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EP1969151A1 - Deformable lightweight structural steel - Google Patents

Deformable lightweight structural steel

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Publication number
EP1969151A1
EP1969151A1 EP06818103A EP06818103A EP1969151A1 EP 1969151 A1 EP1969151 A1 EP 1969151A1 EP 06818103 A EP06818103 A EP 06818103A EP 06818103 A EP06818103 A EP 06818103A EP 1969151 A1 EP1969151 A1 EP 1969151A1
Authority
EP
European Patent Office
Prior art keywords
content
value pairs
connecting line
structural steel
lightweight structural
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06818103A
Other languages
German (de)
French (fr)
Other versions
EP1969151B1 (en
Inventor
Karl-Heinz Spitzer
Hellfried Eichholz
Bianca Springub
Rune SCHMIDT-JÜRGENSEN
Markus SCHÄPERKÖTTER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Salzgitter Flachstahl GmbH
Original Assignee
Salzgitter Flachstahl GmbH
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Filing date
Publication date
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Application filed by Salzgitter Flachstahl GmbH filed Critical Salzgitter Flachstahl GmbH
Publication of EP1969151A1 publication Critical patent/EP1969151A1/en
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Revoked legal-status Critical Current
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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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the invention relates to a deformable lightweight structural steel with TRIP (Transformation Induced Plasticity) and TWIP (Twinning Induced Plasticity) properties according to the preamble of claim 1.
  • Formable lightweight structural steels of this type are known (DE 10 2004 061 284 A1, DE 197 27 759 A1, DE 101 285 44 A1). In the case of these and comparable steels, in the presence of residual stresses in the material, depending on the microstructure and the strength, a hydrogen-induced delayed embrittlement and as a result cracking may occur.
  • the object of the invention is to provide a lightweight steel of the generic type, which does not have the effect of a delayed hydrogen embrittlement while maintaining very good mechanical properties (ductility, strength).
  • the problem mentioned in the problem is solved by a new alloy concept.
  • This is characterized in that a lower C content is assigned to a lower Mn content and a lower C content to a higher Mn content, the C-Mn value pairs in a C-Mn coordinate system being approximately at a straight connecting line which has a distance to the connecting line of in equilibrium between ⁇ - (austenite-kfz) and ⁇ '-phases (martensite-krz) are located C-Mn value pairs.
  • This new alloy concept makes use of the knowledge that the ⁇ -austenite (kfz) and the ⁇ -martensite (hdp) phase have a high hydrogen solubility while the ⁇ '-martensite (krz) phase has a much lower hydrogen solubility having.
  • TRIP effect occurs, depending on the alloy composition, formation of the ⁇ '-martensite phase, e.g. via the metastable ⁇ -martensite phase.
  • the densely packed ⁇ -Martensit phase can be present on the principle of least constraint even after the forming and fold down on discharge in the ⁇ '-martensite phase.
  • the addition of Al and Si is approximately equal.
  • the carbon content is a crucial element in the proposed alloy concept because it stabilizes the austenite phase and displaces the hydrogen from the free lattice sites.
  • alloys have
  • the first alloy example After annealing at 85O 0 C, the first alloy example has a yield strength R p0 , 2 of 480 MPa and a strength of 850 MPa with an elongation A of 58%. These values for the second example also alloy after annealing at 85O 0 C, R p o i2 450 MPa; R m 790 MPa and A 53%.
  • a second parameter is the product of strength x elongation, which is a measure of the material's performance. This value is 49,300 for alloy example 1 and 41,870 (% x MPa) for example 2.
  • the C content is plotted against the Mn content in a coordinate system.
  • the solid straight connecting line shows the C-Mn value pairs which are in balance with respect to the ⁇ -austenite and the ⁇ '-martensite phase taking into account AI and / or Si addition.
  • the dashed connecting line which is at a distance from the equilibrium line, identifies value pairs of the optimal alloy concept, with regard to material properties while avoiding delayed fracture.
  • the shading applied over the dashed connecting line is intended to indicate the qualitative scattering band within which optimum results are still to be expected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)

Abstract

The invention relates to a deformable lightweight structural steel, which exhibits a resistance to hydrogen embrittlement, has TRIP- and TWIP properties and contains the following elements (in wt.-%): C 0.05 to <= 1.0; Al 0.0 to <= 11.0; Si 0.0 to <= 6.0; Al + Si > 0.05; Mn 9.0 to = 25.0; H < 20 ppm, the remainder being composed of iron including usual steel companion elements, whereby different phases are present depending on the alloy composition. According to the invention, said lightweight structural steel is characterized in that a higher C content is associated with a lower Mn content while a low C content is associated with a higher Mn content, the C-Mn value pairs being positioned in a C-Mn coordinate system approximatively on a straight connecting line that is distant from the connecting line of the C-Mn value pairs being in balance between the austenite und martensite phases.

Description

Umformbarer Leichtbaustahl Formable lightweight steel

Beschreibungdescription

Die Erfindung betrifft einen umformbaren Leichtbaustahl mit TRIP- (Transformation Induced Plasticity) und TWIP- (Twinning Induced Plasticity) Eigenschaften gemäß dem Oberbegriff des Anspruches 1.The invention relates to a deformable lightweight structural steel with TRIP (Transformation Induced Plasticity) and TWIP (Twinning Induced Plasticity) properties according to the preamble of claim 1.

Umformbare Leichtbaustähle dieser Art sind bekannt (DE 10 2004 061 284 A1 , DE 197 27 759 A1 , DE 101 285 44 A1 ). Bei diesen und vergleichbaren Stählen kann bei Vorliegen von Eigenspannungen im Material in Abhängigkeit vom Gefüge und der Festigkeit eine durch Wasserstoff ausgelöste verzögerte Versprödung und in Folge dessen eine Rissbildung auftreten.Formable lightweight structural steels of this type are known (DE 10 2004 061 284 A1, DE 197 27 759 A1, DE 101 285 44 A1). In the case of these and comparable steels, in the presence of residual stresses in the material, depending on the microstructure and the strength, a hydrogen-induced delayed embrittlement and as a result cracking may occur.

Zur Überwindung dieses Problems ist bereits vorgeschlagen worden, den Wasserstoffgehalt auf < 20 ppm vorzugsweise auf < 5 ppm zu begrenzen (DE 10 2004 061 284 A1).To overcome this problem, it has already been proposed to limit the hydrogen content to <20 ppm, preferably to <5 ppm (DE 10 2004 061 284 A1).

Dieser Vorschlag ist zwar hilfreich aber nicht ausreichend, da selbst bei niedrig eingestellten Wasserstoffgehalten trotzdem noch der Effekt der Wasserstoffversprödung auftreten kann. Außerdem können bei der Stahlherstellung aus verschiedenen Gründen Überschreitungen des festgelegten Maximalwertes für Wasserstoff vorkommen, die legierungsmäßig zwar toleriert werden können, aber die Gefahr des Auftretens einer Wasserstoffversprödung vergrößern.This suggestion is helpful but not sufficient, since even at low hydrogen levels the effect of hydrogen embrittlement can still occur. Moreover, steelmaking may, for various reasons, exceed the established maximum value for hydrogen which, while tolerated by alloy, increases the risk of hydrogen embrittlement.

Aufgabe der Erfindung ist es einen Leichtbaustahl der gattungsgemäßen Art anzugeben, der unter Beibehaltung sehr guter mechanischer Eigenschaften (Duktilität, Festigkeit) den Effekt einer verzögerten Wasserstoffversprödung nicht aufweist.The object of the invention is to provide a lightweight steel of the generic type, which does not have the effect of a delayed hydrogen embrittlement while maintaining very good mechanical properties (ductility, strength).

Diese Aufgabe wird ausgehend vom Oberbegriff in Verbindung mit den kennzeichnenden Merkmalen des Anspruches 1 gelöst. Vorteilhafte Weiterbildungen sind Gegenstand von Unteransprüchen. Nach der Lehre der Erfindung wird das in der Aufgabenstellung genannte Problem durch ein neues Legierungskonzept gelöst. Dieses zeichnet sich dadurch aus, dass einem niedrigeren Mn-Gehalt ein höherer C-Gehalt und einem höheren Mn-Gehalt ein niedriger C-Gehalt zugeordnet wird, wobei die C-Mn-Wertepaare in einem C-Mn-Koordinatensystem annähernd auf einer geraden Verbindungslinie liegen, die einen Abstand zur Verbindungslinie von im Gleichgewicht zwischen γ- (Austenit-kfz) und α'-Phasen (Martensit-krz) sich befindenden C- Mn-Wertepaaren aufweist.This object is achieved starting from the preamble in conjunction with the characterizing features of claim 1. Advantageous developments are the subject of dependent claims. According to the teaching of the invention, the problem mentioned in the problem is solved by a new alloy concept. This is characterized in that a lower C content is assigned to a lower Mn content and a lower C content to a higher Mn content, the C-Mn value pairs in a C-Mn coordinate system being approximately at a straight connecting line which has a distance to the connecting line of in equilibrium between γ- (austenite-kfz) and α'-phases (martensite-krz) are located C-Mn value pairs.

Bei diesem neuen Legierungskonzept macht man sich die Erkenntnis zu Nutze, dass die γ- Austenit(kfz) und die ε -Martensit(hdp)-Phase eine hohe Wasserstofflöslichkeit besitzen während die α'-Martensit(krz)-Phase eine sehr viel geringere Wasserstofflöslichkeit aufweist. Beim Auftreten des TRIP-Effektes kommt es je nach Legierungszusammensetzung zur Bildung der α'-Martensit-Phase, z.T. über die metastabile ε -Martensit-Phase. In Bereichen, in denen der Werkstoff z.B. unter Druckspannung umgeformt wird, kann dabei die dichter gepackte ε -Martensit-Phase nach dem Prinzip des kleinsten Zwanges auch nach der Umformung vorliegen und bei Entlastung in die α'-Martensit-Phase umklappen.This new alloy concept makes use of the knowledge that the γ-austenite (kfz) and the ε-martensite (hdp) phase have a high hydrogen solubility while the α'-martensite (krz) phase has a much lower hydrogen solubility having. When the TRIP effect occurs, depending on the alloy composition, formation of the α'-martensite phase, e.g. via the metastable ε-martensite phase. In areas where the material is e.g. is converted under compressive stress, the densely packed ε -Martensit phase can be present on the principle of least constraint even after the forming and fold down on discharge in the α'-martensite phase.

Bei diesem Umklappen von der ε -Martensit-Phase in die α'-Martensit-Phase muss der Wasserstoff wegen der niedrigeren Löslichkeit entweichen, und führt entweder atomar oder rekombiniert zur Schwächung des Materials, gegebenenfalls zum Reißen.In this shift from the ε-martensite phase to the α'-martensite phase, the hydrogen must escape because of the lower solubility and, either atomically or recombined, results in weakening of the material, possibly cracking.

Ausgehend von einer Legierung mit C und Mn führt die Zugabe von AI und/oder Si zu einer Destabilisierung der ε -Martensit-Phase. Das verringert die Gefahr einer Wasserstoffversprö- dung bzw. erhöht den Spielraum für den Stahlwerker auch bei Überschreitung des Maximalwertes des Wasserstoffs die abgegossene Schmelze noch als tolerierbar einzustufen. Weniger Abwertungen erhöhen das Ausbringen und damit die Wirtschaftlichkeit des Verfahrens.Starting from an alloy with C and Mn, the addition of Al and / or Si leads to a destabilization of the ε-martensite phase. This reduces the risk of hydrogen embrittlement or increases the latitude for the steelworker, even if the maximum value of hydrogen is exceeded, to classify the discharged melt as tolerable. Less devaluation increases the yield and thus the economic efficiency of the process.

Vorzugsweise ist die Zugabe von AI und Si annähernd gleich groß.Preferably, the addition of Al and Si is approximately equal.

Unabhängig von der Wirkung der Zugabe von AI und/oder Si ist der Kohlenstoffgehalt ein entscheidendes Element im vorgeschlagenen Legierungskonzept, da er die Austenit-Phase stabilisiert und den Wasserstoff von den freien Gitterplätzen verdrängt. Das Streuband um die Verbindungslinie der optimalen C-Mn-Wertepaare für den Gehalt an C sollte =±0,15%, vorzugsweise ±0,1% an für den Gehalt an Mn=±2,5%, vorzugsweise ±1,5% betragen.Regardless of the effect of the addition of Al and / or Si, the carbon content is a crucial element in the proposed alloy concept because it stabilizes the austenite phase and displaces the hydrogen from the free lattice sites. The scatter band around the connecting line of the optimum C-Mn value pairs for the content of C should = ± 0.15%, preferably ± 0.1% for for the content of Mn = ± 2.5%, preferably ± 1.5% be.

Beispielsweise weisen Legierungen mitFor example, alloys have

0,7 % C, 15 % Mn, 2,5 % AI, 2,5 % Si sowie0.7% C, 15% Mn, 2.5% Al, 2.5% Si as well

0,4 % C, 18 % Mn, 2,5 % AI, 2,5 % Si neben hervorragenden mechanischen Eigenschaften, wie nachfolgend angegeben, keine verzögerte Rissbildung ("delayed fracture") auf.0.4% C, 18% Mn, 2.5% Al, 2.5% Si in addition to excellent mechanical properties, as indicated below, no delayed fracture on.

Nach einer Glühung bei 85O0C weist das erste Legierungsbeispiel eine Streckgrenze Rp0,2 von 480 MPa und eine Festigkeit von 850 MPa mit einer Dehnung A von 58 % auf. Diese Werte für das zweite Legierungsbeispiel ebenfalls nach einer Glühung bei 85O0C sind Rpoi2 450 MPa; Rm 790 MPa und A 53 %. Eine zweite Kenngröße ist das Produkt aus Festigkeit x Dehnung, das ein Maß für die Leistungsfähigkeit des Werkstoffes ist. Dieser Wert liegt für das Legierungsbeispiel 1 bei 49.300 und für Beispiel 2 bei 41.870 (% x MPa).After annealing at 85O 0 C, the first alloy example has a yield strength R p0 , 2 of 480 MPa and a strength of 850 MPa with an elongation A of 58%. These values for the second example also alloy after annealing at 85O 0 C, R p o i2 450 MPa; R m 790 MPa and A 53%. A second parameter is the product of strength x elongation, which is a measure of the material's performance. This value is 49,300 for alloy example 1 and 41,870 (% x MPa) for example 2.

In der einzigen Figur ist in einem Koordinatensystem der C-Gehalt über den Mn-Gehalt aufgetragen. Die durchgezogene gerade Verbindungslinie zeigt die C-Mn-Wertepaare, die sich unter Berücksichtigung einer AI- und/oder Si-Zugabe im Gleichgewicht bezüglich der γ- Austenit- und der α' -Martensit-Phase befinden.In the single figure, the C content is plotted against the Mn content in a coordinate system. The solid straight connecting line shows the C-Mn value pairs which are in balance with respect to the γ-austenite and the α '-martensite phase taking into account AI and / or Si addition.

Die gestrichelte Verbindungslinie, die einen Abstand zur Gleichgewichtslinie aufweist, kennzeichnet Wertepaare des optimalen Legierungskonzeptes, hinsichtlich Werkstoffeigenschaften unter Vermeidung einer verzögerten Rissbildung (delayed fracture). Die über die gestrichelte Verbindungslinie gelegte Schraffierung soll das qualitative Streuband andeuten, innerhalb dessen noch optimale Ergebnisse zu erwarten sind. The dashed connecting line, which is at a distance from the equilibrium line, identifies value pairs of the optimal alloy concept, with regard to material properties while avoiding delayed fracture. The shading applied over the dashed connecting line is intended to indicate the qualitative scattering band within which optimum results are still to be expected.

Claims

Patentansprüche claims 1. Umformbarer Leichtbaustahl mit TRIP- und TWIP-Eigenschaften mit den Elementen in Gew.-%1. Transformable lightweight structural steel with TRIP and TWIP properties with the elements in% by weight C 0,05 bis ≤ 1 ,0C is 0.05 to ≤ 1.0 AI O1O bis ≤ 11 ,0AI O 1 O to ≤ 11, 0 Si O1O bis ≤ 6,0Si O 1 O to ≤ 6.0 AI + Si > 0,05Al + Si> 0.05 Mn 9,0 bis ≤ 25,0Mn 9.0 to ≤ 25.0 H < 20 ppm, Rest Eisen einschließlich üblicher stahlbegleitender Elemente, wobei je nach Legierungszusammensetzung unterschiedliche Phasen vorliegen, dadurch gekennzeichnet, dass einem niedrigeren Mn-Gehalt ein höherer C-Gehalt und einem höheren Mn-Gehalt ein niedriger C-Gehalt zugeordnet wird, wobei die C-Mn-H <20 ppm, the remainder being iron, including conventional steel-supporting elements, different phases being present depending on the alloy composition, characterized in that a lower Mn content is assigned a higher C content and a higher Mn content a lower C content; C-Mn Wertepaare in einem C-Mn-Koordinatensystem annähernd auf einer geradenValue pairs in a C-Mn coordinate system approximately on a straight line Verbindungslinie liegen, die einen Abstand zur Verbindungslinie von im Gleichgewicht zwischen γ- (Austenit) und α'-Phasen (Martensit) sich befindenden C-Mn-Wertepaaren aufweist.Connection line, which has a distance to the connecting line of in equilibrium between γ- (austenite) and α 'phases (martensite) are located C-Mn value pairs. 2. Leichtbaustahl nach Anspruch 1 , dadurch gekennzeichnet, dass die Zugabe von AI und Si annähernd gleich groß ist.2. Lightweight steel according to claim 1, characterized in that the addition of Al and Si is approximately equal. 3. Leichtbaustahl nach den Ansprüchen 1 - 2, dadurch gekennzeichnet, dass das Streuband um die Verbindungslinie der optimalen C- Mn-Wertepaare für den Gehalt an C = + 0,15 % und für den Gehalt an Mn = ± 2,5 % beträgt.3. Lightweight steel according to claims 1 - 2, characterized in that the scattering band around the connecting line of the optimal C-Mn value pairs for the content of C = + 0.15% and for the content of Mn = ± 2.5% , 4. Leichtbaustahl nach Anspruch 3, dadurch gekennzeichnet, dass das Streuband für den Gehalt an C = ± 0,1 % und für den Gehalt an Mn = ± 1 ,5 % beträgt. 4. Lightweight steel according to claim 3, characterized in that the scattering band for the content of C = ± 0.1% and for the content of Mn = ± 1, 5%.
EP06818103.1A 2005-12-20 2006-11-22 Process for manufacturing a deformable lightweight structural steel Revoked EP1969151B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005062221A DE102005062221B3 (en) 2005-12-20 2005-12-20 Deformable light alloy steel with TRIP) and TWIP properties useful in production of products having decreased crack liability twinning induced plasticity (TWIP) good ductility and tensile strength without increase in hydrogen embrittlement
PCT/DE2006/002081 WO2007076748A1 (en) 2005-12-20 2006-11-22 Deformable lightweight structural steel

Publications (2)

Publication Number Publication Date
EP1969151A1 true EP1969151A1 (en) 2008-09-17
EP1969151B1 EP1969151B1 (en) 2014-02-26

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EP06818103.1A Revoked EP1969151B1 (en) 2005-12-20 2006-11-22 Process for manufacturing a deformable lightweight structural steel

Country Status (10)

Country Link
US (1) US20090196785A1 (en)
EP (1) EP1969151B1 (en)
KR (1) KR20080081969A (en)
CN (1) CN101405420A (en)
AU (1) AU2006332301B2 (en)
DE (2) DE202005021771U1 (en)
RU (1) RU2430184C2 (en)
UA (1) UA88994C2 (en)
WO (1) WO2007076748A1 (en)
ZA (1) ZA200805306B (en)

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WO2007076748A1 (en) 2007-07-12
AU2006332301A1 (en) 2007-07-12
UA88994C2 (en) 2009-12-10
KR20080081969A (en) 2008-09-10
RU2430184C2 (en) 2011-09-27
EP1969151B1 (en) 2014-02-26
DE102005062221B3 (en) 2007-05-03
AU2006332301B2 (en) 2011-07-28
CN101405420A (en) 2009-04-08
RU2008129694A (en) 2010-01-27
ZA200805306B (en) 2009-04-29
US20090196785A1 (en) 2009-08-06

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