WO2005007914A1 - オーステナイト系耐熱球状黒鉛鋳鉄 - Google Patents
オーステナイト系耐熱球状黒鉛鋳鉄 Download PDFInfo
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- WO2005007914A1 WO2005007914A1 PCT/JP2004/010314 JP2004010314W WO2005007914A1 WO 2005007914 A1 WO2005007914 A1 WO 2005007914A1 JP 2004010314 W JP2004010314 W JP 2004010314W WO 2005007914 A1 WO2005007914 A1 WO 2005007914A1
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- heat
- iron
- spheroidal graphite
- resistant
- 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
- 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
- C22C37/08—Cast-iron alloys containing chromium with nickel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features
- F01N13/16—Selection of particular materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N2530/00—Selection of materials for tubes, chambers or housings
- F01N2530/02—Corrosion resistive metals
Definitions
- the present invention relates to a heat-resistant austenitic spheroidal graphite iron which is suitable for a turbocharger housing for an automobile engine, an exhaust holder, an exhaust system component such as a catalyst case, and the like.
- Turbocharger housing, exhaust case, catalyst case, exhaust case, and turbocharger housing integrated with turbocharger housing and exhaust case, catalyst case, exhaust case -Exhaust system parts for automobile engines are exposed to high temperatures repeatedly due to exhaust gas passing through the interior, and are used under severe and high-temperature conditions.
- a catalyst case-integrated exhaust-hold with an integrated ford are exposed to high temperatures repeatedly due to exhaust gas passing through the interior, and are used under severe and high-temperature conditions.
- high oxidation resistance, high temperature resistance, heat resistance such as thermal crack life are required.
- exhaust parts for automobile engines have conventionally contained high heat-resistant iron such as austenitic spheroidal graphite iron (commonly known as two resists) and large amounts of elements such as Ni, Cr and W. Ferritic and austenitic stainless steels with improved heat resistance have been used.
- a typical austenitic spheroidal graphite iron has a weight ratio of C: 2.0% or less, Si: 4.0—6.0%, Mn: 0.5—1.5%, Ni: 34.0—36.0%, and Cr: 1.5—2.5. % Austenitic spheroidal graphite iron (FCDA-NiSiCr 3552 in JIS G 5510) having an elongation at room temperature of 10% or more and a 0.2% proof stress of 200 N / mm 2 or more.
- This austenitic spheroidal graphite-iron has good elongation at room temperature and good resistance to stiffness and relatively good high-temperature resistance at exhaust gas temperatures below 900 ° C.
- Patent Document 1 JP-A-59-113160 (Patent Document 1) discloses that C: 2.5-3.5%, Si: 1.5-3%, Mn:
- Austenitic spheroidal graphite-iron having a composition consisting of the balance and having excellent heat crack resistance is disclosed.
- C 2.9%, Si: 2.7%, Mn: 1.5%, Cr: 2.0%, Ni: 25.0%, Fe and impurities:
- the remaining amount of yarn was adjusted, and the exhaust gas temperature was 850-200.
- the test stated that no cracks were generated in the 300-hour endurance test under the conditions of ° C.
- This austenitic spheroidal graphite iron has improved heat cracking resistance by reducing the amount of harmful precipitates precipitated in the metal structure by reducing the Si content. Insufficient ductility (room temperature elongation) to resist
- Patent Document 2 JP-A-63-114938 discloses that C: 2.5-3%, Si: 2.6-3.2%, Mn:
- a heat-resistant ferrous iron having a composition consisting of: 0.18-0.7%, and Fe and inevitable impurities: the balance, and exhibiting excellent oxidation resistance especially in an environment subjected to repeated heating and cooling.
- This heat-resistant ferrous iron suppresses the corrosion while suppressing grain boundary precipitation of unavoidable impurities such as P and S by the Nb-added slurries, thereby suppressing the corrosion while strengthening the grain boundaries, and adding Ce, Z or La.
- It is a material that improves the oxidation resistance by making the iridani film dense and strong with kamaki, but has the strength (high temperature resistance) against compressive stress at high temperature acting on the constrained exhaust system parts. Insufficient.
- JP-A-6-128682 discloses that Ni: 13.0 to 40.0%, Si: 3.0 to 10.0%, Fe: substantially the balance, and Nb, Mo, V, Ti and Ta
- Ni: 13.0 to 40.0%, Si: 3.0 to 10.0%, Fe: substantially the balance, and Nb, Mo, V, Ti and Ta One or more elements of: 5-30% by weight of Si
- a highly heat-resistant iron having a composition of about 50% by weight and low oxidation loss is disclosed.
- the example shows the composition of 2.83% by weight, 6.17% by weight, 0.85% by weight of Mn, 0.056% by weight of Mg, 20.3% by weight of Ni, 1.99% by weight of Cr, and 1.6% by weight of Mo ing.
- the ferromagnetic iron contains a large amount of Si as 3.0 to 10.0% by weight and Mo as 5 to 30% by weight of Si, the heat resistance and the high temperature fatigue strength are improved. However, toughness of this iron decreases due to the addition of a large amount of Si. In addition, the mere addition of Mo inhibits the spheroidization of graphite and increases the amount of carbides, and in particular, the ductility at room temperature is insufficient.
- Patent Document 4 discloses, as flaky graphite-iron, C: 3.2-3.7%, Si: 2.0-2.4%, Mn: 0.2-0.8%, P: 0.1 by weight ratio. % Or less, S: 0.1% or less, Cr: 0.1—0.4%, Ni: 0.2—0.6%, Mo: 0.3—0.6%, Sb: 0.02—0.05%, and Fe: In particular, it discloses a steel for a cylinder head in which the thermal fatigue resistance is improved by Sb. In this iron, graphite does not spheroidally deform, so it lacks room temperature elongation, high temperature resistance, and thermal crack life, and particularly has insufficient heat resistance when exposed to exhaust gas of 900 ° C or higher. is there.
- an exhaust system component is disposed behind the engine, which is directly connected to an exhaust gas purifying device to suppress a decrease in exhaust gas temperature when the engine is started and to improve an initial function of the exhaust gas purifying catalyst.
- an exhaust system component is disposed behind the engine, which is directly connected to an exhaust gas purifying device to suppress a decrease in exhaust gas temperature when the engine is started and to improve an initial function of the exhaust gas purifying catalyst.
- the exhaust system components are arranged behind the engine, there is a problem that the surface temperature of the exhaust system components rises excessively because the wind is hard to hit the exhaust system components when the vehicle is running.
- exhaust parts for automobile engines are exposed to sulfur oxides, nitrogen oxides, etc. contained in exhaust gas.
- the exhaust system components for automobile engines have a higher temperature than ever before, such as an increase in the temperature of the exhaust gas passing therethrough and an increase in the surface temperature due to the rear arrangement. Therefore, it is required to cope with severe use conditions.
- Exhaust system components are required to have not only excellent heat resistance but also ductility. Exhaust system parts are subject to vibration and impact during the production process, the assembly process to the engine, and when starting and driving a car. Do not crack or crack the exhaust system parts against the tensile stress generated by vibration or impact! Therefore, sufficient ductility is required. In particular, ductility at low temperatures below room temperature is important because toughness decreases at low temperatures. Generally, ductility at room temperature or lower is a characteristic represented by room temperature elongation.
- these stainless steels have a low content of C and a high melting point as compared with austenitic spheroidal graphite iron, and thus have a problem of poor formability. For this reason, when manufacturing exhaust system parts having a thin and complex shape using stainless steel and steel, there is a problem that not only the raw materials but also the production costs are high, so that the exhaust system parts are expensive.
- Patent Document 1 JP-A-59-113160
- Patent Document 2 JP-A-63-114938
- Patent Document 3 JP-A-6-128682
- Patent Document 4 Japanese Patent Publication No. 7-6032
- an object of the present invention is to provide a production method in which heat resistance such as oxidation resistance, high-temperature resistance, and thermal crack life when exposed to exhaust gas at 900 ° C or higher without impairing room-temperature elongation is improved.
- An object of the present invention is to provide austenitic heat-resistant spheroidal graphite iron having a low cost. Means for solving the problem
- the austenitic spheroidal graphite-iron was studied diligently at 900 ° C or higher (especially at around 1000 ° C) to improve the oxidation resistance, high-temperature resistance, and thermal crack life without impairing room-temperature elongation.
- an appropriate amount of Mo which is a carbide-forming element and has a small tendency to inhibit graphite spheroidization, is included, the precipitation strengthening of the structural matrix structure is achieved, and the high-temperature yield strength of austenitic spheroidal graphite iron is improved.
- the average thermal expansion coefficient up to around 1000 ° C decreases, the thermal strain in the high-temperature region determined by the product of the thermal expansion coefficient and the temperature decreases, and the resulting thermal stress decreases. Due to the synergistic effect of Cr and Mo, the passive film formed on the surface becomes dense and strong, and as a result, the surface oxidation is suppressed and the thermal crack life is prolonged. Or, if an appropriate amount of Sb is contained, black The present inventors have found that the lead spheroidization ratio is maintained at 75% or more to ensure room-temperature elongation and that graphite is prevented from falling off due to internal oxidation, and the present invention has been reached.
- the heat-resistant austenitic spheroidal graphite-iron of the present invention has a Mo content of 1 to 4.5% by weight and a Sn and Z or Sb content of 2 to Sn + Sb of 0.001 to 0.5%.
- the feature is.
- the heat-resistant austenitic spheroidal graphite-iron has a weight ratio of C: l-3.5%, Si: 1-6.5%, Cr: 3% or less, Ni: 10-40%. , Mo: 1-4.5%, Sn and Z or Sb in 2Sn + Sb 0.001-0.5%, graphite spheroidizing element: 0.1% or less.
- the heat-resistant austenitic spheroidal graphite iron of the present invention preferably further contains 0.3% by weight or less of N.
- the austenitic heat-resistant spheroidal graphite iron described above has an ordinary temperature elongation of 2% or more, and a reduction in acidity of 30 mg / cm 2 or less when held in an air atmosphere at 950 ° C for 200 hours. It is preferable that the 0.2% proof stress in an atmosphere of ° C is 55 N / mm 2 or more. Further, it is preferable that the thermal crack life in a thermal fatigue test in which heating and cooling are performed at an upper limit temperature of 950 ° C, a temperature amplitude of 800 ° C, and a constraint rate of 0.5 is 400 cycles or more. Furthermore Rights soaking expansion coefficient in the range of from room temperature to 1000 ° C is 18 X 10- 6 / ° C or less is preferably.
- the heat-resistant austenitic spheroidal graphite iron of the present invention can be used at 900 ° C or lower without impairing room-temperature elongation. It excels in acid resistance when exposed to the above exhaust gas (especially at around 1000 ° C), heat resistance such as high temperature resistance and thermal crack life, and can be manufactured at low cost.
- FIG. 1 is a micrograph (100 ⁇ magnification) showing a metal structure of heat-resistant austenitic spheroidal graphite-iron of Example 12.
- FIG. 2 is a micrograph (100 ⁇ magnification) showing a metal structure of heat-resistant austenitic spheroidal graphite-iron of Comparative Example 9.
- FIG. 3 is a graph showing the relationship between the degree of graphite spheroidal austenitic heat-resistant spheroidal graphite and iron and the room temperature elongation.
- FIG. 4 is a graph showing the relationship between the Mo content of austenitic heat-resistant spheroidal graphite-iron and room temperature elongation.
- FIG. 5 is a graph showing the relationship between the Mo content of austenitic heat-resistant spheroidal graphite and iron and oxidation loss.
- FIG. 6 is a micrograph (magnification: 400 times) showing the metal structure of the heat-resistant austenitic spheroidal graphite / iron of Example 12 after an oxidation test.
- FIG. 7 is a micrograph (magnification: 400 times) showing the metal structure of the heat-resistant austenitic spheroidal graphite / iron of Comparative Example 4 after an oxidation test.
- FIG. 8 is a graph showing the relationship between the Mo content of high-temperature austenitic heat-resistant spheroidal graphite-iron and high-temperature proof stress.
- FIG. 9 is a graph showing the relationship between the Mo content of heat-resistant austenitic spheroidal graphite-iron and the thermal crack life.
- FIG. 10 is a perspective view showing an exhaust system component having an exhaust-hold, a turbocharger housing, and a catalyst case.
- FIG. 11 is a side view showing an example of a turbocharger housing.
- FIG. 12 is a sectional view taken along line AA of FIG. 11.
- FIG. 13 is a perspective view showing an appearance (after a 1,000-cycle endurance test) of the vicinity of a wastegate portion of one housing of a turbocharger made of heat-resistant austenitic spheroidal graphite-iron of Example 12.
- FIG. 14 is a perspective view showing an appearance (after a 540 cycle endurance test) of the vicinity of a waste gate portion of a turbocharger housing made of heat-resistant austenitic spheroidal graphite-iron of Comparative Example 4.
- composition and properties of the heat-resistant austenitic spheroidal graphite-iron of the present invention will be described in detail below.
- the ratio is based on weight unless otherwise specified.
- C is an element that crystallizes graphite and improves the fluidity of the molten metal. If C is less than 1.0%, spheroidal graphite cannot be crystallized, and the fluidity of the molten metal is too low. If the ratio exceeds 3.5%, coarse graphite particles are formed, the spheroidal graphite and iron do not have sufficient room-temperature elongation, and shrinkage cavities are liable to occur during fabrication. Therefore, C is 1-3.5%, preferably 1.5-2.5%.
- Si is an element that contributes to the crystallization of graphite.
- Si is contained in an amount of 1% or more, a passivation film made of silicon oxide is formed near the surface, and the oxidation resistance of the spheroidal graphite-iron is improved.
- the Si force exceeds 3 ⁇ 40.5%, the matrix becomes hard, the decrease in room temperature elongation becomes remarkable, and the machinability also deteriorates. Therefore, the content of Si is 1-6.5%, preferably 4.5-6%.
- Cr combines with carbon in the iron base to precipitate carbides, and has the effect of improving the high-temperature resistance of spheroidal graphite iron by strengthening the precipitation of the base.
- a passive film made of a dense chromium oxide is formed near the surface to improve the oxidation resistance.
- the Cr content is 3% or less, preferably 1 to 3%.
- Ni is an important element for austenite-making the base structure. If Ni is less than 10%, The effect of stabilizing austenite is insufficient. On the other hand, if the Ni content exceeds 40%, the austenite effect is saturated, and only the material cost rises. Therefore, Ni is 10-40%, preferably 25-40%. A more preferred lower limit of Ni is 30%, and a more preferred lower limit of Ni is 36%.
- Mo combines with carbon in the iron base to precipitate carbides, and the precipitation strengthening of the base greatly improves the power resistance over the entire operating temperature range.
- Mo is a carbide forming element, it has a small tendency to inhibit graphite spheroids.However, when Mo is used in combination with Sn, Z, or Sb, the room temperature does not cause a decrease in the number of graphite particles and the degree of graphite spheroidization. Elongation can be improved.
- Mo is an element having a small thermal expansion coefficient
- the average thermal expansion coefficient up to around 1000 ° C is reduced, and the thermal strain in a high-temperature region determined by the product of the thermal expansion coefficient and the temperature is reduced.
- Mo has a synergistic effect with Si and Cr to make the passive film such as silicon oxide and chromium oxide formed on the surface dense and strong, and suppresses surface oxidation to prevent oxidation resistance. Improve.
- the synergistic effect of suppressing the generation of thermal stress and improving the oxidation resistance prolongs the life of the thermal crack.
- Mo exceeds 4.5%, the room temperature elongation and the machinability decrease due to the deterioration of graphite spheroids and the increase of precipitated carbides.
- Mo is 1 to 4.5%, preferably 2 to 4%.
- Sn and Sb also reduce the segregation of graphite by increasing the number of graphite grains, and suppress the decrease in ductility due to the inclusion of Mo by increasing the spheroidization ratio of graphite to 75% or more. Even if up to 6.5% of Si, which has a tendency to reduce ductility, containing Sn, Z or Sb can ensure room-temperature elongation without reducing the number of graphite particles and the degree of graphite spheroidization. . Sn and Sb prevent graphite from falling off due to internal oxidation and improve the oxidation resistance of austenitic heat-resistant spheroidal graphite iron.
- Sn, Z, or Sb concentrates on the matrix side at the interface between graphite and the matrix, diffusing C from the graphite into the matrix, and reacting with oxygen graphite that has penetrated the matrix with the graphite. To suppress the reaction It is inferred.
- 2Sn + Sb is 0.001-0.5%, preferably 0.005-0.5%, and more preferably 0.01-0.4%.
- N has the effect of stabilizing the austenitic structure and improving the high-temperature resistance of the matrix.
- N should be 0.3% or less.
- N is usually an element inevitably contained in austenitic spheroidal graphite-iron at about 0.002 to 0.006%.
- N is contained in a predetermined amount.
- N is preferably 0.01-0.3%, more preferably 0.03-0.2%.
- Mg-based graphite spheroid elements such as pure Mg and Fe-Si-Mg alloy, or Ca-based 0.1% or less of the graphite spherical element.
- the content of Mg is preferably 0.02-0.08%.
- the heat-resistant, austenitic spheroidal graphite-iron of the present invention may contain Mn and Cu within a range that does not impair normal temperature elongation, oxidation resistance, high-temperature resistance, and thermal crack life.
- Mn exceeds 1.5%, which is an element necessary for stabilizing the austenite structure, it deteriorates toughness, and gas defects such as blowholes are liable to be generated, thereby lowering heat resistance.
- Ni forms a solid solution in the matrix to stabilize the austenitic structure, and refines the crystal grains in the matrix to improve the high-temperature resistance and also has the effect of improving oxidation resistance and corrosion resistance. Yes.
- Mn and Cu are contained, it is preferable that Mn is 1.5% or less and Cu is 3% or less.
- P and S are inevitable impurities.
- P is harmful to graphite spheroids, and precipitates at the crystal grain boundaries to lower the sintering resistance and room temperature elongation. Therefore, the content of P is preferably 0.08% or less. Further, S is also harmful to the graphite sphere, so it is preferable to set the content to 0.025% or less.
- the austenitic heat-resistant spheroidal graphite iron of the present invention is used for exhaust system parts for automobile engines exposed to exhaust gas at 900 ° C or more, particularly around 1000 ° C, it can be used at room temperature for elongation, oxidation resistance, and high temperature resistance. It is necessary to combine Therefore, elongation cold 2% or more, 950 ° C 30 mg / cm 2 or less in weight loss by oxidation when kept for 200 hours in an air atmosphere, and 55 N / mm 2 or more at atmospheric atmosphere of 950 ° C 0.2 It is preferable to satisfy the condition of% proof stress.
- the austenite-based heat-resistant spheroidal graphite / iron have a graphite spheroidal ratio of 75% or more, particularly in order to secure normal-temperature elongation and improve high-temperature proof stress.
- the room temperature elongation is less than 0.0%, cracks and cracks occur due to vibrations and impacts applied during the production of exhaust system parts, during assembly to the engine, and at the time of starting or driving a car. There is a risk.
- the room temperature elongation is preferably 2% or more.
- Heat-resistant austenitic spheroidal graphite iron used in exhaust system parts for automobile engines requires heat resistance (oxidation resistance and high-temperature resistance) in addition to room temperature elongation.
- the weight loss by oxidation and the 0.2% resistance to heat at 950 ° C in the atmosphere are indicators of the heat resistance. The lower the oxidation loss and the higher the high-temperature proof stress, the better the heat resistance.
- the exhaust system components are exposed to sulfur oxides, nitrogen oxides and the like contained in the exhaust gas of the engine.
- oxidation occurs, first, an oxide film is formed on the surface, and micro cracks are formed starting from the oxide film.
- the micro cracks are oxidized again to amplify the cracks, and this is repeated, and the cracks propagate greatly to the inside. If the weight loss due to oxidation when kept in an air atmosphere at 950 ° C. for 200 hours exceeds 30 mg / cm 2 , a large number of surface oxide films serving as crack starting points are generated, and the oxidation resistance becomes insufficient. Therefore, the weight loss by oxidation is preferably 30 mg / cm 2 or less.
- the 0.2% proof stress in an air atmosphere at 950 ° C. is less than 55 N / mm 2 , It is difficult to ensure a strength that can withstand the compressive stress acting on the exhaust system component that is used. Therefore, the 0.2% heat resistance in an air atmosphere at 950 ° C. is 55 N / mm 2 or more, and preferably 60 N / mm 2 or more.
- Exhaust system components are required to have a long heat crack life due to repeated operation (heating) and stop (cooling) of the engine. Specifically, in a thermal fatigue test in which heating and cooling are performed at an upper limit temperature of 950 ° C, a temperature amplitude of 800 ° C, and a constraint rate of 0.5, the number of cycles until a crack is broken (thermal crack life) is 400 cycles or more. Is desirable. The thermal crack life under these conditions is an index indicating the degree of heat resistance. If the thermal crack life is less than 400 cycles, the thermal crack life of exhaust system components exposed to exhaust gas above 900 ° C, especially around 1000 ° C is not sufficient.
- the exhaust system component has not only the above-mentioned room temperature elongation, oxidation resistance and high temperature resistance but also a small average thermal expansion coefficient from a room temperature to a high temperature range.
- the thermal strain in the high temperature range which is determined by the product of the coefficient of thermal expansion and the temperature, decreases, and the resulting thermal stress decreases, the thermal crack life of the exhaust system component improves.
- the average coefficient of thermal expansion from room temperature to 1000 ° C is preferably 18 X 10 "V ° C or less! / ,.
- Austenitic heat-resistant spheroidal graphite iron having the chemical composition (% by weight) shown in Table 1 was melted in the air using a high-frequency furnace for 100 kg, then poured out at 1450 ° C or higher and poured at 1300 ° C or higher. A 25 mm X 25 mm X 165 mm block-shaped test material was manufactured.
- Example 117 is a test material within the scope of the present invention
- Comparative Example 113 is a test material outside the scope of the present invention.
- Comparative Examples 13 and 13 are test materials having a Mo content force of less than 1%
- Comparative Examples 419 and 11 are test materials containing no Sn and Sb
- Comparative Example 10 is a Mo content force of 0.5%.
- Comparative Example 12 is a specimen having 2Sn + Sb over 0.5%
- Comparative Example 13 is a specimen having a N content exceeding 0.3%. It is.
- Comparative Example 4 corresponds to a resist D5S (JIS G 5510, JIS-FCDA NiSiCr 352) containing no Mo, Sn and Sb.
- the graphite spheroidization rate of each of the test materials of Example 117 and Comparative Example 111 was measured by the graphite spheroidization rate determination test method of JIS G5502 10.7.4. Table 2 shows the results.
- the metal structures of the test materials of Example 12 and Comparative Example 9 were observed under a microscope.
- FIG. 1 is a micrograph (100 ⁇ magnification) showing the metal structure of the test material of Example 12
- FIG. 2 is a micrograph (100 ⁇ magnification) showing the metal structure of the test material of Comparative Example 9.
- Each test piece was cut out of a flanged test piece having a gauge distance of 50 mm and a gauge diameter of 10 mm, and each test piece was set on an electrohydraulic servo-type tensile testing machine. And room temperature elongation (%) at 25 ° C. were measured. The relationship between the graphite spheroidization rate and the room temperature elongation was examined for each test material.
- Figure 3 shows the relationship between the graphite spheroidization rate and the room temperature elongation.
- the relationship between the Mo content and the room temperature elongation was examined for each test material.
- Figure 4 shows the relationship between Mo content and room temperature elongation.
- the graphite particles exhibited many and good spherical shapes. Further, the graphite spheroid ratio of Example 12 was 84%, and the room temperature elongation was 2.3%, which were both high.
- the structure of the test material of Comparative Example 9 which contains Mo in an excessive amount of 4.87% and does not contain Sn and / or Sb has a small number of graphite particles and is not spheroidal graphite. Were observed. Further, the graphite spheroidization ratio of Comparative Example 9 was 64%, and the room temperature elongation was 0.9%, which were all low.
- Oxidation resistance in an air atmosphere at 950 ° C was evaluated, assuming use in exhaust system parts exposed to exhaust gas at 900 ° C or higher, particularly around 1000 ° C. Specifically, a round bar test piece with a diameter of 10 mm and a length of 20 mm was cut out from each test material, each test piece was kept in the air at 950 ° C for 200 hours, and then shot blasted. The oxidized scale was removed, and the change in weight per unit area before and after the oxidation test (the amount of acidification) was determined. The smaller the weight loss, the better the acid resistance. Table 2 shows the results. In addition, the relationship between the Mo content and the weight loss due to oxidation was investigated for each test material. Fig. 5 shows the results.
- Example 11 containing Mo, Sn and Sb was used.
- the test material had extremely excellent acid resistance.
- Fig. 6 is a micrograph (magnification: 400x) showing the metal structure of the test material of Example 12 after the oxidation test
- Fig. 7 is the oxidation of the test material of Comparative Example 4 containing no Mo, Sn and Sb. It is a micrograph (magnification: 400 times) which shows the metal structure after a test.
- the test material of Example 12 was slightly oxidized on the surface and the graphite was prevented from falling off, whereas the test material of Comparative Example 4 was oxidized and dropped off due to vigorous surface oxidization. An oxide film penetrated the traces of graphite cavities, and further dropped down to part of the black ship inside.
- the Mo content was about the same as 1.4%, and the presence or absence of Sn and Sb was different.
- the comparison of the oxidation loss of the test materials of Example 7 and Comparative Example 5 showed that 2Sn + Sb was 0.0212%.
- the weight loss of oxidation of Example 7 of Example 7 was 19.2 mg / cm 2
- the weight loss of oxidation of Comparative Example 5 containing neither Sn nor Sb was 48.6 mg / cm 2, which was about 2.5 times as large.
- the sample material of Example 12 in which 2Sn + Sb is 0.0294% is compared. In the test material, the oxidative weight loss was 13.5 mg / cm 2 , whereas in the test material of Comparative Example 11 containing no Sn and Sb, the oxidative weight loss was 35.7 mg / cm 2, which was about 2.5 times as much.
- the Mo content in order to improve the oxidation resistance so that the oxidation resistance when kept in an air atmosphere at 950 ° C for 200 hours is 30 mg / cm 2 or less, the Mo content must be 1%. It can be seen that it is necessary to set one 4.5% and 2Sn + Sb 0.001-0.5%. In particular, in Examples 3-6 and 10-14, the power at which the weight loss of oxidation is less than 15 mg / cm 2 To obtain such a low weight loss of acid, it is preferable to set the Mo content to 2-4%. .
- the high-temperature resistance of each test piece was determined by cutting a flanged test piece with a gauge distance of 50 mm and a gauge diameter of 10 mm from each test piece, and pulling each test piece using the electro-hydraulic servo system. It was set in a test machine and measured by measuring 0.2% resistance in an air atmosphere at 950 ° C. Table 2 shows the results.
- FIG. 8 shows the relationship between the Mo content and the high temperature proof stress.
- Examples 7 and 8 and Comparative Example 5 containing approximately the same amount of Mo as approximately 1.4% are compared with respect to high-temperature resistance.
- N and their respective 0.0042%, relative to 0.0048% of (both inevitable level) hot ⁇ Ka test material embodiment containing example 7 and Comparative example 5 is about 57 N / mm 2
- N in deliberately 0.0104% containing the test materials of example 8 is hot ⁇ Ka was about 7 N / mm 2 as high as 64.4N / mm 2.
- Comparative Example 6 containing N at an unavoidable level, 7, each about 58 hot ⁇ Ka test material of 8, 62, 62 N / mm is 2 whereas, in example 10 where intentionally contained on 0.01% more than the N, 12, 14 hot The resistance to heat was about 67, 71, 72 N / mm 2 and about 910 N / mm 2 higher, respectively.
- N in addition to Mo greatly contributes to the improvement of the high-temperature proof stress. This is thought to be because N improves the high-temperature resistance by stabilizing the austenitic structure and strengthening the matrix.
- a high temperature proof stress as high as 60 N / mm 2 or more is required, it can be seen that it is effective to contain N in excess of an unavoidable level.
- N is contained in excess of the upper limit of about 0.42% as in Comparative Example 13, the high temperature resistance is improved, but the room temperature elongation is reduced to 0.8% and the thermal crack life is significantly shortened. This is considered to be due to the fact that excess N caused an increase in the amount of precipitated nitrides and a reduction in the graphite spheroidal ratio, resulting in a decrease in toughness and gas defects such as pinholes during fabrication.
- thermo-hydraulic servo thermal fatigue testing machine Cut out a round bar test piece with a gauge distance of 20 mm and a gauge diameter of 10 mm for each test piece, set each test piece in a thermo-hydraulic servo thermal fatigue testing machine, The mechanical restraint of expansion and contraction, the lower limit of 150 ° C, the upper limit of 750 ° C, 800 ° C and 950 ° C respectively (temperature amplitude of 600 ° C, 650 ° C and 800 ° C respectively), and Under the condition of one cycle of 7 minutes, the heating and cooling cycle was repeated to cause thermal fatigue fracture due to cracks, and the number of cycles until fracture was measured to determine the thermal crack life.
- the constraint rate is represented by (free thermal expansion / elongation under mechanical constraint) / (free thermal expansion / elongation).
- a constraint of 1.0 means that the specimen is heated to, for example, 150 ° C force to 950 ° C This is the case where it is mechanically constrained so that it does not stretch at all.
- a constraint rate of 0.5 is, for example, the case where the free thermal expansion is mechanically constrained so that it extends only 1 mm where the elongation is 2 mm.
- exhaust system parts such as turbocharger housing, exhaust-hold, catalyst case, etc.
- FIG. 9 shows the relationship between the Mo content and the thermal crack life at a temperature of 950 ° C. and a constraint rate of 0.5.
- Example 117 when the Mo content is about 3%, the thermal crack life peaks, and when the Mo content is within the range of 1-14.5% (Example 117), the thermal crack life is 400 cycles or more. It can be seen that On the other hand, the thermal crack life of each of the test materials of Comparative Examples 113 was less than 400 cycles. Thus, the test material of Example 117 had a longer thermal crack life than the test material of Comparative Example 113 because of the suppression of thermal stress in the high-temperature region due to the inclusion of Mo, Sn and Z or It is presumed that this is due to the synergistic effect of ensuring ductility from normal temperature to high temperature range and improving oxidation resistance by containing Sb.
- thermomechanical analyzer (TAS200, manufactured by Rigaku Denki Co., Ltd.). It was heated from room temperature to 1000 ° C, and the average thermal expansion coefficient at room temperature and 1000 ° C was measured from the amount of expansion at every 100 ° C. Table 2 shows the results. Table 3 shows the measured values of the coefficient of thermal expansion in Example 12 and Comparative Example 4 in each temperature range.
- Example 12 Comparative Example 4 Room temperature to 300 ° C 13.9 15.9 Room temperature to 400 ° C 14.6 16.6 Room temperature to 500 ° C 15.3 17.2 Room temperature to 600 ° C 15.8 17.6 Room temperature to 700 ° C 16.1 17.7 Room temperature to 800 ° C 16.4 17.9 Room temperature to 900 ° C 16.7 18.5 Room temperature to 1000 ° C 17.4 19.5
- Table 2 the average thermal expansion coefficient in the range of room temperature one 1000 ° C with the increase of Mo content is reduced, the average thermal expansion coefficient in excess of Mo content force l% is 18 X 10- 6 / ° C or less. Also, from Table 3, in the temperature range from room temperature to 300 to 1000 ° C at every 100 ° C, the thermal expansion coefficient of Example 12 is 1.5 to 2. IX10 compared to Comparative Example 4 containing no Mo, Sn and Sb. — 6 / ° C smaller! / ⁇ When austenitic heat-resistant spheroidal graphite iron is used as an exhaust system component for automobile engines, the average coefficient of thermal expansion in the range of room temperature to 1000 ° C is 18 X 10— to suppress cracks caused by thermal stress. It is desirable to be 6 / ° C or less. For that purpose, the Mo content needs to be 1% or more.
- FIG. 10 shows, as an example of an exhaust system component using the heat-resistant, austenitic spheroidal graphite iron of the present invention, an exhaust system component having an exhaust-hold 1, a turbocharger housing 2, and a catalyst case 4. Show.
- exhaust gas (indicated by an arrow A) from an engine (not shown) is collected by an exhaust holder 1 and a kinetic energy of the exhaust gas is used to generate a turbine in a turbocharger housing 2. (Not shown), and drives a compressor coaxial with this turbine to compress the intake air (indicated by arrow B), By supplying the air to the engine (indicated by arrow C), the output of the engine is increased.
- Exhaust gas from the turbocharger housing 2 enters the catalyst case 4 via the connection 3, and after the harmful substances are reduced by the catalyst in the catalyst case 4, the exhaust gas enters the atmosphere via the noise reduction muffler 5. Released (indicated by arrow D).
- An exhaust gas passage is formed in the exhaust holder 1, the turbocharger housing 2, the connection part 3, and the catalyst case 4.
- the thickness of the exhaust gas passage is, for example, 2.0--4.5 mm for the exhaust holder 1, 2.5--5.5 mm for the turbocharger housing 2, 2.5--3.5 mm for the connection 3, and In case 4, 2.0-2.5 mm.
- FIG. 11 shows an example of the turbocharger housing 2
- FIG. 12 shows a cross section taken along line AA.
- the scroll portion 2a has a conch-shaped cavity, and the cavity has a complex shape in which one force is directed in the other direction to increase the area of the cavity.
- the turbocharger housing 2 is provided with a waste gate portion 2b for opening and closing a valve (not shown) to bypass and discharge excess exhaust gas.
- the waste gate 2b is particularly required to have oxidation resistance because high-temperature exhaust gas flows.
- the exo-storage holder 1 and the turbocharger housing 2 were fabricated from heat-resistant austenitic spheroidal graphite iron having the composition of Example 12, and then machined.
- the obtained exhaust holder 1 and turbocharger housing 2 do not have any structural defects such as shrinkage cavities, poor run-off, gas defects, and the like. Problem did not occur.
- connection part 3 and the catalyst case 4 can be made of the heat-resistant austenitic spheroidal graphite iron of the present invention. If mold division (partition) or molding is possible, the turbocharger housing 2 and the exhaust holder 1 can be integrally constructed, and the turbocharger housing 2 should not be interposed! Alternatively, the catalyst case 4 and the exhaust-hold 1 can be integrally formed.
- An exhaust simulator corresponding to a high-performance gasoline engine with a displacement of 2000 cc and an in-line 4-cylinder was equipped with an austenitic heat-resistant spheroidal graphite-iron extruder holder 1 and a turbocharger housing 2 of Example 12 as well. Assembling and durability tests were performed. The test conditions were a heating / cooling cycle consisting of 10 minutes of heating and 10 minutes of cooling. It was something.
- the exhaust gas temperature at full load was 980 ° C at the inlet of the turbocharger housing 2. Under these conditions, the surface temperature at the junction of the exhaust holder 1 is approximately 900 ° C, and the surface temperature at the seating surface 2c of the wastegate 2b of the turbocharger housing 2 is approximately 950 ° C. Met.
- FIG. 13 shows the appearance (after the end of the 1000-cycle endurance test) of the vicinity of the wastegate portion 2b of the turbocharger housing 2 made of heat-resistant austenitic spheroidal graphite-iron of Example 12.
- Fig. 13 shows the appearance (after the end of the 1000-cycle endurance test) of the vicinity of the wastegate portion 2b of the turbocharger housing 2 made of heat-resistant austenitic spheroidal graphite-iron of Example 12.
- the austenitic heat-resistant spheroidal graphite-iron exo-extruder holder 1 and the turbocharger housing 2 of the twelfth embodiment include structures, machining, endurance tests, etc. , Cutting, assembling, etc.), vibration and impact were applied at room temperature, but no cracks or cracks occurred and it was confirmed that they had sufficient ductility.
- FIG. 14 shows the appearance (after the durability test) of the vicinity of the waste gate portion 2b of the turbocharger housing 2. As shown in FIG. 14, rapid cracking caused a large crack 2d in the wastegate portion 2b and a deformation of the seating surface 2c in about half of the heating and cooling cycle (540 cycles) of Example 12.
- the heat-resistant austenitic spheroidal graphite iron of the present invention has sufficient room-temperature elongation and excellent heat resistance (oxidation resistance, high-temperature resistance, and thermal crack life).
- the austenitic heat-resistant spheroidal graphite iron of the present invention contains iron, which is expensive, but has a high C content compared to stainless steel, and therefore has a low melting point and good formability. The machinability is also good.
- the austenitic heat-resistant spheroidal graphite iron of the present invention If high-yield without the need for advanced manufacturing technology, the exhaust system components (exhaust manifolds, turbochargers, etc.) for thin-walled and complex-shaped automobile engines exposed to exhaust gas above 900 ° C, especially around 1000 ° C Housing and catalyst case) can be manufactured at low cost.
- This exhaust system component has sufficient heat resistance even if it is disposed behind the engine in a severe temperature environment, and can increase the initial performance of the exhaust gas purification catalyst.
- heat-resistant austenitic spheroidal graphite iron of the present invention is used for exhaust system parts for automobile engines
- hearths and carts for incinerators and heat treatment furnaces requiring not only limited room temperature elongation but also heat resistance are required. It can also be used for combustion parts such as
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Abstract
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/564,721 US20060191604A1 (en) | 2003-07-18 | 2004-07-20 | Austenite heat-resistant spheroidal graphite cast iron |
| JP2005511882A JPWO2005007914A1 (ja) | 2003-07-18 | 2004-07-20 | オーステナイト系耐熱球状黒鉛鋳鉄 |
| EP04770825A EP1652949A4 (en) | 2003-07-18 | 2004-07-20 | AUSTENITIC HEAT-RESISTANT BALL GRAPHITE CAST IRON |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-199184 | 2003-07-18 | ||
| JP2003199184 | 2003-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005007914A1 true WO2005007914A1 (ja) | 2005-01-27 |
Family
ID=34074402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2004/010314 Ceased WO2005007914A1 (ja) | 2003-07-18 | 2004-07-20 | オーステナイト系耐熱球状黒鉛鋳鉄 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20060191604A1 (ja) |
| EP (1) | EP1652949A4 (ja) |
| JP (1) | JPWO2005007914A1 (ja) |
| KR (1) | KR20060033020A (ja) |
| CN (1) | CN1826421A (ja) |
| WO (1) | WO2005007914A1 (ja) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009028736A1 (ja) * | 2007-08-31 | 2009-03-05 | Kabushiki Kaisha Toyota Jidoshokki | オーステナイト系鋳鉄とその製造方法およびオーステナイト系鋳鉄鋳物および排気系部品 |
| JP2011179113A (ja) * | 2010-01-14 | 2011-09-15 | Honeywell Internatl Inc | オーステナイトダクタイル鋳鉄 |
| CN103014482A (zh) * | 2012-12-28 | 2013-04-03 | 山东省源通机械股份有限公司 | 耐热耐腐蚀的奥氏体球墨铸铁生产的金属材料及制法 |
| JP2019173110A (ja) * | 2018-03-29 | 2019-10-10 | 虹技株式会社 | 球状黒鉛鋳鉄とその製造方法 |
| WO2022085642A1 (ja) * | 2020-10-23 | 2022-04-28 | 日之出水道機器株式会社 | 鋳造用鉄合金材料および鉄鋳物 |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7431576B2 (en) * | 2005-11-30 | 2008-10-07 | Scroll Technologies | Ductile cast iron scroll compressor |
| US8096793B2 (en) * | 2006-03-22 | 2012-01-17 | Scroll Technologies | Ductile cast iron scroll compressor |
| US8333923B2 (en) * | 2007-02-28 | 2012-12-18 | Caterpillar Inc. | High strength gray cast iron |
| EP1983194A1 (en) * | 2007-04-17 | 2008-10-22 | Scroll Technologies | Ductile cast iron scroll compressor |
| ES2625678T3 (es) * | 2008-02-25 | 2017-07-20 | Wescast Industries, Inc. | Hierro fundido de grafito nodular Ni-25 resistente al calor para su uso en sistemas de escape |
| PL2573199T3 (pl) * | 2010-05-21 | 2018-06-29 | Kabushiki Kaisha Toyota Jidoshokki | Żeliwo austenityczne, produkt odlewniczy z żeliwa austenitycznego i sposób wytwarzania produktu odlewniczego |
| EP2511394B1 (de) * | 2011-04-15 | 2015-05-27 | Siemens Aktiengesellschaft | Gusseisen mit Niob und Bauteil |
| 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 |
| CN103290302A (zh) * | 2012-02-27 | 2013-09-11 | 徐驰 | 高强度合金球墨铸铁曲轴 |
| US9500097B2 (en) * | 2012-04-22 | 2016-11-22 | Precision Turbo & Engine Rebuilders, Inc. | Turbocharger containment assembly |
| WO2014185455A1 (ja) * | 2013-05-14 | 2014-11-20 | 東芝機械株式会社 | 高強度高減衰能鋳鉄 |
| CN103469053B (zh) * | 2013-08-28 | 2016-06-22 | 于佩 | 一种球墨铸铁基础桩管及其制备工艺 |
| CN105018833A (zh) * | 2015-07-09 | 2015-11-04 | 王波林 | 一种等温淬火球铁及其生产推力杆端头的方法 |
| CN105401062A (zh) * | 2015-11-17 | 2016-03-16 | 益阳紫荆福利铸业有限公司 | 一种高镍奥氏体耐腐蚀球墨铸铁 |
| CN105603294B (zh) * | 2015-12-31 | 2017-12-19 | 山东瑞丰达机械股份有限公司 | 提高球墨铸铁离心式泵壳耐磨性能的方法 |
| CN106048396B (zh) * | 2016-07-12 | 2018-05-22 | 中国石油集团济柴动力总厂成都压缩机厂 | 一种耐低温高镍奥氏体球墨铸铁及其制备方法 |
| CN107893189B (zh) * | 2017-10-13 | 2019-09-20 | 滨州渤海活塞有限公司 | 高镁低稀土奥氏体蠕墨铸铁、其制备方法及其应用 |
| CN117004889B (zh) * | 2023-08-10 | 2025-09-23 | 中原内配集团股份有限公司 | 一种球墨钢气缸套及其制备方法 |
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| US6508981B1 (en) * | 2001-05-24 | 2003-01-21 | Wescast Industries, Inc. | High temperature oxidation resistant ductile iron |
| KR100435324B1 (ko) * | 2001-12-27 | 2004-06-10 | 현대자동차주식회사 | 고온 내산화성을 갖는 내열구상흑연주철 |
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- 2004-07-20 WO PCT/JP2004/010314 patent/WO2005007914A1/ja not_active Ceased
- 2004-07-20 CN CNA2004800207976A patent/CN1826421A/zh active Pending
- 2004-07-20 EP EP04770825A patent/EP1652949A4/en not_active Withdrawn
- 2004-07-20 US US10/564,721 patent/US20060191604A1/en not_active Abandoned
- 2004-07-20 KR KR1020067001030A patent/KR20060033020A/ko not_active Withdrawn
- 2004-07-20 JP JP2005511882A patent/JPWO2005007914A1/ja active Pending
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009028736A1 (ja) * | 2007-08-31 | 2009-03-05 | Kabushiki Kaisha Toyota Jidoshokki | オーステナイト系鋳鉄とその製造方法およびオーステナイト系鋳鉄鋳物および排気系部品 |
| JP5384352B2 (ja) * | 2007-08-31 | 2014-01-08 | 株式会社豊田自動織機 | オーステナイト系鋳鉄とその製造方法およびオーステナイト系鋳鉄鋳物および排気系部品 |
| JP2011179113A (ja) * | 2010-01-14 | 2011-09-15 | Honeywell Internatl Inc | オーステナイトダクタイル鋳鉄 |
| CN103014482A (zh) * | 2012-12-28 | 2013-04-03 | 山东省源通机械股份有限公司 | 耐热耐腐蚀的奥氏体球墨铸铁生产的金属材料及制法 |
| JP2019173110A (ja) * | 2018-03-29 | 2019-10-10 | 虹技株式会社 | 球状黒鉛鋳鉄とその製造方法 |
| JP7109226B2 (ja) | 2018-03-29 | 2022-07-29 | 虹技株式会社 | 球状黒鉛鋳鉄とその製造方法 |
| WO2022085642A1 (ja) * | 2020-10-23 | 2022-04-28 | 日之出水道機器株式会社 | 鋳造用鉄合金材料および鉄鋳物 |
| JPWO2022085642A1 (ja) * | 2020-10-23 | 2022-04-28 | ||
| JP7407485B2 (ja) | 2020-10-23 | 2024-01-04 | 日之出水道機器株式会社 | 鋳造用鉄合金材料および鉄鋳物 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1652949A1 (en) | 2006-05-03 |
| CN1826421A (zh) | 2006-08-30 |
| EP1652949A4 (en) | 2008-06-25 |
| KR20060033020A (ko) | 2006-04-18 |
| JPWO2005007914A1 (ja) | 2006-11-24 |
| US20060191604A1 (en) | 2006-08-31 |
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