EP2377960B1 - Kugelgraphit-gusseisen - Google Patents

Kugelgraphit-gusseisen Download PDF

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Publication number
EP2377960B1
EP2377960B1 EP09833255.4A EP09833255A EP2377960B1 EP 2377960 B1 EP2377960 B1 EP 2377960B1 EP 09833255 A EP09833255 A EP 09833255A EP 2377960 B1 EP2377960 B1 EP 2377960B1
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Prior art keywords
content
test piece
test
mass
ductile iron
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French (fr)
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EP2377960A4 (de
EP2377960B2 (de
EP2377960A1 (de
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Takashi Arai
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/04—Cast-iron alloys containing spheroidal graphite
    • 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
    • C21D5/00—Heat treatments of cast-iron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/10—Cast-iron alloys containing aluminium or silicon

Definitions

  • the present invention provides a ductile iron having superior high-temperature strength and oxidation resistance.
  • Ductile iron exhibits excellent high-temperature strength and oxidation resistance, and is used in turbine housings and exhaust manifolds of turbocharger in the diesel engines of passenger vehicles and industrial machinery, and the like.
  • improvements in fuel consumption driven by environmental regulations have resulted in a tendency for increased engine exhaust gas temperatures.
  • Turbine housings and exhaust manifolds are used under conditions where they are subjected to rapid temperature variation as a result of repeated exposure to high temperatures generated by the exhaust gases, and therefore require superior levels of high-temperature strength and oxidation resistance.
  • a high Si and Mo ductile iron (ductile cast iron) is conventionally used as the material for turbine housings, and the service temperature limit is typically not more than 800°C.
  • the service temperature limit is typically not more than 800°C.
  • Examples of other turbine housing materials having superior levels of high-temperature strength and oxidation resistance that may be used instead of high Si and Mo ductile iron include Ni-resist cast iron and stainless cast iron. However, these materials include large amounts of Ni and Cr within the raw materials, meaning the raw material costs are high.
  • patent citation 1 discloses a ductile iron prepared by adding V to a high Si and Mo cast iron.
  • Patent Citation 1 Publication of Japanese Patent No. Patent Citation 2: JP 58 058248 A
  • the present invention has an object of providing a ductile iron that has improved levels of high-temperature strength and oxidation resistance compared with conventional high Si and Mo ductile iron as well as superior ductibility.
  • the ductile iron of the present invention comprises, in terms of mass ratio, carbon: 2.0 to 4.0%, silicon: 3.5 to 5.0%, manganese; not more than 1.0%, chromium: 0.1 to 1.0%, molybdenum: 0.2 to 2.0%, vanadium: 0.1 to 1.0%, magnesium: 0.02 to 0.1%, and optionally one or both of tungsten: 0.1 to 1.0% and niobium: 0.02 to 0.30%, with the remainder being composed of iron and unavoidable impurities.
  • the molybdenum content is optimized, and therefore the cast iron has excellent high-temperature strength as well as superior ductibility.
  • the ductile iron of the present invention also comprises chromium, and because the chromium content is optimized, the cast iron exhibits superior oxidation resistance and ductibility.
  • the ductile iron of the present invention can be used even under temperature conditions of 800°C or higher. Furthermore, production can be conducted at lower cost than that of Ni-resist cast iron or stainless cast steel.
  • the ductile iron described above preferably comprises a mass ratio of tungsten: 0.1 to 1.0%.
  • the ductile iron preferably comprises niobium: 0.02 to 0.30%.
  • the ductile iron preferably comprises tungsten: 0.1 to 1.0% and niobium: 0.02 to 0.30%.
  • the high-temperature strength can be further improved.
  • Carbon (C): C and Si are extremely important elements in cast iron. If the C content is 2.0 mass% or less, then carbides tend to form readily, whereas a C content of 4.0 mass% or greater tends to induce graphite segregation (carbon dross), resulting in a deterioration in the strength and ductibility. Accordingly, the C content is specified as 2.0 to 4.0 mass%. Further, the carbon equivalent value (CE C% + 0.31Si%) is used as an indicator of the castability of the cast iron.
  • the CE value of a typical ductile iron is within a range from 4.3 to 4.5. If this CE value is 4.3 or less, then defects tend to form more easily, whereas a CE value of 4.5 or greater tends to induce carbon dross.
  • the Si content is set to a high value as described below, the C content is preferably within a range from 2.7 to 3.2 mass%.
  • Si has the effects of promoting the graphitization of C and the ferritization of the matrix.
  • the Si content in a typical ductile iron is approximately 2.5 mass%. In the present invention, the Si content is not less than 3.5 mass%. Further, because the toughness of the cast iron deteriorates as the Si content is increased, the upper limit for the Si content is 5.0 mass%. In order to further enhance the oxidation resistance, Si is preferably added in an amount of 4.3% or greater, but because the ductibility of the cast iron decreases and castability decreases due to increase of the CE value as the Si content is increased, the upper limit for the Si content is preferably 4.7 mass%.
  • Mn is an element that is necessary for fixing the S that exists as an unavoidable impurity within the raw material as MnS, thereby rendering the S harmless.
  • Mn also causes formation of matrix pearlite structures, the upper limit for the Mn content is specified as 1.0 mass%.
  • Mo is an element that undergoes solid dissolution within the matrix, thereby improving the tensile strength and yield strength at high temperatures.
  • Mo is added in an amount of not less than 0.2 mass%.
  • the addition of 0.4 mass% or more is particularly desirable. If the Mo content is too high, Mo and C tend to bond together to form carbides, and this causes the hardness to increase and the ductibility to deteriorate. Accordingly, the upper limit for the Mo content is specified as 2.0 mass%. In order to ensure no loss in cutting properties, the upper limit for the Mo content is preferably 1.0 mass%.
  • V Vanadium
  • V is an element that is precipitated as fine carbides within the matrix, causing an increase in the tensile strength and yield strength at high temperatures.
  • V is added in an amount of not less than 0.1 mass%. If the V content is too high, then the ductibility of the cast iron deteriorates, and therefore the upper limit for the V content is specified as 1.0 mass%. Further, because V has a strong tendency to form carbides, it tends to impede the spheroidization of C. Accordingly, the upper limit for the V content is preferably 0.4 mass%.
  • Chromium (Cr) is an element that improves the oxidation resistance at high temperatures.
  • Cr is added in an amount of not less than 0.1 mass%.
  • addition of 0.2 mass% or more of Cr is preferred. If the Cr content is too high, then the ductibility of the cast iron deteriorates, and therefore the upper limit for the Cr content is specified as 1.0 mass%.
  • Cr has a strong tendency to form carbides, meaning it impedes the spheroidization of C and tends to cause the size of the carbide grains within the matrix to coarsen, and therefore the upper limit for the Cr content is preferably 0.4 mass%.
  • Mg Magnesium (Mg): Mg is added in an amount of not less than 0.02 mass% for the purpose of spheroidizing the graphite. However if the Mg content is too high, then carbides are generated and dross defects (the incorporation of oxides) tend to occur, and therefore the upper limit for the Mg content is specified as 0.1 mass%.
  • W is added in an amount of not less than 0.1 mass%.
  • the addition of 0.2 mass% or more is particularly desirable. Because W also has a strong tendency to form carbides, meaning it tends to impede the spheroidization of C, the upper limit for the W content is specified as 1.0 mass%, and is preferably 0.4 mass%.
  • Niobium (Nb) is an element that is precipitated as fine carbides within the matrix, causing an increase in the tensile strength and yield strength at high temperatures.
  • Nb is added in an amount of not less than 0.02 mass%. If the Nb content is too high, then the ductibility of the cast iron deteriorates, and Nb also has a strong tendency to form carbides, meaning it impedes the spheroidization of C and tends to cause the size of the carbide grains within the matrix to coarsen, and therefore the upper limit for the Nb content is specified as 0.30 mass%.
  • a preferred range for the amount of Nb, which realizes a marked strength improvement effect, prevents any significant deterioration in the ductibility and enables an increase in the spheroidization rate of C, is from 0.04 to 0.20 mass%, and a more preferred range is from 0.05 to 0.10 mass%.
  • the spheroidization rate of the graphite is preferably 90% or higher. At a graphite spheroidization rate of 90%, the tensile strength and yield strength at high temperatures can be improved.
  • a turbine housing, exhaust manifold, and turbine housing-integrated exhaust manifold produced using the above ductile iron exhibit excellent high-temperature strength and oxidation resistance, and can be used under temperature conditions of 800°C or higher.
  • a ductile iron having superior high-temperature strength and oxidation resistance as well as excellent ductibility can be produced at low cost.
  • a turbine housing, exhaust manifold, and turbine housing-integrated exhaust manifold produced using the ductile iron of the present invention are able to satisfactorily withstand usage under high-temperature conditions of 800°C or higher.
  • the ductile iron of the present invention is described below in more detail based on a series of examples.
  • Table 1 shows the element composition of ductile iron test pieces of sample numbers 1 to 13.
  • Sample Number Composition (mass%) C Si Mn Mo V W Cr Mg 1 2.98 4.68 0.42 0.41 0.29 - 0.32 0.043 2 2.97 4.67 0.39 0.22 0.28 - 0.32 0.042 3 3.03 4.62 0.40 0.82 0.30 - 0.30 0.040 4 2.99 4.64 0.40 1.83 0.28 - 0.28 0.042 5 2.92 4.65 0.39 0.10 0.30 - 0.29 0.042 6 3.07 4.68 0.38 2.20 0.30 - 0.31 0.040 7 2.97 4.62 0.38 0.39 0.29 - 0.10 0.039 8 3.01 4.67 0.40 0.40 0.31 - 0.82 0.042 9 2.99 4.66 0.41 0.40 0.30 - 0.05 0.043 10 3.00 4.65 0.41 0.39 0.31 - 1.20 0.040 11 3.06 4.63 0.39 0.40 0.30 - - 0.042 12 1.80 4.62 0.40 0.39 0.30 - 0.30 -
  • the spheroidization rate was measured for sample numbers 1 to 13.
  • the spheroidization rate was at least 90% for each of the test pieces of sample numbers 1 to 11 and sample number 13.
  • the spheroidization rate for the test piece of sample number 12 was 50%.
  • test pieces of ductile iron from sample numbers 1 to 13 was measured for yield strength and oxidation resistance at 800°C, and for elongation after fracture at room temperature.
  • the oxidation resistance was evaluated using the oxidation weight loss.
  • test piece was placed inside an electric furnace, and the temperature was held at 800°C for 100 hours under normal atmospheric conditions. Subsequently, the test piece was boiled in an aqueous solution containing 18% NaOH and 3% KMnO 4 , and then boiled in a 10% ammonium citrate solution, thereby removing any oxides from the surface of the test piece. The mass of the test piece was measured prior to heating and was then re-measured following removal of the oxides, and the oxidation weight loss was calculated using formula (1).
  • W d W 0 ⁇ W s / A 0
  • W d the oxidation weight loss (mg/cm 2 )
  • W s the mass (mg) following testing
  • W 0 the mass (mg) prior to testing
  • a 0 the surface area (cm 2 ) of the test piece prior to testing.
  • FIG. 1 illustrates the yield strength ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the yield strength ratio.
  • FIG. 2 illustrates the oxidation weight loss ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the oxidation weight loss ratio.
  • FIG. 3 illustrates the relationship between the Mo content and the elongation ratio after fracture of the test piece (referenced against the test piece of sample number 1).
  • the horizontal axis represents the Mo content
  • the vertical axis represents the elongation ratio after fracture.
  • FIG. 4 illustrates the relationship between the Cr content and the elongation after fracture of the test piece (referenced against the test piece of sample number 1).
  • the horizontal axis represents the Cr content
  • the vertical axis represents the elongation ratio after fracture.
  • a ductile iron having a combination of superior oxidation resistance and superior ductibility was able to be obtained.
  • test piece of sample number 12 which had a very low C content, carbides formed and spheroidization of the carbon was inhibited, resulting in a dramatic fall in the yield strength.
  • Table 2 shows the element composition of ductile iron test pieces of sample numbers 1 and 14 to 18.
  • Sample Number Composition (mass%) C Si Mn Mo V W Cr Mg 1 2.98 4.68 0.42 0.41 0.29 - 0.32 0.043 14 2.99 4.62 0.40 0.40 0.29 0.18 0.30 0.039 15 3.01 4.68 0.40 0.41 0.29 0.31 0.33 0.043 16 3.03 4.60 0.41 0.40 0.30 0.95 0.32 0.045 17 2.98 4.64 0.42 0.39 0.29 0.07 0.30 0.043 18 3.01 4.68 0.40 0.41 0.29 1.21 0.31 0.044
  • test pieces were prepared using sample numbers 14 to 18 and subsequently subjected to ferritization.
  • FIG. 5 illustrates the yield strength ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the ; yield strength ratio.
  • FIG. 6 illustrates the oxidation weight loss ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the oxidation weight loss ratio.
  • FIG. 7 illustrates the relationship between the W content and the elongation ratio after fracture of the test piece (referenced against the test piece of sample number 1).
  • the horizontal axis represents the W content
  • the vertical axis represents the elongation ratio after fracture.
  • Table 3 shows the element composition of ductile iron test pieces of sample numbers 1 and 19 to 22.
  • Sample Number Composition (mass%) C Si Mn Mo V Nb Cr Mg 1 2.98 4.68 0.42 0.41 0.29 - 0.32 0.043 19 3.03 4.58 0.41 0.41 0.31 0.04 0.32 0.041 20 3.00 4.63 0.40 0.41 0.29 0.09 0.31 0.040 21 3.03 4.61 0.40 0.39 0.30 0.27 0.32 0.045 22 3.04 4.60 0.43 0.39 0.30 0.35 0.31 0.041
  • test pieces were prepared with the element compositions detailed for sample numbers 19 to 22. Following a homogenized heat treatment for one hour at 1,200°C, a heat treatment was performed at 915°C for 3 hours to effect ferritization. Measurement of the spheroidization rate using the method described in JIS G 5502 confirmed a spheroidization rate of at least 90% for each of the test pieces. Subsequently, each of the test pieces was measured for yield strength and oxidation weight loss at 800°C.
  • FIG. 8 illustrates the yield strength ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the yield strength ratio.
  • FIG. 9 illustrates the oxidation weight loss ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the oxidation weight loss ratio.
  • sample number 19 and 20 From the results for sample numbers 19 and 20 it was confirmed that since Nb is an element that is precipitated as fine carbides within the matrix, the matrix is strengthened and the yield strength is improved as the Nb content was increased. However, the results from sample materials 21 and 22 revealed that an additional increase in the amount of Nb actually tended to cause a reduction in the yield strength. In particular, sample number 22 exhibited a lower yield strength than that of sample number 1 which contained no Nb. Moreover, as illustrated in FIG. 9 , the oxidation weight loss was independent of the Nb content and remained substantially constant.
  • Table 4 shows the element composition of ductile iron test pieces of sample numbers 1 and 23 to 26.
  • Sample Number Composition (mass%) C Si Mn Mo V W Nb Cr Mg 1 2.98 4.68 0.42 0.41 0.29 - - 0.32 0.043 23 3.02 4.64 0.40 0.42 0.30 0.30 0.04 0.34 0.043 24 3.01 4.67 0.39 0.41 0.29 0.32 0.08 0.35 0.041 25 2.98 4.68 0.41 0.40 0.29 0.31 0.26 0.33 0.044 26 3.01 4.68 0.41 0.41 0.31 0.31 0.35 0.34 0.040
  • test pieces were prepared with the element compositions detailed for sample numbers 23 to 26. Subsequently, a homogenized heat treatment was performed in the same manner as example 3, followed by ferritization. Measurement of the spheroidization rate using the method described in JIS G 5502 confirmed a spheroidization rate of at least 90% for each of the test pieces. Subsequently, each of the test pieces was measured for yield strength and oxidation weight loss at 800°C.
  • FIG. 10 illustrates the yield strength ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the yield strength ratio.
  • FIG. 11 illustrates the oxidation weight loss ratio for each test piece, referenced against the ductile iron test piece of sample number 1.
  • the vertical axis represents the oxidation weight loss ratio.
  • sample number 24 exhibited a higher yield strength than samples containing only one of Nb and W.
  • the yield strength actually decreased.
  • the test piece of sample number 26 exhibited a lower yield strength than the test piece of sample number 1 which contained no added Nb or W.
  • the oxidation weight loss was independent of the Nb content and remained substantially constant.
  • test pieces were prepared with each of the element compositions detailed in Table 5, and a homogenized heat treatment was then performed, followed by ferritization.
  • the spheroidization rate of each test piece was measured using the method described in JIS G 5502. The tensile strength of each test piece at 800°C was also measured.
  • FIG. 12 illustrates the tensile strength ratio for each test piece, referenced against the test piece of sample number 1.
  • the vertical axis represents the tensile strength ratio.
  • the spheroidization rate decreased.
  • the tensile strength at 800°C also decreased.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Claims (4)

  1. Duktiles Eisen, umfassend in Form von Massenanteilen Kohlenstoff: 2,0 bis 4,0%, Silicium: 3,5 bis 5,0%, Mangan: nicht mehr als 1,0%, Chrom: 0,1 bis 1,0%, Molybdän: 0,2 bis 2,0%, Vanadium: 0,1 bis 1,0%, Magnesium: 0,02 bis 0,1% und optional einen oder beide Vertreter von Wolfram: 0,1 bis 1,0% und Niob: 0,02 bis 0,30%, mit einem Rest, der aus Eisen und unvermeidbaren Verunreinigungen besteht.
  2. Duktiles Eisen gemäß Anspruch 1, wobei die Sphäroidisierungsrate von Graphit 90% oder höher ist.
  3. Abgassystemkomponente, hergestellt unter Verwendung des duktilen Eisens gemäß Anspruch 1 oder Anspruch 2.
  4. Abgassystemkomponente gemäß Anspruch 3, wobei die Abgassystemkomponente ein Turbinengehäuse, ein Abgaskrümmer oder ein im Turbinengehäuse integrierter Abgaskrümmer ist.
EP09833255.4A 2008-12-18 2009-07-30 Kugelgraphit-gusseisen Active EP2377960B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008322696A JP5232620B2 (ja) 2008-12-18 2008-12-18 球状黒鉛鋳鉄
PCT/JP2009/063560 WO2010070949A1 (ja) 2008-12-18 2009-07-30 球状黒鉛鋳鉄

Publications (4)

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EP2377960A1 EP2377960A1 (de) 2011-10-19
EP2377960A4 EP2377960A4 (de) 2016-12-14
EP2377960B1 true EP2377960B1 (de) 2018-09-26
EP2377960B2 EP2377960B2 (de) 2022-04-06

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US (1) US20110211986A1 (de)
EP (1) EP2377960B2 (de)
JP (1) JP5232620B2 (de)
KR (1) KR101373488B1 (de)
CN (1) CN102264931B (de)
WO (1) WO2010070949A1 (de)

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ITMI20110861A1 (it) * 2011-05-17 2012-11-18 Fonderia Casati S P A Ghisa a grafite sferoidale ad alto tenore di legante con struttura austenitica, uso di detta ghisa per la fabbricazione di componenti strutturali e componente strutturale realizzato con detta ghisa
CN102489669B (zh) * 2011-12-31 2013-09-25 四川省川建管道有限公司 一种立式退火炉底座的制备方法
DE102012217892A1 (de) * 2012-10-01 2014-05-15 Siemens Aktiengesellschaft Gusseisen mit Niob und Bauteil
CN102978507B (zh) * 2012-11-29 2014-09-24 常州南车汽车零部件有限公司 高硅钼球铁材料及其制备方法
US9587588B2 (en) 2013-07-03 2017-03-07 Ford Global Technologies, Llc Direct inlet axial automotive turbine
CN103320681B (zh) * 2013-07-11 2015-10-21 周世康 一种等温淬火球铁及其淬火工艺
CN103509992A (zh) * 2013-10-15 2014-01-15 沈阳工业大学 一种耐热球墨铸铁研究及制备
CN103820700B (zh) * 2014-01-30 2016-09-14 南车戚墅堰机车车辆工艺研究所有限公司 耐热球墨铸铁及其制备方法
KR102148756B1 (ko) 2014-03-12 2020-08-27 두산인프라코어 주식회사 내열 구상흑연주철, 이의 제조 방법 및 이를 포함하는 엔진 배기계
JP6466727B2 (ja) * 2015-02-06 2019-02-06 日産自動車株式会社 球状黒鉛鋳鉄及び自動車用エンジンの排気系部品
KR101673779B1 (ko) 2015-06-10 2016-11-08 현대자동차주식회사 내열주철
CN105385934B (zh) * 2015-11-20 2017-05-10 平顶山市圣康炊具有限公司 一种搪瓷锅及其制作工艺
CN106011609B (zh) * 2016-07-29 2018-03-02 西峡县内燃机进排气管有限责任公司 一种中硅钼铌球墨铸铁材料及其制备方法
CN106222526B (zh) * 2016-08-25 2017-09-22 共享装备股份有限公司 一种高硅钼球铁材料的合成制备工艺
JP6670779B2 (ja) * 2017-03-16 2020-03-25 株式会社Ｉｊｔｔ 球状黒鉛鋳鉄及び排気系部品

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JP3582400B2 (ja) 1999-04-20 2004-10-27 Ｊｆｅスチール株式会社 耐事故性に優れた遠心鋳造製熱間圧延仕上後段スタンド用複合ロール
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WO2005085488A1 (ja) 2004-03-04 2005-09-15 Hitachi Metals, Ltd. 耐熱鋳鉄及びそれからなる排気系部品
WO2008112720A1 (en) 2007-03-12 2008-09-18 Wescast Industries, Inc. Ferritic high-silicon cast irons

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EP2377960A4 (de) 2016-12-14
KR20110069170A (ko) 2011-06-22
KR101373488B1 (ko) 2014-03-12
EP2377960B2 (de) 2022-04-06
US20110211986A1 (en) 2011-09-01
CN102264931B (zh) 2014-09-03
JP5232620B2 (ja) 2013-07-10
WO2010070949A1 (ja) 2010-06-24
CN102264931A (zh) 2011-11-30
EP2377960A1 (de) 2011-10-19
JP2010144216A (ja) 2010-07-01

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