Relative area of superparamagnetic goethite (in %)
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.
[00161 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.
Sample C Si Al P Mn S N Ti Mo Cu Ni Cr S1 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 - -C1 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%) Sample %
Table 2:Relative area of superparamagnetic goethite (in %)
Claims (5)
1. A steel product consisting of (in wt%):
- Carbon between 0.03 and 0.2 - Manganese between 0.5 and 2.
- Copper between 0.2 and 0.4, - Titanium between 0.01 and 0.07, - Chromium between 0.2 and 0.5, - Nickel between 0.1 and 0.2, - Niobium between 0.02 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%.
- Carbon between 0.03 and 0.2 - Manganese between 0.5 and 2.
- Copper between 0.2 and 0.4, - Titanium between 0.01 and 0.07, - Chromium between 0.2 and 0.5, - Nickel between 0.1 and 0.2, - Niobium between 0.02 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 or 2, comprising no Sn and no Sb.
3. A steel product according to any one of claims 1 to 3, said product being a sheet or beam.
4. Use of a steel product according to any one of the preceding claims, as a product that exhibits an increase in corrosion resistance when exposed to a chlorine-rich environment.
5. Use of a product according to any one of claims 1 to 3 in saline outdoor conditions.
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 (2)
Publication Number | Publication Date |
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CA2793294A1 true CA2793294A1 (en) | 2011-10-06 |
CA2793294C CA2793294C (en) | 2015-09-29 |
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CA2793294A Active CA2793294C (en) | 2010-03-29 | 2010-03-29 | Steel product with improved weathering characteristics in saline environment |
Country Status (12)
Country | Link |
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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) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
CN103074548B (en) * | 2013-01-24 | 2016-02-24 | 宝山钢铁股份有限公司 | A kind of high corrosion resistant type high strength is containing Al weather-resistant steel plate and manufacture method thereof |
JP6180956B2 (en) * | 2014-02-13 | 2017-08-16 | 株式会社神戸製鋼所 | Painted steel with excellent corrosion resistance |
JP6405910B2 (en) * | 2014-11-10 | 2018-10-17 | 新日鐵住金株式会社 | Corrosion resistant steel |
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 |
WO2020084332A1 (en) * | 2018-10-23 | 2020-04-30 | Arcelormittal | Hot-rolled steel plate and a method of manufacturing thereof |
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 |
CN113667883A (en) * | 2021-07-27 | 2021-11-19 | 包头钢铁(集团)有限责任公司 | Manufacturing method of rare earth microalloyed weather-resistant bridge steel for alpine region |
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JPS4925527B1 (en) * | 1969-03-20 | 1974-07-01 | ||
JPS56146853A (en) * | 1980-04-11 | 1981-11-14 | Nippon Steel Corp | Dual-phase steel plate for car with superior weldability and high corrosion resistance |
JP2620068B2 (en) * | 1986-02-14 | 1997-06-11 | 三菱製鋼 株式会社 | Corrosion resistant steel bars for concrete |
JP3456743B2 (en) * | 1994-01-17 | 2003-10-14 | 新日本製鐵株式会社 | Coastal weathering steel |
JPH09118919A (en) * | 1995-10-26 | 1997-05-06 | Sumitomo Metal Ind Ltd | Manufacture of steel product excellent in seawater corrosion resistance |
CA2273334C (en) * | 1996-11-28 | 2006-03-28 | Nippon Steel Corporation | High strength steels having high impact energy absorption properties and a method for producing the same |
KR100334949B1 (en) * | 1997-03-17 | 2002-05-04 | 아사무라 타카싯 | Dual-phase high-strength steel sheet having excellent dynamic deformation properties and process for preparing the same |
JP3783378B2 (en) * | 1997-12-04 | 2006-06-07 | Jfeスチール株式会社 | High-strength steel excellent in weldability and seawater resistance and method for producing the same |
JP4061771B2 (en) * | 1999-04-09 | 2008-03-19 | 住友金属工業株式会社 | Steel with excellent beach weather resistance |
JP2001247935A (en) * | 2000-03-06 | 2001-09-14 | Nkk Corp | Rolled shape steel excellent in earthquake resistance and weather resistance and its producing method |
JP3738645B2 (en) * | 2000-03-17 | 2006-01-25 | 住友金属工業株式会社 | High-tensile cold-rolled steel sheet with excellent electroplating adhesion and ductility and method for producing the same |
TW567231B (en) * | 2001-07-25 | 2003-12-21 | Nippon Steel Corp | Multi-phase steel sheet excellent in hole expandability and method of producing the same |
EP1398390B1 (en) * | 2002-09-11 | 2006-01-18 | ThyssenKrupp Steel AG | Steel with a very fine ferritic and martensitic microstructure having a high tensile strength |
JP4586489B2 (en) | 2004-10-22 | 2010-11-24 | 住友金属工業株式会社 | Steel and structures with excellent beach weather resistance |
JP5256818B2 (en) * | 2008-03-31 | 2013-08-07 | Jfeスチール株式会社 | Method for producing high toughness steel |
-
2010
- 2010-03-29 BR BR112012024642-9A patent/BR112012024642B1/en active IP Right Grant
- 2010-03-29 ES ES10712049.5T patent/ES2544576T3/en active Active
- 2010-03-29 CN CN201080065812.4A patent/CN102884214B/en active Active
- 2010-03-29 WO PCT/EP2010/054086 patent/WO2011120550A1/en active Application Filing
- 2010-03-29 EP EP20100712049 patent/EP2553132B1/en active Active
- 2010-03-29 US US13/637,461 patent/US20130078135A1/en not_active Abandoned
- 2010-03-29 DK DK10712049.5T patent/DK2553132T3/en active
- 2010-03-29 PT PT107120495T patent/PT2553132E/en unknown
- 2010-03-29 CA CA2793294A patent/CA2793294C/en active Active
- 2010-03-29 PL PL10712049T patent/PL2553132T3/en unknown
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2012
- 2012-09-21 ZA ZA2012/07137A patent/ZA201207137B/en unknown
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2015
- 2015-07-30 HR HRP20150826TT patent/HRP20150826T1/en unknown
Also Published As
Publication number | Publication date |
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PL2553132T3 (en) | 2015-10-30 |
HRP20150826T1 (en) | 2015-11-20 |
CA2793294C (en) | 2015-09-29 |
ES2544576T3 (en) | 2015-09-01 |
PT2553132E (en) | 2015-09-10 |
BR112012024642A2 (en) | 2016-06-07 |
DK2553132T3 (en) | 2015-07-27 |
US20130078135A1 (en) | 2013-03-28 |
CN102884214A (en) | 2013-01-16 |
EP2553132B1 (en) | 2015-05-06 |
EP2553132A1 (en) | 2013-02-06 |
WO2011120550A1 (en) | 2011-10-06 |
CN102884214B (en) | 2015-09-09 |
ZA201207137B (en) | 2014-04-30 |
BR112012024642B1 (en) | 2018-02-06 |
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