EP1462533B1 - Alliage de fonte à base de nickel résistant à la chaleur et roues de turbines de cette alliage - Google Patents

Alliage de fonte à base de nickel résistant à la chaleur et roues de turbines de cette alliage Download PDF

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Publication number
EP1462533B1
EP1462533B1 EP04006947A EP04006947A EP1462533B1 EP 1462533 B1 EP1462533 B1 EP 1462533B1 EP 04006947 A EP04006947 A EP 04006947A EP 04006947 A EP04006947 A EP 04006947A EP 1462533 B1 EP1462533 B1 EP 1462533B1
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Prior art keywords
alloy
heat resistant
strength
base heat
resistant cast
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EP1462533A1 (fr
Inventor
Noritaka Daido Steel Co. Ltd. Takahata
Shigeki Daido Steel Co. Ltd. Ueta
Toshiharu Daido Steel Co. Ltd. Noda
Tetsuya Daido Steel Co. Ltd. Shimizu
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Daido Steel Co Ltd
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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%
    • 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

Definitions

  • the present invention concerns a nickel base heat resistant cast alloy and turbine wheels made from the alloy for automobile engines.
  • the invention provides turbine wheels having the strength higher than that of the conventional ones with substantially the same cost.
  • MM-247 contains hafnium, which is expensive, as one of the components of this alloy and the material cost is thus high.
  • HIP process is often used at manufacturing the wheels so that voids may not occur in the cast products and therefore, manufacturing cost is high.
  • the object of the present invention is to provide a nickel-base heat resistant cast alloy used as the material for turbine wheels of automobile engines having the high strength at high temperature to meet the tendency of increasing exhaust gas temperature, and with respect to the material cost, though a little higher, with substantially the same cost, while the heat resistance property and the high temperature strength are about the same as those of MM-247.
  • To provide turbine wheels made of this material is also the object of this invention.
  • the nickel base heat resistant cast alloy of the invention is given in the claims and consists 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 optionally further contains at least one of the group consisting of Mg: up to 0.01%, Ca: up to 0.01% and REM: up to 0.1% and inevitable impurities, provided that [%Al]+[%Ti]+[%Ta], by atomic %, amounts to 12.0-15.5%, that it contains ⁇ / ⁇ '-eutectoid of, by area percantage, 1-15%, that it contains carbides of, by area percentage, 1-5%, and that the "M-value" defined by the formula below (in which % is atomic
  • Ni-base heat resistant cast alloy according to the present invention may contain, in addition to the above mentioned basic alloy components, at least one of the group consisting of Mg: up to 0.01%, Ca: up to 0.01% and REM: up to 0.1%.
  • the main impurities which may be contained in the present Ni-base heat resistant cast alloy of the invention are Fe, Si, Mn, P and S, originated from the raw materials. Depending on the cases, Cu and Mo may also be contained. It is preferable to regulate the contents of the impurities at highest up to the following respective upper limits:
  • Carbon contributes to strengthening of grain boundaries by, in case of an element of the group of Ti, Zr and Hf, or an element of the group of Nb, Ta and V, combining with it to form carbide or carbides thereof.
  • a carbon content less than 0.02% may not give sufficient effect, while a content exceeding 0.50% will cause formation of excess carbide or carbides, which results in decreased corrosion resistance and ductility.
  • Preferable C-content is in the range of 0.05-0.30%, and more preferable range is 0.02-0.20%.
  • Silicon is usually used as a deoxidizing agent at the time of melting and refining the alloy. Though content of a small amount of Si effective as the deoxidizing agent may cause no problem, too much addition will lower the ductility of the alloy. Thus, 1.0% is set as the upper limit. Preferable Si-content is up to 0.5%.
  • Manganese is, like silicon, also added as a deoxidizing agent. Addition in a small amount effective as the deoxidizing agent may cause no problem, however, too much addition will lower the strength and the ductility of the alloy. The upper limit, 1.0%, is thus set.
  • Chromium is the most important element for improving the corrosion resistance of the alloy. It also contributes to increase of the strength by solid solution in the matrix phase. Addition amount less than 4.0% will give little effect, while more than 10.0% lowers the phase stability and the strength and the ductility of the turbine wheel after operation at a high temperature for a long period of time. Preferable range of Cr-content is 6.0-10.0%.
  • Aluminum is an important element forming ⁇ '-phase, and is useful for improving high temperature corrosion resistance. These effects may be week at such a small amount as less than 2.0%. On the other hand, addition exceeding 8.0% causes deposition of much amount of eutectic ⁇ '-phase in casting, and as the result, creep rapture strength will decrease. Preferable range of Al-content is 4.5-5.5%.
  • Cobalt strengthens ⁇ -phase by solid solution. It also dissolves in ⁇ '-phase, which is effective for increasing the strength of the alloy, and strengthens the ⁇ '-phase. Co increases deposition amount of the ⁇ -phase.
  • addition in a large amount is disadvantageous from the viewpoints of the cost. Choosing an addition amount up to 15.0% is recommended. In order to ensure sufficient high temperature properties at 900°C or higher, it is desirable to add Co in an amount of 5.0% or higher.
  • Wolfram contributes greatly to solution strengthening of the ⁇ -phase and increase of the strength.
  • An amount less than 8.0% will give insufficient effect, while an amount exceeding 16.0% lowers the phase stability.
  • the lowered phase stability causes deposition of ⁇ -Cr in the alloy after using for a long while and damages the strength of the wheels.
  • a preferable range of addition is 10.0-14.0%.
  • Tantalum not only combines with carbon to form the carbide, but also dissolves in the ⁇ '-phase to strengthen it. The effect is low at addition amount less than 2.0%. Because Ta is an expensive material like Hf, from the viewpoint of the cost, it is desirable to use it in an amount as small as possible. The upper limit, 8.0%, is thus set.
  • Titanium reacts Ni to form the ⁇ '-phase which is effective in increasing the strength of the alloy.
  • Ti has further effect of replacing Al to contribute to solution strengthening of the ⁇ '-phase, and thus, further improves the strength of the alloy.
  • addition of Ti exceeding 3.0% tends to cause deposition of ⁇ -phase (Ni 3 Ti), which gives disadvantage to the high temperature strength and the ductility of the alloy.
  • Preferable amount of addition is 2.0% or less.
  • Zirconium has both the effect of combining with carbon to form the carbide and the effect of segregating at the grain boundaries to strengthen. These effects are observed at even such a small amount of addition as 0.001%. Due to decrease of the ductility at addition of a large amount the upper limit is set to be 0.200%. An optimum amount of addition may be found in a range up to 0.1%.
  • Effects of adding B are suppressing formation of the ⁇ -phase to prevent decrease of the high temperature strength and the ductility, and further, enhancing the high temperature creep rapture strength.
  • B forms borides with Cr and some other elements. Because melting points of the borides are low, the temperature range of solid-liquid coexisting is board, and thus, castability of the alloy will be improved. To seek these effects, it is necessary to add a suitable amount of B in the range of 0.005% or more. Addition in an excess amount, however, results in decrease of the strength and the ductility of the alloy. Thus, the upper limit of addition is set to 0.300%. Favorable balance of the castability and strength-resilience can be achieved in the range from 0.050 to 0.200%.
  • Mg up to 0.01%
  • Ca up to 0.01%
  • REM up to 0.1%
  • Molybdenum though it dissolves in the matrix of the alloy to contribute to increasing the strength, content at a large amount damages the high temperature oxidation resistance, and thus, the Mo-content should be such amount as up to 1.0%. Copper is also the cause of decreased strength, and therefore, existence of Cu in a large amount is not desirable.
  • the allowable upper limit is 1.0%, and Cu-content or 0.3% or less is preferable. Vanadium brings about the disadvantage of decreased high temperature strength, and the V-content should be limited to less than the upper limit, 1.0%. [ % Al ] + [ % Ti ] + [ % Ta ] : 12.0 ⁇ 15.5 atomic %
  • 1% is necessary for ensuring the workability, particularly, castability of the alloy.
  • the area percentage is less than 1%, voids may occur at the last stage of casting, and the liability of the product wheels will become low.
  • the area percentage exceeds 15%, the eutectoid may become the starting points of fracture.
  • Formation of a suitable amount of carbides is useful for strengthening the grain boundaries and enhance the high temperature strength at 1000°C or higher.
  • the area percentage of the carbides is 1% or more, this effect can be obtained, and when the area percentage exceeds 10%, it is lost.
  • the range of the area percentage of the carbides is 1-5%.
  • the M-value defined by the formula above is a measure for the phase stability.
  • the M-value in the range of 93-98 guaranties the durability of the product turbine wheels. Because the alloy of this invention is used for automobile parts, a higher M-value is advantageous to give longer durability of the parts. However, at an M-value exceeding 98, harmful phases such as ⁇ -phase tend to occur after using for a long period of time, and the durability will decrease.
  • the Ni-base heat resistant cast alloy according to the invention contains no expensive Hf, which is effective for strengthening the alloy, it has creep rapture strength much better than that of 713C alloy which is used most widely as the material for the turbine wheels, and the creep rapture strength of the invented alloy is substantially the same as that of MM-247 containing Hf. Based on the alloy composition, the material cost may be a little higher than that of 713, but still lower than that of MM-247. Because of high castability of the present alloy HIP process is not necessary to apply, and thus, the cost for manufacturing the turbine wheels may not be high. The present invention thus makes it possible to provide turbine wheels, which can meet the anticipated increase of exhaust gas temperature in the near future, at lower prices.
  • Nickel-base heat resistant alloys having the alloy compositions shown in Table 1 (Working Examples) and Table 2 (Control Examples) were produced and cast into ingots weighing 50kg.
  • No.A of the Control Examples is the conventional 713C alloy, and No.B corresponds to MM-247.
  • Properties of these alloys such as [%Al]+[%Ti]+[%Ta] are shown in Table 3 (Working Examples) and Table 4 (Control Examples). Test pieces were taken from the ingots by machining, and they were subjected to creep rapture tests at the conditions of 1000°C and 180MPa. The determined creep properties are shown in Table 3 and Table 4.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Supercharger (AREA)

Claims (3)

  1. Alliage coulé à base de nickel, résistant à la chaleur, caractérisé en ce que l'alliage consiste, en pourcentage pondéral, en C : 0,02-0,50%, Si : jusqu'à 1,0%, Mn : jusqu'à 1,0%, Cr : 4,0-10,0%, Al : 2,0-8,0%, Co : jusqu' à 15,0%, W : 8,0-16,0%, Ta : 2,0-8,0%, Ti : jusqu'à 3,0%, Zr : 0,001-0,200% et B : 0,005-0,300%, le complément étant apporté par du Ni, et l'alliage contient facultativement, en outre, l'un au moins des éléments du groupe consistant en Mg : jusqu'à 0,01%, Ca : jusqu'à 0,01% et métaux de terres rares : jusqu'à 0,1%, et d'inévitables impuretés ; en ce que la somme [% Al]+[% Ti]+[% Ta], en pourcentage atomique, atteint 12,0-15,5% ; en ce que l'alliage contient un eutectoïde y/y', en pourcentage surfacique, de 1-15% ; en ce qu'il contient des carbures, en pourcentage surfacique, de 1-5%, et en ce que la "valeur M", définie par la formule ci-dessous (dans laquelle le pourcentage est un pourcentage atomique), est dans la gamme 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 ] .
    Figure imgb0006
  2. Alliage coulé à base de nickel, résistant à la chaleur, selon la revendication 1, caractérisé en ce que la teneur en impuretés est maîtrisée vis-à-vis des valeurs maximales suivantes : Fe : 5,0%, Mo : 1,0%, Cu ; 0,3%, P : 0,03%, S : 0,03% et V : 1,0%.
  3. Roue-turbine pour moteur automobile fabriquée à partir de l'alliage coulé à base de nickel, résistant à la chaleur, selon la revendication 1 ou 2.
EP04006947A 2003-03-24 2004-03-23 Alliage de fonte à base de nickel résistant à la chaleur et roues de turbines de cette alliage Expired - Lifetime EP1462533B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003080844 2003-03-24
JP2003080844 2003-03-24
JP2004014921 2004-01-22
JP2004014921A JP3753143B2 (ja) 2003-03-24 2004-01-22 Ｎｉ基超耐熱鋳造合金およびそれを材料とするタービンホイール

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EP1462533B1 true EP1462533B1 (fr) 2006-05-31

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US (1) US20040187973A1 (fr)
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JP (1) JP3753143B2 (fr)
CN (1) CN100355923C (fr)
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CN106191531A (zh) * 2016-08-26 2016-12-07 桥运精密部件（苏州）有限公司 一种耐酸腐蚀的合金材料
JP6769341B2 (ja) * 2017-02-24 2020-10-14 大同特殊鋼株式会社 Ｎｉ基超合金
CN107630153A (zh) * 2017-09-14 2018-01-26 上海怀德机电有限公司 一种高温模具用铸造镍基合金
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DE602004000997T2 (de) 2006-11-02
JP3753143B2 (ja) 2006-03-08
EP1462533A1 (fr) 2004-09-29
CN100355923C (zh) 2007-12-19
DE602004000997D1 (de) 2006-07-06
JP2004307999A (ja) 2004-11-04
CN1570171A (zh) 2005-01-26
US20040187973A1 (en) 2004-09-30

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