US3421886A - Cast iron with at least 50% of the graphite in vermicular form and a process for making same - Google Patents

Cast iron with at least 50% of the graphite in vermicular form and a process for making same Download PDF

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US3421886A
US3421886A US713280A US3421886DA US3421886A US 3421886 A US3421886 A US 3421886A US 713280 A US713280 A US 713280A US 3421886D A US3421886D A US 3421886DA US 3421886 A US3421886 A US 3421886A
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graphite
cast iron
iron
magnesium
castings
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Robert Douglas Schelleng
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Huntington Alloys Corp
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International Nickel Co Inc
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    • 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
    • C21C1/10—Making spheroidal graphite 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
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/08—Manufacture of cast-iron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • 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

Definitions

  • a graphitic cast iron consisting essentially of about 2% to about 4% carbon, about 1.5% to about 3.5% silicon, up to about 36% nickel, about 0.005% to about 0.06% magnesium, about 0.001% to about 0.015% of a metal from Group IIIB of the periodic table, about 0.15% to about 0.5% titanium, with said magnesium, Group IIIB metal and titanium contents being eifective to control the occurrence of graphite in said cast iron predominantly in the vermicular form and the balance of said cast iron being essentially iron with other elements and impurities in small amounts which do not materially interfere with the occurrence of graphite in said vermicular form.
  • a process for making said cast iron is also claimed,
  • the present invention is directed to improved graphitic cast iron and, more particularly, to an improved stronger cast iron having a controlled vermicular graphite structure and having essentially the foundry characteristics of flake graphite cast iron.
  • ductile iron i.e., cast iron containing graphite in a spheroidal form
  • the foundry industry has undergone a revolution in regard to the ability of the industry to provide castings having very high strength and useful levels of ductility as compared to gray cast iron containing graphite in the flake form.
  • Ductile iron is now well established as a foundry product and the use of this material in the form of castings in industry is expanding each year. The increased tonnage of ductile iron which is sold each year may properly be taken as an indication of the acceptance which castings made of the material have secured in industry.
  • ductile iron exhibits inferior foundry characteristics as compared with gray cast iron, and for that reason has not found favor in those applications Where good foundry characteristics are of paramount importance.
  • the expression good foundry characteristics is used in the industry to include such factors as fluidity, improved resistance to the formation of shrinkage cavities in sections which are diflicult to feed, freedom from dross defects, low chilling tendency, etc. It is considered in the foundry industry that flake graphite gray cast iron has good foundry characteristics. With particular reference to the problem of shrinkage in castings, it is unquestionable that the shrink properties of gray cast iron castings are more favorable than is the case in "ice the higher strength ductile iron castings.
  • gray cast iron is used to denote cast iron having its uncombined carbon in the form of ordinary, unmodified flakes.
  • the automotive engine block has traditionally been produced as a gray iron casting.
  • foundries producing engine block castings have been required to produce lighter and lighter castings having thinner and thinner wall sections in response to demands of automotive designers for lighter engines having higher power-to-weight ratios and in response to a powerful competitive thrust from die cast aluminum engine blocks.
  • ductile iron In order to supply the demand for such castings, it would be desirable to employ ductile iron therein so that the markedly higher strength and modulus of elasticity of this material as compared to gray iron could be used with advantage.
  • the foundry characteristics of ductile iron are such that it is difficult to produce sound and leak-proof thin-Walled castings of complicated configuration in the material on a production basis.
  • the high strength of ductile iron as compared to gray iron would also appear to be useful in other castings such as lightweight brake drums and ingot molds.
  • the thermal conductivity of ductile iron is lower than that of gray iron and this undesirable characteristic has inhibited the adoption of ductile iron in such applications and in other applications requiring high thermal conductivity and resistance to thermal shock.
  • a cast iron material having its uncombined carbon in the vermicular form is capable of satisfying this demand.
  • its graphite is in vermicular rather than flake form such a material possesses substantially greater strength and ductility than gray cast iron of the same composition, and, on the other hand, because the form of its graphite is more nearly flake-like than nodular such a material possesses substantially better foundry characteristics than ductile iron.
  • vermicular graphite is used in this application to denote the type of graphite identified by that name and depicted in the paper by Donoho published in Modern Castings for July, 1961 at pages -71, inclusive.
  • Vermicular graphite structures have sporadically and on rare occasions been observed in connection with unsuccessful attempts to produce ductile iron in which insuflicient or incorrect nodularizing treatments were employed. Such structures have, however, been of unpredictable occurrence and unknown cause. Being thus uncontrollable and unreproducible, vermicular structures have not heretofore been regarded by the foundry industry as being of any practical utility. The vermicular graphite form has, rather, been looked upon as a manifestation of failure in the production of ductile iron.
  • Still another object of the invention is to provide a gray cast iron product having improved strength while having improved thermal conductivity and thermal shock resistance as compared to a ductile iron of the same base composition.
  • a further object of the invention is to provide a casting having the basic composition of gray cast iron, having improved strength as compared to gray cast iron of the same base composition and having improved foundry characteristics as compared to ductile iron of the same base composition.
  • FIGURE 1 is a reproduction of a photomicrograph taken at 100 diameters depicting the vermicular graphite microstructure which it is the object of the invention to produce;
  • FIGURES 2A, 2B, 2C and 2D are reproductions of photomicrographs taken at 100 diameters depicting vermicular graphite structure in cast iron produced in accordance with the invention over a range of magnesium contents;
  • FIGURES 3A, 3B and 3C are reproductions of photomicrographs taken at 100 diameters depicting the production of spheroidal graphite structures when an element essential to the present invention is omitted from the cast iron composition;
  • FIGURE 4 is a reproduction of a photograph taken at three-fourths actual size depicting the longitudinal section of a poorly fed complicated valve body casting demonstrating, in comparison to FIGURE 5, that improved soundness is obtained in castings produced in accordance with the invention.
  • FIGURE 5 is a reproduction of a photograph taken at three-fourths actual size depicting the longitudinal section of a similar casting to that shown in FIGURE 4 to illustrate the foundry characteristics of ductile iron under the same conditions.
  • FIG. 1 shows the structure of cast iron containing about 0.01% magnesium which was converted from Type A flake graphite to vermicular graphite by the addition of about 0.005 cerium.
  • the retained magnesium content of the cast iron must be maintained within a very narrow range lying just below the spheroid-producing amount for the particular composition being treated. Increasing the magnesium content above this range results almost immediately in a predominantly or fully spheroidal structure. Because of the extreme difliculty of maintaining the magnesium content within the requisite limits, the inevitable variabilty of the composition of cast iron from heat to heat, and for other reasons as well, vermicular structures cannot be obtained through the use of magnesium-cerium treatments alone on other than an uncontrollable, hit-and-miss basis.
  • titanium if added in suflicient quantity;
  • the present invention comprises a graphitic cast product having the graphite predominantly in a vermicular form and containing about 0.005% or about 0.01% to about 0.06% magnesium, about 0.15% to about 0.5% titanium, about 0.001% to about 0.01% or 0.015% of a metal, e.g., cerium, from Group III-B of the periodic table, not more than about 0.02% or 0.025% sulfur, and the balance a gray cast iron composition.
  • a metal e.g., cerium
  • the carbon content is about 2% to about 4%
  • the manganese content is about 0.1% to about 2.5%, or more when nickel is high enough to make the alloy austenitic
  • the silicon content is about 1.5% to about 3.5%, more advantageously, not exceeding 3%.
  • the product may contain up to about 1.0% chromium, up to about 2% molybdenum, up to about 0.5% vanadium, up to about 0.2% phosphorus, up to about 0.2% zirconium, up to about 0.05% aluminum, etc.
  • the nickel content of the alloy may optionally be as high as about 36% as, for example, in castings having an austenitic matrix and containing about 20% or more nickel.
  • austenitic castings may contain about 2% of chromium.
  • the elements copper, tin, lead, antimony and bismuth are undesirable impurities in the special cast material provided in accordance with the invention since these elements interfere with the controlled production of vermicular graphite in castings contemplated by the invention in that they undesirably increase the tendency to form spheroidal graphite.
  • the copper content should not exceed about 0.5% and the tin content should not exceed about 0.03% when the magnesium content is about 0.04% or higher.
  • the tolerance for copper and tin are increased until at a magnesium content of about 0.02% a copper content up to about 2% and a tin content up to about 0.15% may be permitted without an undesirable formation of spheroidal graphite being encountered.
  • the lead content should not exceed about 0.01% and the antimony and bismuth contents should not exceed about 0.01% each.
  • the special cast material provided in accordance with the invention contains 3% to 3.6%
  • Castings produced within the more advantageous ranges of composition exhibit freedom from shrinkage porosity and low chilling tendency in combination with moderately high strength.
  • Nickel is an important alloying element in the special cast material since it provides an improvement in matrix properties, particularly strength, and does not detrimentally affect the graphite structure. Thus, at nickel contents up to about 5%, each additional percent of nickel will provide an increase in tensile strength of the castings of about 6,000 pounds per square inch (p.s.i.).
  • the carbide-forming elements chromium, molybdenum and vanadium do not appear to affect the formation of the desired vermicular graphite structure but do increase the chilling propensity of castings containing these elements. Accordingly, in any application in which chill control is a factor, the use of these elements generally is avoided.
  • the special cast material provided in accordance with the invention may have any matrix structure characterizing corresponding alloyed and unalloyed gray cast irons in the as-cast and/or heat treated conditons.
  • the as-cast matrix microstructure may be ferritic, pearlitic, austenitic, martensitic, acicular, etc.
  • the magnesium does not exceed about 0.04%, since in such irons occurrence of undesired graphite forms such as spheroids with the resulting occurrence of undesirable solidification shrinkage is avoided and increased chilling propensity is minimized.
  • the titanium content is at least about 0.2%.
  • oxide films form on the surface of the liquid iron which tend to cause surface defects on the castings produced.
  • cerium is absent, flake graphite forms and the strength of the iron is low.
  • the cerium content exceeds approximately 0.01%, e.
  • vermicular graphite in the absence of the required amount of titanium is a matter of difficulty characterized by a higher tensile strength as compared to that of gray cast iron having the same base composition.
  • the castings have a true modulus on the order of about 20 to about 22x10 psi. and have a useful ductility.
  • the castings have improved fatigue resistance as compared to gray cast iron castings 'of the same base composition.
  • other elements from Group IIIB of the periodic table such as yttrium, lanthanum or other element of the lanthanide or rare earth metal series may be employed in the place of cerium.
  • Mischmetal e.g., an alloy containing about 50% cerium and about 25% lanthanum with the remainder being comprised of other rare earth elements, is a satisfactory cerium-containing addition material for the production of castings in accordance with the invention. It is found in practice that, 'when such a mischmetal alloy is added to molten cast iron, lanthanum recovery is only about one-half as great as is the cerium recovery. Those skilled in the art will appreciate that cerium or other Group III-B metal can be added to the molten cast iron both in metallic form or in the form of a compound, e.g., oxides, etc., which are reducible to metal in the bath.
  • compositions of a number of castings produced in accordance with the invention are set forth in the following Table I and the tensile properties determined from 1-inch keel bar castings in the ascast condition are set forth in the following Table II. 'In each case, the melts were inoculated with 0.5%, by weight, of a calcium-bearing grade of ferrosilicon containing about silicon.
  • melts set forth in the above table were produced using a mischmetal alloy containing about 50% cerium and about 25% lanthanum and contained cerium and lanthanum in a ratio of about 4 to 1. Numbers in parentheses are estimated.
  • melts were produced containing about 3.5% carbon, 51,1 L8 21 6X100 179 :0 05 about 2.3% silicon, about 0.3% manganese and the hal- 17 m 1 44 O 9 0 2,) 106 108 i l ance essentially iron.
  • the melts were desulfurized to about f 0.005% sulfur by calcium carbide injection.
  • Titanium was 13 143 Y/5 introduced into one series of melts in an amount of about 19 53,8 4 g 5 17s v, 0.32% to 0.34% while the titanium content of the other eri w l5 r 'n an sium 20 51.1 4M m 163 95% V, 5 es as about 00 A; Va ious a iounts of ma e m 3, and cerium were employed The treated metal in each case 21 47.4 44.0 1.0 170 1007 V.
  • Iron of this invention About 0.11 0.6 Titanium 0.320.34% Gray iron About 0.12 1.0 Ductile iron About 0.08 0.34 +95%V 2.
  • Nora-Damping capacities were detennined by applying to SDCCmlCHs 80%V 2C 402 42.2 0.0 143 of the test materials a vibrational stress initially varying between 4,003 50% V 2]) 50, 0 4g, 0 g 5 151 p.s.i. in compression and 1,000 psi. in compression and measuring tn relative rates at which the amplitude of vibration decreased initially '11tnni 0 015% when the imposed vibration was shut oti.
  • vermicular graphite structure of the special cast product produced in accordance with the invention is not materially affected by variations in section size over the range from about /4 inch up to about 4 inches as illustrated by data set forth in the following Tables IV and V.
  • the chilling propensity of the special cast material is lower than that of a ductile iron casting and is approximately proportional to the magnesium content, in the absence of other carbide-forming elements. It is accordingly advantageous in applications in which chilling propensity is to be minimized, as, for example, in thin-sectioned castings having wall thicknessess on the order of inch or less, to operate at magnesium contents in the lower end of the range set forth hereinbefore. In such instances, it may also be advantageous to desulfurize the molten iron to a level not exceeding about 0.02% prior to treatment with magnesium, titanium and cerium or other Group IIIB element. It will also be appreciated than when the magnesium content is low, e.g., on the order of about 0.01%, precautions must be taken to insure that at least an effective magnesium content not combined with sulfur as MgS is present in the iron.
  • valve body test castings of complicated configuration were made using the two materials in identical molds designed to provide poor feeding conditions.
  • the special casting of the invention contained 3.73% carbon, 2.21% silicon, 0.18% manganese, 0.010% magnesium, 0.25% titanium, 0.009% cerium and had graphite in the vermicular form.
  • the ductile iron casting was made in the same base iron, contained about 0.05% magnesium and had spheroidal graphite.
  • the castings were sectioned longitudinally and were photographed with the casting in accordance with the invention being depicted in FIGURE 4 and the ductile iron casting being depicted in FIGURE 5. As shown in FIG- URE 4, the casting according to the invention was almost completely sound while the ductile iron casting was characterized by severe shrinkage cavities in the poorly fed areas.
  • melt of gray cast iron composition is established, i.e., a cast iron melt having such graphitizing power that is cast, at least after a graphitizing inoculation, it would be a gray cast iron substantially devoid of massive carbides such as occur in white cast iron.
  • sulfur content of the meltexceeds about 0.02% it is advantageous to reduce the sulfur content of the melt to about 0.02% or lower by means of common desulfurizing techniques, including the use of magnesium.
  • Any of the common furnaces employed in the production of foundry gray cast iron can be employed to produce the special cast material provided in accordance with the invention.
  • the melt is brought to a proper temperature for casting, e.g., a temperature in the range of about 2600 F.
  • a graphitizing inoculant such as ferrosilicon, e.g., an alloy containing 85% silicon, about 0.5% calcium, and the balance essentially iron, in an amount sufiicient to introduce about 0.5% silicon, e.g., about 0.3% to about 0.7% silicon, is made to the treated melt and the melt is then cast.
  • a graphitizing inoculant such as ferrosilicon, e.g., an alloy containing 85% silicon, about 0.5% calcium, and the balance essentially iron
  • sufiicient to introduce about 0.5% silicon e.g., about 0.3% to about 0.7% silicon
  • the instant inoculation procedure wherein a few grams of powdered inoculating alloy, e.g., ferrosilicon, is introduced into the feeder gate prior to pouring the casting, advantageously may be employed.
  • Usual heat treating procedures employed in the art to decompose carbides and/or pearlite may also be applied to the castings produced in accordance with the invention.
  • a graphitic cast iron consisting essentially of about 2% to about 4% carbon, about 1.5% to about 3.5% silicon, up to about 36% nickel, about 0.005% to about 0.06% magnesium, about 0.001% to about 0.015% of a metal from Group IIIB of the periodic table, about 0.15% to about 0.5% titanium, with said magnesium, Group IIIB metal and titanium contents being effective to control the occurrence of graphite in said cast iron so that at least 50% is in the vermicular form and the balance of said cast iron being essentially iron with other elements and impurities in small amounts which do not materially interfere with the occurrence of graphite in said vermicular form.
  • a graphitic cast iron according to claim 2 containing about 3% to about 3.6% carbon, about 2% to about 2.6% silicon, about 0.2% to about 0.7% manganese, about 0.01% to about 0.04% magnesium, about 0.2% to about 0.5 titanium and about 0.001% to about 0.01% cerium.
  • a graphitic cast iron according to claim 1 containing about 0.01% to about 0.04% magnesium and about 0.2% to about 0.5 titanium.
  • a process for producing graphitic cast iron having at least 50% of the graphite in the vermicular form which comprises establishing a bath of gray cast iron containing about 2% to about 4% carbon, and up to about36% nickel, adjusting the titanium content of said bath to about 0.15% to about 0.5 incorporating about 0.005 to about 0.06% magnesium and about 0.001% to about 0.015 of a Group III-B metal into said bath the contents of titanium, magnesium, and the Group IIIB metal being eifective to control the occurrence of graphite in said cast iron so that at least about 50% is in the vermicular form in the finishing casting, and casting metal from the resulting bath in an inoculated condition to provide a casting consisting essentially of about 2% to about 4% carbon, up to about 36% nickel, about 1.5 to about 3.5% silicon, about 0.005 to about 0.06% magnesium, about 0.001% to about 0.015% of Group III-B metal and about 0.15% to about 0.5% titanium, not more than 2,749,238 6/1956 Millis

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Cited By (20)

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DE2842524A1 (de) * 1978-05-18 1979-11-29 Microalloying Int Inc Verfahren zur herstellung von gusseisen
WO1982003410A1 (en) * 1981-03-31 1982-10-14 Linkert Reinhold Method for the preparation of vermicular graphite cast iron and device allowing to implement such method
EP0074624A2 (de) * 1981-09-15 1983-03-23 Georg Fischer Aktiengesellschaft Radnabe für Personen- oder Lastwagen
US4596606A (en) * 1984-09-04 1986-06-24 Ford Motor Company Method of making CG iron
FR2597376A1 (fr) * 1986-04-17 1987-10-23 Caffier Barreau Anc Ets Pieces moulees en fonte, notamment moules de verrerie, a structure de fonte variable dans l'epaisseur des pieces
GB2190333A (en) * 1986-05-16 1987-11-18 York Trailer Co Ltd Brake drum and hub assembly
US4737199A (en) * 1985-12-23 1988-04-12 Ford Motor Company Machinable ductile or semiductile cast iron and method
US4806157A (en) * 1983-06-23 1989-02-21 Subramanian Sundaresa V Process for producing compacted graphite iron castings
EP1266870A2 (en) * 2001-06-12 2002-12-18 Owens-Brockway Glass Container Inc. Glassware forming mold and method of manufacture
US6733565B1 (en) 2002-04-24 2004-05-11 Rodney L. Naro Additive for production of irons and steels
US20070122302A1 (en) * 2005-11-30 2007-05-31 Scroll Technologies Ductile cast iron scroll compressor
US7618473B1 (en) 2003-10-27 2009-11-17 Rodney L. Naro Method for improving operational efficiency in clogged induction melting and pouring furnaces
US20110171016A1 (en) * 2010-01-14 2011-07-14 Honeywell International Inc. Austenitic ductile cast iron
WO2012047824A1 (en) * 2010-10-04 2012-04-12 Graham Packaging Company, L.P. Blow molding clamping linkage system
US8366437B2 (en) * 2010-10-04 2013-02-05 Graham Packaging Company, L.P. Angle link pivot bracket for wheel
US8388333B2 (en) 2010-09-30 2013-03-05 Graham Packaging Company, L.P. Systems for purging polyethylene terephthalate from an extrusion blow molding apparatus
US8807977B2 (en) 2010-10-04 2014-08-19 Graham Packaging Company, L.P. Cam follower slide for mold clamping linkage system
JP2016017208A (ja) * 2014-07-08 2016-02-01 友鉄工業株式会社 プレス金型材
US9404400B2 (en) * 2008-08-01 2016-08-02 Daf Trucks N.V. Cylinder head with valve seat and method for the production thereof
US11377717B2 (en) 2016-09-13 2022-07-05 Tupy S.A. Vermicular cast iron alloy and internal combustion engine head

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US2873188A (en) * 1956-02-10 1959-02-10 Union Carbide Corp Process and agent for treating ferrous materials
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US2485761A (en) * 1947-03-22 1949-10-25 Int Nickel Co Gray cast iron having improved properties
US2488511A (en) * 1949-01-25 1949-11-15 British Cast Iron Res Ass Nodular cast iron and the manufacture thereof
US2749238A (en) * 1949-09-10 1956-06-05 Int Nickel Co Method for producing cast ferrous alloy
US2542655A (en) * 1949-09-17 1951-02-20 Int Nickel Co Gray cast iron
US2841489A (en) * 1951-02-07 1958-07-01 Int Nickel Co Nodular cast iron and process of making same
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Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2842524A1 (de) * 1978-05-18 1979-11-29 Microalloying Int Inc Verfahren zur herstellung von gusseisen
WO1982003410A1 (en) * 1981-03-31 1982-10-14 Linkert Reinhold Method for the preparation of vermicular graphite cast iron and device allowing to implement such method
EP0074624A2 (de) * 1981-09-15 1983-03-23 Georg Fischer Aktiengesellschaft Radnabe für Personen- oder Lastwagen
EP0074624A3 (en) * 1981-09-15 1985-04-10 Georg Fischer Aktiengesellschaft Hub for vehicle wheels
US4806157A (en) * 1983-06-23 1989-02-21 Subramanian Sundaresa V Process for producing compacted graphite iron castings
US4596606A (en) * 1984-09-04 1986-06-24 Ford Motor Company Method of making CG iron
AU577616B2 (en) * 1984-09-04 1988-09-29 Ford Motor Company Of Canada Limited Cg cast iron
US4737199A (en) * 1985-12-23 1988-04-12 Ford Motor Company Machinable ductile or semiductile cast iron and method
FR2597376A1 (fr) * 1986-04-17 1987-10-23 Caffier Barreau Anc Ets Pieces moulees en fonte, notamment moules de verrerie, a structure de fonte variable dans l'epaisseur des pieces
EP0246936A1 (fr) * 1986-04-17 1987-11-25 ANCIENS ETABLISSEMENTS CAFFIER & BARREAU Pièces moulées en fonte, notamment moules de verrerie, à structure de fonte variable dans l'épaisseur des pièces
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