WO2010070949A1 - 球状黒鉛鋳鉄 - Google Patents
球状黒鉛鋳鉄 Download PDFInfo
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- WO2010070949A1 WO2010070949A1 PCT/JP2009/063560 JP2009063560W WO2010070949A1 WO 2010070949 A1 WO2010070949 A1 WO 2010070949A1 JP 2009063560 W JP2009063560 W JP 2009063560W WO 2010070949 A1 WO2010070949 A1 WO 2010070949A1
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- cast iron
- spheroidal graphite
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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
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- 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
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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
- C22C37/10—Cast-iron alloys containing aluminium or silicon
Definitions
- the present invention provides spheroidal graphite cast iron having high high-temperature strength and oxidation resistance.
- Spheroidal graphite cast iron is excellent in high-temperature strength and oxidation resistance, and is used in the turbine housing and exhaust manifold of diesel turbochargers for passenger cars and industrial machinery.
- the engine exhaust gas temperature tends to rise to improve fuel efficiency associated with recent environmental regulations.
- Turbine housings and exhaust manifolds are used under conditions that undergo rapid temperature changes, such as being repeatedly exposed to high temperatures by exhaust gas, and therefore require high high-temperature strength and oxidation resistance.
- High SiMo spheroidal graphite cast iron (ductile cast iron) is used as a conventional turbine housing material, and the service temperature limit is 800 ° C. or lower.
- the service temperature limit is 800 ° C. or lower.
- Patent Document 1 discloses ferritic spheroidal graphite cast iron obtained by adding V to high SiMo cast iron.
- the spheroidal graphite cast iron of Patent Document 1 can improve the high temperature strength at a temperature exceeding 800 ° C., the oxidation resistance is insufficient.
- An object of the present invention is to provide a spheroidal graphite cast iron having improved high-temperature strength and oxidation resistance and superior ductility as compared with conventional high SiMo spheroidal graphite cast iron.
- the spheroidal graphite cast iron of the present invention has a mass ratio of carbon: 2.0 to 4.0%, silicon: 3.5 to 5.0%, manganese: 1.0% or less, chromium : 0.1-1.0%, molybdenum: 0.2-2.0%, vanadium: 0.1-1.0%, magnesium: 0.02-0.1%, the balance being iron and Consists of inevitable impurities.
- the spheroidal graphite cast iron of the present invention has high high-temperature strength and excellent ductility because the molybdenum content is optimized. Further, the spheroidal graphite cast iron of the present invention contains chromium and is excellent in oxidation resistance and ductility because the chromium content is optimized. Thereby, it can be used even in a temperature range of 800 ° C. or higher. Moreover, it can be manufactured at a lower price than double resist cast iron or stainless cast steel.
- the above spheroidal graphite cast iron preferably further contains tungsten: 0.1 to 1.0% by mass ratio.
- tungsten 0.1 to 1.0% by mass ratio.
- niobium 0.02 to 0.30%.
- tungsten 0.1 to 1.0% and niobium: 0.02 to 0.30%.
- the high temperature strength can be further improved by optimizing the contents of tungsten, niobium, or both tungsten and niobium.
- Carbon (C): C and Si are extremely important components in cast iron. When the C content is 2.0% by mass or less, carbides are easily generated, and when the C content is 4.0% by mass or more, segregation of graphite (carbon dross) is caused and strength and toughness are lowered. Therefore, the C content is set to 2.0 to 4.0% by mass. Moreover, there exists carbon equivalent CE C% + 0.31Si% as a parameter
- Si has the effect of graphitization of C and ferrite of the base.
- the Si content of general spheroidal graphite cast iron is about 2.5% by mass.
- Si content shall be 3.5 mass% or more.
- an upper limit shall be 5.0 mass%.
- the addition of 4.3% or more is preferable.
- the ductility of cast iron decreases as the Si content increases, the CE value increases and the castability decreases.
- the upper limit is 4.7% by mass.
- Mn is an element necessary to fix and detoxify S, which is an inevitable impurity of the material, in the form of MnS. However, since it is a base pearlite structure forming element, the upper limit of the Mn content was set to 1.0 mass%.
- Mo is an element that improves the tensile strength and yield strength at high temperatures by dissolving in the matrix.
- Mo is added in an amount of 0.2% by mass or more.
- addition of 0.4% by mass or more is particularly preferable.
- the upper limit of the Mo content is set to 2.0% by mass. In order not to impair the machinability, the upper limit is preferably 1.0% by mass.
- V Vanadium
- V is an element that improves tensile strength and yield strength at high temperatures by precipitating as fine carbides in the matrix.
- V is added in an amount of 0.1% by mass or more. If the V content increases, the ductility of cast iron is impaired, so the upper limit is made 1.0 mass%.
- V is an element that hinders the spheroidization of C because it has a strong tendency to form carbides. Therefore, the upper limit is preferably set to 0.4% by mass.
- Chromium (Cr) is an element that improves oxidation resistance at high temperatures.
- Cr is added in an amount of 0.1% by mass or more. In order to further improve the oxidation resistance, the addition of 0.2% by mass or more is particularly preferable. If the Cr content increases, the ductility of the cast iron is impaired, so the upper limit is made 1.0 mass%. Further, Cr has a strong tendency to form carbides, and is an element that hinders the spheroidization of C, and the carbide size in the matrix becomes coarse, so the upper limit is preferably made 0.4 mass%.
- Magnesium (Mg) Mg is added in an amount of 0.02% by mass or more for the purpose of spheroidizing the graphite. However, if the Mg content increases, carbides and dross (oxide entrapment) defects occur, so the upper limit is made 0.1 mass%.
- Nb is an element that improves tensile strength and yield strength at high temperatures by precipitating as fine carbides in the matrix.
- 0.02% by mass or more of Nb is added.
- Nb content increases, the ductility of cast iron is impaired, Nb is an element that has a strong tendency to generate carbides and prevents C from being spheroidized, and the carbide size in the matrix becomes coarse, so the upper limit is set to 0.0. 30% by mass.
- a preferred addition range in which the effect of improving the strength appears remarkably, prevents a decrease in ductility and increases the spheroidization ratio of C is 0.04 to 0.20% by mass, and more preferably 0.05 to 0.10% by mass It is.
- the spheroidization rate of the graphite is 90% or more.
- the spheroidization rate of graphite is 90%, the tensile strength and proof stress at high temperatures can be improved.
- the turbine housing, exhaust manifold, and turbine housing integrated exhaust manifold manufactured using the above spheroidal graphite cast iron are excellent in high-temperature strength and oxidation resistance, and can be used in a temperature range of 800 ° C. or higher.
- the above composition makes it possible to produce spheroidal graphite cast iron having excellent high-temperature strength and oxidation resistance and having excellent ductility at low cost.
- the turbine housing, the exhaust manifold, and the turbine housing integrated exhaust manifold manufactured using the spheroidal graphite cast iron of the present invention can sufficiently withstand use even at a high temperature of 800 ° C. or higher.
- 6 is a graph showing the 0.2% yield strength ratio of sample materials of sample numbers 1 to 13 when the sample material of sample number 1 is used as a reference.
- 6 is a graph showing the oxidation loss ratio of sample materials of sample numbers 1 to 13 when the sample material of sample number 1 is used as a reference. It is a graph which shows the relationship between Mo content and the breaking elongation ratio of a test material (based on the test material of sample number 1). It is a graph which shows the relationship between Cr content and the breaking elongation ratio of a test material (based on the test material of sample number 1).
- 6 is a graph showing the 0.2% proof stress ratio of specimens Nos. 1 and 14 to 18 when the specimen No. 1 is used as a reference.
- 6 is a graph showing the oxidation weight loss ratio of sample materials of sample numbers 1 and 14 to 18 when the sample material of sample number 1 is used as a reference. It is a graph which shows the relationship between W content and the breaking elongation ratio (reference
- FIG. 7 is a graph showing the oxidation loss ratio of sample materials of sample numbers 1, 23 to 26 when the sample material of sample number 1 is used as a reference.
- 3 is a graph showing the tensile strength ratio (based on the sample material of sample number 1) of the sample materials of sample numbers 1, 15, 20, 24, and 31 to 34.
- Table 1 shows the component compositions of the ferritic spheroidal graphite cast iron specimens of sample numbers 1 to 13.
- the spheroidization rate of the specimens of sample numbers 1 to 13 was measured by the method described in JIS G5502.
- the spheroidization rates of the test materials of sample numbers 1 to 11 and 13 were each 90% or more.
- the spheroidization rate of the test material of sample number 12 was 50%.
- the oxidation resistance was evaluated by oxidation weight loss.
- the test material was put in an electric furnace and kept at 800 ° C. for 100 hours in an air atmosphere. Thereafter, the test material was boiled in 18% NaOH + 3% KMnO 4 solution and then boiled in 10% ammonium citrate solution to remove oxides on the surface of the test material. The mass of the test material before heating and after removal of the oxide was measured, and the oxidation loss was calculated by the formula (1).
- W d (W 0 ⁇ W s ) / A 0 (1)
- W d is the weight loss after oxidation (mg / cm 2 )
- W s is the mass after the test (mg)
- W 0 is the mass before the test (mg)
- a 0 is the surface area of the specimen before the test (cm 2 ).
- FIG. 1 shows the 0.2% proof stress ratio of each specimen when the spheroidal graphite cast iron specimen of sample number 1 is used as a reference.
- the vertical axis represents the 0.2% yield strength ratio.
- FIG. 2 the oxidation weight loss ratio of each test material when the spheroidal graphite cast iron test material of sample number 1 is used as a reference is shown.
- the vertical axis represents the oxidation weight loss ratio.
- FIG. 3 shows the relationship between the Mo content and the breaking elongation ratio of the test material (based on the test material of sample number 1).
- the horizontal axis represents the Mo content
- the vertical axis represents the breaking elongation ratio.
- FIG. 4 shows the relationship between the Cr content and the breaking elongation ratio of the test material (based on the test material of sample number 1).
- the horizontal axis represents the Cr content
- the vertical axis represents the breaking elongation ratio.
- the test materials of sample numbers 1 to 6 with different Mo contents showed 0.2% yield strength improvement as the Mo content increased.
- the oxidation loss was almost constant regardless of the Mo content.
- the elongation at break (ductility) decreased as the Mo content increased. That is, by setting the Mo content to 0.2 to 2.0 mass%, it was possible to obtain a spheroidal graphite cast iron having both high high-temperature strength and excellent ductility.
- the specimen No. 12 having a low C content had a 0.2% proof stress significantly reduced because carbides were formed and carbon spheroidization was hindered.
- the sample material of Sample No. 13 having a low Si content was inferior in oxidation resistance.
- Table 2 shows the component compositions of the ferritic spheroidal graphite cast iron specimens of sample numbers 1, 14 to 18.
- Sample materials Nos. 14 to 18 were prepared and ferritized by the same method as in Example 1. When the spheroidization rate was measured by the method described in JIS G5502, it was confirmed that all the test materials had a spheroidization rate of 90% or more.
- FIG. 5 shows the 0.2% proof stress ratio of each specimen when the spheroidal graphite cast iron specimen of sample number 1 is used as a reference.
- the vertical axis represents the 0.2% yield strength ratio.
- FIG. 6 shows the oxidation weight loss ratio of each specimen when the spheroidal graphite cast iron specimen of sample number 1 is used as a reference.
- the vertical axis represents the oxidation weight loss ratio.
- FIG. 7 shows the relationship between the W content and the breaking elongation ratio of the specimen (based on the specimen of sample number 1).
- the horizontal axis represents the W content
- the vertical axis represents the breaking elongation ratio.
- Example 3 shows the component compositions of the ferritic spheroidal graphite cast iron specimens of Sample Nos. 1 and 19-22.
- Test materials having the component compositions of sample numbers 19 to 22 were prepared in the same manner as in Example 1. After a homogenization heat treatment at 1200 ° C. for 1 hour, the heat treatment was performed at 915 ° C. for 3 hours to make a ferrite. When the spheroidization rate was measured by the method described in JIS G5502, it was confirmed that the spheroidization rate of each test material was 90% or more. Thereafter, the 0.2% yield strength and oxidation loss at 800 ° C. were measured.
- FIG. 8 shows the 0.2% proof stress ratio of each specimen when the spheroidal graphite cast iron specimen of sample number 1 is used as a reference.
- the vertical axis represents the 0.2% yield strength ratio.
- FIG. 9 shows the oxidation weight loss ratio of each test material when the spheroidal graphite cast iron test material of sample number 1 is used as a reference.
- the vertical axis represents the oxidation weight loss ratio.
- Example 4 shows the component compositions of the ferritic spheroidal graphite cast iron specimens of Sample Nos. 1 and 23 to 26.
- Sample materials having the component compositions of Sample Nos. 23 to 26 were prepared in the same manner as in Example 1. Thereafter, the same homogenization heat treatment as in Example 3 was performed, and then ferrite was formed. When the spheroidization rate was measured by the method described in JIS G5502, it was confirmed that the spheroidization rate of each test material was 90% or more. Thereafter, the 0.2% yield strength and oxidation loss at 800 ° C. were measured.
- FIG. 10 shows the 0.2% proof stress ratio of each specimen when the spheroidal graphite cast iron specimen of sample number 1 is used as a reference.
- the vertical axis represents the 0.2% yield strength ratio.
- FIG. 11 shows the oxidation weight loss ratio of each test material when the spheroidal graphite cast iron test material of sample number 1 is used as a reference.
- the vertical axis represents the oxidation weight loss ratio.
- Example 5 With respect to the component compositions of Sample Nos. 1, 15, 20, and 24, the Mg content was reduced, respectively, to obtain test materials of Sample Nos. 31 to 34. Table 5 shows the component composition of each test material.
- FIG. 12 shows the tensile strength ratio of each test material when the test material of sample number 1 is used as a reference.
- the vertical axis represents the tensile strength ratio.
Abstract
Description
炭素(C):鋳鉄においてはCとSiは極めて重要な成分である。C含有量が2.0質量%以下では炭化物を生成しやすく、4.0質量%以上では黒鉛の偏析(カーボンドロス)を引き起こし、強度及び靭性が低下する。そのため、C含有量を2.0~4.0質量%とする。また、鋳鉄の鋳造性を表す指標として、炭素当量CE=C%+0.31Si%がある。一般的な球状黒鉛鋳鉄のCE値は4.3~4.5である。4.3以下では欠陥が生じやすくなり、4.5以上ではカーボンドロスを引き起こす。本発明では、後述するようにSi含有量を高く設定するため、好ましくはC含有量を2.7~3.2質量%の範囲とする。
本発明の球状黒鉛鋳鉄を用いて作製されたタービンハウジング、エキゾーストマニホールド、及びタービンハウジング一体型エキゾーストマニホールドは、800℃以上の高温であっても十分使用に耐え得るものとなる。
電気炉内に供試材を入れ、大気雰囲気中にて、800℃で100時間保持した。その後、18%NaOH+3%KMnO4溶液中にて供試材を煮沸した後、10%クエン酸アンモニウム溶液中で煮沸し、供試材表面の酸化物を除去した。加熱前及び酸化物除去後の供試材の質量を測定し、式(1)により酸化減量を算出した。
Wd = (W0-Ws)/A0 ・・・(1)
ここで、Wdは酸化減量(mg/cm2)、Wsは試験後の質量(mg)、W0は試験前の質量(mg)、A0は試験前の供試材の表面積(cm2)である。
しかし、図3に示すように、Mo含有量が増加するほど、破断伸び(延性)が低下した。
すなわち、Mo含有量を0.2~2.0質量%とすることにより、高い高温強度と優れた延性とを両立させた球状黒鉛鋳鉄とすることができた。
すなわち、Cr含有量を0.1~1質量%とすることにより、優れた耐酸化性と優れた延性とを両立させた球状黒鉛鋳鉄とすることができた。
以上の結果から、W含有量を0.1~1質量%とすることにより、高温強度を更に向上させることができた。
すなわち、Nb含有量を0.02~0.3質量%とすることにより、高温強度を更に向上させることができた。
このように、W及びNbの両方を含有させることにより、高温強度を向上させることができた。
このように、球状化率を90%以上とすることにより、高温強度を向上させることができた。
Claims (7)
- 質量比で炭素:2.0~4.0%、シリコン:3.5~5.0%、マンガン:1.0%以下、クロム:0.1~1.0%、モリブデン:0.2~2.0%、バナジウム:0.1~1.0%、マグネシウム:0.02~0.1%を含有し、残部が鉄及び不可避的不純物から構成される球状黒鉛鋳鉄。
- 質量比でタングステン:0.1~1.0%を更に含有する請求項1に記載の球状黒鉛鋳鉄。
- 質量比でニオブ:0.02~0.30%を更に含有する請求項1に記載の球状黒鉛鋳鉄。
- 質量比でタングステン:0.1~1.0%及びニオブ:0.02~0.30%を更に含有する請求項1に記載の球状黒鉛鋳鉄。
- 黒鉛の球状化率が90%以上であることを特徴とする請求項1乃至請求項4のいずれか1項に記載の球状黒鉛鋳鉄。
- 請求項1乃至請求項5のいずれか1項に記載の球状黒鉛鋳鉄を用いて製造された排気系部品。
- 前記排気系部品が、タービンハウジング、エキゾーストマニホールド、またはタービンハウジング一体型エキゾーストマニホールドである請求項6に記載の排気系部品。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US13/127,403 US20110211986A1 (en) | 2008-12-18 | 2009-07-30 | Ductile iron |
CN200980146974.8A CN102264931B (zh) | 2008-12-18 | 2009-07-30 | 球墨铸铁 |
EP09833255.4A EP2377960B2 (en) | 2008-12-18 | 2009-07-30 | Spheroidal graphite cast iron |
KR1020117010779A KR101373488B1 (ko) | 2008-12-18 | 2009-07-30 | 구상 흑연 주철 |
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JP2008-322696 | 2008-12-18 | ||
JP2008322696A JP5232620B2 (ja) | 2008-12-18 | 2008-12-18 | 球状黒鉛鋳鉄 |
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US (1) | US20110211986A1 (ja) |
EP (1) | EP2377960B2 (ja) |
JP (1) | JP5232620B2 (ja) |
KR (1) | KR101373488B1 (ja) |
CN (1) | CN102264931B (ja) |
WO (1) | WO2010070949A1 (ja) |
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WO2008112720A1 (en) * | 2007-03-12 | 2008-09-18 | Wescast Industries, Inc. | Ferritic high-silicon cast irons |
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Also Published As
Publication number | Publication date |
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KR20110069170A (ko) | 2011-06-22 |
KR101373488B1 (ko) | 2014-03-12 |
JP2010144216A (ja) | 2010-07-01 |
EP2377960B1 (en) | 2018-09-26 |
CN102264931B (zh) | 2014-09-03 |
JP5232620B2 (ja) | 2013-07-10 |
EP2377960A4 (en) | 2016-12-14 |
EP2377960B2 (en) | 2022-04-06 |
EP2377960A1 (en) | 2011-10-19 |
CN102264931A (zh) | 2011-11-30 |
US20110211986A1 (en) | 2011-09-01 |
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