EP2240619B1 - Acier résistant au fluage - Google Patents

Acier résistant au fluage Download PDF

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Publication number
EP2240619B1
EP2240619B1 EP08717748.1A EP08717748A EP2240619B1 EP 2240619 B1 EP2240619 B1 EP 2240619B1 EP 08717748 A EP08717748 A EP 08717748A EP 2240619 B1 EP2240619 B1 EP 2240619B1
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EP
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Prior art keywords
creep
resistant steel
steel according
weight
steel
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Not-in-force
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EP08717748.1A
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German (de)
English (en)
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EP2240619A1 (fr
Inventor
Mohamed Nazmy
Markus Staubli
Andreas KÜNZLER
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Ansaldo Energia Switzerland AG
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General Electric Technology GmbH
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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
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron

Definitions

  • the invention relates to steels based on 9-12% chromium, which are used for rotors in the power plant sector. It concerns the choice and the proportionate tuning of special alloying elements which allow the setting of an exceptionally good creep resistance at temperatures of 550 ° C and above in this material.
  • the steel according to the invention should also have a high toughness after long-term aging, so that it can be used both in gas and steam turbines.
  • Maragingitic-hardening steels based on 9-12% chromium are widely used materials in power plant technology. They were developed for use in steam power plants at operating temperatures above 600 ° C and steam pressures above 250 bar to increase the efficiency of power plants. Under these operating conditions, the creep resistance and the oxidation resistance of the material play a special role.
  • chromium in the abovementioned range not only provides good resistance to atmospheric corrosion but also complete through-hardenability of thick-walled forgings, for example as monobloc rotors or as rotor disks in gas and steam turbines.
  • Proven alloys of this type usually contain about 0.08 to 0.2% carbon, which in solution allows the setting of a hard martensitic structure.
  • a good combination of heat resistance and ductility of martensitic steels is made possible by a tempering treatment in which the precipitation of carbon in the form of carbides with simultaneous recovery of the dislocation substructure forms a particle-stabilized subgrain structure.
  • the tempering behavior and the resulting properties can be effectively influenced by the choice and proportionate tuning of specific carbide formers such as Mo, W, V, Nb and Ta.
  • German steel X20CrMoV12.1 known under DIN.
  • the contents of Cr, Mo, W were optimized taking into account N, Nb and / or B to improve creep and creep rupture strengths for 600 ° C applications.
  • the carbides such as M 23 C 6 .
  • the Ni contents were limited to values of less than 0.25% in these steels.
  • the fracture toughness values are disadvantageous, which does not play a major role in steam turbine applications and can therefore be neglected, but must be avoided in gas turbine applications.
  • EP 0 931 845 A1 a nickel-containing 12% chromium steel similar in structure to the German steel X12CrNiMo12, in which reduces the element molybdenum compared to the known steel X12 CrNiMo12, but an increased content of tungsten was alloyed.
  • DE 198 32 430 A1 is a further optimization of the X12CrNiMo12 similar steel with the name M152 disclosed in which by the addition of rare earth elements, the embrittlement tendency in the temperature range between 425 and 500 ° C is limited.
  • EP 0 866 145 A2 describes a new class of martensitic chromium steels with nitrogen contents in the range of 0.12 to 0.25% and in EP 1 158 067 A1 with nitrogen contents of 0.12 to 0.18%, wherein the weight ratio V / N is in the range between 3.5 and 4.2.
  • the entire structure of the structure is controlled by the formation of special nitrides, in particular vanadium nitrides, which can be distributed in a variety of ways by forging, austenitizing, controlled cooling or annealing. While strength is achieved through the nitriding's curing effect, the aim is to achieve high ductility through the distribution and morphology of the nitrides, but above all by limiting grain coarsening during forging and during solution heat treatment.
  • US2002020473 discloses a high-chromium, heat-resistant, ferritic steel having the following composition (in% by weight): 0.02 to 0.15% C, 0.05 to 1.5% Mn, ⁇ 0.03% P, ⁇ 0.015% S, 8 to 13% Cr, 1.5 to 4% W, 2 to 6% Co, 0.1 to 0.5% V, 0.01 to 0.15% Ta, 0.01 to 0.15% Nb, 0.001 to 0.2% Nd, ⁇ 0.02% N, 0.0005 to 0.02% B, 0.001 to 0.05 % Al, at least one of Ca ( ⁇ 0.02%), Y ( ⁇ 0.2%), La ( ⁇ 0.2%) and Hf ( ⁇ 0.2%), remainder Fe.
  • composition in% by weight
  • a heat resistant steel with good toughness properties is known for use as a turbine rotor, which has the following chemical composition (% by weight): 0.05-0.30 C, 0.20 or less Si, 0-1.0 Mn, 8-14 Cr, 0.5-3.0 Mo, 0.10-0.50 V, 1.5-5.0 Ni, 0.01-0.5 Nb, 0.01-0.08 N, 0.001-0.020 B, balance iron and unavoidable impurities. Boron microalloying results in precipitates at the grain boundaries and increases the time stability of the carbonitrides at high temperatures, but higher levels of B reduce the toughness of the steel. Disadvantages of this proposed composition are also the relatively high permitted Si values of 0.2%. Although Si serves advantageously as a deoxidizer at the time of melting, parts of it remain as oxides in the steel, which is disadvantageous in a reduced toughness.
  • the invention has for its object to provide a 9-12% Cr steel, which is characterized over the prior art by increased creep strength at temperatures of 550 ° C and above and which improved resistance to embrittlement in long-term aging and a has relatively high toughness, so that it can be used especially in gas turbine, but also in steam turbine power plants. It should preferably find application for rotors of turbomachinery, so that the efficiency and the output can be increased over the known prior art.
  • the core of the invention is a steel having the following chemical composition (in% by weight): 0.08 to 0.16 C, 9.0 to 12.0 Cr, 0.1 to 0.5 Mn, 2.3 to 3 Ni, 1.5 to 2.0 Mo, 0.1 to 0.4 V, 0.01 to 0.06 Nb, 0.02 to 0.08 N, 0.001 to 2 Ta, 0.001 to 0.5 La, 0.0001 to 1 Pd, 0.004 to 0.012 B, maximum 0.005 P, maximum 0.005 S, maximum 0.05 Si, maximum 0.005 Sn, balance iron and unavoidable impurities ,
  • the steel according to the invention particularly preferably has the following chemical composition (in% by weight): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.007 B, 0.005 P, 0.005 S, 0.05 Si, 0.005 Sn, balance iron and unavoidable impurities.
  • the advantage of the invention is that the inventive alloy compared to the known from the prior art alloys of similar composition, but without B addition or without La and Pd addition, with the same heat treatment improved creep properties at temperatures of 550 ° C and above, while also good toughness properties (elongation, impact work) and improved resistance to embrittlement during long-term aging can be achieved.
  • a starting structure which is characterized by a tough matrix and the presence of heat-resistant nitrides, borides and carbides.
  • the toughness of the base matrix is adjusted by the presence of substitution elements, preferably nickel.
  • substitution elements preferably nickel.
  • the contents of these substitution elements are determined to provide optimal unfolding of both martensite hardening and particle hardening by precipitation of special nitrides, e.g. As vanadium nitrides or niobium nitrides, to set the highest heat resistance possible.
  • both hardening mechanisms lower the ductility. Characteristically, a minimum ductility is observed in the area of secondary hardening. This minimum ductility need not be caused exclusively by the actual precipitation hardening mechanism. A certain embrittlement contribution may also be provided by segregation of impurities to the grain boundaries or possibly also by near-order adjustments of dissolved alloy atoms.
  • nickel contents above 2% by weight are expected to lower the Ac1 temperature (which is the temperature at which ferrite begins to convert to austenite during heating) to temperatures below 700 ° C. So if the strength is increased by lowering the tempering temperature below 700 ° C, then in the presence of increased nickel contents during tempering with a partial conversion of ferrite into austenite can be expected. This is associated with a certain ductility-promoting grain regeneration. However, it should be noted that the carbide precipitation above the Ac1 temperature is only incomplete, since the solubility of the austenite-stabilizing element carbon in austenite is greater than in the ferrite.
  • the austenite which forms is not sufficiently stabilized, so that a larger volume fraction of the reformed austenite undergoes further martensitic transformation in the post-anneal cooling.
  • a certain ductility contribution of nickel can come into solid solution as a substitution element. This can be explained electron-theoretically in such a way that the element nickel feeds additional, free electrons into the iron grid and thereby makes the iron alloys even more "metallic".
  • Manganese is on the left side next to the element iron in the periodic system of elements. It is an electron-poorer element, so its action in solid solution should be distinctly different from that of nickel. Nonetheless, it is an austenite stabilizing element which greatly lowers the Ac1 temperature, but leaves no particularly positive but rather unfavorable effect on ductility.
  • manganese is understood to be an impurity element which promotes temper embrittlement substantially. Therefore, the content of manganese is usually limited to very small amounts.
  • a weight proportion of 9-12% chromium allows good through-hardenability of thick-walled components and ensures sufficient oxidation resistance up to a temperature of 550 ° C.
  • a proportion by weight of less than 9% impairs the through-hardenability.
  • Contents above 12% lead to the accelerated formation of hexagonal chromium nitrides during the tempering process, which, in addition to nitrogen, also cures vanadium, thus reducing the effectiveness of vanadium nitride curing.
  • the optimum chromium content is 10.5 to 11.5%.
  • the range to be specified should take into account the metallurgical possibilities in the range between 0.1 and 0.5% by weight, preferably between 0.1 and 0.25%, in particular at 0.2% for manganese and at max. 0.05% by weight for silicon.
  • Nickel is used as an austenite stabilizing element to suppress delta ferrite. In addition, it is said to improve ductility as a dissolved element in the ferritic matrix.
  • Nickel contents of 2.3 to about 3% by weight make sense. Nickel contents above 4% by weight increase the austenite stability such that after solution heat treatment and tempering an increased proportion of retained austenite or tempering austenite can be present in the tempered martensite.
  • the nickel content is preferably 2.3 to 2.8, in particular 2.5% by weight.
  • Molybdenum improves creep strength by solid solution hardening as a partially dissolved element and precipitation hardening during a long-term stress.
  • An excessively high proportion of this element leads to embrittlement during long-term aging, which is due to the precipitation and coarsening of Laves phase (W, Mo) and Sigma phase (Mo).
  • the range for Mo is 1.5 to 2% by weight, preferably 1.6 to 1.8% by weight, in particular 1.7% by weight.
  • V / N ratio sometimes also increases the stability of the vanadium nitride over the chromium nitride.
  • the specific content of nitrogen and vanadium nitrides depends on the optimum volume fraction of the vanadium nitrides, which are to remain as insoluble primary nitrides during the solution annealing. The greater the total content of vanadium and nitrogen, the greater is the proportion of vanadium nitrides, which no longer goes into solution and the greater the grain refining effect.
  • the preferred content of nitrogen is in the range from 0.02 to 0.08% by weight, preferably 0.025 to 0.055% by weight, particularly preferably 0.04% by weight N, and that of vanadium is in the range between 0.1 and 0.4% by weight. , preferably 0.2 to 0.3% by weight, and especially at 0.25% by weight.
  • Niobium is a strong nitride former that aids the grain refining effect. In order to keep the volume fraction of the primary nitrides small, their total proportion must be limited to 0.1% by weight. Niobium dissolves in vanadium nitride in small amounts and can thus improve the stability of the vanadium nitride. Niobium is added in the range between 0.01 and 0.06% by weight, preferably 0.02 to 0.04% by weight, and in particular at 0.03% by weight.
  • Ta influences the creep resistance positively. Addition of 0.001 to 2% by weight of Ta has the effect, on the one hand, that due to the greater tendency of tantalum to form carbides as chromium, the precipitation of undesired chromium carbides at the grain boundaries and, on the other hand, the undesirable depletion of the mixed crystal in chromium are reduced.
  • the preferred range for Ta is 0.005 to 0.1% by weight, in particular a Ta content of 0.01% by weight should be set.
  • the carbon content should therefore be limited upwards to 0.16% by weight.
  • Another disadvantage is the fact that carbon increases the hardening during welding.
  • the preferred carbon content is in the range between 0.10 and 0.14% by weight, preferably 0.12% by weight.
  • the boron content should be limited to 40 to 120 ppm.
  • La 2 S 3 Lanthanum binds the sulfur in the steel through the formation of lanthanum sulfide La 2 S 3 .
  • La 2 S 3 is much more stable than MnS 2 . It has a melting point of> 2100 ° C, while MnS 2 decomposes at high temperatures to release S.
  • stable sulfide formers in steel such as La are much better than Mn.
  • the grain size is advantageously reduced by the micro-alloying with La, which also has an advantageous effect if the material is tested non-destructively by ultrasonic methods.
  • a grain size ASTM 6 was determined by the applicant, whereas for a 12% Cr steel microblasted with B and La, the grain size at the same austenitizing temperature only remains ASTM 7 was.
  • the weldability of the 12% Cr steels is improved.
  • the content of La should be 0.001 to 0.5% by weight, preferably 0.01 to 0.1% by weight, especially 0.05% by weight.
  • Pd forms an ordered Fe-Pd L1 0 intermetallic phase with the iron of the steel, the ⁇ "phase.
  • This stable ⁇ " phase increases the high temperature creep strength by stabilizing grain boundary precipitates such as M 23 C 6 and acts thus have a positive effect on the creep properties.
  • palladium has the disadvantage of high costs.
  • the Pd content of the proposed steel should be in the range of 0.0001 to 1, preferably 0.0005 to 0.01 wt%, with a content of 0.001 wt% being particularly suitable.
  • the investigated inventive alloy L2 had the following chemical composition (in% by weight): 0.12 C, 11.5 Cr, 0.2 Mn, 2.5 Ni, 1.7 Mo, 0.25 V, 0.03 Nb, 0.04 N, 0.01 Ta, 0.05 La, 0.001 Pd, 0.0070 B, 0.05 Si, 0.005 P, 0.005 S, 0.005 Sn, balance iron and unavoidable impurities.
  • the comparative alloy VL1 used was a prior art commercial steel of the type X12CrNiMoV11-2-2 having the following chemical composition (in% by weight): 0.10-0.14 C, 11.0-12.0 Cr, 0.25 Mn, 2.0-2.6 Ni, 1.3-1.8 Mo, 0.2-0.35 V, 0.02-0.05 N, 0.15 Si, 0.026 P and 0.015 S.
  • Fig. 1 shows the creep properties for the two alloys VL1 and L2, ie the creep rupture strength and the 1% yield strength at 550 ° C.
  • the mean times to break and to reach a 1% elongation are thus shown, depending on the voltage at 550 ° C.
  • the alloy L2 according to the invention advantageously requires significantly longer times when the same voltage is applied until a 1% elongation is reached than the comparison alloy VL1. In the time to break (creep strength), this difference is even more evident, since the in Fig. 1 Alloy L2 samples with an arrow have not yet broken. In the case of the alloy L2 according to the invention, a clear shift to longer is here Recognize times, which is of particular advantage for the planned use as a gas turbine or steam turbine rotor.
  • Fig. 3 the fracture toughnesses and impact energies at room temperature are compared for the two investigated alloys in the above-described heat treatment state (without aging). Despite the significantly better creep properties at high temperatures (see Fig. 1 and 2 ), the toughness of the alloy according to the invention scarcely deteriorates.
  • the alloy according to the invention is distinguished on the one hand by a very good creep resistance at temperatures of 450 ° C., preferably 550 ° C., and above, and is thus superior to the conventional 12% Cr steels.
  • This is mainly due to the influence of boron, tantalum and palladium, which are alloyed in the specified range. Boron, tantalum and palladium stabilize the M 23 C 6 precipitates, which play a significant strengthening role during creep, with Pd additionally forming a stable intermetallic phase with the iron, which also contributes to increasing creep resistance.
  • the dislocation density is maintained until breakage, thus improving creep strength of the steel.
  • a similar effect on increasing creep strength is found in Ta and Pd.
  • the alloy of the present invention has improved resistance to embrittlement upon long-term aging and comparatively high toughness. This is due to the addition of lanthanum in the specified range, because both the grain size is reduced as well as stable lanthanum sulfide La 2 S 3 are formed.
  • the inventive alloy is thus particularly advantageous for rotors in gas and steam turbines, which are exposed to high inlet temperatures of about 550 ° C, can be used advantageously.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Heat Treatment Of Articles (AREA)

Claims (27)

  1. Acier résistant au fluage, caractérisé par la composition chimique suivante (indications en % en poids) : 0,08 à 0,16 C, 9,0 à 12,0 Cr, 0,1 à 0,5 Mn, 2,3 à 3 Ni, 1,5 à 2,0 Mo, 0,1 à 0,4 V, 0,01 à 0,06 Nb, 0,02 à 0,08 N, 0,001 à 2 Ta, 0,001 à 0,5 La, 0,0001 à 1 Pd, 0,004 à 0,012 B, maximum 0,005 P, maximum 0,005 S, maximum 0,05 Si, maximum 0,005 Sn, le reste étant constitué de fer et des impuretés inévitables.
  2. Acier résistant au fluage selon la revendication 1, caractérisé par 2,3 à 2,8 % Ni.
  3. Acier résistant au fluage selon la revendication 2, caractérisé par 2,5 % Ni.
  4. Acier résistant au fluage selon la revendication 1, caractérisé par 10 à 12 % Cr.
  5. Acier résistant au fluage selon la revendication 4, caractérisé par 10,5 à 11,5 % Cr.
  6. Acier résistant au fluage selon la revendication 1, caractérisé par 0,10 à 0,14 % C.
  7. Acier résistant au fluage selon la revendication 6, caractérisé par 0,12 % C.
  8. Résistant au fluage selon la revendication 1, caractérisé par 0,10 à 0,25 % Mn.
  9. Acier résistant au fluage selon la revendication 8, caractérisé par 0,20 % Mn.
  10. Acier résistant au fluage selon la revendication 1, caractérisé par 1,6 à 1,8 % Mo.
  11. Acier résistant au fluage selon la revendication 10, caractérisé par 1,7 % Mo.
  12. Acier résistant au fluage selon la revendication 1, caractérisé par 0,2 à 0,3 % V.
  13. Acier résistant au fluage selon la revendication 12, caractérisé par 0,25 % V.
  14. Acier résistant au fluage selon la revendication 1, caractérisé par 0,02 à 0,04 % Nb.
  15. Acier résistant au fluage selon la revendication 14, caractérisé par 0,03 % Nb.
  16. Acier résistant au fluage selon la revendication 1, caractérisé par 0,025 à 0,055 % N.
  17. Acier résistant au fluage selon la revendication 16, caractérisé par 0,04 % N.
  18. Acier résistant au fluage selon la revendication 1, caractérisé par 0,005 à 0,012 % B.
  19. Acier résistant au fluage selon la revendication 18, caractérisé par 0,007 % B.
  20. Acier résistant au fluage selon la revendication 1, caractérisé par 0,005 à 0,1 % Ta.
  21. Acier résistant au fluage selon la revendication 20, caractérisé par 0,01 % Ta.
  22. Acier résistant au fluage selon la revendication 1, caractérisé par 0,01 à 0,1 % La.
  23. Acier résistant au fluage selon la revendication 22, caractérisé par 0,05 % La.
  24. Acier résistant au fluage selon la revendication 1, caractérisé par 0,0001 à 1 % Pd.
  25. Acier résistant au fluage selon la revendication 24, caractérisé par 0,0005 à 0,01 % Pd.
  26. Acier résistant au fluage selon la revendication 25, caractérisé par 0,001 % Pd.
  27. Acier résistant au fluage selon l'une des revendications 1 à 26, caractérisé en ce qu'il est utilisé pour des rotors de turbomachines thermiques.
EP08717748.1A 2007-03-29 2008-03-13 Acier résistant au fluage Not-in-force EP2240619B1 (fr)

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CH5062007 2007-03-29
PCT/EP2008/053004 WO2008119638A1 (fr) 2007-03-29 2008-03-13 Acier résistant au fluage

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EP2240619A1 EP2240619A1 (fr) 2010-10-20
EP2240619B1 true EP2240619B1 (fr) 2017-01-25

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US (1) US8147748B2 (fr)
EP (1) EP2240619B1 (fr)
JP (1) JP5256279B2 (fr)
CN (1) CN101743336B (fr)
WO (1) WO2008119638A1 (fr)

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CN101743336B (zh) 2007-03-29 2011-12-14 阿尔斯托姆科技有限公司 抗蠕变钢
CH700482A1 (de) * 2009-02-19 2010-08-31 Alstom Technology Ltd Schweisszusatzwerkstoff.
JP5578893B2 (ja) * 2010-03-12 2014-08-27 株式会社日立製作所 蒸気タービンの摺動部を有する部材
CH704427A1 (de) * 2011-01-20 2012-07-31 Alstom Technology Ltd Schweisszusatzwerkstoff.
JP5608280B1 (ja) * 2013-10-21 2014-10-15 大同工業株式会社 チェーン用軸受部、その製造方法、及びそれを用いたチェーン

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JP2010522825A (ja) 2010-07-08
US20100040502A1 (en) 2010-02-18
CN101743336B (zh) 2011-12-14
US8147748B2 (en) 2012-04-03
EP2240619A1 (fr) 2010-10-20
CN101743336A (zh) 2010-06-16
JP5256279B2 (ja) 2013-08-07

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