EP2518174A2 - Cgi cast iron and a production method for the same - Google Patents
Cgi cast iron and a production method for the same Download PDFInfo
- Publication number
- EP2518174A2 EP2518174A2 EP10839697A EP10839697A EP2518174A2 EP 2518174 A2 EP2518174 A2 EP 2518174A2 EP 10839697 A EP10839697 A EP 10839697A EP 10839697 A EP10839697 A EP 10839697A EP 2518174 A2 EP2518174 A2 EP 2518174A2
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- EP
- European Patent Office
- Prior art keywords
- cast iron
- magnesium
- present
- content
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910001018 Cast iron Inorganic materials 0.000 title claims abstract description 123
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 81
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 31
- 239000010439 graphite Substances 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000010079 rubber tapping Methods 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910001126 Compacted graphite iron Inorganic materials 0.000 abstract description 15
- 238000005266 casting Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 22
- 229910001060 Gray iron Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002054 inoculum Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910001562 pearlite Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 229910001141 Ductile iron Inorganic materials 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001584785 Anavitrinella pampinaria Species 0.000 description 1
- 101100437784 Drosophila melanogaster bocks gene Proteins 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/08—Manufacture of cast-iron
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/08—Making cast-iron alloys
Definitions
- the present invention relates to cast iron and a method of producing the same, and more particularly, to cast iron having an improved casting property and stable tensile strength and yield strength by controlling the contents of components added to iron, and a method of producing the cast iron.
- Cast iron according to the present invention corresponds to hypereutectic compacted graphite iron (CGI) cast iron that can be applied to the cylinder block of diesel engines with high output.
- CGI hypereutectic compacted graphite iron
- Cast iron is the material that is generally used for cylinder blocks in the related art, common grade cast iron is usually gray cast iron.
- the gray cast iron is called gray cast iron because carbon is decomposed and produced into graphite in casting and the surface shows gray.
- cast iron has differences in accordance with the shape, size, and distribution state of graphite contained in the base and the tensile strength of gray cast iron generally called cast iron is about 147.1 to 196.1MPa.
- the gray cast iron has a limit in use for the material of the cylinder block of engines having high explosive pressure, because the strength is low although a cast property, damping capacity, and thermal conductivity are excellent.
- the spherical graphite cast iron is cast iron of which the toughness is improved by changing graphite shown in common cast iron (gray cast iron) into a spherical structure from the original foliaceous structure.
- the spherical graphite cast iron is also called nodular cast iron or ductile cast iron.
- the spherical graphite cast iron has excellent abrasion resistance, heat resistance, corrosion resistance, has a higher modulus of elasticity than that of common gray cast iron, has a Brinell Hardnes of even about 200, and also has a cutting property better than that of common cast iron having the same hardness.
- the spherical graphite cast iron has high strength required for cylinder blocks, but has an insufficient casting property and low thermal conductivity to be produced in a complicate shape, such that it has a limit in use for cylinder bocks having complicated shapes.
- CGI Cosmetic Graphite Iron
- the CGI cast iron may be produced by accurately controlling the content of magnesium (Mg) when tapping molten spherical graphite cast iron, which is produced by melting spherical graphite cast iron, into a ladle for carrying original molten metal produced by a furnace to another place.
- Mg magnesium
- the present invention provides cast iron of which tensile strength and yield strength are controlled within the ranges of 500 to 600MPa and 350 to 450MPa, respectively, by controlling the contents of carbon (C), silicon (Si), manganese (Mn), copper (Cu), tin (Sn), and magnesium (Mg) with a range that ensures stable properties without causing poor casting.
- An object of the present invention is to provide cast iron having stable properties and structure by accurately controlling the amount of magnesium (Mg).
- Mg magnesium
- Another object of the present invention is to establish a chemical composition and a production method which make it possible to producing cast iron for a cylinder block that can be applied to high-output and high-power diesel engines by providing stable tensile strength and yield strength and appropriate hardness.
- the present invention provides a cast iron for use with cylinder block of an engine comprising carbon (c) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, magnesium (Mg) of 0.008 to 0.018 wt%, phosphorus (P) of 0.04 wt% or less, sulfur (S) of 0.02 wt% or less, and the balance of ferrum (Fe), an the entire weight.
- tensile strength of the cast iron is 500 to 600MPa. Further, according to another exemplary embodiment of the present invention, yield strength of the cast iron is in the range of 350 to 450MPa. Meanwhile, a Brinell Hardness value (BHW) of the cast iron is 255 to 280.
- BHW Brinell Hardness value
- CE Carbon Equivalent
- nodularity of graphite produced by the carbon is 5 to 20% in the cast iron.
- the present invention provides a method of producing cast iron, comprising: producing original molten cast iron by melting a cast iron material, which contains carbon (C) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, phosphorous (P) of 0.04 wt% less, sulfur (S) of 0.02 wt% or less, and the balance of ferrum (Fe), in the entire weight, in a furnace; providing copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt% in a ladle that is a container for tapping the original molten cast iron melted in a furnace; producing molten cast iron by tapping the produced original molten cast iron with the ladle with copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.
- CGI cast iron with stable mechanical properties is achieved by putting a predetermined amount of magnesium (Mg) and appropriate amounts of copper (Cu) and tin (Sn) into a ladle, which is a container for tapping an original molten cast iron melted in a furnace, tapping the original molten cast iron into the laddle, and crystallizing the graphite to be stable CGI.
- Mg magnesium
- Cu copper
- Sn tin
- CE Carbon Equivalent
- the tapping temperature of the original molten metal is adjusted to be 1520°C.
- the cast iron according to the present invention it is possible to estimate nodularity of graphite contained in cast iron from the content of magnesium contained in the molten cast iron and to estimate the range of strength according to the nodularity.
- the content of magnesium may depend on the necessary strength and the content is 0.008 to 0.018 wt% to be applied to the cylinder block of high-output diesel engines.
- the present invention it is possible to provide cast iron with tensile strength in the range of 500 to 600 MPa, yield strength in the range of 350 to 450 Mpa, and Brinell Hardness in the range of 255 to 280, by precisely controlling the amount of magnesium (Mg) and controlling the amounts of copper (Cu) and tin (Sn).
- the cast iron according to the present invention has stable tensile strength and yield strength and appropriate hardness, the cast iron can be used to manufacture cylinder blocks that can be applied to high-output and high-power diesel engines.
- CGI cast iron having a uniform structure and strength that is high enough to be used for the cylinder block of high-power diesel engines, by precisely controlling the amount of magnesium (Mg). Further, it is possible to produce CGI cast iron having various hardness and tensile strength by controlling the amount of copper (Cu) and tin (Sn) that is alloy elements.
- Cast iron according to the present invention contains carbon (c) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, magnesium (Mg) of 0.008 to 0.018 wt%, phosphorus (P) of 0.04 wt% or less, sulfur (S) of 0.02 wt% or less, and the balance of ferrum (Fe), an the entire weight.
- the basic material of the cast iron is ferrum (Fe).
- Carbon is added for crystallization of compacted graphite, and when the content of carbon in cast iron is less than 3.65 wt%, a chilling behavior is observed in a thin-walled part, and when it is above 3.75 wt%, graphite nodularity retraction and poor flow are generated. Therefore, the content of carbon is limited within 3.65 to 3.75 wt% in the present invention to prevent the defects in high-strength cylinder block having various thicknesses.
- Silicon maximizes the amount of crystallization of compacted graphite and increases strength of cast iron when being added at the optimum ratio with carbon.
- the content of silicon is less than 2.0 wt%, the amount of crystallization of compacted graphite decreases, and when it is above 2.25 wt%, ductility decreases, such that the content is set within 2.0 to 2.25 wt%.
- Manganese is added to make graphite fine and stabilize pearlite, and in the cast iron according to the present invention, when the content of manganese is less than 0.3 wt%, hardness decreases, and when it is above 0.6 wt%, brittleness increases, such that the content is set within 0.3 to 0.6 wt%.
- Copper is an element for compacted graphitization and promote creation of pearlite and makes it fine, such that it is an element for ensuring strength.
- iron according to the present invention when the content of copper is less than 1.2 wt%, lack of strength is caused, but even if the content is above 1.4 wt%, there is no additional effect corresponding to the excessive amount. Therefore, the content of copper is set within 1.2 to 1.4 wt% in the present invention.
- Tins is a very strong element for promoting creation of pearlite and added to improve strength, similar to copper.
- the content of tin is less than 0.07 wt%, strength decreases and when it is added over 0.10 wt%, brittleness rapidly increases, such that the content is set within 0.07 to 0.10 wt%.
- Magnesium has function of graphite nodularity and promotes creation and growth of the nucleus of compacted graphite.
- the content of magnesium is less than 0.008 wt%, graphite becomes flaky, and when it is above 0.018 wt%, nodularity of graphite increases and poor retraction is caused, such that the content is limited within 0.008 to 0.018 wt%.
- Phosphorous is also a kind of impurity naturally added from the air in the process of producing cast iron. Phosphorous stabilizes pearlite but when the content is above 0.04 wt%, brittleness rapidly increases and this is in association with poor retraction due to segregation. Therefore, in the cast iron according to the present invention, it is preferable to maintain the content of phosphorous at 0.04 wt% or less.
- Sulfur functions as a creation site of compacted graphite, but when the content is above 0.02 wt%, it is required to add more magnesium in order to create compacted graphite. That is, when the content of sulfur increases above a predetermined range, with the content is magnesium limited, compacted graphite becomes flaky. Therefore, it is necessary to maintain the content of sulfur at 0.02 wt% or less in the cast iron according to the present invention.
- Ferrum is the main substance of cast iron according to the present invention. The balance except for the components described above is ferrum.
- carbon equivalent is 4.35 to 4.5.
- the carbon equivalent is defined by carbon + (silicon + phosphorous) X 1/3 and the value may be adjusted to control the properties and quality of the product.
- tensile strength of the cast iron is 500 to 600MPa and yield strength is 350 to 450MPa.
- nodularity of graphite produced by the carbon is 5 to 20%.
- a process of producing cast iron according to the present invention is described with reference to FIG. 4 .
- original molten cast iron 110 is produced by melting a cast iron material containing carbon (C) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, phosphorous (P) of above 0 and 0.04 wt% less, sulfur (S) of above 0 and 0.02 wt% or less, and the balance of ferrum (Fe), in the entire weight, in a furnace 100.
- C carbon
- Si silicon
- Mn manganese
- P phosphorous
- S sulfur
- Fe ferrum
- a ladle 200 with the other components 210 of copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt% is prepared, in which the ladle 200 is a container for tapping the original molten cast iron melted in a furnace.
- the molten cast iron 110 is produced by tapping the produced original molten cast iron with the ladle 200 with copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt%.
- Cu copper
- Sn tin
- Mg magnesium
- the tapping temperature can be adjusted to be 1,520°C.
- the CE Carbon Equivalent
- the CE may be adjusted to be 4.35 to 4.5 in the original molten cast iron.
- the amount of magnesium to be added is determined by checking the content of magnesium contained in the molten cast iron in the ladle 200.
- the original molten cast iron was carried to the ladle with the magnesium, a predetermined amount of magnesium is contained in the molten cast iron in the ladle. Nevertheless, the content of magnesium contained in the molten cast iron in the ladle is checked again to more precisely controlled the content of magnesium in consideration of loss of magnesium while carrying the ladle, and when it is determined that it needs to add magnesium, magnesium is added again.
- a thermal analysis system 300 may be used to check the content of magnesium.
- Magnesium of which the amount to be added is determined is added to the molten cast iron in the ladle. According to an exemplary embodiment of the present invention, it may be possible to add magnesium, using a wire shape of magnesium 500.
- Another inoculant that is generally used in a process of producing cast iron may be added with magnesium.
- a silicon-based inoculant may be added.
- the silicon-based inoculant may be obtained from those on the market.
- the kind and content of the inoculant may be easily selected and determined by those skilled in the art, if necessary.
- Other inoculants may also be shaped in a wire type 500.
- Cast iron is completed by injecting the molten metal with magnesium into a mold 400.
- Cast iron according to Examples 1 to 10 and Comparative example 1 to 10 was produced in accordance with the composition in the following Table 1 [Table 1] Unit: wt% Items C Si Mn Cu Sn Mg P S Fe Example 1 3.650 2.240 0.440 1.360 0.090 0.017 0.031 small balance Example 2 3.680 2.190 0.400 1.340 0.090 0.010 0.031 small balance Example 3 3.700 2.110 0.390 1.410 0.080 0.011 0.031 small balance Example 4 3.710 2.080 0.400 1.330 0.100 0.009 0.034 small balance Example 5 3.680 2.140 0.380 1.260 0.080 0.011 0.031 small balance Example 6 3.680 2.180 0.430 1.340 0.090 0.018 0.026 small balance Example 7 3.710 2.130 0.400 1.290 0.070 0.013 0.031 small balance Example 8 3.690 2.050 0.400 1.350 0.100 0.014 0.033 small balance Example 9 3.710 2.130 0.400 1.290 0.070 0.013 0.031 small balance Example 10 3.700 2.140 0.430
- S is an element that is unavoidably contained in the raw material of cast iron and the process of producing cast iron, such that it is not separately added but the content is maintained at 0.02 wt% or less.
- the content of carbon was adjusted by measuring the CE by using a CE meter before tapping and temperature was fitted to 1,146°C with respect to TL (Liquidous Temperature), thereby preparing original molten metal.
- a ladle was prepared by adding magnesium (Mg), copper (Cu), and tin (Sn) and the original molten metal was tapped to the ladle while the tapping temperature is uniformly maintained around about 1,520°C .
- the amount of magnesium to be added in consideration of the content of magnesium that will be finally contained was determined by thermally analyzing the tapped original molten metal, the alloy amount of a wire type of magnesium was injected into a mold at 1,410°C after the alloy elements are adjusted.
- Carbon equivalent (CE), tensile strength (TS), yield strength (YS), hardness (Hardness), and nodularity of the cast iron produced in accordance with the composition in Table 1 were measured and shown in Table 2.
- the hardness is Brinell Hardness and an HBW brinell hardness value.
- the tensile strength was within 500 to 600 MPa(N/mm 2 ), the yield strength was 350 to 450 MPa(N/mm 2 ), and the HBW brinell hardness value was 255 to 280.
- the cast iron according to the present invention has stable tensile strength and yield strength and appropriate hardness, such that the cast iron may be easily used to manufacture a cylinder block that can be applied to high-output and high-power diesel engines.
- nodularity was in the range of 5 to 20% in the CGI cast iron according to the present invention.
- FIGS. 2 and 3 can be referred for the relationship between tensile strength and yield strength according to nodularity of the CGI cast iron produced as described above. As shown in FIGS. 2 and 3 , it is possible to provide the cast iron of which the tensile strength and the yield strength are in the ranges of 500 to 600MPa and 350 to 450Mpa, respectively, with good quality of product.
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- Metallurgy (AREA)
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- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
Description
- The present invention relates to cast iron and a method of producing the same, and more particularly, to cast iron having an improved casting property and stable tensile strength and yield strength by controlling the contents of components added to iron, and a method of producing the cast iron. Cast iron according to the present invention corresponds to hypereutectic compacted graphite iron (CGI) cast iron that can be applied to the cylinder block of diesel engines with high output.
- Recently, it is required to reduce the contents of environmental pollutants such as Cox or NOx discharged from engines due to strictly enforced environmental regulation.
- For diesel engines, it is necessary to increase the explosive pressure of the engines in order to reduce the exhaust amount of environmental pollutants such as Cox or NOx. It needs to increase the strength of the cylinder block of the engines in order to increase the explosive pressure of the engines.
- Cast iron is the material that is generally used for cylinder blocks in the related art, common grade cast iron is usually gray cast iron. The gray cast iron is called gray cast iron because carbon is decomposed and produced into graphite in casting and the surface shows gray.
- In general, cast iron has differences in accordance with the shape, size, and distribution state of graphite contained in the base and the tensile strength of gray cast iron generally called cast iron is about 147.1 to 196.1MPa. The gray cast iron has a limit in use for the material of the cylinder block of engines having high explosive pressure, because the strength is low although a cast property, damping capacity, and thermal conductivity are excellent.
- There is spherical graphite cast iron as cast iron produced by improving the properties of gray cast iron. The spherical graphite cast iron is cast iron of which the toughness is improved by changing graphite shown in common cast iron (gray cast iron) into a spherical structure from the original foliaceous structure. The spherical graphite cast iron is also called nodular cast iron or ductile cast iron. The spherical graphite cast iron has excellent abrasion resistance, heat resistance, corrosion resistance, has a higher modulus of elasticity than that of common gray cast iron, has a Brinell Hardnes of even about 200, and also has a cutting property better than that of common cast iron having the same hardness.
- However, the spherical graphite cast iron has high strength required for cylinder blocks, but has an insufficient casting property and low thermal conductivity to be produced in a complicate shape, such that it has a limit in use for cylinder bocks having complicated shapes.
- Therefore, CGI (Compacted Graphite Iron) that has both the high strength and predetermined elongation of the spherical graphite cast iron while having the excellent casting property, damping capacity, and thermal conductivity of the gray cast iron is used as the next generation material for cylinder blocks.
- The CGI cast iron may be produced by accurately controlling the content of magnesium (Mg) when tapping molten spherical graphite cast iron, which is produced by melting spherical graphite cast iron, into a ladle for carrying original molten metal produced by a furnace to another place.
- It is necessary to accurately control the amount of magnesium and melting/tapping temperatures in order to ensure stable mechanical properties (tensile strength) in CGI cast iron, and for this purpose, an accurate control device, an experienced worker, and using high-quality pig iron with low contents of impurities are required. There is a problem in that poor quality and poor casting of CGI cast iron are frequently generated by differences in various requirements such as the content of magnesium, the tapping position, the tapping temperature, and the tapping speed, even under accurate control.
- The present invention provides cast iron of which tensile strength and yield strength are controlled within the ranges of 500 to 600MPa and 350 to 450MPa, respectively, by controlling the contents of carbon (C), silicon (Si), manganese (Mn), copper (Cu), tin (Sn), and magnesium (Mg) with a range that ensures stable properties without causing poor casting.
- An object of the present invention is to provide cast iron having stable properties and structure by accurately controlling the amount of magnesium (Mg). In particular, it is an object of the present invention to provide cast iron that can be applied to the cylinder block of high-output and high-power diesel engines.
- Another object of the present invention is to establish a chemical composition and a production method which make it possible to producing cast iron for a cylinder block that can be applied to high-output and high-power diesel engines by providing stable tensile strength and yield strength and appropriate hardness.
- The present invention provides a cast iron for use with cylinder block of an engine comprising carbon (c) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, magnesium (Mg) of 0.008 to 0.018 wt%, phosphorus (P) of 0.04 wt% or less, sulfur (S) of 0.02 wt% or less, and the balance of ferrum (Fe), an the entire weight.
- According to an exemplary embodiment of the present invention, tensile strength of the cast iron is 500 to 600MPa. Further, according to another exemplary embodiment of the present invention, yield strength of the cast iron is in the range of 350 to 450MPa. Meanwhile, a Brinell Hardness value (BHW) of the cast iron is 255 to 280.
- According to an exemplary embodiment of the present invention, CE (Carbon Equivalent) of the cast iron is 4.35 to 4.5.
- According to an exemplary embodiment of the present invention, nodularity of graphite produced by the carbon is 5 to 20% in the cast iron.
- The present invention provides a method of producing cast iron, comprising: producing original molten cast iron by melting a cast iron material, which contains carbon (C) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, phosphorous (P) of 0.04 wt% less, sulfur (S) of 0.02 wt% or less, and the balance of ferrum (Fe), in the entire weight, in a furnace; providing copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt% in a ladle that is a container for tapping the original molten cast iron melted in a furnace; producing molten cast iron by tapping the produced original molten cast iron with the ladle with copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt%; determining the amount of magnesium to be added by checking the content of magnesium contained in the molten cast iron in the ladle; adding magnesium of which the amount to be added is determined to the molten cast iron in the ladle; and injecting the molten cast iron added with the magnesium into a mold.
- In the present invention, CGI cast iron with stable mechanical properties is achieved by putting a predetermined amount of magnesium (Mg) and appropriate amounts of copper (Cu) and tin (Sn) into a ladle, which is a container for tapping an original molten cast iron melted in a furnace, tapping the original molten cast iron into the laddle, and crystallizing the graphite to be stable CGI.
- According to an exemplary embodiment of the present invention, CE (Carbon Equivalent) is adjusted to be 4.35 to 4.5 in the original molten cast iron.
- Further, according to an exemplary embodiment of the present invention, the tapping temperature of the original molten metal is adjusted to be 1520°C.
- According to an exemplary embodiment of the present invention, it may be possible to inoculate magnesium by using a wire type of magnesium inoculant in the adding of magnesium.
- In the cast iron according to the present invention, it is possible to estimate nodularity of graphite contained in cast iron from the content of magnesium contained in the molten cast iron and to estimate the range of strength according to the nodularity.
- In the present invention, the content of magnesium may depend on the necessary strength and the content is 0.008 to 0.018 wt% to be applied to the cylinder block of high-output diesel engines.
- According to the present invention, it is possible to provide cast iron with tensile strength in the range of 500 to 600 MPa, yield strength in the range of 350 to 450 Mpa, and Brinell Hardness in the range of 255 to 280, by precisely controlling the amount of magnesium (Mg) and controlling the amounts of copper (Cu) and tin (Sn).
- Since the cast iron according to the present invention has stable tensile strength and yield strength and appropriate hardness, the cast iron can be used to manufacture cylinder blocks that can be applied to high-output and high-power diesel engines.
- According to the present invention, it is possible to produce CGI cast iron having a uniform structure and strength that is high enough to be used for the cylinder block of high-power diesel engines, by precisely controlling the amount of magnesium (Mg). Further, it is possible to produce CGI cast iron having various hardness and tensile strength by controlling the amount of copper (Cu) and tin (Sn) that is alloy elements.
-
-
FIG. 1 is a graph illustrating the relationship between the content of magnesium (Mg) and nodularity of graphite. -
FIG. 2 is a graph illustrating the relationship of nodularity of graphite, tensile strength, and yield strength. -
FIG. 3 is a table showing the relationship between the content of magnesium (Mg) and tensile strength and a representative structure of cast iron (for reference, 1 MPa is 1N/mm2). -
FIG. 4 is a view simply showing an example of a process of producing cast iron according to the present invention. - The present invention will be described in more detail with reference to detailed examples.
- Cast iron according to the present invention contains carbon (c) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, magnesium (Mg) of 0.008 to 0.018 wt%, phosphorus (P) of 0.04 wt% or less, sulfur (S) of 0.02 wt% or less, and the balance of ferrum (Fe), an the entire weight. The basic material of the cast iron is ferrum (Fe).
- Next, the components and contents of the cast iron in the present invention are described.
- Carbon is added for crystallization of compacted graphite, and when the content of carbon in cast iron is less than 3.65 wt%, a chilling behavior is observed in a thin-walled part, and when it is above 3.75 wt%, graphite nodularity retraction and poor flow are generated. Therefore, the content of carbon is limited within 3.65 to 3.75 wt% in the present invention to prevent the defects in high-strength cylinder block having various thicknesses.
- Silicon maximizes the amount of crystallization of compacted graphite and increases strength of cast iron when being added at the optimum ratio with carbon. In the cast iron according to the present invention, when the content of silicon is less than 2.0 wt%, the amount of crystallization of compacted graphite decreases, and when it is above 2.25 wt%, ductility decreases, such that the content is set within 2.0 to 2.25 wt%.
- Manganese is added to make graphite fine and stabilize pearlite, and in the cast iron according to the present invention, when the content of manganese is less than 0.3 wt%, hardness decreases, and when it is above 0.6 wt%, brittleness increases, such that the content is set within 0.3 to 0.6 wt%.
- Copper is an element for compacted graphitization and promote creation of pearlite and makes it fine, such that it is an element for ensuring strength. In the case iron according to the present invention, when the content of copper is less than 1.2 wt%, lack of strength is caused, but even if the content is above 1.4 wt%, there is no additional effect corresponding to the excessive amount. Therefore, the content of copper is set within 1.2 to 1.4 wt% in the present invention.
- Tins is a very strong element for promoting creation of pearlite and added to improve strength, similar to copper. In the cast iron according to the present invention, when the content of tin is less than 0.07 wt%, strength decreases and when it is added over 0.10 wt%, brittleness rapidly increases, such that the content is set within 0.07 to 0.10 wt%.
- Magnesium has function of graphite nodularity and promotes creation and growth of the nucleus of compacted graphite. In the cast iron according to the present invention, when the content of magnesium is less than 0.008 wt%, graphite becomes flaky, and when it is above 0.018 wt%, nodularity of graphite increases and poor retraction is caused, such that the content is limited within 0.008 to 0.018 wt%.
- Phosphorous is also a kind of impurity naturally added from the air in the process of producing cast iron. Phosphorous stabilizes pearlite but when the content is above 0.04 wt%, brittleness rapidly increases and this is in association with poor retraction due to segregation. Therefore, in the cast iron according to the present invention, it is preferable to maintain the content of phosphorous at 0.04 wt% or less.
- It is realistically difficult to make the content of
phosphorous 0 in the raw material components of cast iron, and even if the content of phosphorous in the raw material components of cast iron is 0, phosphorous would be contained in the process of producing cast iron. Therefore, it is important to keep the content of phosphorous not more than 0.04 wt% in the present invention. - Sulfur functions as a creation site of compacted graphite, but when the content is above 0.02 wt%, it is required to add more magnesium in order to create compacted graphite. That is, when the content of sulfur increases above a predetermined range, with the content is magnesium limited, compacted graphite becomes flaky. Therefore, it is necessary to maintain the content of sulfur at 0.02 wt% or less in the cast iron according to the present invention.
- It is realistically difficult to make the content of
sulfur 0 in the raw material components of cast iron, and even if the content of sulfur in the raw material components of cast iron is 0, sulfur would be contained in the process of producing cast iron. Therefore, it is important to keep the content of sulfur not more than 0.02 wt% in the present invention. - Ferrum is the main substance of cast iron according to the present invention. The balance except for the components described above is ferrum.
- According to an exemplary embodiment of the present invention, carbon equivalent is 4.35 to 4.5. In the cast iron according to the present invention, when the carbon equivalent is less than 4.35, the thin-walled part is chilled, and when it is above 4.5, retraction and poor flow is caused by excessive primary graphite, such that the content is limited within 4.35 to 4.5. The carbon equivalent (CE) is defined by carbon + (silicon + phosphorous) X 1/3 and the value may be adjusted to control the properties and quality of the product.
- According to an exemplary embodiment of the present invention, tensile strength of the cast iron is 500 to 600MPa and yield strength is 350 to 450MPa.
- According to an exemplary embodiment of the present invention, in the cast iron, nodularity of graphite produced by the carbon is 5 to 20%.
- A process of producing cast iron according to the present invention is described with reference to
FIG. 4 . - According to a method of producing cast iron of the present invention, original
molten cast iron 110 is produced by melting a cast iron material containing carbon (C) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, phosphorous (P) of above 0 and 0.04 wt% less, sulfur (S) of above 0 and 0.02 wt% or less, and the balance of ferrum (Fe), in the entire weight, in afurnace 100. - A
ladle 200 with theother components 210 of copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt% is prepared, in which theladle 200 is a container for tapping the original molten cast iron melted in a furnace. - The
molten cast iron 110 is produced by tapping the produced original molten cast iron with theladle 200 with copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt%. - According to an exemplary embodiment of the present invention, the tapping temperature can be adjusted to be 1,520°C.
- Meanwhile, according to an exemplary embodiment of the present invention, the CE (Carbon Equivalent) may be adjusted to be 4.35 to 4.5 in the original molten cast iron.
- The amount of magnesium to be added is determined by checking the content of magnesium contained in the molten cast iron in the
ladle 200. - Since the original molten cast iron was carried to the ladle with the magnesium, a predetermined amount of magnesium is contained in the molten cast iron in the ladle. Nevertheless, the content of magnesium contained in the molten cast iron in the ladle is checked again to more precisely controlled the content of magnesium in consideration of loss of magnesium while carrying the ladle, and when it is determined that it needs to add magnesium, magnesium is added again.
- According to an exemplary embodiment of the present invention, a
thermal analysis system 300 may be used to check the content of magnesium. - Magnesium of which the amount to be added is determined is added to the molten cast iron in the ladle. According to an exemplary embodiment of the present invention, it may be possible to add magnesium, using a wire shape of
magnesium 500. - Another inoculant that is generally used in a process of producing cast iron may be added with magnesium. For example, a silicon-based inoculant may be added. The silicon-based inoculant may be obtained from those on the market. The kind and content of the inoculant may be easily selected and determined by those skilled in the art, if necessary. Other inoculants may also be shaped in a
wire type 500. - Cast iron is completed by injecting the molten metal with magnesium into a
mold 400. - Cast iron according to Examples 1 to 10 and Comparative example 1 to 10 was produced in accordance with the composition in the following Table 1
[Table 1] Unit: wt% Items C Si Mn Cu Sn Mg P S Fe Example 1 3.650 2.240 0.440 1.360 0.090 0.017 0.031 small balance Example 2 3.680 2.190 0.400 1.340 0.090 0.010 0.031 small balance Example 3 3.700 2.110 0.390 1.410 0.080 0.011 0.031 small balance Example 4 3.710 2.080 0.400 1.330 0.100 0.009 0.034 small balance Example 5 3.680 2.140 0.380 1.260 0.080 0.011 0.031 small balance Example 6 3.680 2.180 0.430 1.340 0.090 0.018 0.026 small balance Example 7 3.710 2.130 0.400 1.290 0.070 0.013 0.031 small balance Example 8 3.690 2.050 0.400 1.350 0.100 0.014 0.033 small balance Example 9 3.710 2.130 0.400 1.290 0.070 0.013 0.031 small balance Example 10 3.700 2.140 0.430 1.320 0.090 0.017 0.030 small balance Comparative Example 1 3.810 2.220 0.110 1.150 0.090 0.012 0.034 small balance Comparative Example 2 3.710 2.090 0.290 0.820 0.070 0.008 0.024 small balance Comparative Example 3 3.780 1.970 0.110 0.870 0.070 0.000 0.019 small balance Comparative Example 4 3.690 2.220 0.080 1.100 0.120 0.011 0.036 small balance Comparative Example 5 3.780 2.010 0.110 0.890 0.070 0.000 0.018 small balance Comparative Example 6 3.620 2.230 0.480 1.650 0.090 0.020 0.028 small balance Comparative Example 7 3.720 2.090 0.460 1.390 0.090 0.022 0.029 small balance Comparative Example 8 3.710 2.090 0.430 1.430 0.100 0.024 0.025 small balance Comparative Example 9 3.650 2.190 0.370 1.230 0.090 0.020 0.031 small balance Comparative Example 10 3.690 2.370 0.290 0.810 0.070 0.017 0.023 small balance - First, in accordance with the composition in Table 1, original molten metal containing carbon (C), silicon (Si), Manganese (Mn), and phosphorous (P) was prepared. Sulfur (S) is an element that is unavoidably contained in the raw material of cast iron and the process of producing cast iron, such that it is not separately added but the content is maintained at 0.02 wt% or less.
- The content of carbon was adjusted by measuring the CE by using a CE meter before tapping and temperature was fitted to 1,146°C with respect to TL (Liquidous Temperature), thereby preparing original molten metal.
- A ladle was prepared by adding magnesium (Mg), copper (Cu), and tin (Sn) and the original molten metal was tapped to the ladle while the tapping temperature is uniformly maintained around about 1,520°C .
- The amount of magnesium to be added in consideration of the content of magnesium that will be finally contained was determined by thermally analyzing the tapped original molten metal, the alloy amount of a wire type of magnesium was injected into a mold at 1,410°C after the alloy elements are adjusted.
- Carbon equivalent (CE), tensile strength (TS), yield strength (YS), hardness (Hardness), and nodularity of the cast iron produced in accordance with the composition in Table 1 were measured and shown in Table 2. The hardness is Brinell Hardness and an HBW brinell hardness value.
[Table 2] Items C.E Tensile strength (N/mm2) Yield strength (N/mm2) Hardness (HBW) Nodularity (%) Example 1 4.410 514.0 422.0 267.3 17.8 Example 2 4.420 521.0 342.5 259.5 8.5 Example 3 4.410 537.0 418.5 260.5 7.5 Example 4 4.410 550.8 418.8 273.3 11.6 Example 5 4.400 562.5 424.5 265.0 18.0 Example 6 4.420 570.0 434.0 271.3 19.9 Example 7 4.430 576.3 427.3 261.8 18.2 Example 8 4.380 579.5 441.8 279.0 14.4 Example 9 4.430 584.0 430.8 272.5 18.3 Example 10 4.420 584.8 438.3 269.0 21.1 Comparative Example 1 4.560 356.3 371.0 261.5 9.2 Comparative Example 2 4.410 412.5 345.8 244.3 17.5 Comparative Example 3 4.440 480.3 379.5 248.0 Impossible to measure Comparative Example 4 4.440 480.7 372.0 256.7 5.1 Comparative Example 5 4.460 481.0 390.0 248.0 Impossible to measure Comparative Example 6 4.370 602.8 443.8 275.3 22.0 Comparative Example 7 4.430 609.0 433.3 261.8 36.4 Comparative Example 8 4.420 629.0 442.5 273.8 29.7 Comparative Example 9 4.390 636.3 462.3 281.8 42.0 Comparative Example 10 4.490 654.3 448.0 266.0 59.3 - As described above, it can be seen that in the cast iron according to the examples of the present invention the tensile strength was within 500 to 600 MPa(N/mm2), the yield strength was 350 to 450 MPa(N/mm2), and the HBW brinell hardness value was 255 to 280.
- As described above, the cast iron according to the present invention has stable tensile strength and yield strength and appropriate hardness, such that the cast iron may be easily used to manufacture a cylinder block that can be applied to high-output and high-power diesel engines.
- For reference, the result of observing the relationship between the nodularity of cast iron and the amount of magnesium was show in
FIG. 1 . As shown inFIG. 1 , it can be seen that nodularity was in the range of 5 to 20% in the CGI cast iron according to the present invention. -
FIGS. 2 and3 can be referred for the relationship between tensile strength and yield strength according to nodularity of the CGI cast iron produced as described above. As shown inFIGS. 2 and3 , it is possible to provide the cast iron of which the tensile strength and the yield strength are in the ranges of 500 to 600MPa and 350 to 450Mpa, respectively, with good quality of product.
Claims (9)
- A cast iron for use with a cylinder block of an engine comprising:carbon (c) of 3.65 to 3.75 wt%;silicon (Si) of 2.0 to 2.25 wt%;manganese (Mn) of 0.3 to 0.6 wt%;copper (Cu) of 1.2 to 1.4 wt%;tin (Sn) of 0.07 to 0.10 wt%;magnesium (Mg) of 0.008 to 0.018 wt%;phosphorus (P) of 0.04 wt% or less;sulfur (S) of 0.02 wt% or less; andthe balance of ferrum (Fe), an the entire weight
- The cast iron of claim 1, wherein tensile strength is 500 to 600MPa.
- The cast iron of claim 1, wherein yield strength is 350 to 450MPa.
- The cast iron of claim 1, wherein carbon equivalent is 4.35 to 4.5.
- The cast iron of claim 1, wherein nodularity of graphite produced by the carbon is 5 to 20%.
- A method of producing cast iron, comprising:producing original molten cast iron by melting a cast iron material, which contains carbon (C) of 3.65 to 3.75 wt%, silicon (Si) of 2.0 to 2.25 wt%, manganese (Mn) of 0.3 to 0.6 wt%, phosphorous (P) of above 0 and 0.04 wt% less, sulfur (S) of above 0 and 0.02 wt% or less, and the balance of ferrum (Fe), in the entire weight, in a furnace;providing copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt% in a ladle that is a container for tapping the original molten cast iron melted in a furnace;producing molten cast iron by tapping the produced original molten cast iron with the ladle with copper (Cu) of 1.2 to 1.4 wt%, tin (Sn) of 0.07 to 0.10 wt%, and magnesium (Mg) of 0.008 to 0.018 wt%;determining the amount of magnesium to be added by checking the content of magnesium contained in the molten cast iron in the ladle;adding magnesium of which the amount to be added is determined to the molten cast iron in the ladle; andinjecting the molten cast iron added with the magnesium into a mold.
- The method of claim 6, wherein carbon equivalent in the original molten cast iron is 4.35 to 4.5.
- The method of claim 6, wherein the tapping temperature is adjusted to be 1,520°C.
- The method of claim 6, wherein magnesium is added by using a wire type of magnesium in the adding of magnesium.
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PCT/KR2010/008730 WO2011078500A2 (en) | 2009-12-22 | 2010-12-08 | Cgi cast iron and a production method for the same |
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EP2785882B1 (en) * | 2011-11-30 | 2016-01-20 | Federal-Mogul Corporation | High modulus wear resistant gray cast iron for piston ring applications |
CN103195689A (en) * | 2013-04-24 | 2013-07-10 | 东莞市金瑞五金制品有限公司 | Compressor |
KR102279874B1 (en) * | 2014-12-24 | 2021-07-20 | 두산인프라코어 주식회사 | Nodular graphite cast iron and preparation method thereof, and component for hydraulic device prepared thereby |
KR102388131B1 (en) * | 2015-02-04 | 2022-04-19 | 현대두산인프라코어(주) | Compacted graphite cast iron and engine component comprising the same |
WO2018079887A1 (en) * | 2016-10-28 | 2018-05-03 | 한국생산기술연구원 | Flake graphite cast iron and casting and production method thereof |
CN112322962B (en) * | 2020-11-06 | 2022-04-12 | 中原内配集团股份有限公司 | Vermicular graphite cast iron and preparation method thereof |
CN114836680A (en) * | 2021-02-01 | 2022-08-02 | 上海海立电器有限公司 | Casting material, compressor cylinder and casting method thereof, and rotor type compressor |
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WO2003045625A2 (en) * | 2001-11-27 | 2003-06-05 | Tupy Fundições Ltda. | Vermicular cast iron of high machinability |
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JP2624886B2 (en) * | 1990-09-19 | 1997-06-25 | 株式会社日立製作所 | Elevator equipment |
SE502227C2 (en) * | 1993-12-30 | 1995-09-18 | Sintercast Ab | Process for the continuous provision of pretreated molten iron for casting compact graphite iron articles |
US20030024608A1 (en) * | 1997-10-14 | 2003-02-06 | Camcast Industries Pty., Ltd. | Iron alloy containing molybdenum |
SE520028C2 (en) * | 1998-07-03 | 2003-05-13 | Sintercast Ab | Process for the preparation of compact graphite iron alloy, this article, and the use of compact graphite alloy |
JP3812925B2 (en) * | 1998-07-24 | 2006-08-23 | 日産ディーゼル工業株式会社 | Compact vermicular graphite cast iron for engine cases |
KR20030087484A (en) * | 2002-05-10 | 2003-11-14 | 현대자동차주식회사 | A composition of compacted graphite iron ferrite |
KR100836399B1 (en) * | 2006-11-13 | 2008-06-09 | 현대자동차주식회사 | method for manufacturing CGI Cast Iron |
KR20090093291A (en) * | 2008-02-29 | 2009-09-02 | 현대자동차주식회사 | CGI Cast Iron |
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JPH09202935A (en) * | 1996-11-15 | 1997-08-05 | Hitachi Ltd | Compacted vermicular graphite cast iron and sliding device using the same |
WO2001038593A1 (en) * | 1999-11-23 | 2001-05-31 | Sintercast Ab | New cast iron alloy and method for making the same |
WO2003045625A2 (en) * | 2001-11-27 | 2003-06-05 | Tupy Fundições Ltda. | Vermicular cast iron of high machinability |
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US20120301346A1 (en) | 2012-11-29 |
CN103938067A (en) | 2014-07-23 |
WO2011078500A3 (en) | 2011-11-10 |
EP2518174A4 (en) | 2014-05-07 |
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CN102666896B (en) | 2014-10-29 |
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