SG10202013010SA - Method and apparatus for producing steel pipes having particular properties - Google Patents
Method and apparatus for producing steel pipes having particular propertiesInfo
- Publication number
- SG10202013010SA SG10202013010SA SG10202013010SA SG10202013010SA SG10202013010SA SG 10202013010S A SG10202013010S A SG 10202013010SA SG 10202013010S A SG10202013010S A SG 10202013010SA SG 10202013010S A SG10202013010S A SG 10202013010SA SG 10202013010S A SG10202013010S A SG 10202013010SA
- Authority
- SG
- Singapore
- Prior art keywords
- pipe
- cooling medium
- cooling
- shaping
- zone
- Prior art date
Links
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
- 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
- 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
- C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
-
- 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
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)
Description
Method and Apparatus for Producing Steel Pipes Having Particular Properties
The invention relates to a method for producing pipes made of steel having improved strength and improved toughness of the material.
In addition, the invention relates to a device for producing pipes having a special profile of properties, consisting of a device for applying a cooling medium to the surface of the pipe.
In manufacturing seamless pipes, the properties of the material of the pipe wall may exhibit substantial variations locally and from one lot to the next. These differences in properties are usually based on an irregular microstructure and an unfavorable steel composition and/or an increased proportion of contaminants and accompanying elements.
For pipes that are subjected to high stresses, a microstructure that meets these requirements and is uniform within narrow limits over the length of the pipe as well as coaxially in the pipe wall while also having a material composition that is free of harmful elements should be obtained for the reasons given above.
Pipes that are 7 meters or more long and have an outside diameter of less than 200 mm with a wall thickness of less than 25 mm can be subjected to a heat treatment only with a great deal of complexity, but such a heat treatment produces a uniformly fine structure with the desired microstructure over the entire volume of the pipe while minimizing bending at a right angle to the longitudinal direction.
There are known methods in which a pipe is rotated about its axis and is cooled on the outside surface and/or on the inside surface. However, such heat treatment methods presuppose an approximately uniformly high temperature of the material over the length of the pipe in order to achieve a homogeneous microstructure in the wall.
The goal of the present invention is to provide a method with which, during the production of a pipe by hot forming, in particular by stretch reducing, the pipe is treated downstream in a step that increases the strength and improves the toughness of the pipe material.
In addition, another object of the present invention is to create a device for producing pipes with which after heat shaping, pipes having the desired profile of properties over the entire length of the pipe can be produced.
This goal is achieved with a generic method in which a cooling medium at an elevated pressure is applied by direct rapid cooling after a heat shaping, in particular after shaping by means of stretch reduction, such that a cooling medium at an elevated pressure and at a temperature greater than 700°C but less than 1050°C in passage is applied to the outside surface of the pipe over its circumference for a length amounting to more than 400 times the wall thickness of the pipe and this is accomplished within a period of at most 20 sec after the last shaping, the cooling medium being applied in an amount which yields a uniform cooling rate of more than 1°C/sec of the pipe wall in rapid cooling over the length of the pipe to a temperature in the range of 500°C to 250°C, after which the pipe is cooled further to room temperature in air.
Especially high and uniform mechanical material values, in particular toughness values can be achieved by the inventive method if the onset of rapid cooling of the outside surface of the pipe occurs at a temperature of less than 950°C.
For an integrated tempering treatment, it may also be advantageous if a targeted reheating of the pipe wall surface area is performed after the rapid cooling with further cooling of the pipe in air.
To optimize the quality of the pipe and/or to improve the quality of the pipe material, in a refinement of the method, it may be essential to the invention for steel having the following concentrations of the respective alloy elements and accompanying elements and/or impurities in wit% to be used for producing the pipe:
Carbon (C) 0.03 t0 0.5
Silicon (Si) 0.1510 0.65
Manganese (Mn) 0.5t02.0
Phosphorus (P) max. 0.03
Sulfur (S) max. 0.03
Chromium (Cr) max. 1.5
Nickel (Ni) max. 1.0
Copper (Cu) max. 0.3
Aluminum (Al) 0.01 to 0.09
Titanium (Ti) max. 0.05
Molybdenum (Mo) max. 0.8
Vanadium (V) 0.0210 0.2
Nitrogen (N) max. 0.04
Niobium (Nb) max. 0.08
Iron (Fe) remainder.
If the method is used to produce seamless pipes with a length of greater than 7 meters, in particular up to 200 meters, an outside diameter of more than 20 meters but less than 200 meters, a wall thickness of more than 2.0 mm but less than 25 mm, then the increased pipe quality can reduce the need for stockpiling with a substantial advantage and can minimize damages due to breakage with substantial repair costs.
With a limited carbon content, at least one element of the steel may advantageously contain the elements, where the amounts are given in wt%, with regard to a homogeneous high pipe quality:
Carbon (C) 0.05 up to 0.35
Phosphorus (P) max. 0.015
Sulfur (S) max. 0.005
Chromium (C) max. 1.0
Titanium (Ti) max. 0.02.
The additional object of the invention to create a device for producing pipes made of steel with an increased strength and improved toughness of the material by rapid cooling after shaping consisting of a device for applying a cooling medium to a pipe surface is achieved by the fact that, after the last shaping mill in the direction of rolling, a switchable cooling through-zone having a plurality of distributor rings for the cooling medium that can be positioned in different ways in the longitudinal direction and are arranged concentrically around the rolled material is designed with at least three nozzles each directed essentially toward the axis, whereby each distributor ring or each group of same can be supplied with the cooling medium in a process that is regulated based on throughput.
With the inventive device, it is advantageously possible to subject pipes of different longitudinal extents and different diameters and wall thicknesses to a targeted heat treatment from the rolling heat such that the desired microstructure, which is represented uniformly over the length of the pipe, can be obtained.
It has been found to be especially advantageous with regard to the uniformity of the structure both circumferentially and in the longitudinal direction of the pipe wall if the nozzles each create a pyramid-shaped cooling medium flow which expands in the direction of spraying.
The cooling medium flow may be designed as a spray stream of cooling medium, usually water, and/or as a spray mist of cooling medium and air and/or as a gas stream.
Advantageous results with regard to a uniformly high quality of the pipe have also been achieved when the cooling medium flow has a rectangular cross-sectional shape and the longer axis of the rectangle is directed obliquely to the axis of the pipe.
Switchability and controllability of throughput of the cooling medium flows in the cooling through-zone are essential to the present invention.
If a supply of cooling medium to the cooling through-zone can be switched as a function of the position of the pipe ends in this zone, then penetration of cooling medium into the interior of the pipe can be prevented in an advantageous manner, so that essentially unilateral interior cooling in the cross section can be prevented and bending as well as the development of an irregular microstructure can be suppressed.
Control systems for pipe cooling with position sensors and temperature sensors to control the cooling medium streams are used to advantage according to the present invention.
The present invention is explained in greater detail below on the basis of examples which illustrate only one type of embodiment.
Example 1: Using pipe precursor material from the same parent melt having a chemical composition in wt% according to Table 1: [Designation | C | Si [ Mn [ P | S | CG | Ni | Co | Al [ Mo | Fe
Pipe blank | 0.1819 | 0.2910 | 1.4231 remainder diameter ultimately pipes having the following dimensions were produced:
Pipe length (rolling length) (L) 19,300.00 mm
Pipe diameter (0) 146.00 mm
Pipe wall thickness 9.70 mm
After the last step and/or after the final shaping in the discharge station of the stretch reducing plant, the pipe was introduced into a cooling through-zone at a temperature of 880°C after a period of 12 sec.
Assuming the defined conversion behavior of the steel, the cooling medium flow was directed only at the outside surface of the pipe in investigations on individual lots in pipe production, such that a cooling rate of approx. 6°C/sec was measured by adjusting the cooling medium flow at the following final temperatures:
Temperature Identification of the sample
T1=850°C PI
T2 =480°C P2
T3 =380°C P3
T4=300°C P4
After achieving these specified final cooling temperatures, the cooling medium supply was shut down and the pipe was cooled further to room temperature at a low intensity essentially in stationary air.
Samples were taken of the pipes that had been heat treated in various ways and labeled as P1 through P4 and then tests of materials were performed on these samples.
A determination of the microstructure revealed that there was an advantageously directional structure in each case, essentially without texture but with a grain size and structure distribution which depend on the final cooling temperature.
Figure 1 shows the structure of sample P1, where the grain size is 20 um to 30 um with a high ferrite content. The remaining component of the structure was mainly perlite.
Figure 2 shows a much smaller average grain size of sample P2 of approx. 5 um to 8 um, which correlates with a low final cooling medium temperature of T2 = 480°C. In addition, the perlite content in the ferrite has a finer structure and the amount is slightly geater.
Figure 3 shows that the material of sample P3 has a fine grain due to a high seed count conversion and recrystallization of the structure at a final cooling temperature of T3 = 380°C and also has largely homogeneously distributed ferrite regions which increase strength. Perlite and the structure of the upper intermediate stage and/or upper bainite were the other constituents of the refined structure.
Figure 4 shows the structure of pipe wall P4, which was formed in rapid cooling after shaping to a final cooling temperature T4 = 300°C. Extremely fine-grained ferrite phases, which are globulitic due to end limitation with fine lamellar perlite and intermediate stage components in the lower bainite range, result in high strength values with improved strain results for the material.
In cooling of the pipe wall at a rate of greater than 1°C/sec immediately after hot shaping of the basic iron material, an austenite structure shaped in this way can be largely undercooled with respect to the equilibrium resulting in a conversion of the structure as a function of the extent of the undercooling and the seed state. The desired uniform microstructure can be established advantageously by means of the inventive method over the entire length of a pipe and surprisingly also over its cross section and this microstructure also determines the properties of the material. In other words, if fundamental material properties are required of a pipe, choice of an alloy is indicated. An advantageous and favorable profile of properties of the material which is provided can be achieved through an inventive method in the device according to the invention.
Figure 5 shows in a bar graph the measured values for strain limit (Rp) (0.2) [MPa], tensile strength (Rm) [MPa], necking (Ac) [%] and toughness (KV450) [J] of the samples P1 through
P4, i.e., as a function of the mechanical properties of the material which are achieved through the different cooling parameters in the refining technology.
With the same steel composition, the strain limit of the material of the pipe wall can be increased from 424 [MPa] to 819 [MPa] while at the same time the decline in strain values from 26 [%] to [%] can be minimized, which causes the toughness of the material to decline from 170 [J] to 160 [J].
At high final cooling temperatures as is the case for sample material P1 for example, there is a great deal of recrystallization and formation of large grains, which imparts high toughness and necking to the material but causes a comparatively low level of strength.
Cooling to lower ambient temperatures increases the strength of the pipe wall and naturally also slightly reduces the necking and toughness of the material, as illustrated on the basis of samples
P2, P3 and P4.
With the inventive method, microstructures can also be adjusted in the material in a targeted manner, yielding the profile of properties of the pipe wall. For example, a high measure of conversion to a lower bainite structure can be achieved in sample pipe P4 by means of a low conversion temperature, so an increased toughness of the material could be achieved.
Figure 6 shows the measured hardness values over the length of the pipe of experimental pipes
P1 and P4. It has been found that a scattering S of the material hardness over the length of the pipe is also reduced with an increase in hardness [HRB] and strength levels of the material due to intensified application of cooling medium.
Figure 7 shows the hardness curve of the material in the quadrants as a function of the thickness of the pipe wall of experimental pipe P2.
The measurement results of the four quadrants Q1 to Q4 are averages of four measurements spaced a distance apart in each quadrant in the external, central and internal areas of the pipe wall.
As also shown by the comparison of the respective hardness values over the cross section of the pipe wall in the quadrants, there are only extremely minor differences in material strength, so the achievable quality of the product is represented by using the inventive method and such a device.
Claims (4)
- Patent ClaimsI. A device for producing seamless oilfield pipes having a length of greater than 7 m, in particular up to 200 m, an external diameter of greater than 20 mm but smaller than 200 mm, and a wall thickness of greater than 2.0 mm but smaller than 25 mm, of steel having an increased strength and improved toughness of the material by rapid cooling after shaping, in particular after shaping the pipe by means of stretch production, consisting of a device for applying cooling medium to the surface of a pipe, characterized in that, arranged downstream from the last shaping mill in the direction of rolling , a swilchable cooling through-zone having a plarality of distributor rings that can be positioned in different positions in the longitudinal direction and are arranged concentrically around the rolled material are provided for a cooling medium, wherein each distributor ring has at least three nozzles directed essentially toward the axis, and wherein cach distributor ring or each group of same can be supplied with cooling medium in a throughput-regulated process.
- 2. The device according to Claim 1, characterized in that the nozzles each establish a pyramid-shaped cooling medium stream which widens in the direction of the spray.
- 3. The device according to Claim 2, characterized in that the cooling medium stream has a rectangular cross-sectional shape and the longer axis of the rectangle is directed obliquely toward the axis of the pipe.
- 4. The device according to Claim 3, characterized in that the supply of cooling medium fo the cooling through-zone can be switched as a function of the position of the pipe ends in the Zone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0181408A AT507596B1 (en) | 2008-11-20 | 2008-11-20 | METHOD AND DEVICE FOR PRODUCING STEEL TUBES WITH SPECIAL CHARACTERISTICS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SG10202013010SA true SG10202013010SA (en) | 2021-02-25 |
Family
ID=41785584
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SG10202013010SA SG10202013010SA (en) | 2008-11-20 | 2009-11-16 | Method and apparatus for producing steel pipes having particular properties |
| SG10201500738QA SG10201500738QA (en) | 2008-11-20 | 2009-11-16 | Method and apparatus for producing steel pipes having particular properties |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SG10201500738QA SG10201500738QA (en) | 2008-11-20 | 2009-11-16 | Method and apparatus for producing steel pipes having particular properties |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US9394582B2 (en) |
| EP (2) | EP2356262B1 (en) |
| JP (1) | JP2012509398A (en) |
| KR (2) | KR101760654B1 (en) |
| CN (1) | CN102224265A (en) |
| AR (1) | AR075551A1 (en) |
| AT (1) | AT507596B1 (en) |
| BR (2) | BR122017014778B1 (en) |
| CA (1) | CA2748046C (en) |
| EA (1) | EA021245B1 (en) |
| ES (2) | ES2569103T3 (en) |
| HR (2) | HRP20160591T1 (en) |
| MX (1) | MX2011005110A (en) |
| PL (2) | PL2682485T3 (en) |
| SG (2) | SG10202013010SA (en) |
| UA (1) | UA98088C2 (en) |
| WO (1) | WO2010057235A1 (en) |
| ZA (1) | ZA201102056B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021488B (en) * | 2010-11-30 | 2013-05-08 | 攀钢集团钢铁钒钛股份有限公司 | Steel for nuclear-island seamless steel tube and production method thereof |
| CN102367560B (en) * | 2011-11-09 | 2013-06-19 | 南京钢铁股份有限公司 | High-strength corrosion-resisting straight welded pipe steel and manufacture method thereof |
| AR096272A1 (en) * | 2013-05-31 | 2015-12-16 | Nippon Steel & Sumitomo Metal Corp | SEAMLESS STEEL TUBE FOR DRIVING PIPES USED IN AGRICULTURAL ENVIRONMENTS |
| DE102019205724B4 (en) | 2019-04-18 | 2026-06-11 | Sms Group Gmbh | Cooling device for seamless steel pipes |
| DE102020212926A1 (en) | 2020-10-14 | 2022-04-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for forming a semi-finished product and device for carrying out the process |
| CN120155478A (en) * | 2023-12-15 | 2025-06-17 | 通用汽车环球科技运作有限责任公司 | Method for producing uncoated press-hardened steel in tubular form |
| CN120394628A (en) * | 2024-02-01 | 2025-08-01 | 通用汽车环球科技运作有限责任公司 | Battery cell housing comprising hardened steel |
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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 |
| DE3311629C2 (en) * | 1983-03-28 | 1986-08-14 | Mannesmann AG, 4000 Düsseldorf | Process for the production of seamless steel tubes |
| JPS62263924A (en) * | 1986-05-07 | 1987-11-16 | Sumitomo Metal Ind Ltd | Production of tough steel pipe |
| US5186769A (en) * | 1990-08-16 | 1993-02-16 | The Algoma Steel Corporation, Limited | Seamless steel tube manufacture |
| US5487795A (en) * | 1993-07-02 | 1996-01-30 | Dong Won Metal Ind. Co., Ltd. | Method for heat treating an impact beam of automotive vehicle door and a system of the same |
| JPH0888515A (en) * | 1994-09-19 | 1996-04-02 | Advantest Corp | FM deviation amount measuring instrument |
| DE19506858C1 (en) * | 1995-02-14 | 1996-01-18 | Mannesmann Ag | Roll pass design for 3-roll passes of mandrel-less tube reducing mills |
| JPH08253817A (en) * | 1995-03-17 | 1996-10-01 | Hitachi Ltd | Hardening method and equipment for rolling rolls |
| JPH10237583A (en) * | 1997-02-27 | 1998-09-08 | Sumitomo Metal Ind Ltd | High tensile steel and method for producing the same |
| JP4182556B2 (en) * | 1997-12-11 | 2008-11-19 | Jfeスチール株式会社 | Seamless steel pipe manufacturing method |
| DE19962891A1 (en) * | 1999-12-23 | 2001-06-28 | Sms Demag Ag | Method and device for cooling hot-rolled profiles |
| JP4608739B2 (en) * | 2000-06-14 | 2011-01-12 | Jfeスチール株式会社 | Manufacturing method of steel pipe for automobile door reinforcement |
| US7459033B2 (en) * | 2002-06-19 | 2008-12-02 | Nippon Steel Corporation | Oil country tubular goods excellent in collapse characteristics after expansion and method of production thereof |
| CN100420758C (en) * | 2002-10-01 | 2008-09-24 | 住友金属工业株式会社 | High-strength seamless steel pipe with excellent hydrogen-induced cracking resistance and preparation method thereof |
| CN1208143C (en) * | 2002-11-25 | 2005-06-29 | 宝山钢铁股份有限公司 | Method for mfg of high-quality seamless steel pipe |
| JP2005298861A (en) * | 2004-04-08 | 2005-10-27 | Nippon Steel Corp | Steel pipe cooling method and cooling device |
| US20060169368A1 (en) * | 2004-10-05 | 2006-08-03 | Tenaris Conncections A.G. (A Liechtenstein Corporation) | Low carbon alloy steel tube having ultra high strength and excellent toughness at low temperature and method of manufacturing the same |
| NO345938B1 (en) * | 2006-02-08 | 2021-11-01 | Thermatool Corp | Spray cooling systems for heat-treated metal products |
| EP2006396B1 (en) * | 2006-03-28 | 2018-05-16 | Nippon Steel & Sumitomo Metal Corporation | Process for production of seamless pipes |
| CN101153373B (en) * | 2006-09-27 | 2010-10-06 | 宝山钢铁股份有限公司 | A kind of manufacturing process of oil casing pipe steel |
| JP5020689B2 (en) * | 2007-04-17 | 2012-09-05 | 新日本製鐵株式会社 | Machine structure steel pipe with excellent machinability |
-
2008
- 2008-11-20 AT AT0181408A patent/AT507596B1/en not_active IP Right Cessation
-
2009
- 2009-10-19 AR ARP090104006A patent/AR075551A1/en not_active Application Discontinuation
- 2009-11-16 CA CA2748046A patent/CA2748046C/en active Active
- 2009-11-16 HR HRP20160591TT patent/HRP20160591T1/en unknown
- 2009-11-16 EA EA201100799A patent/EA021245B1/en not_active IP Right Cessation
- 2009-11-16 KR KR1020167032619A patent/KR101760654B1/en active Active
- 2009-11-16 EP EP09763823.3A patent/EP2356262B1/en active Active
- 2009-11-16 UA UAA201107654A patent/UA98088C2/en unknown
- 2009-11-16 ES ES09763823.3T patent/ES2569103T3/en active Active
- 2009-11-16 CN CN200980146610XA patent/CN102224265A/en active Pending
- 2009-11-16 SG SG10202013010SA patent/SG10202013010SA/en unknown
- 2009-11-16 PL PL13187253T patent/PL2682485T3/en unknown
- 2009-11-16 WO PCT/AT2009/000439 patent/WO2010057235A1/en not_active Ceased
- 2009-11-16 JP JP2011536700A patent/JP2012509398A/en active Pending
- 2009-11-16 MX MX2011005110A patent/MX2011005110A/en active IP Right Grant
- 2009-11-16 BR BR122017014778-1A patent/BR122017014778B1/en active IP Right Grant
- 2009-11-16 PL PL09763823T patent/PL2356262T3/en unknown
- 2009-11-16 ES ES13187253.3T patent/ES2625085T3/en active Active
- 2009-11-16 EP EP13187253.3A patent/EP2682485B1/en active Active
- 2009-11-16 SG SG10201500738QA patent/SG10201500738QA/en unknown
- 2009-11-16 BR BRPI0921077-6A patent/BRPI0921077B1/en active IP Right Grant
- 2009-11-16 KR KR1020117014023A patent/KR101694679B1/en active Active
- 2009-11-16 US US13/128,838 patent/US9394582B2/en active Active
-
2011
- 2011-03-18 ZA ZA2011/02056A patent/ZA201102056B/en unknown
-
2017
- 2017-06-01 HR HRP20170838TT patent/HRP20170838T1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN102224265A (en) | 2011-10-19 |
| EA201100799A1 (en) | 2011-12-30 |
| ES2569103T3 (en) | 2016-05-06 |
| KR20110095376A (en) | 2011-08-24 |
| WO2010057235A1 (en) | 2010-05-27 |
| MX2011005110A (en) | 2011-05-30 |
| US20110272067A1 (en) | 2011-11-10 |
| BR122017014778B1 (en) | 2018-10-16 |
| HRP20170838T1 (en) | 2017-08-25 |
| EP2356262A1 (en) | 2011-08-17 |
| EP2356262B1 (en) | 2016-03-09 |
| PL2682485T3 (en) | 2017-09-29 |
| AT507596A1 (en) | 2010-06-15 |
| AR075551A1 (en) | 2011-04-20 |
| EP2682485B1 (en) | 2017-03-15 |
| US9394582B2 (en) | 2016-07-19 |
| AT507596B1 (en) | 2011-04-15 |
| KR101694679B1 (en) | 2017-01-10 |
| ES2625085T3 (en) | 2017-07-18 |
| ZA201102056B (en) | 2011-11-30 |
| EP2682485A1 (en) | 2014-01-08 |
| UA98088C2 (en) | 2012-04-10 |
| CA2748046A1 (en) | 2010-05-27 |
| SG10201500738QA (en) | 2015-03-30 |
| JP2012509398A (en) | 2012-04-19 |
| BRPI0921077B1 (en) | 2018-01-16 |
| KR101760654B1 (en) | 2017-08-04 |
| BRPI0921077A2 (en) | 2015-12-15 |
| CA2748046C (en) | 2018-01-09 |
| HRP20160591T1 (en) | 2016-07-01 |
| EA021245B1 (en) | 2015-05-29 |
| PL2356262T3 (en) | 2016-08-31 |
| KR20160137675A (en) | 2016-11-30 |
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