EP1851351B1 - Austenitischer nichtrostender stahl - Google Patents

Austenitischer nichtrostender stahl Download PDF

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EP1851351B1
EP1851351B1 EP06708260A EP06708260A EP1851351B1 EP 1851351 B1 EP1851351 B1 EP 1851351B1 EP 06708260 A EP06708260 A EP 06708260A EP 06708260 A EP06708260 A EP 06708260A EP 1851351 B1 EP1851351 B1 EP 1851351B1
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steel
stainless steel
austenitic stainless
wires
steel according
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EP1851351A1 (de
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Mario Cusolito
Marco Valsecchi
Pedro M. Corcuera Amurzia
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RODACCIAI SpA
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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
    • C22C38/18—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

Definitions

  • the present invention relates to a new austenitic stainless steel with a low nickel content which has special characteristics in terms of corrosion resistance in given environments, deformability and suitability for work-hardening.
  • the steel according to the present invention is characterized by the following chemical composition: 0.03 % ⁇ carbon ⁇ 0.07 % 7.0 % ⁇ manganese ⁇ 8.5 % 0.3 % ⁇ silicon ⁇ 0.7 % sulphur ⁇ 0.030 % phosphorus ⁇ 0.045 % 16.5 % ⁇ chromium ⁇ 18.0 % 3.5 % ⁇ nickel ⁇ 4.5 % 0.1 % ⁇ molybdenum ⁇ 0.5 % 1.0 % ⁇ copper ⁇ 3.0 % 0.1 % ⁇ nitrogen ⁇ 0.3 % the difference consisting in iron and common process impurities.
  • a very important characteristic of the new steel is the small amount of nickel it contains: it is in fact well known that the price of this element is unstable, with a continuous tendency to increase, resulting in continuous variations in the costs of the articles produced with materials which contain this element.
  • Austenitic stainless steel is an iron and carbon alloy containing various other elements, the main ones of which are chromium and nickel. The combination of these elements gives the steel a basic property of corrosion resistance owing to the formation of a protective surface film which is due to the presence of a chromium content of at least 1.11% and whose qualities are improved by the presence of nickel and other elements.
  • Other typical properties of austenitic stainless steels are the very low magnetic permeability (non-magnetic property), heat resistance, cold deformability and suitability for work-hardening. Owing to these properties, austenitic stainless steels are used in a very wide range of applications.
  • the most well known and widely used type of austenitic stainless steel contains about 18% chromium 10% nickel and has always been referred to as 18/10 steel.
  • this steel In the European standard EN 10088-3 1997 this steel has been called X5CrNi18-1 and has been attributed the steel number 1.4301. In the United States standard AISI this steel is called 304.
  • the percentage by weight chemical composition envisaged for this steel by the European standard is as follows:
  • the maximum sulphur content coincides with that of basic steel, so that in fact this is not another steel, but only a variation of the same type 1.4301 obtained by dividing the analytical range permitted by sulphur. Sulphur has the capacity to weaken the metallic matrix and therefore improve the machinability during the swarf removal operations. At the same time, however, sulphur, even though present in limited amounts, modifies the corrosion resistance. This micro-resulphurised variant is cited here because below it will often be used for comparison with the type 1.4301 steel and with the steel of this invention.
  • 1.4301 steel has extremely broad technological and corrosion properties such it has been become very widely established in the engineering sector as a structural material as well as in the environmental sector: it is in fact widely employed in the transportation, architecture and the domestic sectors, being used at high temperatures and in corrosive environments.
  • the type 1.4301 is the most well known, widespread and researched in the sector of austenitic stainless steels and therefore is used as a reference type for comparing the characteristics of other austenitic stainless steels.
  • the type 1.4307 - X2CrNi18-9 (AISI 304L in the US standards) is a steel similar to the preceding one, but with a limited carbon content which improves the intergranular corrosion resistance.
  • the chemical composition of type 1.4307 steel is as follows:
  • the type 1.4306 - X2CrNi19-11 is a further low-carbon variant with a greater content of nickel which is added in order to improve the cold deformability and the corrosion resistance.
  • the chemical composition of this type is as follows:
  • the type 1.4567 - X3CrNiCul8-9-4 is a version with the addition of copper in large amounts for the purpose of improving the cold deformability: it is used for those particular cold-pressed products where the preceding types are unable to withstand the extreme deformation, such as, for example, hexagonal socket head screws.
  • the chemical composition is as follows:
  • the main characteristics of an austenitic stainless steel are its corrosion resistance, non-magnetic nature, cold-deformability and suitability for work-hardening. These characteristics are obtained by modifying various factors, including the chemical composition: in addition to chromium and nickel, the other secondary elements have an important effect.
  • the effect of chromium, referred to as “alphagenic” tends to stabilize the ferritic phase of the materials (alpha phase): other elements, such as silicon and molybdenum, behave in the same manner as chromium, although to a lesser degree.
  • nickel which is a "gammagenic" element, and therefore has a stabilizing effect on the austenitic phase (gamma phase): various elements such as carbon, nitrogen, copper and manganese behave in the same manner as nickel.
  • austenitic stainless steels with low nickel contents have been researched: some of these, which are more widely used and have been known for some time, are included in various standards and used because of their specific characteristics. Others have been recently developed with the aim of obtaining some of the basic characteristics of austenitic stainless steel. In fact, by suitably increasing the content of the less costly "gammagenic" elements (nitrogen, copper and manganese), it is possible to obtain an austenitic stainless steel which is equally stable, but has a low percentage content of nickel (and therefore a price which is less dependent on the fluctuations of the cost of nickel) and with one or more technological properties the same as those of normal conventional austenitic steels with a higher nickel content. Austenitic steels with a low nickel content are for example described in EP593158 , EP694626 , EP896072 , EP969113 e WO 00/26428 .
  • the subject of the present invention is a steel having a nickel content which is markedly lower than that of basic steel type 1.4301 (AISI 304) and which, with suitable balancing of the other elements, has many properties similar to the corresponding properties of basic steel type 1.4301 (AISI 304); it has the composition shown below: 0.03 % ⁇ carbon ⁇ 0.07 % 7.0 % ⁇ manganese ⁇ 8.5 % 0.3 % ⁇ silicon ⁇ 0.7 % sulphur ⁇ 0.030 % phosphorus ⁇ 0.045 % 16.5 % ⁇ chromium ⁇ 18.0 % 3.5 % ⁇ nickel ⁇ 4.5 % 0.1 % ⁇ molybdenum ⁇ 0.5 % 1.0 % ⁇ copper ⁇ 3.0 % 0.1 % ⁇ nitrogen ⁇ 0.3 % where the difference consists in iron and common process impurities.
  • the steel according to the present invention may be obtained by means of the conventional processes for the preparation of austenitic stainless steels, such as those for example described in "ASM Specialty Handbook - Stainless Steels” edited by "The Material Information Society” - USA.
  • it has the composition indicated below: 0.04 % ⁇ carbon ⁇ 0.06 % 7.5 % ⁇ manganese ⁇ 8.0 % 0.4 % ⁇ silicon 0.6 % 0.002 % ⁇ sulphur 0.004 % 0.030 % ⁇ phosphorus ⁇ 0.035 % 17.0 % ⁇ chromium ⁇ 17.5 % 3.8 % ⁇ nickel ⁇ 4.2 % 0.1 % ⁇ molybdenum ⁇ 0.3 % 2.0 % ⁇ copper ⁇ 2.5 % 0.15 % ⁇ nitrogen ⁇ 0.2 %
  • the sulphur is less than 0.005 %.
  • the nickel is higher than 4.0 %.
  • the carbon is about 0.055 %
  • the manganese is about 7.50 %
  • the silicon is about 0.52 %
  • the sulphur is about 0.003 %
  • the phosphorus is about 0.032 %
  • the chromium is about 17.0 %
  • the nickel is about 4.0 %
  • the molybdenum is about 0.19 %
  • the copper is about 2.0 % and/or the nitrogen is about 0.17 %.
  • the steel according to the present invention presents a higher resistance to "stress corrosion cracking" (also called “delayed corrosion”) than the steels commonly known in the art and, in particular, than those disclosed by WO 00/26428 , EP896072 or EP969113 .
  • Stress corrosion cracking also called “delayed corrosion”
  • Such a higher resistance can be explained through the selected nickel range of between 3.5 and 4.5% by weight, as for instance subsequently demonstrated by J. Charles, Stainless Steel '05, Proceedings of the 5th European Congress Stainless Steel Science and Market, Seville, September 27-30, 2005 (pages 19-26 ).
  • the drawing of the rolls is performed by means of successive passes through the tools (drawing dies) which deform the product, gradually decreasing its cross-section.
  • the reference stainless steel 1.4301 (AISI 304) is able to withstand drawing reductions of up to 88%. Beyond these values the work-hardening is such that the material breaks and is no longer capable of being deformed.
  • the stainless steel according to this invention under identical conditions, is able to withstand drawing with reductions in the cross-section in the region of 92-94%.
  • Table 1 shows the tensile strength and elongation at break values of the steel according to the invention for various degrees of reduction during drawing, compared with two reference steels: steel type 1.4307 with a low carbon content (about 0.02%) and steel type 1.4301 with a slightly higher carbon content (0.04%).
  • Figure 1 shows in graph form the tensile strength values as a function of the drawing reduction for these steels, while Figure 2 shows the same type of comparative graph relating this time to the percentage elongation at break value.
  • the work-hardening is due to the partial and progressive transformation of part of the austenite into martensite, which is the hardest component of steel.
  • a metallographic study was carried out on samples taken from materials in the annealed and work-hardened state, these revealing both the deformation of the grain, with elongation in the drawing direction, and the austenite-martensite transformation.
  • Figure 3 shows a longitudinal metallographic cross-section through the product in an ultra work-hardened state of the wire obtained with the new steel, in which the work-hardening lines due to the martensitic transformation are clearly visible.
  • Figure 4 shows the same type of cross-section carried out on a sample of the reference steel type 1.4301 (AISI 304).
  • the relative magnetic permeability measures the ratio between the magnetic permeability of a material ⁇ and that of a vacuum ⁇ 0 .
  • ⁇ r ⁇ ⁇ 0
  • the magnetic permeability of a material ⁇ (measured in Henry/metre [H/m]) is defined by the ratio between the magnetic induction value B and the value of the magnetizing force H.
  • the magnetic permeability of a material basically measures the ferromagnetism, i.e. the property of a steel to react with a magnetic field of given value.
  • An austenitic steel in the solubilized state, and hence with a totally austenitic structure, is completely non-magnetic: when it is subjected to a magnetic field, for example that of a magnet, it does not react.
  • An austenitic steel in the work-hardened state for example after undergoing drawing reductions, is increasingly more magnetic depending on the percentage of austenite transformed into martensite (basically dependent on the drawing reduction and the chemical composition).
  • the magnetic permeability in a stainless steel assumes particular importance both in the case of more complex applications (e.g. solenoid valve bodies, where the part must not be influenced by the magnetic field of excitation of the valve), but also for more straightforward applications, where recognition of the material is simply carried out by means of a magnet, as in the case of laundry drying frames sold at markets or in supermarkets: if the wire of the laundry drying rack is not attracted by the magnet, it is recognised as being austenitic stainless steel and is much more highly valued than the corresponding wire made of ferritic stainless steel or even galvanized iron, which are both highly ferromagnetic.
  • the possibility of obtaining drawn wires with high work-hardening values (required by the product itself in order to withstand the load of wet laundry), without any significant variation in the magnetic permeability, results in the invention being particularly suitable for this type of use.
  • the characteristics of the screws produced were determined by means of tensile tests carried out in accordance with the standard UNI EN ISO 3506 part 1 edition February 2000 and HV 500 microhardness tests.
  • Figure 6 shows the microhardness values determined at various points in the longitudinal section of the screws DIN 933 M5 x 25 produced.
  • Figure 7 shows the microhardness values detected at various points of the cross-section of screws DIN 912 M5 x 12.
  • Corrosion-resistance tests were carried out using samples obtained by means of machine-tool processing of solubilized wire rod.
  • Table 3 Corrosion tests carried out on samples obtained from solubilized wire rod Test in 20% sulphuric acid -- 1 cycle of 96 hours at +20°C Test in 65% nitric acid ASTM A262 test C 3 cycles at 48 hours at boiling temperature - change of solution with each new cycle Test in 6% ferric chloride ASTM G-48 1 cycle of 72 hours at 22°C +/-2
  • the new steel in fact has a performance perfectly in keeping with that of the reference types and only in the nitric acid test is the corrosion value slightly higher than that of the type 1.4307 micro-resulphurised steel.
  • both the steels used for comparison had an extremely low carbon content (type 1.4307 corresponds to the type AISI 304L, Low Carbon): the new steel is therefore not affected, all other conditions being equal, by the C content which is higher than in the basic comparison steels.
  • the steel according to the invention in the solubilized state and on test pieces obtained by means of machining, has corrosion-resistance properties which are practically the same as those of the reference steels.
  • Table 4 lists the types of materials which underwent this type of test, their diameters and the associated working conditions. Table 4: Wire samples subjected to corrosion tests Quality Diameter State Reference number European standard AISI standard mm 1.4301 304 2.30 Partially work-hardened 1 1.4301 304 2.00 Solution annealed 2 1.4301 304 1.30 Work-hardened 3 New steel 1.40 Solution annealed 4 New steel 1.40 Work-hardened 5 New steel 2.25 Solution annealed 6 New steel 2.00 Partially work-hardened 8
  • Table 5 instead lists the tests which these samples underwent and the reference standards.
  • Table 5 Corrosion tests on wire Test Reference standard Duration Neutral saline mist UNI ISO 9227 NSS 168 / 400 hours Copper acetic acid mist UNI ISO 9227 CASS 120 hours Kesternich cycles (corrosion in an industrial atmosphere) DIN 50018 21 4 cycles of 24 hours consisting of 8 hours exposure to SO 2 and 16 hours exposure to the laboratory air Immersion test in a solution of NaCl 2M with pH 6.6 -- 168 hours Intercrystalline corrosion test ASTM A262 test E 24 hours in copper/copper sulphate/sulphuric acid solution
  • the behaviour of the new steel and the 1.4301 steel is instead greatly influenced by the degree of work-hardening: as known from the literature, the best corrosion resistance is obtained with the material in the solution annealed state, while it is worsened by work-hardening. It was noted, however, that the behaviour of the steel considered in this study is midway between the type 1.4301 and the type 14016.
  • test pieces After attack, all the test pieces were able to be bent through 180° without any signs of cracking or flaking on the surface subject to tensile stress.
  • the corrosion tests carried out were particularly numerous and covered all the possible ranges of applications such that it was possible to determine the characteristics of the new material with a wide series of tests.
  • the rapid hot tensile tests were carried out at a decidedly high temperature (900°C) compared to the operating temperatures normally permitted.
  • the results show that the new steel has a behaviour very similar to that of the normal reference steel, type 1.4301, while only the type with a higher carbon content (1.4310) has a slightly higher hot strength, even though it as of the same order of magnitude.
  • the basic stainless steel 1.4301 (AISI 304) is resistant for fairly long periods in a high temperature oxidising environment: in particular the most common uses for this material are those which envisage stays in air up to about 500°C.
  • the new steel was also tested for its resistance to temperatures higher than room temperature by means of air heating tests inside a muffle furnace. The results can be seen in Figure 10 .
  • the resistance was evaluated by measuring the depth of surface oxidation, i.e. the loss of diameter as a result of oxidation. It is possible to note that the new steel behaves in a manner perfectly similar to that of the of the various types with a high nickel content up to a temperature of higher than 800°C. As mentioned, the temperatures commonly used for normal austenitic steels (belonging to the family of 1.4301 steel) are about 500°C, while for higher temperatures refractory alloys (with high nickel contents) or superalloys (nickel based alloys, not belonging to the family of steels) are used. The new steel is therefore perfectly utilisable at the same temperatures at which the basic type is used since there is no variation in its characteristics.
  • the new stainless steel according to the present invention with a low nickel content possesses technical characteristics similar or comparable to those of steel type 1.4301.
  • the main advantage of this new steel from the commercial point of view is its lesser dependency on the nickel market and therefore its greater stability from a price point of view. From the technical point of view, the main advantage is the extremely high suitability for drawing which allows a large reduction during drawing and a small number of intermediate annealing operations.
  • the new material is particularly suitable as a substitute for traditional types of steel in certain specific applications

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Claims (15)

  1. Verwendung eines austenitischen rostfreien Stahls mit der folgenden Zusammensetzung nach Gewicht: 0 , 03 % < Kohlenstoff < 0 , 07 %
    Figure imgb0053
     7 , 0 % < Mangan < 8 , 5 %
    Figure imgb0054
     0 , 3 % < Silizium < 0 , 7 %
    Figure imgb0055
     Schwefel ≤ 0 , 030 %
    Figure imgb0056
     Phosphor ≤ 0 , 045 %
    Figure imgb0057
     16 , 5 % < Chrom < 18 , 0 %
    Figure imgb0058
     3 , 5 % < Nickel < 4 , 5 %
    Figure imgb0059
     0 , 1 % < Molybd ⁢ a ¨ ⁢ n < 0 , 5 %
    Figure imgb0060
     1 , 0 % < Kupfer < 3 , 0 %
    Figure imgb0061
     0 , 1 % < Stickstoff < 0 , 3 % ,
    Figure imgb0062
    der Rest bestehend aus Eisen und Verunreinigungen, für die Herstellung von Gegenständen ausgewählt aus: Drähten für landwirtschaftliche Verwendung, Drähten für die häusliche Verwendung, elektrische Haushaltsanwendungen, Gitter, Gepäckablagen, Fahrradspeichen; Drähten für Wäschetrocknergestelle; Drähten und Schrauben für elektronische Bauteile; Drähten für das Bauwesen, für Maschenwerk und für Haken verwendet auf Schieferdächern; Drähten und Zuganker für industrielle Öfen.
  2. Verwendung eines austenitischen rostfreien Stahls nach Anspruch 1, gekennzeichnet durch: 0,04 % < Kohlenstoff < 0,06 %.
  3. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Absprüche, gekennzeichnet durch: 7,5 % ≤ Mangan < 8,0 %.
  4. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 0,4 % < Silizium < 0,6 %.
  5. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: Schwefel < 0,005 %.
  6. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 0,002 % < Schwefel < 0,004 %.
  7. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 0,030 % < Phosphor < 0,035 %.
  8. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 17,0 % ≤ Chrom < 17,5 %.
  9. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 3,8 % < Nickel < 4,2 %.
  10. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 0,1 % < Molybdän < 0,3 %.
  11. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 2,0 % ≤ Kupfer < 2,5 %.
  12. Verwendung eines austenitischen rostfreien Stahls gemäß einem der vorhergehenden Ansprüche, gekennzeichnet durch: 0,15 % < Stickstoff < 0,2%.
  13. Verwendung eines austenitischen rostfreien Stahls gemäß Anspruch 1 mit der folgenden Zusammensetzung nach Gewicht: 0 , 04 % < Kohlenstoff < 0 , 06 %
    Figure imgb0063
     7 , 5 % ≤ Mangan < 8 , 0 %
    Figure imgb0064
     0 , 4 % < Silizium < 0 , 6 %
    Figure imgb0065
     0 , 002 % < Schwefel < 0 , 004 %
    Figure imgb0066
     0 , 030 % < Phosphor < 0 , 035 %
    Figure imgb0067
     17 , 0 % ≤ Chrom < 17 , 5 %
    Figure imgb0068
     3 , 8 % < Nickel < 4 , 2 %
    Figure imgb0069
     0 , 1 % < Molybd ⁢ a ¨ ⁢ n < 0 , 3 %
    Figure imgb0070
     2 , 0 % ≤ Kupfer < 2 , 5 %
    Figure imgb0071
     0 , 15 % < Stickstoff < 0 , 2 % ,
    Figure imgb0072
    der Rest bestehend aus Eisen und Verunreinigungen.
  14. Verwendung eines austenitischen rostfreien Stahls gemäß Anspruch 1 mit der folgenden Zusammensetzung nach Gewicht:
    Kohlenstoff 0,055 %
    Mangan 7,50 %
    Silizium 0,52 %
    Schwefel 0,003 %
    Phosphor 0,032 %
    Chrom 17,0 %
    Nickel 4,0 %
    Molybdän 0,19 %
    Kupfer 2,0 %
    Stickstoff 0,17 %,
    der Rest bestehend aus Eisen und Verunreinigungen.
  15. Gegenstände enthaltend oder bestehend aus austenitischem rostfreien Stahl gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie ausgewählt sind aus: Drähten für landwirtschaftliche Verwendung, Drähten für die häusliche Verwendung, elektrische Haushaltsanwendungen, Gitter, Gepäckablagen, Fahrradspeichen; Drähten für Wäschetrocknergestelle; Drähten und Schrauben für elektronische Bauteile; Drähten für das Bauwesen, für Maschenwerk und für Haken verwendet auf Schieferdächern; Drähten und Zuganker für industrielle Öfen.
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EP05425070A EP1690957A1 (de) 2005-02-14 2005-02-14 Rostfreier austenitischer Stahl
PCT/EP2006/050923 WO2006084919A1 (en) 2005-02-14 2006-02-14 Austenitic stainless steel
EP06708260A EP1851351B1 (de) 2005-02-14 2006-02-14 Austenitischer nichtrostender stahl

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ES (1) ES2390678T3 (de)
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WO2006084919A1 (en) 2006-08-17
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US20080206088A1 (en) 2008-08-28
EP1690957A1 (de) 2006-08-16
ES2390678T3 (es) 2012-11-15
CA2597750A1 (en) 2006-08-17
AU2006212194A1 (en) 2006-08-17
EP1851351A1 (de) 2007-11-07

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