CN1764734A - Steel for producing high tensile structural components with excellent toughness at low temperatures and uses of such a steel - Google Patents
Steel for producing high tensile structural components with excellent toughness at low temperatures and uses of such a steel Download PDFInfo
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- CN1764734A CN1764734A CN200580000079.7A CN200580000079A CN1764734A CN 1764734 A CN1764734 A CN 1764734A CN 200580000079 A CN200580000079 A CN 200580000079A CN 1764734 A CN1764734 A CN 1764734A
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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Abstract
The invention relates to a high tensile steel that has excellent ductile fracture values J integral even at low temperatures so that the danger of a fracture of the structural component produced from said steel is reduced to a minimum even under unfavorable and very hard working conditions. The inventive steel comprises (in % by weight) 0.08 - 0.25 % C, 0.10 - 0.30 % Si, 0.80 - 1.60 % Mn, = 0.020 % P, = 0.015 % S, the sum of P and S content being = 0.030 %, 0.40 - 0.80 % Cr, 0.30 - 0.50 % Mo, 0.70 - 1.20 % Ni, 0.020 - 0.060 % Al, 0.007 - 0.018 % N, = 0.15 % V, = 0.07 % Nb, the sum of V and Nb content being = 0.020 %, and the remainder iron and unavoidable impurities. The inventive steel is especially suitable for producing high tensile chains.
Description
The present invention relates to the high-strength parts steel that a kind of production has good low-temperature flexibility.For example, such steel can be used for making fixing and clamps needed block of load or gripping unit.Especially, these steel are processed to form hot rolling bar steel, rolled wire or bright steel, are made into to weld the round steel chain then again.
Requirement to the aforementioned type steel proposes in DIN17115.Except good deformability and same good welding adaptability, for satisfying the stress requirement that occurs owing to actual, steel also must have good intensity and property of toughness.
Comprise (by weight percentage) respectively for achieving this end high-quality steel 23MnNiCrMo53 and 23MnNiCrMo54 known and that in DIN17115, describe in detail: 0.20 to 0.26% carbon ,=0.25% silicon, 1.10 to 1.40% manganese, respectively account for 0.020% p and s, the total amount of p and s is no more than 0.035%, if necessary, also comprise 0.020 to 0.050% aluminium, can reach 0.014% nitrogen and 0.40 to 0.60% chromium.In the 23MnNiCrMo52 steel, also add 0.20 to 0.30% molybdenum and 0.70 to 0.90% nickel, and also comprised 0.50 to 0.60% molybdenum and 0.90 to 1.10% nickel in the 23MnNiCrMo54 steel.
Disclose in the open text of Chinese patent CN-1281906 that another kind of manufacturing is used for fixing or the chain steel of mooring ship or drilling unit.The summary of the disclosure text can obtain in the WPINDEX database, wherein disclose this known ladle and drawn together (by weight percentage): 0.25 to 0.35% carbon, 0.15 silicon to 0.30%, 1.45 manganese to 1.75%, 0.90 chromium to 1.40%, 1.00 nickel to 1.20%, 0.45 molybdenum to 0.65%, 0.02 niobium to 0.06%, 0.020 aluminium to 0.05%, can reach 0.020% phosphorus, can reach 0.15% with interior sulphur, can reach 0.20% copper, can reach 0.03% tin, can reach 0.01% antimony, can reach 0.04% arsenic, can reach 0.005% boron, can reach 0.009% nitrogen, can reach 0.0020% with interior oxygen, can reach 0.0002% hydrogen, all the other are iron and unavoidable impurities, and wherein carbon equivalent also must be greater than 1.4.
Although practical experience shows known steel and has satisfied under the envrionment temperature intensity and flexible requirement, will go wrong under lower temperature, particularly for toughness.
Even therefore the purpose of this invention is to provide a kind of high-strength steel that also has excellent toughness at low temperatures, like this, even under disadvantageous, arduous operational condition, all risks of breakage by the parts that this steel is made also can drop to minimum.The useful purposes of this steel also will describe in detail at this.
About this steel, according to the present invention, this purpose can realize it being because the high-strength parts that have a good low-temperature toughness according to production of the present invention have following component (by weight percentage) with steel:
Carbon: 0.08 to 0.25%;
Silicon: 0.10 to 0.30%;
Manganese: 0.80 to 1.60%;
Phosphorus :=0.020%;
Sulphur :=0.015%;
The total content of p and s=0.030%;
Chromium: 0.40 to 0.80%;
Molybdenum: 0.30 to 0.50%;
Nickel: 0.70 to 1.20%;
Aluminium: 0.020 to 0.060%;
Nitrogen: 0.007 to 0.018%;
Vanadium :=0.15%;
Niobium :=0.07%;
The total content of vanadium and niobium=0.020%, all the other are iron and unavoidable impurities.
Under the situation of steel of the present invention, can select various alloy compositions to obtain to satisfy best the performance curve of all requirements.The content of chromium, nickel and nitrogen that this will be set by the present invention and the minimum value of niobium and content of vanadium and obtain.If observe the content range of these alloying elements that the present invention sets, improved hardness retentivity and thin especially crystalline-granular texture in the time of just accessing extra high toughness, good hardening capacity and tempering.Steel of the present invention also has very high property capable of cold forming and very high intensity under the precision work state.It also has the feature of high notch shock toughness and low fracture apperance transition temperature (fracture appearance transition temperature), and brittle rupture is only just occurred when temperature significantly is lower than the brittle rupture temperature of steel commonly known in the art.
Carbon content guarantees that in 0.08 to 0.25% weight range steel of the present invention has good low-temperature resistance.If carbon content just can produce positive especially effect in this respect in 0.16 to 0.23% weight range.
Hardness retentivity when the good hardening capacity of steel of the present invention and tempering is obtained in 0.30 to 0.50% weight range at 0.40 to 0.80% weight range and in conjunction with molybdenum content by limiting chromium content.This realization can be owing to chromium content being adjusted in 0.40 to 0.65% weight range and molybdenum content is adjusted in 0.35 to 0.50% weight range and increased in conjunction with definite degree of effect.
Nickel content has brought good low-temperature flexibility 0.70 to 1.20% particularly in 0.75 to 1.00% the weight range time, and steel of the present invention is outstanding especially in this point.
Aluminium content is 0.020 to 0.060% particularly in 0.020 to 0.045% the weight range, and nitrogen content makes steel of the present invention have thin especially crystalline-granular texture 0.007 to 0.018% particularly in 0.007 to 0.015% the weight range.
At last, content of niobium is limited to maximum 0.07% weight percents though content of vanadium is limited to maximum 0.15% weight percents, has guaranteed to improve the fine grained structure that temperature still can keep needs even steel of the present invention comprises the niobium of at least 0.02% weight percent and the fact of vanadium altogether.Be surprisingly found out that in this respect so this effect just can take place especially reliably if steel of the present invention does not contain vanadium.Therefore, according to preferred scheme, do not contain vanadium in the steel of the present invention, perhaps it only occurs as unavoidable impurities.
Even it is stable that close grain still keeps in tempering-quench treatment process.Therefore, the autstenitic grain size of finish machining steel of the present invention is usually less than ASTM10.Obviously greater than the fineness of known steel, according to the standard of DIN17115, known steel need have the autstenitic grain size of ASTM5 to the fineness of steel construction of the present invention.
Even therefore the invention provides a kind of steel that still has excellent toughness at low temperatures.Because the favourable combination of its characteristic, even under disadvantageous, arduous operational condition, the risk of breakage of the parts of being made by steel of the present invention also can drop to minimum.
Steel of the present invention preferably is processed into rolled iron.The purpose of this processing is to keep steel of the present invention the thinnest possible crystalline-granular texture by each procedure of processing.This not only is included in the procedure of processing of carrying out in the heating and the operation of rolling, comprises that also parts produce before and the anneal of carrying out afterwards.According to the present invention,, yet, can avoid adopting too high rolling temperature in order to suppress coarse grained formation although can select diffusion process to occur in heating and the feasible heat-processed of rolling condition.Can also eject the temperature selected in the further deformation process by energy controlled in thermal deformation process to keep the fine grained structure that suits the requirements.On the meaning of the structural state that " freezing " finally obtained, the discharge of accelerated heat immediately can stop undesirable precipitation process after the last deforming step, otherwise this precipitation process will cause hardness and flexible to descend.Alternative, can produce precipitation state by long heat treatment with respect to size and the needed carbonitride of distribution situation, thereby obtain steel in the relatively low strength of materials of hot-rolled state, this strength of materials is that the steel cold forming process of formation individual components is needed.
Because steel particular performances spectrum of the present invention (property spectrum), it is particularly suitable for producing high-strength parts with cold shaping and tempering subsequently-quenching technology.For example, these parts can be carrying, traction, lifting, transportation or the device that fixedly has the load of maximum intensity grade.These goods that can be referred to as " braking and gripping unit " comprising: as, tie point, suspension hook, clip, metal ring, chain, joint, stopping element, rocking arm, pillar, axle and ratchet anchor clamps, shack and analogue.
Coupling device with structural element of good service performance also can be made by steel of the present invention.These structural elements are: as, bolt or other connections or force transmission element are as screw, clamp, pole or analogue.
The particularly suitable Application Areas of steel of the present invention is to make chain.Even the chain of making according to the steel of component of the present invention also can stand heavy loading reliably under very low temperature, and without any the fracture or the danger of similar broken ring.Thereby, even the round steel chain that the harshest requirement also can be satisfied particularly welds the round steel chain, can make by steel of the present invention.
The parts of being made by steel of the present invention have the intensity of 1200Mpa at least usually, particularly surpass 1550Mpa, 1600Mpa or 1650Mpa.Should be emphasized that about this point: under the intensity of 1550Mpa at least, the fracture apperance transition temperature FATT the highest usually of the parts of being made by steel of the present invention is-60 ℃.This ultimate temperature significantly is lower than the fracture apperance transition temperature of known steel.
Be the notch shock working value equally significantly, the notch shock working value of the parts of being made by steel of the present invention is usually greater than 45J and each the independent parts technology fracture initiation toughness J-60 ℃ the time
ICGreater than 170N/mm, particularly greater than 185N/mm.Fracture initiation toughness J
ICBe a value that in ASTM1820, limits, be used for estimating the ductile fracture trend of steel.
Also can find out the high tenacity degree of steel of the present invention, the elongation at break of the parts of being made by this types of steel is higher than 28%.
Be described in more detail the present invention hereinafter with reference to an embodiment.
A kind of ladle is drawn together (by weight percentage)
0.19% carbon;
0.20% silicon;
1.31% manganese;
0.005% phosphorus;
0.010% sulphur;
The total content of p and s=0.015%;
0.45% chromium;
0.37% molybdenum;
0.88% nickel;
0.400% aluminium;
0.008% nitrogen;
0.01% vanadium;
0.06% niobium;
(total content of vanadium and niobium=0.07%),
All the other are iron and unavoidable impurities,
This steel is melted and is processed to form rolled iron.For guaranteeing products obtained therefrom the thinnest possible crystalline-granular texture after the hot rolling, rolling temperature remains on lower level in course of hot rolling.In addition, for the heat that dissipation thermoforming self produces, between each rolling step, to cool off rolled products.The fine grained structure that will the gained hot-rolled product be quenched present when steel leaves the hot rolling path immediately after the hot rolling to freeze, thus this structure also will keep in procedure of processing subsequently reliably.
Hot rolling and for setting after the long heat treatment that a useful intensity carries out for subsequently cold shaping, rolled iron is shaped to form chain link, and these chain links are in case assembling just makes its closure by welding.
The fine grained structure of the chain of making in this way is ASTM11, and intensity is 1270N/mm
2, the fracture apperance transition temperature FATT that measures under this intensity is-70 ℃.Their notch shock working value is 557J under-60 ℃ probe temperature, and elongation at break is 28%.
The ductile fracture value J that has drawn steel of the present invention in the accompanying drawings is the variation tendency of 0.4 crackle expansion REW to standard initial crack length a/w with temperature during for-60 ℃.As can be seen, when relevant technically stable crackle expands beginning, fracture initiation toughness J
ICBe 185N/mm
2
Claims (23)
1. a production has the high-strength parts steel of good low-temperature toughness, and it has following component (by weight percentage):
Carbon: 0.08 to 0.25%;
Silicon: 0.10 to 0.30%;
Manganese: 0.80 to 1.60%;
Phosphorus :=0.020%;
Sulphur :=0.015%;
The total content of p and s=0.030%;
Chromium: 0.40 to 0.80%;
Molybdenum: 0.30 to 0.50%;
Nickel: 0.70 to 1.20%;
Aluminium: 0.020 to 0.060%;
Nitrogen: 0.007 to 0.018%;
Vanadium :=0.15%;
Niobium :=0.07%;
The total content of vanadium and niobium=0.020%, all the other are iron and unavoidable impurities.
2. according to the described steel of claim 1, it is characterized in that carbon content is in 0.16% to 0.23% weight range.
3. according to the described steel of aforementioned any claim, it is characterized in that manganese content is in 1.00% to 1.35% weight range.
4. according to the described steel of aforementioned any claim, it is characterized in that chromium content is in 0.40% to 0.65% weight range.
5. according to the described steel of aforementioned any claim, it is characterized in that molybdenum content is in 0.35% to 0.50% weight range.
6. according to the described steel of aforementioned any claim, it is characterized in that nickel content is in 0.75% to 1.00% weight range.
7. according to the described steel of aforementioned any claim, it is characterized in that aluminium content is in 0.020% to 0.045% weight range.
8. according to the described steel of aforementioned any claim, it is characterized in that nitrogen content is in 0.007% to 0.015% weight range.
9. according to the described steel of aforementioned any claim, it is characterized in that its autstenitic grain size is less than ASTM10.
10. the purposes of the steel of forming according to aforementioned any claim, be used to produce high-strength parts, it is to be undertaken by cold shaping and tempering-quench treatment subsequently.
11. according to the described purposes of claim 10, it is characterized in that, described parts be carry, drag, promote, the device of transportation or permanent load.
12., it is characterized in that described parts are to be used for the device that structural element connects according to the described purposes of claim 10.
13., it is characterized in that described parts are chains according to each described purposes in the claim 10 to 12.
14., it is characterized in that described chain is the round steel chain according to the described purposes of claim 13.
15., it is characterized in that described chain welds according to claim 13 or 14 described purposes.
16., it is characterized in that described parts have the intensity of 1200Mpa at least according to each described purposes in the claim 10 to 15.
17., it is characterized in that described intensity is 1550Mpa at least according to the described purposes of claim 16.
18., it is characterized in that described intensity is 1600Mpa at least according to claim 16 or 17 described purposes, particularly 1650Mpa at least.
19., it is characterized in that under the intensity of 1550Mpa at least, the fracture apperance transition temperature FATT the highest of described parts is-60 ℃ according to each described purposes in the claim 10 to 18.
20., it is characterized in that the notch shock merit is greater than 45J according to each described purposes in the claim 10 to 19.
21., it is characterized in that the technology fracture initiation toughness JIC of described component materials is greater than 170N/mm according to each described purposes in the claim 10 to 20
2
22., it is characterized in that described technology fracture initiation toughness JIC is greater than 185N/mm according to the described purposes of claim 21
2
23., it is characterized in that the elongation at break of described parts is higher than 28% according to each described purposes in the claim 10 to 22.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04002612.2 | 2004-02-05 | ||
| EP04002612A EP1561833B1 (en) | 2004-02-05 | 2004-02-05 | Steel for manufacturing of high strength elements with an excellent low temperature toughness and use thereof |
| PCT/EP2005/001163 WO2005075693A1 (en) | 2004-02-05 | 2005-02-04 | Steel for producing high tensile structural components with excellent toughness at low temperatures and uses of such a steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1764734A true CN1764734A (en) | 2006-04-26 |
| CN1764734B CN1764734B (en) | 2010-12-08 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580000079.7A Active CN1764734B (en) | 2004-02-05 | 2005-02-04 | Steel for producing high tensile structural components with excellent toughness at low temperatures and uses of such a steel |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20070107808A1 (en) |
| EP (1) | EP1561833B1 (en) |
| JP (1) | JP2007520633A (en) |
| CN (1) | CN1764734B (en) |
| AT (1) | ATE359382T1 (en) |
| BR (1) | BRPI0503588B1 (en) |
| DE (1) | DE502004003457D1 (en) |
| DK (1) | DK1561833T3 (en) |
| ES (1) | ES2286518T3 (en) |
| WO (1) | WO2005075693A1 (en) |
| ZA (1) | ZA200507292B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451529A (en) * | 2013-08-23 | 2013-12-18 | 苏州长盛机电有限公司 | Aluminum-titanium-iron alloy material |
| CN103930581A (en) * | 2011-10-26 | 2014-07-16 | 路德-李格和蒂茨链条有限公司 | Hardening steel for lifting, fastening, clamping and/or lashing means and connecting elements, component for lifting, fastening, clamping and/or lashing technology, connecting element and method for production thereof |
| CN104532143A (en) * | 2014-12-22 | 2015-04-22 | 江阴兴澄特种钢铁有限公司 | Mining large-specification and high-strength chain steel and preparation method thereof |
| CN108603260A (en) * | 2016-02-19 | 2018-09-28 | 新日铁住金株式会社 | Steel |
| CN108603259A (en) * | 2016-02-19 | 2018-09-28 | 新日铁住金株式会社 | Steel |
| CN109026974A (en) * | 2018-09-26 | 2018-12-18 | 安徽博耐克摩擦材料有限公司 | A kind of automobile brake cable |
| CN109058278A (en) * | 2018-09-26 | 2018-12-21 | 安徽博耐克摩擦材料有限公司 | A kind of braking automobile line |
| CN109266975A (en) * | 2018-10-25 | 2019-01-25 | 青岛天赢智能工业股份有限公司 | A kind of high intensity high/low-temperature impact tough alloy and its preparation and heat treatment process |
| CN112912527A (en) * | 2018-10-26 | 2021-06-04 | 株式会社Posco | Steel sheet for pressure vessel having excellent low-temperature toughness and excellent ductility, and method for producing same |
| CN116623103A (en) * | 2023-05-16 | 2023-08-22 | 南京钢铁股份有限公司 | Breaking force 120 kN-level high-strength chain and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005034140A1 (en) * | 2005-07-19 | 2007-01-25 | Rud-Kettenfabrik Rieger & Dietz Gmbh U. Co. | High strength steel chain for the low temperature range |
| CN101407893B (en) * | 2008-11-25 | 2011-04-06 | 武汉钢铁(集团)公司 | High strength, high heat input welding property, fire resistant and earthquake resistant steel for construction and production method thereof |
| US10947610B2 (en) | 2018-08-21 | 2021-03-16 | Exxonmobil Upstream Research Company | Mooring chains comprising high manganese steels and associated methods |
| CN110484818B (en) * | 2019-09-03 | 2020-08-14 | 山东钢铁股份有限公司 | Steel for rubber core support of oil blowout preventer and production method thereof |
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| US5282906A (en) * | 1992-01-16 | 1994-02-01 | Inland Steel Company | Steel bar and method for producing same |
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| AU663023B2 (en) * | 1993-02-26 | 1995-09-21 | Nippon Steel Corporation | Process for manufacturing high-strength bainitic steel rails with excellent rolling-contact fatigue resistance |
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| CN1108397C (en) * | 2000-06-02 | 2003-05-14 | 江阴兴澄钢铁有限公司 | High-strength, high-toughness and corrosion resistant mooring chain steel and its production process |
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-
2004
- 2004-02-05 AT AT04002612T patent/ATE359382T1/en active
- 2004-02-05 DK DK04002612T patent/DK1561833T3/en active
- 2004-02-05 EP EP04002612A patent/EP1561833B1/en not_active Expired - Lifetime
- 2004-02-05 ES ES04002612T patent/ES2286518T3/en not_active Expired - Lifetime
- 2004-02-05 DE DE502004003457T patent/DE502004003457D1/en not_active Expired - Lifetime
-
2005
- 2005-02-04 US US10/551,506 patent/US20070107808A1/en not_active Abandoned
- 2005-02-04 CN CN200580000079.7A patent/CN1764734B/en active Active
- 2005-02-04 WO PCT/EP2005/001163 patent/WO2005075693A1/en active Application Filing
- 2005-02-04 BR BRPI0503588-0B1A patent/BRPI0503588B1/en active IP Right Grant
- 2005-02-04 JP JP2006551811A patent/JP2007520633A/en active Pending
- 2005-09-09 ZA ZA200507292A patent/ZA200507292B/en unknown
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930581A (en) * | 2011-10-26 | 2014-07-16 | 路德-李格和蒂茨链条有限公司 | Hardening steel for lifting, fastening, clamping and/or lashing means and connecting elements, component for lifting, fastening, clamping and/or lashing technology, connecting element and method for production thereof |
| CN103451529A (en) * | 2013-08-23 | 2013-12-18 | 苏州长盛机电有限公司 | Aluminum-titanium-iron alloy material |
| CN103451529B (en) * | 2013-08-23 | 2015-09-16 | 苏州长盛机电有限公司 | A kind of Aluminum-titanium-iralloy alloy material |
| CN104532143A (en) * | 2014-12-22 | 2015-04-22 | 江阴兴澄特种钢铁有限公司 | Mining large-specification and high-strength chain steel and preparation method thereof |
| CN104532143B (en) * | 2014-12-22 | 2016-11-16 | 江阴兴澄特种钢铁有限公司 | A kind of mining big specification, high-test chain steel and preparation method thereof |
| CN108603259A (en) * | 2016-02-19 | 2018-09-28 | 新日铁住金株式会社 | Steel |
| CN108603260A (en) * | 2016-02-19 | 2018-09-28 | 新日铁住金株式会社 | Steel |
| CN109026974A (en) * | 2018-09-26 | 2018-12-18 | 安徽博耐克摩擦材料有限公司 | A kind of automobile brake cable |
| CN109058278A (en) * | 2018-09-26 | 2018-12-21 | 安徽博耐克摩擦材料有限公司 | A kind of braking automobile line |
| CN109266975A (en) * | 2018-10-25 | 2019-01-25 | 青岛天赢智能工业股份有限公司 | A kind of high intensity high/low-temperature impact tough alloy and its preparation and heat treatment process |
| CN109266975B (en) * | 2018-10-25 | 2021-08-31 | 青岛天赢智能工业股份有限公司 | High-strength high-low-temperature impact toughness alloy and preparation and heat treatment process thereof |
| CN112912527A (en) * | 2018-10-26 | 2021-06-04 | 株式会社Posco | Steel sheet for pressure vessel having excellent low-temperature toughness and excellent ductility, and method for producing same |
| CN116623103A (en) * | 2023-05-16 | 2023-08-22 | 南京钢铁股份有限公司 | Breaking force 120 kN-level high-strength chain and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007520633A (en) | 2007-07-26 |
| BRPI0503588B1 (en) | 2013-09-10 |
| ES2286518T3 (en) | 2007-12-01 |
| DE502004003457D1 (en) | 2007-05-24 |
| EP1561833B1 (en) | 2007-04-11 |
| WO2005075693A1 (en) | 2005-08-18 |
| ATE359382T1 (en) | 2007-05-15 |
| DK1561833T3 (en) | 2007-08-20 |
| ZA200507292B (en) | 2007-04-25 |
| EP1561833A1 (en) | 2005-08-10 |
| US20070107808A1 (en) | 2007-05-17 |
| CN1764734B (en) | 2010-12-08 |
| BRPI0503588A (en) | 2006-03-07 |
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