CN100355923C - Nickel base heat resistant cast alloy and turbine wheels made thereof - Google Patents
Nickel base heat resistant cast alloy and turbine wheels made thereof Download PDFInfo
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- CN100355923C CN100355923C CNB2004100714741A CN200410071474A CN100355923C CN 100355923 C CN100355923 C CN 100355923C CN B2004100714741 A CNB2004100714741 A CN B2004100714741A CN 200410071474 A CN200410071474 A CN 200410071474A CN 100355923 C CN100355923 C CN 100355923C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
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- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
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Abstract
Disclosed is a nickel-base super heat resistant cast alloy, from which turbine wheels of automobile engines can be manufacture by casting. The alloy consists essentially of, by weight %, C: 0.02-0.50%, Si: up to 1.0%, Mn: up to 1.0%, Cr: 4.0-10.0%, Al: 2.0-8.0%, Co: up to 15.0%, W: 8.0-16.0%, Ta: 2.0-8.0%, Ti: up to 3.0%, Zr: 0.001-0.200% and B: 0.005-0.300% and the balance of Ni and inevitable impurities, provided that, [%Al]+[%Ti]+[%Ta], by atomic %, amounts to 12.0-15.5%, that it contains gamma/gamma'-eutectoid of, by area percentage, 1-15%, that it contains carbides of, by area percentage, 1-10%, and that the 'M-value' determined by the alloy composition is in the range of 93-98. The turbine wheels withstand temperature increase of exhaust gas.
Description
Technical field
The present invention relates to a kind of nickel base heat resistant cast alloy and the motor car engine turbine wheel of alloy preparation thus.It is basic identical but intensity is higher than the turbine wheel of conventional turbine machine impeller to the invention provides cost.
Background technology
Because it is motor car engine belongs to the parts of direct contact high-temp waste gas with turbine wheel, therefore, very strict to the requirement of its resistance toheat and enough hot strength.Up to now, INCONEL 713C (hereinafter being abbreviated as " 713C ") has been used as the turbine wheel material of way-train.The existing in actual applications long history of this alloy (Japanese patent gazette Sho.42[1967]-11915).On the other hand, the intensity Mar-M247 (hereinafter being abbreviated as " MM-247 ") that is higher than 713C has been used as the material of the turbine wheel of work (such as the turbine wheel of the engine of rally car) down of mal-condition more.This alloy also has been widely known by the people and has been used for many years (Japanese patent gazette Sho.47[1972]-13204).
But people's prediction is owing to the raising of bus engine output rating, and the temperature of waste gas will raise greatly in the near future, and 713C then because its hot strength is not enough, possibly can't satisfy this demand.On the other hand, MM-247 contains a kind of alloying constituent hafnium (hafnium) of costliness, so material cost is too high.And, do not produce the space in the foundry goods in order to make, adopt HIP technology when making impeller usually, therefore, production cost is higher.
For many years, in order to address these problems, people make great efforts untiringly, have proposed the turbine wheel by nickel base heat resistant cast alloy preparation, and the creep-rupture strength of this alloy is higher than 713C (Japanese patent gazette Hei.11[1998]-131162 and 2000-169924).Yet these materials comprise the alloy composition that contains niobium (niobium) (the former contains 0.5-3.5%, then all contain 6.0-8.0%), and this has just brought new problem: the easy segregation of niobium.And these alloys contain molybdenum (both is 1.0-5.0%), thereby high-temperature oxidation is not very high.So, save cost and the angle that improves advantage from balance, can't say to have made and make us well-content low-cost nickel base heat resistant cast alloy.
Summary of the invention
The purpose of this invention is to provide a kind of nickel base heat resistant cast alloy as motor car engine turbine wheel material, it has higher high temperature strength to satisfy the demand of spent air temperture rising trend, as for material cost, although it is high slightly, but substantially the same, and its resistance toheat and hot strength and MM-247 are about the same.The turbine wheel that material preparation thus is provided also is a purpose of the present invention.
Nickel base heat resistant cast alloy of the present invention is made up of following substantially: in weight %, C:0.02-0.50%, Si: be up to 1.0%, Mn: be up to 1.0%, Cr:4.0-10.0%, Al:2.0-8.0%, Co: be up to 15.0%, W:8.0-16.0%, Ta:2.0-8.0%, Ti: be up to 3.0%, Zr:0.001-0.200% and B:0.005-0300%, surplus is nickel and unavoidable impurities, condition is [%Al]+[%Ti]+[%Ta], in atom %, total amount is 12.0-15.5%, and contains γ/γ ' eutectoid of 1-15% (area percent), in area percent, the carbide that contains 1-10%, and with " the M-value " of following formula (wherein % is atom %) definition in the scope of 93-98:
M=0.717[%Ni]+1.142[%Cr]+2.271[%Ti]+1.9[%Al]+2.117[%Nb]+1.55[%Mo]+0.777[%Co]+3.02[%Hf]+2.224[%Ta]+1.655[%W]+2.994[%Zr]
DESCRIPTION OF THE PREFERRED
Nickel base heat resistant cast alloy of the present invention can comprise, and except the above-mentioned basic alloy composition of mentioning, is selected from Mg: be up to 0.01%, Ca: be up to 0.01%, and REM: be up at least a in 0.1%.
Fe, Si, Mn, P and the S of the major impurity that may exist in the nickel base heat resistant cast alloy of the present invention for being introduced by raw material according to different situations, also can comprise Cu and Mo.Preferably adjust foreign matter content respectively to its following maximum value: Fe: be up to 5.0%, Mo:1.0%, Cu:03%, P:0.03%, S:0.03% and V:1.0%.
The effect of alloying constituent and as above limit the reason of alloy compositions will be below and restriction above-mentioned [%Al]+[%Ti]+[%Ta], the area percent of γ/γ ' eutectoid, the importance of the area percent of carbide and " M-value " makes an explanation together.
C:0.02-0.50%, preferred 0.05-030%, more preferably 0.05-0.20%.
If have a kind of element to be selected from i, Zr and Hf or be selected from Nb, Ta, V, carbon can form the reinforcement that one or more carbide promote crystal boundary by combining with it.Being lower than 0.02% carbon content may not have enough effects, is higher than 0.50% content and then can causes the formation of excessive carbide, thereby cause the reduction of corrosion resistance nature and extension performance (ductility).Preferred C content is in the scope of 0.05-0.30%, and more preferably scope is 0.02-0.20%.
Si: be up to 1.0%.
Silicon is often used as reductor when alloy melting and refining.Though, may not can causing problem as the effectively Si of reductor on a small quantity, a large amount of addings then can reduce the ductility of alloy.Therefore, be set at higher limit with 1.0%.Preferred Si content is up to 0.5%.
Mn: be up to 1.0%.
Similar with silicon, manganese also adds as reductor.May not can cause problem as the effectively manganese of reductor on a small quantity, still, a large amount of addings will reduce the intensity and the ductility of alloy.Therefore setting its higher limit is 1.0%.
Cr:4.0-10.0%。
Chromium is to improve the most important element of alloy corrosion resistance energy.By solid solution in matrix phase, it also helps to improve intensity.Be lower than 4.0% almost not effect of add-on, surpass 10.0% intensity and the ductility that then can reduce after phase stability and turbine wheel at high temperature work long hours.The preferable range of Cr content is 6.0-10.0%.
Al:2.0-8.0%。
Aluminium is the important element that forms γ '-phase, and helps to improve the high temperature corrosion-resisting performance.Its content is lower than at 2.0% o'clock, and these effects may be less.On the other hand, add-on surpasses 8.0% can cause a large amount of low depositions of molten γ '-phase altogether in castingprocesses, the result, and creep-rupture strength will reduce.The preferable range of Al content is 4.5-5.5%.
Co: be up to 15.0%.
Cobalt is by solution strengthening γ-phase.It also is dissolved in γ '-phase, thereby can effectively improve alloy strength and strengthen γ '-phase.Co increases the deposition of γ-phase.Yet because Co is a kind of expensive material, from the cost angle, a large amount of addings is disadvantageous.Suggestion selects to be up to 15.0% add-on.In order to ensure having enough high-temperature behaviors when 900 ℃ or the higher temperature, wish to add 5.0% or more Co.
W:8.0-16.0%
Tungsten goes far towards the solution strengthening of γ-phase and the raising of intensity, and being lower than 8.0% amount can not fully work, and then can reduce phase stability but be higher than 16.0% amount.The reduction of phase stability can cause using after the long period deposition of α-Cr in the alloy, and destroys the intensity of turbine wheel.Preferred its add-on scope is 10.0-14.0%.
Ta:2.0-8.0%。
Tantalum not only combines with carbon and forms carbide, and is dissolved in γ '-phase and makes its reinforcement.It is less that its content is lower than effect in 2.0% o'clock.Because tantalum is the same with Hf to be expensive material, so from the cost viewpoint, wish that its consumption is the least possible.Therefore the capping value is 8.0%.
Ti: be up to 3.0%.
γ '-mutually, this phase can effectively improve the intensity of alloy to titanium with Ni reaction formation.Ti also has the effect that replaces Al promotion γ '-phase solution strengthening, therefore, can also improve the intensity of alloy.Yet, cause η phase (Ni easily above 3.0% Ti add-on
3Ti) deposition, thus be unfavorable for the hot strength and the ductility of alloy.Preferred add-on is 2.0% or lower.
Zr:0.001-0.200%。
Zirconium has the effect that combines the formation carbide and strengthen at grain boundary segregation with carbon simultaneously concurrently.Even these effects also can be observed when very little add-on (as 0.001%).Owing to add the reduction that affiliation causes ductility in a large number, so its higher limit is set at 0.200%.Optimum add-on may be in being up to 0.1% scope.
B:0.005-0.300%, preferred 0.050-0.200%.
The effect that adds B is to suppress the reduction of the formation of η phase with prevention hot strength and ductility, and, can also improve creep rupture strength at high temperatures.B also can form boride with Cr and some other element simultaneously.Because the fusing point of boride is low, the wider range of solid-liquid coexistence, so castability will improve before the alloy.In order to realize these effects, be necessary to add 0.005% or more an amount of B.Yet, add the reduction that excessive meeting causes alloy strength and ductility.So the higher limit of add-on is set at 0.300%.In the scope of 0.050-0.200%, can obtain the well balanced of castability and intensity-toughness (resilience).
One or more are selected from Mg: be up to 0.01%, Ca: be up to 0.01% and REM: be up to 0.1%.
Magnesium and calcium are all strengthened at grain boundary segregation.REM has same effect.Any-kind or multiple described element all be unsuitable for a large amount of addings because this can cause the reduction of alloy strength and ductility.So the higher limit of add-on is set at Mg and Ca0.01%, REM0.1%.
Adjust extremely following higher limit of foreign matter content:
Fe:5.0%, Mo:1.0%, Cu:0.3%, P:0.03%, S:0.03% and V:1.0%.
Use under the situation of scrap iron (a kind of cheap raw material) preparing in order to reduce production costs, various impurity will be introduced the product alloy.The element of most possibly sneaking into is Fe, and it is to room temperature-and following intensity of high temperature, corrosion-resistant. performance all is harmful to.The Fe content ultimate value that allows is 5.0%, preferred 3.0% or lower.Phosphorus can cause intensity to reduce at grain boundary segregation, thereby not wishing has higher P content.Yet it is inevitable still having a certain amount of existence in the alloy.The P ultimate value that allows is 0.03%.Sulphur is the same with P, also is the element that reduces intensity, and S content is preferably limited to 0.03% or lower.Molybdenum, though it is dissolved in alloy substrate and helps to improve intensity mutually, its high-content can destroy high-temperature oxidation resistance, therefore, Mo content should be to be up to 1.0%.Cu also is the reason that intensity reduces, thereby, do not wish that Cu exists in a large number yet, the higher limit of permission is 1.0%, preferred 0.3% or lower.The long-pending harm of bringing is the reduction of hot strength, and V content should be limited in less than higher limit 1.0%.
[%Al]+[%Ti]+[%Ta]:12.0-15.5at%
In order to ensure alloy enough intensity and workability, must satisfy this condition.Exceed these scopes and will have following harm.If total amount is lower than 12.0% (lower value), then can not obtain satisfied intensity, if total amount is higher than 15.5% (higher limit), crackle then appears in the foundry goods easily.
The area percent of γ/γ ' eutectoid: 1-15%.
For guaranteeing the workability of alloy, particularly castability, it is necessary keeping lower value 1%.If this area percent is lower than 1%, will produce the space in the final stage of casting, the reliability of product wheel will reduce.On the other hand, if area percent is higher than 15%, eutectoid just may become the starting point of crackle.
The area percent of carbide: 1-10%, preferred 1-5%.
An amount of being formed with of carbide is beneficial to the reinforcement crystal boundary, and the hot strength when improving 1000 ℃ or higher temperature.When the area percent of carbide is 1% or when higher, can obtain this effect.When its area percent surpasses 10%, then there is not this effect.The area percent scope of preferred carbide is 1-5%.
M-value: 93-98.
M value by the following formula definition is to weigh a standard of phase stability.M value in the 93-98 scope can be guaranteed the weather resistance of product turbine wheel.Because alloy of the present invention is used for auto parts, so higher M value helps making part to have longer weather resistance.Yet, when the M value surpasses 98, just being easy to generate harmful phase (as the σ phase) after the use long period, its weather resistance will reduce.
Though, nickel base heat resistant cast alloy of the present invention does not contain the expensive Hf that but can effectively strengthen alloy, but its creep-rupture strength is better than being widely used as most the 713C alloy of turbine wheel material greatly, and the creep-rupture strength of alloy of the present invention is identical with the MM-247 that contains Hf basically.Based on alloying constituent, material cost may be higher slightly than 713C, but still be lower than MM-247.Because alloy of the present invention has higher castability, does not need to adopt HIP technology, therefore, the production cost of turbine wheel is may not can very high.Therefore, the invention enables with low price provide a kind of can satisfy predicted that will the raise turbine wheel of demand of spent air temperture in the near future becomes possibility.
Embodiment
Preparation has the Refractoloy of alloying constituent shown in table 1 (work embodiment) and table 2 (comparative examples) and it is cast as the ingot casting of heavy 50kg.Comparative examples No.A is conventional 713C alloy, and No.B is corresponding M M-247.The performance of these alloys is shown in table 3 (work embodiment) and table 4 (comparative examples) as [%Al]+[%Ti]+[%Ta].By the mechanical workout sampling, under the condition of 1000 ℃ and 180MPa, it is carried out the creep rupture test then from the ingot casting.The creep property of measuring is shown in table 3 and table 4.
About the alloy of work embodiment No.8 and No.9, the area percent of γ/γ ' eutectoid is adjusted into 3.2% (No.8 and No.9) and 18.5 (No.8A and No.9A) by the rate of cooling of regulating after the casting.Also under identical condition, 1000 ℃ and 180MPa carry out the creep test to this sample.The results are shown in table 5.Comparing for convenience, is that data under 7.1% situation have been listed as once again in table 5 with area percent.
Table 1 alloying constituent (work embodiment)
Numbering | C | Si | Mn | Cr | Co | W | Ta | Al | Ti | Zr | B | Other |
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 | 0.15 0.13 0.16 0.11 0.13 0.12 0.14 0.12 0.11 0.05 0.18 0.14 0.13 0.12 0.04 0.10 0.11 0.13 0.14 0.14 | 0.06 0.11 0.08 0.07 0.12 0.42 0.14 0.08 0.07 0.13 0.12 0.12 0.10 0.13 0.12 0.14 0.11 0.09 0.10 0.12 | 0.08 0.07 0.06 0.06 0.04 0.06 0.39 0.08 0.07 0.06 0.08 0.09 0.10 0.06 0.05 0.08 0.09 0.12 0.11 0.09 | 8.1 4.3 5.9 7.4 9.0 7.9 7.3 6.2 6.3 8.2 9.2 7.3 8.2 9.3 8.2 8.2 8.3 8.2 8.4 7.3 | 11.6 9.1 - 12.2 10.9 9.2 10.0 13.6 12.8 10.4 11.4 9.1 11.2 10.9 10.1 10.1 10.6 10.1 10.9 9.1 | 11.9 10.3 13.1 8.3 14.2 11.1 13.2 11.2 10.9 123 13.0 13.0 9.3 12.2 12.1 11.6 12.1 12.2 12.4 13.0 | 4.9 5.1 4.5 4.7 2.2 7.6 5.1 3.2 7.9 4.6 4.5 4.8 4.6 4.7 4.7 4.3 4.6 4.6 4.3 4.8 | 5.2 5.0 5.2 5.3 5.6 5.1 4.1 6.8 2.1 5.3 5.2 4.9 5.1 5.4 5.3 5.2 5.3 5.3 5.2 4.9 | 1.1 1.0 1.4 1.3 1.2 0.9 2.6 0.4 2.9 0.9 1.0 1.4 0.9 1.1 1.2 0.9 1.1 1.0 0.9 1.4 | 0.05 0.04 0.05 0.04 0.05 0.04 0.05 0.03 0.04 0.03 0.05 0.01 0.18 0.04 0.05 0.04 0.05 0.05 0.05 0.01 | 0.015 0.015 0.013 0.020 0.018 0.016 0.015 0.011 0.013 0.013 0.014 0.015 0.012 0.006 0.14 0.003 0.002 0.056 0.260 0.058 | - - - - - - - - - - - - - - - Mg0.005 Ca0.006 - - - |
Table 2 alloying constituent (comparative examples)
Numbering | C | Si | Mn | Cr | Co | W | Ta | Al | Ti | Zr | B | Other |
A B C D E F | 0.15 0.12 0.19 0.11 0.12 0.10 | 0.12 0.12 0.11 0.12 0.09 0.12 | 0.08 0.06 0.08 0.06 0.08 0.09 | 8.3 12.0 8.4 9.5 9.1 8.6 | 10.0 - 9.8 14.2 9.5 10.3 | 10.0 - 9.8 14.2 9.5 10.3 | 2.9 - 4.7 5.8 4.7 4.5 | 5.6 5.9 5.1 5.2 5.1 5.2 | 1.1 0.8 1.2 2.9 1.0 1.1 | 0.05 0.15 0.16 0.05 0.04 0.05 | 0.015 0.015 0.014 0.015 0.012 0.012 | Mo0.7 Hf1.5 Mo4.0 Nb2.3 - - Fe5.3 S0.1 |
Table 3 result (work embodiment)
No. | Ti+Al+Ta (atom %) | γ/γ '-roll over altogether body (area percent) | Carbide (area percent) | The M-value | Creep property | |
Life-span (hour) | Unit elongation | |||||
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 | 12.58 12.28 12.45 12.19 12.73 12.89 12.21 14.33 12.16 12.25 12.29 12.30 12.19 12.86 12.76 12.22 12.67 12.52 12.03 12.30 | 3.9 2.5 3.3 2.0 4.1 4.6 2.7 12.2 2.1 2.4 2.6 2.7 2.5 9.2 3.6 2.7 3.1 4.0 3.9 2.7 | 4.2 3.8 4.1 4.7 4.3 4.2 3.9 4.0 4.5 1.3 4.2 3.7 3.8 3.6 1.1 4.2 4.4 4.7 4.9 37 | 94 92 93 94 95 94 94 95 94 93 94 94 93 95 94 94 94 94 94 94 | 47 45 48 44 45 44 45 47 42 41 45 43 48 47 43 46 45 52 46 48 | 3 4 3 3 4 5 3 4 6 7 4 3 4 4 5 4 4 6 7 6 |
Table 4 result (comparative examples)
No. | Ti+Al+Ta (atom %) | γ/γ-eutectoid (area percent) | Carbide (area percent) | The M-value | Creep property | |
Life-span (hour) | Unit elongation | |||||
A B C D E F | 13.61 13.63 12.30 14.52 12.15 12.40 | 8.5 3.2 7.3 6.2 1.9 2.3 | 4.7 3.2 5.7 3.9 4.0 4.2 | 96 96 95 99 96 95 | 46 14 32 36 34 38 | 3 11 2 4 5 4 |
Table 5
Numbering | γ/γ '-roll over altogether body (area percent) | Creep property | |
Life-span (hour) | Unit elongation | ||
8 8A 9 9A | 12.2 18.1 2.1 0.4 | 47 36 42 | 4 10 6 |
(producing many casting flaws) |
Claims (3)
1. nickel base heat resistant cast alloy, this alloy is made up of following substantially: in weight %, C:0.02-0.50%, Si: be up to 1.0%, Mn: be up to 1.0%, Cr:4.0-10.0%, Al:2.0-8.0%, Co: be up to 15.0%, W:8.0-16.0%, Ta:2.0-8.0%, Ti: greater than 0 to being up to 3.0%, Zr:0.001-0.200% and B:0.005-0.300%, surplus is nickel and unavoidable impurities, foreign matter content adjustment wherein is up to following higher limit separately: Fe:5.0%, Mo:1.0%, Cu:0.3%, P:0.03%, S:0.03% and V:1.0%, condition is [%Al]+[%Ti]+[%Ta], in atom %, total amount is 12.0-15.5%, and contains γ/γ ' eutectoid of 1-15%, in area percent, the carbide that contains 1-10%, in area percent, and with " the M-value " of following formula (wherein % is atom %) definition in the scope of 93-98:
M=0.717[%Ni]+1.142[%Cr]+2.271[%Ti]+1.9[%Al]+2.117[%Nb]+1.55[%Mo]+0.777[%Co]+3.02[%Hf]+2.224[%Ta]+1.655[%W]+2.994[%Zr]
2. according to the nickel base heat resistant cast alloy of claim 1, wherein this alloy also comprises and is selected from Mg: be up to 0.01%, Ca: be up to 0.01% and REM: be up at least a in 0.1%.
3. motor car engine turbine wheel by each described nickel base heat resistant cast alloy preparation among the claim 1-2.
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JP2004014921A JP3753143B2 (en) | 2003-03-24 | 2004-01-22 | Ni-based super heat-resistant cast alloy and turbine wheel using the same |
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- 2004-03-23 EP EP04006947A patent/EP1462533B1/en not_active Expired - Lifetime
- 2004-03-23 US US10/806,439 patent/US20040187973A1/en not_active Abandoned
- 2004-03-23 DE DE602004000997T patent/DE602004000997T2/en not_active Expired - Lifetime
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CN106191530A (en) * | 2015-04-20 | 2016-12-07 | 中南大学 | Nickel-base alloy and the article formed by alloy |
CN106191530B (en) * | 2015-04-20 | 2018-08-24 | 中南大学 | Nickel-base alloy and the article formed by alloy |
Also Published As
Publication number | Publication date |
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DE602004000997T2 (en) | 2006-11-02 |
JP3753143B2 (en) | 2006-03-08 |
EP1462533B1 (en) | 2006-05-31 |
EP1462533A1 (en) | 2004-09-29 |
DE602004000997D1 (en) | 2006-07-06 |
JP2004307999A (en) | 2004-11-04 |
CN1570171A (en) | 2005-01-26 |
US20040187973A1 (en) | 2004-09-30 |
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